Title of the Invention
LIGHT EMITTING ELEMENT AND METHOD FOR MANUFACTIIRING LIGHT
EMITTINGELEMENT
Technical Field
[0001] The present invention relates to a light emitting element and a method for
manufacturing the light emitting element.
Background Art
[00021 Light emitting elements expected as next-generation of displays or illumination
devices include an organic EL element (organic Electro-Luminescence element o¡
organic light emitting diode). In the organic EL element, a hole injected from a hole
injecring layer and electron injected fiom an electron injecting layer are carried to a lighf
emitfing layer respectively, then the hole and electron are recombined on an organic
molecule in a light emitting part of the light emitting layer to excite the organic
molecule, thereby generating light emission. Therefore, when the organic EL element is
used as the display device or the illumination device, the light from the light emittíng
layer is required to be efficientþ extracted from the surface ofthe organic EL element.
In order to meet this demand, PATENT LITERATURE 1 discloses that a diffraction
grating substrate is provided on a light extraction surface of the organic EL element.
[0003] In the organic EL element, moisture and oxygen may reduce luminance,
luminous efficiency, and the like. In order to prevent such deterioration, the organic EL
element is used in a state that the light emitting part (organic layer) is sealed with a
sealing member. Methods for sealing the light emitting part include a method referred
to as "surface sealing (cover sealing)" and a method refe¡red to as "fiame sealing". The
surface sealing is a method for sealing the light emitting part by covering the light
emitting part with adhesive (sealing adhesive) or the like. The frame sealing is a
method as described in PATENT LITERATURE 2. Nameiy, in a structure having a
sealing membe¡ such as sealing glass, which is disposed on a light emitting part on a
substrate, the periphery of the sealing membe¡ is sealed with adhesive. It is said that it
is possible to elongate the service life of the frame-sealed. element by frlling a sealed
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space of the structure with a desiccant or the like.
Citâtion List
Patent Literature
[00041 PATENT LITERATURE 1: Japanese Patent Application Laid-open No. 2006-
236748
PATENT LITERATURE 2: Japanese Patent Application Laid-open No. 2012-
t74410
Summary of Invention
Technical Problem
[0005] It is known that the frame sealing performed for the organic EL element having
the diffraction grating substrate has the following problem. Namely, moisture a¡d
oxygen penetrate through a file or minute concave-convex layer exposed to the outside
of the sealed space, which results in deterio¡ation of the element. Thus, in PATENT
LITERATURE 2, the minute concave-convex layer is positioned within the sealed
space. In this method, however, the sealing adhesive adheres not to the surface of the
minute concave-convex layer but rather to a flat substrate surface, and thus it is difficult
to obtain the adhesive force improving effect which would be otherwise brought about
by the surface area increasing effect and the catching effect ofthe concave-convex
surface ofthe minute concave-convex layer. Having no adhesive force improving effect
may lead to insuffrcient sealing performance to cause the dete¡ioration of the light
emitting element, or may lead to insufflrcient adhesion between the adhesive and the
substrate to cause the exfoliation (peeing ofÐ of the adhesive after the sealing. An
object ofthe present invention is to provide a light emitting eiement which includes a
concave-convex skucture layer funcrioning as a diffiaction grating and a light emitting
part which is seaied by frame sealing (frame-sealed) with suffrcient sealing
perfonnance, thereby preventing the deterioration of the service life ofthe light emitting
element, and a method for manufachring the light emitting element.
Solution to the Problem
[00061 According to a first aspect ofthe present invention, there is provided a light
emitting element including:
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a base member;
a sealing member disposed to face the base member;
a concave-convex structure layer;
a first electrode;
an organic layer;
a second electrode; and
an adhesive layer,
wherein the concave-convex structue layet the first electrode, the organic layer,
a:rd the second electrode are formed on the base member in that order;
the adhesive layer is positioned between the base member and the sealing
member; and
an outer periphery of the concave-convex structure layer is positioned between
an inner periphery of the adhesive layer and an outer periphery of the adhesive layer.
[0007ì In the light emitting element, at least one of the fust electrode and the second
electrode may include an overlapping part overlapping both of the concave-convex
structure layer and the adhesive layer. The overlapping patt may have a concave-convex
surface reflecting or showing concavities and convexities of the concave-convex
structure layer. The inner periphery of the adhesive layer may adhere to the concaveconvex
struchrre layer or the concave-convex surface reflecting or showing the
concavities and convexities ofthe concave-convex structure layer.
[0008ì In the iight emitting element, the organic layer may be positioned such that a
predetermined space is provided between the adhesive layer and the organic layer.
[0009] In the light emitting element, the outer periphery ofthe concave-convex structure
layer may be formed as an inclined surface, and an angle between the outer periphery of
the concave-convex st¡uctue layer and a surface of the base member is not more than
80'.
[0010] In the light emitting element, a space, which is sealed by the base member, the
sealing member disposed to face the base member, and the adhesive layer, maybe frlled
with infiliing.
[0011] In the light emitting element, the outer periphery of the concave-convex structure
layer may be positioned roughly halfivay between the outer periphery and the inner
periphery of the adhesive layer sealing the space.
+
[00121 In the light emitting element, the concave-convex structure layer may be made of
a sol-gel material.
[0013] According to a second aspect of the present invention, there is provided a
method for manufacturing a light emitting element, including the steps of:
forming a concave-convex structure layer on a base member;
forming a first electrode on the concave-convex struchlre 1a)¿er;
forming an organic layer on the first eiectrode;
forming a second electrode on the organic layer; and
disposing a sealing member to face the base member such that the concaveconvex
structure layer, the first electrode, the organic layer, and the second electrode,
those of which are fonned on the base member, are positioned between the base
member a¡d the sealing member; and forming an adhesive layer between the base
member and the sealing member,
wherein the adhesive layer is fonned such that an outer periphery ofthe concaveconvex
structue layer is positioned between an irurer periphery of the adhesive layer
and an outer periphery of the adhesive iayer.
[0014] In the method for manufacturing the light emitting element, it is prefe¡red that
tle adhesive layer be formed in a position in which the adhesive layer has no contact
with the organic layer.
[0015] In the method for manufacturing the light emitting element, it is preferred that
the concave-convex structure layer be formed such that an angle between the outet
periphery ofthe concave-convex structure layer and a surface ofthe base member is not
mo¡e than 80o.
[0016] According to a third aspect of the present invention, there is provided a light
emitting element including:
a base member;
a sealing member disposed to face the base member;
a first concave-convex stmcture layer having a first concave-convex pattem;
a second concave-convex skucture layer having a second concave-convex
pattem;
a first electrode;
an organic layer;
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a second electrode; and
an adhesive layer,
whe¡ein the fi¡st concave-convex structure layer and the second concave-convex
struchrre layer, which is positioned with a predetermined distance f¡om the fi¡st
concave-convex structure layer, are formed on the base member;
a stacked body of the first electrode, the organic layer, and the second electrode
is fonned on the first concave-convex pattern;
the adhesive layer is formed between the base member and the sealing member
to suround the stacked body; and
the second concave-convex struchre layer is disposed not to penetrate the
adhesive layer.
[0017] In the light emitting element, the second concave-convex pattem maybe
different frorn the first concave-convex pattem. The second concave-convex pattem
may be identical to the first concave-convex pattem.
[0018] In the light emitting element, a side surface of the second concave-convex
structure layer may be fonned as an inclined surface, and an angle between the side
surface ofthe second concave-convex structure layer and a surface of the base member
is not more than 80". Further, an outer periphery of the first concave-convex structure
layer may be formed as an inclined surface, and an angle between the outer periphery of
the first concave-convex structue layer and a surface of the base membe¡ is not more
than 80".
Advantageous Effects of Invention
[0019] The light emitting element ofthe present invention includes the concave-convex
sûuctwe layer functioning as a diffraction grating, and thus light extraction efficiency
thereof is excellent. Further, a light emitting part is sealed by frame sealing with
sufficient sealing performance, and thus deterioration of the organic layer (light emitting
paf) due to moisture and oxygen is prevented and the light emitting element of the
present invention has a long service life. Therefore, the light emitting element of the
present invention is very useful in various devices such as displays and illumination
devices.
Brief Description of I)rawings
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[0020] Figs. 1(a) and 1(b) schematically depict a light emitting element according to an
embodiment of the present invention, wherein Fig. 1(a) is a schematic top view and Fig.
1(b) is a schematic cross-sectional view as viewed in the I-I direction ofFig. 1(a).
Fig. 2 is a schematic cross-sectional view ofa specifrc form or shape of the light
emitting element according to the embodiment.
Figs. 3(a) to 3(g) conceptually depict a concave-convex sûrlcture layer formation
process by a liftoff method.
Figs. 4(a) to 4(e) conceptually depict a concave-convex structure layer formation
process by a ffV curing method.
Figs. 5(a) to 5(c) conceptually depict a concave-convex structu¡e layer formation
process by another aspect of the IJV curing method.
Figs. 6(a) to 6(c) each depict a design of an exposure mask for concave-convex
structure layer formation, wherein Fig. 6(a) is a design ofan exposure mask used in each
ofExamples 1 and 3, Fig. 6(b) is a design of an exposure mask used in Example 2, and
Fig. 6(c) is a design ofan exposure mask used in Comparative Example 2.
Fig. 7 is a schematic top view of a substrate with a first electrode formed in
Example 1.
Fig. 8 is a schematic cross-sectional view ofa light emitting element of
Comparative Example 1.
Fig. 9 is a schematic cross-sectional view ofa light emitting element of
Comparative Example 2.
Fig. 10 schematically depicts a method for evaluating the adhesion property of
an optical element manufactured in each ofExampies and Comparative Examples.
Fig. 1 1 is a table showing evaluation results of the adhesion property and the
mrmbe¡ of dark spots of the optìcal elements manufactured in Examples and
Comparative Examples (indicated as "Ex." and "Com. Ex." in Fig. 11).
Fig. 1 2(a) is a schematic plan view of the concave-convex structure layer of the
optical element according to the embodiment, and Fig. 12(b) is a cross-section profile
taken along the cutting-plane line in Fig. 12(a).
Fig. 13 is a schematic cross-sectionai view ofa light emitting element ofthe first
modified embodiment.
Fig. 14 is a schematic cross-sectional view ofa light emitting element of the
second modified embodiment.
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Description of Embodiments
[0021] In the following, an explanation will be made with reference to the drawings
about an embodiment of a light emitting element and a method for manufacturing the
light emitting element according to the present invention.
[00221 [Light emitting element]
Fig. 1(a) is a schematic top view depicting a light emitting element 100
according to this embodiment, and Fig. 1(b) is a schematìc cross-sectional view thereof.
The light ernitting element 100 includes a plate-shaped base member 40, a sealing
member 101 which is disposed to face a surface of the base member 40 with a space 105
intervening therebetween, a concave-convex structure layff 142, a first electrode 92, an
otganic layer 94, a second electrode 98, and an adhesive layer 103. In the space 105, the
concave-convex structure layer 142, the first electrode 92, the orga:ric layer 94, and the
second electrode 98 are formed on the base member 40 in that order. As depicted in
Figs. 1(a) and i(b), the center of the base member 40 is defined as O, and an in-plane
direction is defined as an XY direction and a direction perpendicular to the XY
direction, namely, a height direction ofthe light emitting element 100 is defrned as a Z
direction. In this embodiment, the adhesive layer 103 is a rectangular frame body
having an opening at its center. The adhesive layer 103 is arranged in a state of being
sandwiched between the base member 40 and the sealing member 101 in the height
direction (Z direction). In this structure, an inner circumferential su¡face 103si of the
adhesive layer 103 constituting the frame body defines the space 105, and an outer
circumferential surface 103so ofthe adhesive layer 103 constituting the frame body
defuies a boundary, which is parallel to the height direction ofthe light emitting element
100, between the adhesive layer 103 and an extemal space.
[0023] In this embodiment, the concave-convex struchue layer 142 formed on the base
member 40 has a rectangular shape of which planar structure þlanar shape) is smaller to
some extent than that ofthe base member 40. Al outer periphery 142c of the concaveconvex
structure layer 142 is positioned within the planar shape (planar area) of the base
member 40. The adhesive layer 103 is the frame body as described above. A part, of
the outer circumferential surface 103so, which makes contact with the base member 40
or any one ofthe layers formed thereon is refered to as an outer periphery 103b ofthe
adhesive layer 103, and a part, of the inner ci¡cumferentiai surface 103si, which makes
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contact with the base member 40 or any one of the layers foÍned thereon is refened to
as an inner periphery 103a of the adhesive layer 103 (see Fig. 1(b)). As will be
described later, the concave-convex structure layer 142 is disposed such that the outer
periphery 142c of the concave-convex structure layer 142 is positioned between the
inner periphery l03a and the outer periphery 103b ofthe adhesìve layer 103 in an XY
plane. In order to show a planer positional relation between the concave-convex
structue layer 142 and the adhesive layer 103, the illustration of the sealing member
1 0 1 is omitted and the outer periph ery l42c of the concave-convex structure layer 1 42 is
indicated by a dot-and-dash line in Fig. 1 (a) . In this configuration or arrangement, the
concave-convex structüe layer 142 is contained in (positioned within) the space 105
which is closed by the outer circumferential sur{ace 103so of the adhesive layer 103, the
base member 40, and the sealing member 101, and thus the concave-convex structure
layer 742 is not exposed to the outside ofthe adhesive layer 103 (aûnospheric air).
Therefore, moisture and oxygen are prevented ftom penetrating through the concaveconvex
structure layer 142 and entering the sealed space 105. As a result, the organic
layer 94 and the like is less likely to be deteriorated and the service life ofthe light
emitling element 100 is elongated. Further, the inner periphery i03a of the adhesive
layer may adhere to the concave-convex surface of the concave-convex structure layer
or the concave-convex surface of the first electrode, the organic layer or the second
electrode, which reflects concavities and convexíties ofthe concave-convex structure
layer . Allowing the inner periphery 103a of the adhesive layer to adhere to the
concave-convex surfaces provides tight corurection between the adhesive layer 103 and
the base member 40 and the tight connection is maintained for a long period of time
after the sealing. Thus, no exfoliation occu¡s and the service life of the light emitting
element improves.
[0024]
The base member 40 is not particularly limited, and it is possible to
appropriately use any known transpa¡ent substrate which can be used for the light
emitting element. Those usable as the base member 40 include, for example, a substrate
made ofa kansparent inorganic material such as glass; substrates made ofresins such as
poiyester þolyethylene terephthalate, polybutylene terephthalate, polyethylene
naphthalate, and the like), an acrylic-based resin (poþmethyì methacrylate and the like),
polycarbonate, poþinyl chloride, a st¡nene-based resin (ABS resin and the like), a
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cellulose-based resin (triacetyl cellulose and the like), a polyimide-based resin
þolyìmide resin, poþimideamide resin, and the like) and cycloolefrn pol;,mer; a stacked
substrate obtained by forming, on the surface ofa substrate made of any one of the
foregoing resins, a gas barrier layer made of an inorganic material such as SiN, SiOz,
SiC, SiO.\, TiOz, or AlzO¡ and/or a gas barrier layer made of a resin materìal; and a
stacked substrate obtained by alternately stacking, on a substrate made of any one of the
foregoing resins, the gas barier layers made of the inorganic material or the resin
matenal. In terms of uses of the light emitting element, the base member 40 desirably
has the heat resistance and the weather resistance to lfV light and the like. Thus, base
members made of inorganic materials such as glass and quarts substrates are more
preferably used. Especially, when the base member 40 is made of the inorganic
material, the concave-convex structüe layer I42 may be made of an inorganic material
such as a sol-gel material. In this case, the difference between the refractive index of the
base member 40 and the ref¡active index of the concave-convex strucfvelayer 142 is
small and unintended refraction andlor reflection in the light emitting element 100 can
be prevented. Thus, the base member 40 is preferably made of any inorganic materiai.
It is allowable to perform a surface treatment or provide an easy-adhesion layer on the
base membe¡ 40 to improve an adhesion propdrty. Further, it is allowable to form a
concave-convex structure having a lens function, a light diffusion function, and the like,
or to put a film or the like having the similar functions, on a surface of the base member
40 opposite to the surface on which the concave-convex structure layer 142 is formed.
It is preferred that the thickness of the base member 40 be in a range of 1 to 2000 prn.
[0025]
80'),
the following situation may occur. Namely, when a fihn of the füst electrode 92 or the
second electrode 98 is formed by a sputtering method or vapor deposition method, the
deposited material has diffrculty in reaching to the outer periphery (side surface) 142c of
the concave-convex stmcture layer and the surface ofthe base member in the vicinity of
the outer periphery 142c. This causes the fihn fonned in these areas to have a small
thickness. The unevenness ofthe fikn thickness may result in any failure such as
breaking or disconnecting of electrodes. On the other hand, when the outer periphery
(side surface) 142c of the concave-convex structure layer 142 is inclined such that the
taper angle 0 of the concave-convex structure layer satisfres 0 < 80', the deposited
material can satisfactorily reach to the outer periphery (side surface) 142c of the
concave-convex structure layer and the surface of tJre base member in the vicinity ofthe
outer periphery 142c. This prevents the first electrode 92 and the second electrode 98,
which have been formed on the outer periphery (side surface) 142c of the concaveconvex
structure layer and the vicinity thereof, from having small thicknesses. Namel¡
the fust electrode 92 and the second electrode 98 can be forrned to have uniform film
thicknesses respectively, unlike the case in which the taper angle 0 of the concaveconvex
structure layer is nearly vertical (0 > 80').
[0035] When the adhesive force between the base member 40 and the concave-convex
structure layer 142 is weak, an adhesion iayer may be provided between the base
member 40 and the concave-convex structure layer 142. The adhesion layer may be
made of a silane coupling agent or the like. Those usable as the silane coupling agent
include, for example, agents having an acrylic group and agents having a methacryl
group such as KIIM-5103 þroduced by SHIN-ETSU CHEMICAL, CO., LTD.) and
KBM-503 þroduced by SHIN-ETSU CHEMICAL, CO., LTD.).
[0036] The coating layer may be formed on the surface ofthe concave-convex sûucture
layer 142- It is preferred that the thickness ofthe coating layer be tn arange o125%o to
150% of the staldard deviation of depth of concavities and convexities of the concave-
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convex structure layel 142. Such a coating layer can cover any foreign matter and
defect which night be present on the surface of the concave-convex structure layer.
Thus, leak current in the light emitting element can be effectively prevented. The light
emitting element, in which the coating layer having a thickness within the above range
has been forrned on the concave-convex struchrre layer, has good light extraction
efficiency.
[00371 Those usable as the material ofthe coating layer (coating material) include for
example, sol-gel materials such as SiO', TiO*, ZnO, ZrOz, AbOz, ZnS, BaTiO:, SrTiOz,
and indiumtin oxide (ITO); cured products of resin compositions; SiO*, SiN,,, SiO.Ny
and the like formed by using the polysilazane solution as the raw material, those of
which have been cited as usable materials of tle concave-convex shuchrre layer 142;
and those obtained by mixing each of the above materials with any known particles,
filler, ultraviolet absorbent material, etc. It is especially preferred that the material of
the coating layer be identical to the material of the concave-convex structure layer.
When the coating material is identical to the material of the concave-convex structure
layer, reflection of light at an interface between the coating layer and the concaveconvex
structure layer can be prevented. As a sol-gel material solution used in
formation of the coating layer, it is prefened that a diluted solution, which is diluted
with a solvent to be weaker than the sol-ge1 material solution used in forrnation ofthe
concave-convex structure layer, be used. ln such a case, the coating layer can be easily
fonned to have a predetermined film thickness which is thirmer than the concaveconvex
stfucture layer.
[0038] The silane coupling agent may be used as the coating material. The use of the
silane coupling agent can improve the adhesion property between the coating lâyer and a
layer, such as an electrode, to be formed on the coating layer. This develops the
resistance in the cleaning step and the high temperature treatment step included in the
production process of an optical element. The type or kind of silane coupling agent
used for the coating layer is not particularly limited, and those usable as the silane
coupling agent include, for example, an organic compound represented by RSiX: (R is
an organic functional group containing at least one selected from a vinyl group, a
glycidoxy group, an acryl group, a methacryl group, an amino group, and a mercapto
group, and X is a halogen element or an alkoxyl group).
1n[
0039] It is allowable to provide a gas barrier layer on the surface of the concaveconvex
structure layer 142 or the surface of the coating layer in order to keep out
moisture and gas such as oxygen.
[0040]
The first electrode 92 may be a transparent electrode so that the light from the
organic layer 94 formed on the fust electrode 92 passes toward the base membe¡ 40. It
is preferred that the first electrode 92 be stacked such that the surface of the first
electrode 92 maintains or shows the concave-convex skuch¡re formed in the surface of
the concave-convex structure layer 142. Although Fig. 1(a) dçicts the configuration in
which the first electrode 92 is formed to cover tle concave-convex structure layer 142
except for an area in (on) which a lead-out wiring ofthe second electrode 98 as
described later is to be formed a¡d the vicinity thereof, it is not necessarily required to
cover the concave-convex structue layer 142. The anangement and the shape ofthe
first electrode 92 are not particularly limited.
[0041] Those usable as the material of the first electrode 92 include, for example,
indium oxide, zinc oxide, tin oxide, índium-tin oxide (ITO) which is a composite
material thereof, gold, platinum, silver, and copper. Of these materials, ITO is
preferable from the viewpoint of transparency and electrical conductivity. The thickness
of the first electrode 92 is preferably within a range of 20 to 500 nm. When the
thickness is less than the lower limit, the eiectrìcal conductivity is more likely to be
insufficient. When the thrckness exceeds the upper limit, there is possibility that the
transparency is so insufficient that the emitted EL light cannot be extracted to the
outside sufficientþ. Further, there is fear that the surface of the first electrode 92 can
not maintain or show the concave-convex structure formed in the surface ofthe
concave-convex structure layer 142 depending on the depth ofconcavities and
convexities of the concave-convex structure layer 142.
[0042]
As depicted in Figs. 1(a) and 1(b), the organic layer 94 is fo¡med on the first
electrode 92 to have a range or area smaller than the concave-convex structue layer
142. Namel¡ an outer periphery 94c of the organic layer 94 is positioned inside the
outer periphery 142c ofthe concave-convex structure layer 142 and thus the organic
layer 94 can be sealed by the adhesive layer i03 and the sealing member 1O1. The
la
otgarrìc lãyer 94 is not particularly limited, provided that it is usable as an organic layer
of the organic EL element. As the o rganic layer 94, any known organic layer can be
used as appropriate. The surface of the organic layer 94 may maintain the shape ofthe
concave-convex shucture layer 142 or may be fTaI without maintaining the shape of the
concave-convex structure layer 142. The organic layer 94 maybe a stacked body of
various organic thin films. For example, the organic layer 94 may be a stacked body of
a hole transporting la¡rer, a light-emitting layer, and an electron transporting layer.
Those usable as the material ofthe hole transporting layer include, for example,
aromatic diamine compounds such as phthalocyanine derivatives, naphthalocyanine
derivatives, porphyrin derivatives, N,N'-bis(3-methylphenyl)-(1,1 '-biphenyl)-4,4'-
diamiìre (TPD), and 4,4'-bis[N-(naphtþl)-N-phenyl-amino]biphenyl(o-NPD); oxazole;
oxadiazole; triazole1' inrcJazole; imidazolone; stilbene derivatives; plrazoline
derivatives; tetrahydroimidazole; polyarylalkane; butadiene; and 4,4',4"-tris(N-(3-
methylphenyl)N-phenylamino)kiphenylamine (m-MTDATA). The examples of
materials of the hole tmnsporting layer, however, are not limited to the above. By
providing the light emitting layer, a hole injected from the first electrode 92 and electron
injected from the second electrode 98 are recombined to occur light emission. Those
usable as the material of the light emitting layer include, for example, metallo-organic
complex such as anthracene, naphthalene, pyrene, tetracene, coronene, perylene,
phthaloperylene, naphthaloperylene, diphenylbutadiene, tehaphenylbutadiene,
coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, and aluminumquinolinol
complex (Alq3); tri-þ{erphenyl-4-yl)amine; I-aryI-2,5-di(2-ffnenyl) pynole
derivatives; pyran; quinacridone; rubren; distyrylbenzene derivatives; distyryl arylene
derivatives; distyryl amine derivatives; and various fluorescent pigments or dyes.
Further, it is prefened that light-emitting materials selected f¡om the above compounds
be mixed as appropriate ând then used. Fufhermore, it is possible to preferably use a
material system generating emission oflight from a spin multiplet, such as a
phosphorescence emitting material generating emission ofphosphorescence and a
compound including, in a part ofthe molecules, a constituent portion forrned by the
above materials. The phosphorescence emitting material preferably includes hear,y
metal such as iridium. A host material having high carrier mobility may be doped with
each ofthe light-emitting materials as a guest material to generate the light emission
using dipole-dipole interaction (Forster mechanism) or electron exchange inte¡action
r1
(Dexter mechanìsm). Those usable as the material of the electron transporting layer
include, for example, heterocyclic tetracarboxylic anhydrides such as nitro-substituted
fluo¡ene derivatives, diphenylquinone derivatives, thioplran dioxide derivatives, and
naphthaleneperylene; and metallo-organic complex such as carbodiimide, fluorenylidene
methane derivatives, anthraquino dimethane and anthrone derivatives, oxadiazole
derivatives, and aluminum-quinolinol complex (41q3). Further, in the oxadiazole
derivatives mentioned above, it is also possible to use, as an electron transpofing
material, thiadiazole derivatives in which oxygen atoms of oxadiazole rings are
substituted by sulfur atoms and quinoxaline derivatives having quinoxaline rings known
as electron attractive group. Furthermore, it is also possible to use a polymeric material
in which the above materials are introduced into a macromolecular chain or the above
materials are made to be a main chain of the macromolecular chain. It is noted that the
hole transporting layer or the electron transporting layer may also function as the iightemitting
layer.
[0043] From the viewpoint of facilitating the electron injection fiom the second
electrode 98, a layer made of a metal fluoride or metal oxide such as lithium fluoride
(LiF) or LizOl, a highly active alkaline earth metai such as Ca, Ba, or Cs, an organic
insulating material, or the like may be provided as an electron injection layer between
the organic layer 94 and the second electrode 98. Fufher, from the viewpoint of
facilitating the hole injection from the first electrode 92, it is allowable to provide, as a
hole injection layer between the org antc layer 94 and the first electrode 92, a layer made
of triazol derivatives, oxadiazole derivative, imidazole derivative, polyarylalkane
derivatives, pyrazoline and pyrazolone derivatives, phenylenediamine derivative,
arylamine derivatives, amino-substituted calcone derivatives, oxazole derivatives,
styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene
derivatives, silazane derivatives, aniline-based copo11.rners, or electroconductive highmolecular
oligomar, particularly thiophene oligomer.
[00441 Furthermore, when the organic layer 94 is a stacked body formed ofthe hole
transporting layer, the light emitting layer, and the electron transpoÍing layer, the
thicknesses of the hole transporting layer, the light emitting layer, and the electron
transporting layer are preferably within a range of 1 to 200 nm, a range of 5 to 100 nm,
and a range of 5 to 200 nm, respectively.
[0045]
2-e
Materials of the second electrode 98 are not particularly limited, and a substance
having a small work function can be used as appropriate. For example, the second
eiectrode 98 may be a metal electrode using alumimrm, MgAg, MgIn, AlLi, or the like.
The thickness of the second electrode 98 is preferably in a range of 50 to 500 nm. When
the thickness is less than the lower limit, the electrical conductivity is more likely to be
decreased. When the thickness exceeds the upper limit, there is such a possibility that
the repair might be difficult to perform when any short circuit occurs between the
electrodes. The second electrode 98 may be stacked such that the surface of the second
electrode 98 maintains or shows the concave-convex structure formed in the surface of
the concave-convex struchJre layer 142-
[0046]
The adhesive layer 103 is formed between the base member 40 and the sealing
member 101 as described later to overlap the outer periphery (side surface) 142c ofthe
concave-convex structure layer 142. In this configuration or arrangement, the outer
periphery (side surface) l42c of the concave-convex structure layer 1 42 is positioned
between the inner periphery 103a and the outer periphery 103b of the adhesive layer
103. Note that the phase "the outer periphery (side surface) 142c ofthe conoave-convex
structure layer 142 is positioned between the inner periphery 103a and the outer
periphery 103b ofthe adhesive layer 103" means as foiiows. Namely, apaÍ of the outer
periphery (side surface) 142c of the concave-convex structure layer 142 may be inside
the ilner periphery 103a of the adhesive layer 103 (on the side, ofthe inner periphery
103a, close to the center of tÏe base member) and it is not necessary that the whole
circumferentiai part of the outer periphery (side surface) 1 42c of the concave-convex
structure layer 142 is positioned between the inner periphery 103a and the oute¡
periphery 1 03b of the adhesive layer 1 03 . In other words, the above phase includes a
case in which a part of the outer periphery (side surface) I 42c of the concave-convex
structure layer 142 is positioned in the sealed space 105. In this arrangement, the
concave-convex structue layer 142 is not exposed to the outside of the adhesive layer
103 (atmospheric air), and thus moisture ald oxygen are prevented from penetrating
through the concave-convex structure layer 142 and entering the sealed space 105.
Therefore, the organic layer 94 a¡d the like is less likely to be dete¡iorated and the
service life of the light emitting element is elongated. Furthe¡ in this arrangement, the
inner periphery 103a of the adhesive layer 103 adheres to the concave-convex surface of
u
I
I
the concave-convex structure layer 142 o¡ the concave-convex surface of the first
elecnode 92, the organic layer 94 or the second electrode 98 reflecting or showing
concavities and convexities of the concave-convex structue layer 1 42 . In addition to
the above, when the outer periphery (side surface) 142c ofthe concave-convex structure
layer 142 is inclined as depicted in Fig. 2, the inner periphery 103a ofthe adhesive layer
103 adheres to the concave-convex surface of the concave-convex structure layer 142 or
the concave-convex surface of the first electrode 92, the organic layer 94 or the second
electrode 98 reflecting or showing concavities and convexities ofthe concave-convex
structüe lâyer 142. Allowing the adhesive layer 103 to adhere to the concave-convex
surfaces provides not only chemical adhesion brought abouf by the adhesive but also
"catching" and the like broughl about by concavities and convexities to make
mechanical releasing (mechanical exfoliation) more difficult. Further, allowing the
adhesive layer 103 to adhere to the concave-convex surfaces provides an increased
interface area. Such effects skengthen the adhesion (connection) between the base
member 40 and the adhesive layer 103. As a result, the organic layer 94 is sealed more
reliably. Further, the high adhesive force is maintained for a long period of time after
the sealing and no exfoliation occurs. Such high adheSive force allows the adhesive
layer i03 to have a narrower line width, thereby making it possibie to increase an area of
the organic layer (light emitting part). In order to effectively extract the light emitted
from the organic layer 94, it is preferred that the adhesive layer 103 be fonned with a
predetermined distance D from the organic layer 94, i.e., in a state that the adhesive
layer 103 is not brought into contact with the organtc layer 94. It is preferred that the
distance D be, for example, not less than 1 pm. For the purpose of achieving both good
adhesion strength and good sealing performance, it is preferred that the outer periphery
(side surface) 142c ofthe concave-convex stmcture layer 142 be positioned roughly
halfivay between the inner periphery 1 03 a and the outer periphery 1 03b of the adhesive
layer 103.
[0047] As the material of the adhesive layer 103, adhesives widely used for glass, a
plastic substrate, and the like can be used without limitation. Those usable as the
material of the adhesive layer 103 include, for example, polyvinyl acetate-based
adhesives; photocurable and therrnosetting acrylic adhesives having a reactive vinyl
group such as acrylic acid-based oligomer a¡rd methacrylic acid-based oligomer; epoxy
resin adhêsives; moishtre curing õ?e adhesives such as 2-cyanoacylic acid ester;
L2-
ethylene copolyrner-based adhesives; polyester-based adhesives; polyìmide-based
adhesives; arnino resin-based adhesives made ofa urea resin, a melamine resin, and the
like; phenol resin-based adhesives; polyurethane-based adhesives; reactive (meth)acrylic
adhesives; and rubber-based adhesives. Of the above adhesives, the acrylic adhesives,
the epoxy-based adhesives, etc. are especially preferable. The epoxy-based adhesives,
which contract or sh¡ink to a lesser extent at the time of curing, are parlicularly
preferable.
[0048] The epoxy-based adhesives include, for example, an epoxy resin composition
made of an epoxy resin a:ed a curing agent. The adhesive force of the epoxy resin
composition is generated by its curing reaction, which is brought about by mixing a
compound containing an epoxy goup with the curing agent containing amines and acid
an}ydride.
[0049] The epoxy-based adhesives usable in the present invention are exemplified, for
example, by Cemedine EP-001 produced by CEMEDINE Co., ltd.; 3950, 395I aú,3952
of3950 series, 2083,2086 and 2087 of2080 series, and2230 aú,22308 of2230 series,
and 3124C produced by ThreeBond Holdings Co., Ltd.; MOS07 and MOS1O of Bond
MOS series produced by Konishi Co., Ltd.; ULTIGHT 1540 and the like of ULTIGHT
1500 series produced by TOHO KASEI CO., LTD.; and XNR5 57 6/5576LV,
)c{R55 1 6/55 16HV/55 1 62, )C{R5570,'1 47 o rUF{Z 1 I 6, T 47 0rUF(7 13 4, T 41 o :UF'T t32,
T470[JR71248-LV, and the like produced by Nagase ChemteX Corporation.
[0050] The acrylic-based adhesives include, for example, an adhesive containing an
acrylic-based adhesive component, an energy-rây curable component and a
thermosetting adhesive component. The acrylic-based adhesives usable in the present
invention are exemplified, for example, by 3003,30278,30338,30428, and the like
produced by ThreeBond Holdings Co., Ltd.; and Cemedine Y600, Cemedine Y600H,
and the like produced by CEMEDINE CO., ltd.
[0051] The rubber-based adhesives include, for example, one obtained in such a manner
that adhesive elastomer, an adhesion-imparting agent, a softening agent, and the like are
mixed with one another. The adhesive elastomer is at least one kind of adhesive
elastomer selected, for example, from natural rubber composed mainly ofcis-1,4-
poþisoprene; synthetic rubber composed mainly of styrene-butadiene rubber (SBR),
polyisobutylene, butyl rubber, and the like; and block rubber composed mainly of
23
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!:.:
styrene-butadiene-styrene copolymer rubber (SBS), styrene-isoprene-styrene copol¡'mer
rubber (SIS), and the like. The adhesion-imparting agent is a thermoplastic resin
containing an amorphous oligomer (middle-molecular weight pollnner of a dimer or
more), the amorphous oligomer being a liquid or solid at normal temperature and having
a molecular weight in a range of hundreds to about ten thousand, such as a rosin-based
resin, a terpene-based resin, a petroleum resin, and a chroman-indene resin. The
softening agent is exemplified, for example, by mineral oil, liquid polybutene, liquid
poþisobutylene, and liquid polyacrylic ester.
[0052] Examples of vinyl ether adhesives include an adhesive composed of a
homopolymer such as vinyl methyl ether, vinyl ethyl ether or vinyl isobutyl ether, an
adhesive composed ofa copolyrner of acrylate and vinyl ether such as vinyl methyl
ether, vinyl ethyl ether or vinyl isobutyl ether (adhesive elastomer), and the like. Each
of the above-described vínyl ether adhesives may be mixed with the above-described
adhesion-impafing agent, softening agent, or the like.
[0053] Examples of silicone-based adhesives include one obtained in such a manner
that a polyner (or adhesive eiastomer) containing a residual silanol group (SiOþ at an
end of a polymer chain is mixed with the above-described adhesion-imparting agent,
softening agent, or the hke. The pollmer containing a residual silanol group is
represented by polydimethylsiloxane or polydimethyldiphenylsiloxane having high
molecular weight.
[00541
The sealing member 101 is disposed to face the base member 40 with the space
(sealed space) i 05 intervening therebetween. The space 105 is sealed with the base
member 40, the sealing member 1 0 1 , and the adhesive layer 1 03 . The concave-convex
structure layer 142, the fÍst electrode 92, the organic layer 94, and the second electrode
98 are positioned within the sealed space 105.
[0055] The sealing member 101 may be any member provided that it is made of a
material having a high gas barrier property. Examples of the sealing member 101
include any known gas barrier films used for packaging materials and the like, such as a
plastic film in which silicon oxide or aluminum oxide is deposited; a laminate (stacked
object) formed of a ceramic layer and an impact-attenuating polymer layer; metal foil
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laminated with a pollaner film; a sealing can made of glass; a sealing can made of
metal; and an engraved glass.
[0056] The sealed space 105 is filled with an inactive or inert gas or the like. Nz ca¡ be
used as the inactive gas, and instead ofNz, a noble gas such as He or Ar is preferably
used. Further, a noble gas obtained by mixing He with Ar is also preferable. The ratio
of the inactive gas in gases is preferably in a range of 90 to 100% by volume. Or, the
sealed space 105 may be filled with infilling such as a solid or liquid resin, glass, an
inactive oil such as a fluorine-based inactive oil, or a gel material. It is prefered that the
infilling be transparent or cloudy. Further, a water-absorbing substance may be
disposed in the sealed space 105. The water-absorbing substance is exemplified, for
example, by barium oxide. Specifically, for example, high-purity barium oxide powder
produced by Signra-Aldrich Co. LLC. can be disposed in the sealed space 105 bybeing
put or stuck on the sealing member 101 by using a fluororesin-based semi-transparent
film with adhesive (MICROTEX S-NTF8031Q produced by NITTO DENKO
CORPORATION) or the 1ike. Altematively, any commercially available waterabsorbing
substances produced, for example, by W.L. Gore & Associates and Futaba
Corporation are preferably used.
[0057] [First modified embodiment of light emitting element]
An explanation will be made about a modified embodiment of the light emitting
element 100. As depicted in Fig. 13, in the case of a light emitting element 100a of the
modified embodiment, the concave-convex structure layer 142 includes not only the
concave-convex pattem (first concave-convex pattem) 142p functioning as the
diffracting grating but also a concave-convex pattem (second concave-convex pattem)
142q different from the concave-convex pattem 142p. In the light emitting element
100a, the first electrode 92, the organic layer 94, and the second electrode 98 are formed
in that order on the first concave-convex pattem 142p functioning as the diffraction
grating, and the adhesive layer 103 or the lead-out part of the electrode is fo¡med on the
second concave-convex pattem i42q. Like the light emitting element 100, the outer
periphery (side surface) i42c of the concave-convex structure layer i42 ofthe light
emitting element 100a may be formed as an inclined surface.
[0058] In addition to the inegular concave-convex pattem as described above, the
second concave-convex pattem l42qmay be any pattern such as a dot shucture; a prism
st¡ucture; a stripe structure formed of lines and spaces; a pillar structure such as a
0í
cylindrical shape, a conical shape, a truncated cone shape, a triangle pole shape, a
triangular plramid shape, a truncated triangular pyramid shape, a square pole shape, a
quadrangular pyramid shape, a truncated quadrangular pyramid shape, a polygonal
column shape, a polygonal pyramid shape, or a truncated polygonal pyramid shape; or a
hole stnrcture. Altematively, the second concave-convex pattem 142q may be an
iregular minute concave-convex pattern formed by a sandblasting method. Note that,
in the present application, when the second concave-convex pattem 142q and the first
concave-convex pattem 142p have the same shape (for example, both of the patterns
l42q and 142p are formed to be the above irregular pattern), the second concave-convex
pallern 142q arLd the first concave-convex pattern 142p may have mutually different
pitches and/or heights (depths) of concavities and convexities. Such a case is also
regarded as the case "the second concave-convex pattem is different from the first
concave-convex pattenf'. The main purpose of the second concave-convex pattem
142q is adhesion, and thus the pitch of concavities and convexities of the second
coûcave-convex p allem l42qcanbe smaller than that of the first concave-convex
paftem 142p, as depicted in Fig. 13. As a different form ftom Fig. 13, the second
concave-convex p atterr. l42qmay be a pattem in which minute concavities and
convexities are further provided on a surface of the concave-convex pattem, which has
the pitch and depth (height) of concavities and convexities which are the same as those
of the frst concave-convex pattern. Allowing the adhesive layer 103 to adhe¡e to the
surface having the second concave-convex pattem 142q provides the following effects.
Namel¡ "catching" and the like makes mechanical releasing (mechanical exfoliation)
more difficult and concavities and convexities increase an inte¡face area. Such effects
strengthen the adhesion (connection) between the base member 40 and the adhesive
layer 1 03 . As a result, the organic layer 94 is sealed more reliably. Further, the high
adhesive fo¡ce is maintained for a long period of time afier the sealing and no
exfoliation occurs. Such high adhesive force allows the adhesive layer 103 to have a
narrower line width, thereby making it possible to increase an area ofthe organic layer
(light emitting part).
[0059] [Second modified embodiment of light emitting element]
An explanation will be made about a light emitting element 100b of anothe¡
modified embodiment. As depicted in Fig. 14, the light emitting element 100b includes
the plate-shaped base member 40, the sealing member 10i which is disposed to face a
2-Ã
surface of the base member 40 with the space 105 intervening therebetween, the first
electrode 92, the organic layer 94, the second electrode 98, and the adhesive layer 103,
similarly to the light emitting element 100. The light emitting element 100b further
includes a first concave-convex struchre layer 242 having a first concave-convex
paftern242p formed in a su¡face thereof and a second concave-convex structure layer
342 having a second concave-conv ex paftern342p formed in a surface thereof. As
depicted in Fig. 14, an in-plane direction of the base member 40 is defined as an XY
direction and a direction perpendicular to the XY direction, namely, a height direction of
the light emitting element 100b is defined as a Z direction.
[0060] Materials of the base member 40, the sealíng member 101, the first electrode 92,
the organic layer 94, the second electrode 98, and the adhesive layer 103 ofthe light
emitting element 101b are identicai to materials of those of the light emitting element
100. The first concave-convex structure layer 242 and the second concave-convex
structure layer 342 a¡e made of the same material as that ofthe concave-convex
stmctüe layer 142 of the light emitting element i00. In view of easy manufacturing, it
is preferred that the material of the fi¡st concave-convex shucture layer 242 be identical
to the material of the second concave-convex structure layer 342.
[0061] The first concave-convex strucíre layer 242 is formed on the base membe¡ 40
and has a rectangular shape of which planar structure (a structure or a shape in an XY
plane) which is smaller to some extent than that of the base member 40. An outer
periphery 242c of the fÍst concave-convex struchre layer 242 is positioned within the
planar shape (planar area) of the base member 40. In the space 105, the fust concaveconvex
structure I ayer 242,lhe ftrst electrode 92, the organtc layer 94, and the second
electrode 98 are formed on the base member 40 in rhat order. The second concaveconvex
structure layer 342 is fomed on the base member 40 around the first concaveconvex
struch.ne layer 242 wifh a predetermined distance G from the outer periphery
242c of the fitst concave-convex strucítre layer 242.
[0062] Similar to the light emitting element 100, the adhesive layer 103 of the light
emitting element 100b is a rectangular frame body having an opening at its center in the
XY plane. The adhesive layer 103 is disposed in a state ofbeing sandwiched between
the base member 40 and the sealing member 101 in the height direction (Z direction). In
this configuration or arrangement, the inner circumferential surface 103si ofthe
adhesive layer 103 constituting the frame body defines the space 105, and tÏe outer
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ci¡cumferential surface l03so of the adhesive layer 103 constituting the fiame body
defines a boundary, which is parallel to the height direction of the light emitting element
1 00b, between the adhesive layer and an extemal space. A part, of the outer
circunferential surface 103so ofthe adhesive layer 103, which makes contact with the
base member 40 or any one ofthe layers formed thereon is referred to as the outer
periphery 103b ofthe adhesive iayer 103, and a part, of the inner ci¡cumferential surface
103si ofthe adhesive layer 103, which makes contact with the base member 40 or any
one of the layers formed thereon is referred to as the inner periphery 103a ofthe
adhesive layer 103 (see Fig. l4).
[0063f In the light emitting element 100b, the outer periphery 242c of the fi¡st concaveconvex
structure layer 242 is disposed only inside the outer periphery 103b of the
adhesive layer 103 (on the side of the sealed space 105) in the XY plane, i.e., the outer
peiphery 242c of the first concave-convex structure layer 242 is not disposed outside
the outer periphery 103b of the adhesive layer i03. Although Fig. i4 depicts the
configuration in which the outer periphery 242c of lhe {[st concave-convex structure
layer 242 is disposed inside the inner periphery 103a of the adhesive layer 103 (on the
side close to the sealed space 105), the outer periphery 242c ofthe frst concave-convex
structure layer 242 may be disposed between the inner periphery 103a and the outer
periphery 103b ofthe adhesive layer 103.
[0064] The second concave-convex structure layer 342 is disposed not to penetrate the
adhesive layer 103. More specifically, the second concave-convex struchre layer 342 is
disposed not to penetrate both the outer periphery 103b and the i¡ner periphery 103a of
the adhesive layer 103 within the XY plane (i.e., not to extend beyond the distance
between the outer periphery 103b and the inner periphery 103a ofthe adhesive layer 103
within the XY plane). Namely, side su¡faces 342c ofthe second concave-convex
structure layer 342 are disposed not to extend out ofboth the inside (the side close to the
sealed space 105) and the outside of the adhesive layer 103. For example, as depicted
on the right side ofFig. 14, the second concave-convex structure layer 342maybe
formed between the inner periphery 103a and the outer periphery 103b ofthe adhesive
layer 103; and as depicted on the left side of Fig. 14, the second concave-convex
structüe layer 342 may be formed to range from a position between the inner periphery
103a a¡d the outer periphery 103b ofthe adhesive layer 103 to the outside (outside of
the sealed space 105) ofthe outer periphery 103b of the adhesive layer 103. As a
I
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different form from Fig. 14, the second concave-convex struchrre layer 342maybe
formed to range from a position between the inner periphery i 03a and the outer
periphery 103b ofthe adhesive layer 103 to the inside of the inner periphery 103a ofthe
adhesive layer 103 (the side ofthe sealed space 105). The second concave-convex
structue layer 342 may be an aggregate having independent concave-convex layers
which a¡e not connected to each other. In this case, each of the concave-convex layer
may be disposed not to penetrate both the outer periphery 103b and the inner periphery
103a ofthe adhesive layer 103 within the XY plane (i.e., not to extend beyond the
distance between the outer periphery 103b and the inner periphery 103a ofthe adhesive
layer 1 03 within the XY plane) . As long as such a condition is satisfied, the second
concave-convex structure layer 342 may be formed of any or all of: the concave-convex
layer disposed only in the position between the inner periphery 103a and the outer
periphery 103b of the adhesive layer 103; the concave-convex layer disposed to mnge
fiom the position between the inner periphery 103a and the outer periphery 103b ofthe
adhesive layer 103 to the outside ofthe outer periphery 103b; and the concave-convex
layer disposed to range from the position between the inner periphery 103a and the outer
periphery 103b ofthe adhesive layer 103 to the inside ofthe inner periphery 103a.
[0065] In the above configuration or arrangement, the first concave-convexlayer 242
and the second concave-convex layer 342 are not allowed to penetrate the adhesive layer
103, and thus moisture and oxygen are prevented from penetrating through the first
concave-convex structure layer 242 and/or the second concave-convex structure layer
342 and enreing the sealed space 105. Thus, the deterioration of the o rganíc layer 94
and the like is prevented and the service life of the light emitting element 100b is
improved. Further, the adhesive layer 103 may adhere to the concave-convex surface
(second concave-convex pattem) 342p ofthe second concave-convex structure layer 342
or the concave-convex surface of the hrst electrode 92, the organic layer 94 or the
second elect¡ode 98, which reflects the second concave-convex pattem 342p. Allowing
the adhesive layer 103 to adhere to the concave-convex surfaces provides high adhesive
force between the adhesive layer 103 and the base member 40 and the high adhesive
force (comecting force) is maintained for a long period of tirne after the sealing. Thus,
no exfoliation occurs a¡d the service life of the light emitting element 100b imp¡oves.
In this embodiment, even when the adhesion layer 103 is applied with accompanfng
some positional deviation, no problem occurs as long as the first concave-convex
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structure layer 242 and the second concave-convex structure layer 342 does not
penetmte the adhesive layer 103.. Thus, the control of coatüg (application) position of
the adhesive layer is easy and the light emitting element having high reliability can be
produced at a high yield.
[0066] In the light emitting element 100b, the outer periphery (side surface) 242c of the
first concave-convex structue layer 242 atdlor the side surfaces 342c of the second
concave-convex structure layer 342 may be an inclined surface in which an angle 0 (0'),
which is formed by the outer periphery 242c (side surface 342c) and the surface of the
base member 40, is not more than 80". This configuration allows each of the fi¡st
elechode 92 and the second electrode 98 to be formed in a uniform thickness on the
outer periphery (side surface) 242c of t},e fitst concave-convex structtrelayer 242, the
side surfaces ofthe second concave-convex skucture layer 342, and the vicinities
thereof, thereby preventing any failure such as breaking or disconnecting ofelectrodes.
[0067] In addition to the irregular concave-convex pattem as described above, the first
concave-convex p attem 242p and the second concave-convex pattern 342p may be any
pattern such as a dot structure; a prism structure; a stripe structure fo¡med of lines and
spaces; a pillar structure such as a cylindrical shape, a conìcal shape, a truncated cone
shape, a triangle pole shape, a trìangular plramid shape, a truncated triangular plramid
shape, a square pole shape, a quadrangular pyramid shape, a truncated quadmngular
pyramid shape, a polygonal column shape, a polygonal pyramid shape, or a truncated
poiygonal pyramid shape; or a hole struchtre. Alternatively, the first concave-convex
paftern 242p and the second concave-convex patt em 342p may be an irregular minute
concave-convex pattem formed by a sandblasting method. As depicted in Fig. 14, the
second concave-convex patte¡n 342p may be different from the fust concave-convex
pattem 242p . It is especially preferred that the first concave-convex patlern 242p be an
inegular structure (pattem) functioning as the diffiaction grating and that the second
conoave-convex p allern 342p be a pattem capable of strongly adhering to the adhesive
layer
,103,
for example, a pattem with a large surface area such as a pattern having a
small pitch of concavities a:rd convexities. The second concave-convex pattern 342p is
not required to have the function as the difûaction grating. As a different form from
Fig. 13, the second concave-convex pattem342p rmay be a pattern in which minute
concavities and convexities are further provided on a surface of the concave-convex
pattern, which has the pitch and depth (height) of concavities and convexities which are
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the same as those of the first concave-convex pattem 242p. Allowing the adhesive layer
103 to adhere to the surface having the second concave-convex pattem 342p provides
the following effects. Namely, "catching" and the like makes mecha:rical releasing
(mechanical exfoliation) more difficult and concavities and convexities increase an
interface area. Such effects strengthen the adhesion (connection) between the base
member 40 and the adhesive layer 103. As a result, the organic layer 94 is sealed more
reliably. Further, the hrgh adhesive force is maintained for a long period of time after
the sealing and no exfoliation occurs. Such high adhesive force allows the adhesive
layer 103 to have a nar¡ower line width, thereby makrng it possible to increase an area of
the organic layer (light emitting part). As a different form from Fig. 14, the second
concave-convex p aítem 342p may be identical to the first concave- coîvex patterr, 242p-
[0068] [Method fcir manufacturing light emitting element]
Subsequentl¡ an explanation will be made about a method for manufacturing
the light emitting element 100 of the above embodiment. The manufacturing method
mainly includes a step for manufacturing (forming) a stacked body including the light
emitfing part of the light emitting element and a sealing step for sealing the stacked
body with the sealing member and the adhesive layer. At first, the concave-convex
structure layer is fomed on the base member. The concave-convex structure layer can
be formed, for example, by a lift-off method or UV curing method as described below.
[0069] The lift-off method is usable when the concave-convex structure layer is forrned
by using a sol-gel material, a thermosetting material such as a thermosetting resin, or a
photocurable material. In the following, the case in which the concave-convex structure
layer is formed by using the sol-gel material will be explained as an example. The liftoff
method mainly includes: a step for forming a resist pattem on the base member; a
step for preparing a solution of the sol-gel material; a step for coating the base member
wit}r the solution of the sol-gel material; a step for pressing a mold having a transfer
pattern thereon against the coating film which has been dried for a predetermined time;
a pre-baking step for subjecting the coating film pressed with the mold to the preþ
¿lçing; a releasing (exfoliation or peeling off) step for releasing fueeling) the mold from
the coating fihn; a main baking step for subjectíng the coating frlm to the main baking;
ald a step for removing the resist from the base member. The steps wiil be explained
below with reference to Fig. 3.
[0070]
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As depicted in Fig. 3(a), a cleaned base member 4O is coated with a resist 20. It
is allowable to perfom a surface treatment or provide an easy-adhesion layer on the
base member 40 in order to improve an adhesion property, and to provide a gas barrier
layer in order to keep out moisture and gas such as oxygen. Any photoresist may be
used as the resist 20. As the coating method for the resist 20, it is possible to use any
coating method including, for example, a bar coating method, a spin coating method, a
spray coating method, a dip coating method, a die coating method, and an ink-jet
method. The bar coating method, the die coating method, and the spin coating method
are prefemble, because the base member having a relatively large area can be coated
uniformly with the resist and the coating can be quickly completed.
[0071] After the resist 20 applied on the base member 40 is dried, the resist 20 is
exposed to light using a mask 501, as depicted in Fig. 3(a). Developing the resist 20
with a developer removes a part, ofresist, in the position in which the concave-convex
structure layer is to be formed, as depicted in Fig. 3(b). It is preferred that the resist be
patterned such that a cross section shape of the residual resist 20 has an inverted taper
shape in which the cross section areâ of the residual resist 20 inc¡eases from the
interface with the base member toward the resist surface by, for example, a method as
described in Japanese Patent No. 2,989,064. Such patterning makes an edge þeriphery)
of the resist 20 an inclined surface, thereby making it possible to make the outer
periphery 142c of the concave-convex structure layer the inclíned (tapered) surface.
[0072]
The soi-gel material (sol), which is a material of the concave-convex structure
layer, is prepared. For example, when silica is slmthesized on the base member by the
sol-gel method, a sol-gel material of metal alkoxide (silica precursor) is prepared.
Examples of the silica precursor include tetraalkoxide monomers tepresented by
tetraalkoxysilane such as tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetra-ipropoxysilane,
tetra-n-propoxysilane, tetra-i-butoxysilane, tetra-n-butoxysilane, tetrasec-
butoxysilane, and tetra{-butoxysilane; trialkoxide monomers represented by
trialkoxysilane such as methyltrimethoxysilane, ethyltrimethoxysilane,
propyitrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane,
methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane,
isopropyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane,
ethyltripropoxysilane, propyltripropoxysilane, isopropyltripropoxysilane,
oo
phenyltripropoxysilale, methyltriisopropoxysilane, ethyltriisopropoxysilane,
propyltriisopropoxysilane, isopropyltriisopropoxysilane, phenyltriisopropoxysilane,
hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane,
trifluoropropyltrimethoxysilane, octyltriethoxysilane, perfluorodecyltriethoxysilane, 4-
trifluoro methylphenylhiethoxysilane, and tolyltriethoxysilane; dialkoxide monomers
represented by dialkoxysilane such as drmethyldimethoxysilane,
dimethyldiethoxysilane, dimethyldipropoxysilane, dimetþldiisopropoxysilane,
dimethyldi-n-butoxysilane, dimethyldi-i-butoxysilane, dimethyldi-sec-butoxysilane,
dimethyldi-t-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane,
diethyldipropoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-ibutoxysilane,
diethyldi-sec-butoxysilane, diethyldi-t-butoxysilane,
dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane,
dipropyldiisopropoxysilane, dipropyldin-butoxysilane, dipropyldi-i-butoxysilane,
dipropyldi-sec-butoxysilane, dipropyldi-t-butoxysilane, diisopropyldimethoxysilane,
diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane,
diisopropyldi-n-butoxysilane, diisopropyldi-i-butoxysilane, diisopropyldi-secbutoxysilane,
diisopropyldi-t-butoxysilane, diphenyldimethoxysilane,
diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane,
diphenyldi-n-butoxysilane, diphenyldi-i-butoxysilane, diphenyldi-sec-butoxysilane, and
diphenyldi+-butoxysilane; monomers having vinyl group such as vinyltrimethoxysilane
and vinyltriethoxysilane; monomers having epoxy group such as 2-13,4-
epoxycyclohexyi)ethyltrimethoxysilane, 3-glycidoxlpropylmethyldimethoxysilane, 3-
gþidoxypropyltrimethoxysilane, 3-glycídoxypropylmethyldiethoxysilane, and 3-
gþidoxypropyltriethoxysilane; monomers having styryl group such as pstyryltrimethoxysilane;
monomers having methacrylic group such as 3-
methacryloxypropylrnethylrlimethoxysilane, 3-methacryloxypropyltrirnethoxysilane, 3-
methacryloxypropylmethyldiethoxysilane, and 3-methacryloxlpropyltriethoxysilane;
monomers having acrylic goup such as 3-acryloxlpropyltrimethoxysilane; monomers
having amino group such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrìmethoxysilane, 3-
aminopropyltriethoxysilane,3-triethoxysiþ1-N-(1,3-dimethyl-butylidene)propylamine,
and N-phenyl-3-aminopropyltrimethoxysilane; monomer having ureide group such as 3-
ureidepropyltriethoxysilane; monomers having mercapto group such as 3-
3s
'í:.
,:.
l*
I
It
I
i
ii
mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
monomers having sulfide group such as bis(triethoxysilylpropyl) tetrasulfide; monomers
having isocyanate group such as 3-isocyanatopropyltriethoxysilane; pol¡rmers obtained
by polyrnerizing the foregoing monomers in small amounts; and composite mate¡ials
characterized in that firnctional group and,/or pollaner is/are introduced into a part of the
material as described above. Further, a part of or all ofthe alkyl group and the phenyl
group may be substituted with fluorine. Iurther, examples of the silica precursor
include metal acetylacetonate, metal carboxylate, oxychloride, chloride, and mixtures
thereof. The silica precrrrsor, however, is not limited to the above examples. In
addition to Si, examples ofthe metal species include Ti, Sn, Al, Zn, Zr, In, and mixtures
thereof, but are not limited thereto. It is also possible to use any appropriate mixture of
precursors of the oxides of the above metals. Further, a hydrophobization treatment
may be performed on each of the sur{aces. Any known method for the
hydrophobization treatment may be used. For example, in a case of the surface ofsilica,
the hydrophobization treatment can be performed with dimethyldichlorosilane,
trimethylalkoxysilan, etc., or with a silicone oil and a trimethylsilylating agent such as
hexamethyl-disilazane. Altematively, it is also allowable to employ a surface treatment
method for a surface of metal oxide powder with supercritical carbon dioxide. Futher,
it is possible to use, as the silica precursor, a silane coupling agent having, in its
molecule, a hydrolysis group having the affinity and the reactivity with silica and an
organic firnctional group having the water-repellence. For example, the¡e are
exemplified by silane monomer such as n-octyltriethoxysilane, methyltriethoxysilane,
and methyltrimethoxysilane; vinylsilane such as vinyltriethoxysilane,
vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)si1ane, and
vinylmethyldimethoxysilane; methacrylsilane such as 3-
methacryloxypropyltriethoxysilane and 3-methacryloxlpropyltrimethoxysilane;
epoxysilane such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-
glycidoxlpropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane; mercaptosilane
such as 3-mercaptopropyltrimethoxysiiane and 3-mercaptopropyltriethoxysilane;
sulñusilane such as 3 -octanoylthio- l-propyltriethoxysilane; aminosilane such as 3-
aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-
aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
3tt
and 3-(N-phenyl)-aminopropyltrimethoxysilane; and pollnners obtained by poll.rnerizing
the monomers as described above.
[0073] Each of the sol-gel materials produces amorphous silica by being subjected to
hydrolysis and polycondensation reaction. An acid such as hydrochloric acid or an
alkali such as ammonia is added in order to adjust the pH ofthe solution as a s¡mthesis
condition. A material (photoacid generator or photobase generator), which generates an
acid or alkali by inadiation with light such as ultraviolet rays, may be added. The pH is
preferably not more than 4 or not less than 10. Water may be added to perform the
hydrolysis. The amount ofwater to be added can be not less than 1.5 times, with respect
to the amount of metal alkoxide species, in the molar ratio. It is also possible to use, as
the sol-gel material, a material other than the silica. For example, a titanium-based
material, a material based on indium tin oxide (ITO), AbOz, Z{Jz, ZnO,'|iOz, ZnS,
ZrO,Ba'fiOz, SrTiOz, etc. may be used.
[00741 Those usable as the solvent for the sol-gel material include, for example,
alcohols such as methanol, ethanol, isopropyl alcohol (IPA), and butanol; aliphatic
hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane; aromatic
hydrocarbons such as benzene, toluene, xylene, and mesitylene; ethers such as diethyl
ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone,
isophorone, and cyclohexanone; ether alcohols such as butoxyethyl ether, hexyloxyethyl
alcohol, methoxy-2-propanol, and benzyloxyethanol; gþols such as ethylene gþol and
propylene glycol; glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol
dimethyl ether, and propylene glycol monomethyl ether acetate; esters such as ethyl
acetate, ethyl lactate, and y-butyrolactone; phenols such as phenol and chlorophenol;
amides such as N,N-dimethylformamide, N,N-dimetþlacetamide, and Nmethylplrrolidone;
halogen-containing solvents such as chlorofonn, methylene chloride,
tetrachlo¡oethane, monochlorobenzene, and dichlorobenzene; hetero-element containing
compounds such as carbon disulfide; water; and mixture solvents thereof. Especially,
ethanol and isopropyl alcohol are preferable. Furthe¡ a mixture of water and ethanol
and a mixture of water and isopropyl alcohol are also prefe¡able.
[00751 As an additive of the sol-gel material, it is possible to use polyethylene gþo1,
polyethylene oxide, hydroxypropylcellulose, and polyvinyl alcohol for viscosity
adjustment; alkauolamine such as triethanolamine, fJ-diketone such as acetylacetone, pketoester,
formamid, dimetylformamide, dioxane, and the like, as a solution stabilizer.
2(
I:
I
[0076]
As depicted in Fig. 3(c), the base member 40 is coated with the prepared sol-gel
material to form a coating {lm 142a. As the coating method, it is possible to use any
coating method including, for example, a bar coating method, a spin coating method, a
spray coating method, a dip coating method, a die coating method, and an ink-jet
method. The bar coating method, the die coaling method, and the spin coating method
are preferable, because the base member having a relatively large area can be coated
uniformly with the sol-gel material and the coating can be quickly completed prior to
curing (gelation) of the sol-ge1 material.
[0077] After the coating of the base member with the sol-gel material, the base member
is kept (held) in the atmospheric air or reduced pressure in order to evaporate the solvent
contained in the coating film 142a. After lhe coating of the base member with the solge1
material, the pol]'merization reaction ofthe precursor proceeds as tlle evaporation of
the solvent proceeds, and the physical property such as the viscosity of sol-gel material
also changes in a short time. From the viewpoint ofthe stability of concave-convex
pattem formation, it is preferred that drying time which enables a good pattern transfer
have a sufficiently wide range. The range of the drying time which enables a good
pattem transfer can be adjusted by the drying temperature (holding temperature), the
drying pressure, the kind of sol-gel material, the ratio of mixed so1-gel materials, the
solvent amount used at the time ofpreparation ofthe sol-gel material (concentration of
sol-gel material), etc. It is preferred that the holding temperahlre stay constant in a
range of 10 to 100oC, more preferably in a range of 10 to 30'C. When the holding
temperahrre is higher than this range, the gelation reaction of the coatin g ñlm 142a
proceeds rapidly before the pressing step, which is not preferable. When the holding
temperature is lower than this range, the gelation reaction of the coating flJm l42a
proceeds siowly before the pressing step, which reduces the productivity and is not
preferable.
[00781
After the drying step, a mold 80 having a predetermined minute concave-convex
pattem is pressed against the coating film 142a, as depicted in Fig. 3(d). The pressing is
performed by the conventional pressíng system or a roiling system using a pressing ro11.
[0079]
3L
I
The mold 80 used in this embodiment may be a film-shape mold which is
flexible and has a concave-convex transfer pattern on a surface thereof. Those usable as
the material for the mold 80 include, for example, organic materials such as silicone
resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate
(PC), cycloolefin polyner (COP), polynethyl methacrylate (PMMA), polystltene (PS),
pollmide (PI), and polyarylate; metallic materials such as nickel, copper, and
aiuminium; and inorganìc materials such as glass. The materials for the mold 80 are not
limited to the above examples, and any material can be used. The concave-convex
pattem may be formed directly in each of the materials, or may be formed of another
material with which the base member formed of the above-material(s) is coated or
covered. It is possible to use photocurable resin, thermosetting resin, and thermoplastic
resin as another material. A surface treatment or an easy-adhesion treatment may be
performed between the base member and another material in order to improve the
adhesion property. Further, a mold-release treafinent may be performed on each
concave-convex pattem surface as needed.
[0080] The concave-convex pattem of the mold 80 may be formed by any method. For
example, the concave-convex pattem ofthe mold 80 may be any pattern such as a
microlens a¡ray structure or a structure having the light scatte¡ing firnction, light
diffracting function, etc. The concave-convex pattem may be, for example, an irregular
concave-convex pattem in which pitches ofconcavities and convexities are non-uniform
and orientations of concavities and convexities have no directionality. In order thai the
concave-concave structure layer to which the concave-convex pattem ofthe mold 80 has
been ûansfer¡ed works as the diffraction grating, the average pitch ofconcavities and
convexities of the mold 80 is preferably in a range of 100 to 1,500 nm. When the
average pitch ofconcavities and convexities is less than the lower limit, pitches are so
small relative to the wavelengths of the visible light that the diff¡action of light by
concavities and convexities ofthe concave-concave structure layer to which the
concave-convex pattem of the mold 80 has been transferred is not likely to occur. On
the other hand, when the average pitch exceeds the upper limit, the diffraction angle is
so small that the functions as the diff¡acting grating are more likely to be lost. The
average pitch of concavities and convexities is more preferably in a range of 200 to
1,200 nm. The average value of depth distribution of concavities and convexities of the
mold 80 is preferably in a range of 20 to 200 nm. When the average value of the deptå
g+
I
-*******-Ê':
il.'l
l''
I
I
L.ì
ìr
distribution ofconcavities and convexities is less than the lower limit, the height is so
short relative to the wavelengths of the visible light that the required diffiaction is less
likely to occur. On the other hand, when the average value exceeds the upper limit, the
intensity of diffracted light becomes non-uniform, which in tum results in the following
tendency. Namely, the electrìc field distribution in the light emitting layer of the
resulting light emitting element becomes non-uniform, thereby causing the electric field
to concentrate on a certain position or area in the light emitting layer and thus causing
any leak current to be easiìy generated, and/or shortening the service life. The average
value ofthe depth distribution ofconcavities and convexities is more preferably in a
range of 30 to .150 nm. The standard deviation of depth of convexities and concavities
is preferably in a range of 10 to 100nm. When the standard deviation of depth of
convexities and concavities is less than the lower limit, the height is so short relative to
the wavelengths of the visible light that the required diffraction is less likely to occur.
On the other hand, when the standard deviation exceeds the upper limit, the intensity of
diffracted light becomes non-uniform, which in tum results in the following tendency.
Namely, the electric field distribution in the light emitting layer ofthe resulting light
emitting element becomes non-uniform, thereby causing the electric field to concentrate
on a certain position or area in the light emitting layer and thus causing any leak curent
to be easily generated, and/or shortening the service 1ife. The standard deviation of
depth ofconvexities and concavities is more preferably in a range of 15 to 75 nm.
[0081] An explanation will be made about an exemplary method for producing the mold
80 used in this embodiment. A master block pattern for forming the concave-convex
pattern of the mold is ma¡ufactu¡ed first. It is preferred that the concave-convex pattern
ofthe master block be formed by a method of utilizing the self-organization or selfassembly
(micro phase separation) ofa block copoll.mer by heating, as described in
Intemational Publication No. WO2072/096368 of the applicants of the present invention
(hereinafter referred to as "BCP (Block Copol¡aner) thermal annealing method" as
appropriate), a method ofheating and cooling a vapor deposited film on a poll.rner film
to form concavities and convexities of wrinkles on a surface ofpollnner, as disclosed in
Intemational Publication No. WO2011/007878 A1 of the applicants of the present
invention (hereinafter referred to as "BKL (Buckling) method" as appropriate), or a
method ofutilizíng the self-organization or self-assembly ofa block copol¡..mer under a
solvent aûaosphere (hereinafter referred to as "BCP solvent armealing method" as
Qq
appropriate) which will be described below. The photolithography method may be
utilized instead of the BCP thermal annealing method, BKL method and BCP solvent
annealing method. In addition to the above methods, examples of the method for
manufachrring the concave-convex pattern of the master block include microfabrication
or fine-processing methods including a cutting (cutting and processing) or machining
method, an electron-beam direct imaging method, a particle beam processing method, a
scanning probe processing method, and the like; a fine-processing method using the
self-organization or self-assembly of fine particles; and a sandblasting method. When
the pattem is fomred by the BCP thermal annealing method or the BCP solvent
annealing method, although the pattern made of any material can be used, the material ís
preferably a block copolyrner composed ofa combination of two selected from the
group consisting of a styrene-based polymer such as polystyren; polyalþl methacrylate
such as polymethyl methacrylate; poþthylene oxide; polybutadiene; polyisoprene;
polyvinylplridine; and poiylactic acid.
[0082] The BCP solvent anlrealing method is a method as follows. Namely, a thin frlm
of the block copolymer which has been applied on a substrate and dried is subjected to a
solvent annealing (solvent phase separation) process under an atmosphere of vapor of an
organic solvent to form a phase separation structure of the block copolyrner in the thin
fihn, instead of performing the first heating step, the etching step and the second heating
step ìn the BCP thermal amealing method described nWO20l2/096368. With this
solvent annealing process, the self-organization ofthe block copollmer is advanced, and
the block copolymer undergoes the micro phase separation into the concave-convex
structure.
[00831 For exampie, the solvent annealing process can be carried out by providing the
atmosphere ofvapor ofthe organic solvent inside a tightly sealable container such as a
desiccator, and exposing the thin film ofthe block copolymer as the objective under this
atmosphere. The concentration of vapor of the organic solvent is preferably high for the
purpose of promoting the phase separation of the block copolymer, in particular, it is
preferred that the concentration ofthe organic solvent vapor be a concentration in which
the pressure of the organic solvent vapor is saturated vapor pressure, wherein not only
the phase separation of the block copolyler is promoted but also the concentration of
the organic solvent vapor can be controlled or managed relatively easily. For example,
when the organic solvent is chloroform, the saturated vapor amount (quantiry) is known
31
I
l,
I
I
to be in a range of 0.4 dlro 2.5 g/l at room temperature (0 to 45'C). If the time of the
organic solvent annealing process using chloroform or the like is excessively long, there
is such a tendency that poþthylene oxide is deposited on the surface of the coating film
and/o¡ the concave-convex shape þattem) formed by the phase separation is collapsed
(loosened). The treatment time of the solvent armealing process may be 6 to 168 hours,
preferably 12 to 48 hours, and more preferably i2 to 36 hours. If the time of the process
is excessively long, the concave-convex shape is collapsed. If the time of the process is
excessively short, grooves of the concave-convex structure are shallow and a paÍ or
member produced by transferring the concave-convex pattern ofthe manufactured mold
has an insufficient light difftaction effect.
[00841 The organic solvent used in the solvent annealing process is preferably an
organic solvent of which boiling point is in a range of 20 to 120"C. It is possible to use,
for example, chloroform, dichloromethane, toluene, tetrahydrofiran (THF), acetone,
carbon disulfide, and mixture solvents thereof. Among these solvents, cbloroform,
dichloromethane, acetone, and a mixture solvent of acetone/carbon disulfide are
preferable. The atmosphere temperature ofthe solvent annealing is preferably in a range
of 0 to 45'C. If the atmosphere temperature of the solvent amealing is higher than
45oC, the concave-convex struchr¡e formed on the thi¡ fil¡n is blunt or dull (loosened),
causing the concave-convex structure to be collapsed easily. In an environment lower
than 0"C, the organic solvent is hardly evaporated, and the phase separation of the block
copolymer hardly occurs.
[0085] It is allowabie to perform the heating process to the concave-convex structure of
the thin film obtained by the solvent amealing process. Since the concave-convex
structure has been already formed by the solvent annealing process, the heating process
is performed to loosen or smooth the formed concave-convex structure. Note that the
heating process is not necessarily required. The heating process may be useful when
any protrusion is generated on a part of the surface ofthe concave-convex structure after
the solvent annealing process on account of any cause and,/or when it is intended to
adjust the cycle þeriod or pitch) and the height of the concave-convex structure. For
example, the heating temperature can be not less than the glass kansition temperatures
of the polymer segments constituting the block copol¡mrer. For example, the heating
temperahrre can be not less than the glass transition temperatures of the homopol¡rmers
It-o
and not mo¡e than a temperature higher than the glass transition temperatures by 70"C.
The heating process can be performed in the atmosphere of the atmospheric air by using,
for example, an oven. Fu¡ther, the concave-convex struch¡re of the thin film obtained
by the solvent annealing process may be subjected to etching by inadiation with energy
rays represented by ultraviolet rays such as excime¡ UV light, or etching by a dry
etching method such as reactive ion etching (RIE). The concave-convex structure ofthe
thin film which has been subjected to the etching may be subjected to the heating
process.
[0086] After forming the master block with the pattem by means of the BCP thermal
annealing method, BKL method, or BCP solvent annealing method, fur1her, a mold to
which the pattem is transfered can be formed by an electroforming method or the like,
as follows. At first, a seed layer functioning as an electroconductive layer for an
electroforming process can be formed on the master block, which has the pattem to be
transferred, by means ofnon-electrol¡tic plating, sputtering, vapor deposition, or the
like. The thickness ofthe seed layer is preferably not less tha¡ 10 nm to uniformize a
cunent densþ during the subsequent electroforming process, and thereby making the
thickness of a metal layer accumulated by the subsequent electroforming process
uniform. Those usable as the material of the seed layer include, for example, nickel,
copper, gold, silver, platinum, titanium, cobalt, tin, zinc, chrome, gold-cobalt alloy,
gold-nickel alloy, boron-nickel alloy, solder, copper-nickel-chromium alloy, tin-nickel
alloy, nickel-palladium alloy, nickel-cobalt-phosphorus alloy, and alloy thereof.
Subsequently, the metal layer is accumulated on the seed layer by the electroforming
(electroplating). The entire thickness of the metal layer including the thickness of the
seed layer can be, for example, in a range of 10 to 3000 pm. As the material ofthe
metal layer accumulated by the electroforming, it is possible to use any of metal species
as described above which can be used as the seed layer. Nickel is preferably used in
view of the wear resistance, the releasing (exfoliation or peeling off) property, and the
like as the mold of the metal substrate. In this case, nickel is preferably used also for the
seed layer. Considering ease of the subsequent processes for forming the mold such as
pressing to the resin layer, releasing, and cleaning, the formed metal layer desirably has
appropriate hardness a¡d thickness.
H
[0087] The metal layer including the seed layer obtained as desc¡ibed above is released
(peeled off) from the master block having the concave-convex struchtre to obtain a
metal substrate. As the releasing method, the metal layer may be peeled off physically,
or materials composing the pattem of the master block may be dissolved and removed
by using an organic solvent dissolving them, such as toluene, tetrahydrofuran (THF),
and chloroform. When the metal substrate is peeled off flom the naster block, a
remaining materiai component on the metal substrate can be removed by cleaning. As
the cleaning method, it is possible to use wet cleaning using a surfactant etc., or dry
cleaning usíng ultraviolet rays and/or plasma. Altematively, for example, the remaining
material component may be attached to or adhere to an adhesive agent or a bonding
agent then be removed. Accordingly, the metal substrate to which the pattern has been
transferred from the master block can be obtained.
[00881 A flexible mold such as the film-shaped mold can be manufactured by
kansferring the concave-convex structure (pattern) ofthe obtained metal substrate to a
film-shaped supporting substrate. For example, after the supporting substrate is coated
with curable resin, the resin layer is cured while the concave-convex structure ofthe
metal substrate is being pressed against the resin layer. The supporting substrate is
exemplified, for example, by base members made of inorganic materiais such as glass;
base members made of organic materials such as silicon resin, polyethylene
terephthalate (PET), polyethylene naphtlralate (PEN), poþarbonate (PC), cycloolefin
polymer (COP), pollnnethyl methacrylate (PMMA), polystyrene (PS), polyimide (PI),
and polyarylate; and metallic materials such as nickel, copper, and aluminium. The
thickness of the supporting substrate may be in a range of 1 to 500 pm.
[00891 Examples of the curable resin include resins such as photocurable resins,
thermosetting resins, moisture curing type resins, chemical curing lype resins (twoliquid
mixing þpe resins), etc. Specifically, the curable resin is exemplified by various
resins including, for example, monomers, oligomers, and polyrners ofthose based on
epoxy, acrylic, methacrylic, vinyl ether, oxetane, urethane, melamine, urea, polyester,
polyolefin, phenol, crossJinking type liquid crystal, fluorine, silicone, polyamide, etc.
The thickness of the curable resin is preferably in a range of 0.5 to 500 pm. When the
thickness is less than the lower limit, heights of concavities and convexities formed on
the surface of the cured resin layer are likely to be insuffrcient. When the thickness
exceeds the upper limit, the influence of volume change in the resin upon curing is
+2-
r,.
likely to be so large that the formation of the shape ofconcavities and convexities is
liable to be unsatisfactory.
[0090] As a method for coating the suppo¡ting substrate with the curable resin, for
example, it is possible to adopt various coating methods such as a spin coating method,
a spray coating method, a dip coating rr¡ethod, a dropping method, a gravue printing
method, a screen printing method, a relief printing method, a die coating method, a
cutain coating method, al bk-jet method, and a sputtering method. Further, conditìons
for curing the curable resin depend on the kind of the resin to be used. For example, the
curing temperature is preferably in a range ofroom temperature to 250'C, and the
curing time is preferably in a range of 0.5 minute to 3 hours. Altematively, a method
may be employed in which the curable resin is cured by being irradiated with energy
rays such as ultraviolet light or electron beams. In such a case, the amount of the
irradiation is preferably in a range of20 rr.Jlclrr:2 to 5 I/cÍ|.
[0091] Subsequently, the metal substrate is detached f¡om the curable resin layer afÍer
the curing. The method for detaching the metal substrate is not limited to a mechanical
releasing (exfoliating or peeling off) method, and any known method can be adopted.
Accordingly, it is possible to obtain the mold 80 with the resin film having the cured
resin layer in which concavities a¡d convexities are formed on the suppo¡ting substrate.
[0092]
After the mold 80 is pressed against the coating fi1m 142a made of the sol-gel
material, the coating film 742a may be slbjected to pre-baking by using aheater 32 as
depicted in Fig. 3(e). The pre-baking promotes the geiation ofthe coating film 142a to
solidifu the pattem, thereby making the pattem be less likely to be collapsed during the
releasing or exfoliation. When the pre-baking is performed, the heating is preferably
performed at a temperature in a range of 40 to 150'C in the atmospheric ai¡. As the
healer 32, it is possible to use, for example, an infrared heater, hot-air heating, and a hot
plate. It is not necessarily required to perform the pre-baking.
[0093]
After the pressing step or the pre-baking step, the mold 80 is released or peeled
off from the coating film 142a made of the sol-gel material. As a method for releasing
the mold 80, any known rele¿sing method can be adopted. The mold 80 may be
¡eleased while the coating film l42aberngheated. Ir this case, gas generated from the
Irz
"t'.
Il.
t-i:..
t:,
|:.
I
coating fikn 142a is allowed to escape, thereby preventing generation ofbubbles in the
coafingñln 142a.
[00941
After the mold 80 is released from the coating frlm 142a on the base member 40,
the coating film l42a is subjected to main baking, for example, il an oven 34, as
depicted in Fig. 3(f. The hydroxyl group and the like contained in the coating film
142a is desorbed or eliminated by the main bakíng to further harden (solidifi) the
coating film 142a. It is preferred that the main baking be performed at tempeÉtures of
200 to 1,200'C for about 5 minutes to about 6 hours. In such a manner, the coating film
142a is cured, and the concave-convex structure layer 142 havtng the concave-convex
pattem 142p which coresponds to the concave-convex pattern ofthe mold 80 is
obtained. In this situation, the coating film 142a is amorphous, crystalline, or in a
mixture state of the amorphous and the crystalline, depending on the baking temperature
and baking time. Fufiher, when a material, which generates an acid or alkali by
iradiation with light such as ultraviolet rays, is added to the sol-gel material, a step of
curing the coating fi'm 142a, in which the coating film 1 42a made of the sol-gel
material is cured by irradiation with energy rays represented by ultraviolet rays such as
excimer IIV light, may be included in tJre concave-convex pattem transfer process.
[0095]
After the coating film 142a is cured to form the concave-convex structure layer
142, the resist 20 and the concave-convex structure layer 142 on the resist 20 are
stripped and removed as depicted in Fig. 3(g). The resist 20 is stripped by using any
resist stripping liquid. As described above, the concave-convex structure layer 142
having a desired concave-convex pattem 142p is formed on the base member 40 by the
liftoff method.
[0096f Instead ofthe liftoff method, the concave-convex skucture layer 142 canbe
formed on the base member 40 by the UV curing method. The UV curing method can
be used when the concave-convex structüe layer is formed by using a ffV curable resin,
a so1-gel material containing a photoacid generator or the like. In the following, the case
in which the concave-convex struchrre layer is formed by using the IJV curable resin
will be explained as an example witl reference to Fig. 4. Instead of the IIV curable
resin, it is allowable to use, for example, the sol-gel material to which the photoacid
++
generator such as hexafluorophosphate aromatic sulfonium salt which generates acid by
light is added; the sol-gel material to which B-diketone represented by acet¡rlacetone
which forms chemical modifrcation (cheiation) which can be removed by being
inadiated with light is added; and the like. Further, it is allowable that the concaveconvex
struchne layer 142be formed of a resin which can be cured by an active energyray
other than the UV light, and the resin be irradiated with the active energy ray other
than the IfV üght, instead of being irradiated with the UV light.
[0097] At first, as depicted in Fig. 4(a), the cleaned base member 40 is coated with a
IJV curable resin 142b. It is allowable to perform a surface treatment or provide an
easy-adhesion layer on the base member 40 in order to improve an adhesion property,
and to provide a gas barrier layer in order to keep out moisture and gas such as oxygen.
As a coating method of the UV curable resin, it is possible to use any coating method
including, for example, a bar coating method, a spin coating method, a spray coating
method, a dip coating method, a die coating method, ald an ink-jet method. The bar
coating method, the die coating method, and the spin coating method are preferable,
because the base member having a relatively large area can be coated uniformly with the
IJV curable resin and the coating can be quickly completed.
[0098] After the base member 40 is coated with the ffV curable ¡esin 142b, the mold 80
having the predetermined minute concave-convex pattern is pressed against the coating
film 142b made ofthe UV curable resin, as depicted in Fig. ft). The pressing can be
performed by the conventional pressing system or the rolling system using the pressing
roll. As the mold 80, one similar to the mold explained in the liftoff method can be
used. After the pressing with the mold 80, the coating fihn 142b made of the fry
curable resin is partially irradiated with UV light using an exposure mask 501 for the
concave-convex structue layer, as depicted in Fig. 4(c). Thus, the part, of the coating
film 742b, exposed with the UV light is cured. A concave-convex pattern of the moid
80 is transferred to the cured coating fllm 142b. Arranging the exposwe mask 501 and
the mold 80 v/ith a distance intervening therebetween during UV light irradiation allows
the UV light to go around the lower side of lightshielding portions of the exposure
mask 501, thereby making it possible to cure the IJV curable resin into a tapered shape.
In this case, the outer periphery 142c of the cured coating filn remaining on the base
member 40 after removal of an uncured coating film 142b as described later is fomed
ÞY
as the inclined surface, and thus the concave-convex structure layer 142, ofwhich oute¡
periphery 142c is formed as the inclined surface, can be obtained.
[0099] A film-shaped mold, in which a fihn-shaped photomask is used as a supporting
substrate, may be prepared, and the pressing and the exposure for the fIV curable resin
142b may be performed using this fikn-shaped mold.
[0100] Subsequently, as depicted in Fig. 4(b), the mold 80 is released from the coating
film l42b and the concave-convex structue layer 142. After releasing ofthe mold 80,
the uncured coating film 142b is removed. The removal ofthe uncured coating film
142b can performed such that the uncured coating fi1m 142b is dissolved by a solvent,
such as isopropyl alcohol (IPA). Removing the uncured coating film 142b in such a
manner allows only the cured coating film 142b to remain on the base member as
depicted in Fig. 4(e), thereby forming the concave-convex structure layer 142 having the
concave-convex pattem 142p, which corresponds to the concave-convex pattern ofthe
mold 80.
[0101ì In the IIV curing method, the concave-convex pattern of the concave-convex
structure layer is formed by using the mold, and the unnecessary part(s) or pofion(s) of
the coating film made of the lfV curable malerial is(are) removed tbrough the curing by
mask exposure and the dissolution. Instead ofusing the mold 80 depicted in Fig. 4(b), a
mold 80a including concave portions corresponding to the shape ofthe concave-convex
structure layer 142 as depicted in Fig. 5(b) may be used to form the concave-convex
structure layer 142 without the exposure by use of the mask and the dissolution of
uncured tIV curable resin. At first, as depicted in Fig. 5(a), the base member 40 is
coated with the IJV curable resin 142b. Then, the mold 80a is pressed against the
coating film 142b as depicted in Fig. 5(b). After the pressing with the mold 80a, the
coating film l 42b is cured by being irradiated with IIV light. After curing of the coating
ñlm 142b, the mold 80a is ¡eleased from the coating film 142b and thus the concaveconvex
structure layer 142 havrtg a shape which corresponds to the shape of the mold
80a is formed as depicted in Fig. 5(c). In this case, when apart, of the mold 80a,
coresponding to the outer periphery 142c ofthe concave-convex structure layer 142 is
formed as an inclined surface, the outer periphery 142c ofthe concave-convex structure
layer 142 is formed as the inclined surface. The material ofthe concave-convex
shucture layer 142 is not limited to the IJV curabie material, and may be a thermosetting
material such as a sol-gel material. When the sol-ge1 material is used for the concavel+
L
I
l
i.:,1
t"
convex structure I ayer 142, it is preferred that heating by use of a heater be performed
instead of tIV light irradiation, and main baking be performed after the releasing of the
mold 80a.
[0102]
After the concave-convex structure layer is forrned on the base member by the
liftoff method or the IIV curing method, the base member and the concave-convex
structüe layer are cleaned with a brush in order to remove foreign matters and the like
adhered to the base member and the concave-convex struchlre layer, and then an organic
matter and the like is removed with an organic solvent and an alkaline cleaning agent
using an aqueous solvent. Next, as depicted in Fig. 1(b), the first eleckode 92 is stacked
on the concave-convex structure layer 142 such that the concave-convex structure
formed in the surface ofthe concave-convex shuchrre layer 142 is maintained on the
first electrode 92 (see Fig. 1(b)). The flust electrode 92 having the concave-convex
pattem is formed, accordingly. As a method for stacking the fust electrode 92, it is
possible to appropriately use any known method including, for example, an evaporation
method, a sputtering method, and a spin coating method. Among these methods, the
sputtering method is preferably employed from the viewpoint of improvíng the adhesion
property. Note that during the sputtering, the base membe¡ may be exposed to a high
temperature of about 300'C. The first electrode 92 is coated with photoresist, and then
the photoresist is exposed with a mask pattem for the first electrode, and developed by a
developer. After that, the fi¡st electrode is etched with an etching solution, thereby
obtaining the patterned first electro de 92 havrrg a predetermined pattem. It is preferred
to clean the obtained first electrode 92 with the brush and to remove any organic matter
and the like with the organic solvent and the alkaline clea.ning agent using the aqueous
solvent, followed by performing a lfV ozone treaùrent.
[0103]
Next, the organic layer 94 is stacked on the first electrode 92 (see Fig. 1(b)). As
a method for stacking the organic layer 94, it is possible to appropriately use any known
method including, for example, an evaporation method, a sputtering method, a spin
coating method, and a die coating method. The patteming of the organic layer 94 can be
performed by any known method such as patteming by use of a mask. As depicted in
Figs. 1(a) and 1(b), the organic layer 94 is forrned in a range or area narower than that
++
of the concave-convex structur€ layer 142 such that the outer periphery of the organic
layer 94 and the outer periphery ofthe concave-convex structure layer 142 are
positioned while being separated from each other by a predetermined distance. As a
result, the concave-convex structure layer 142 is pafiaily exposed without being
covered with the organic layer 94 and/or a part (outer circumference) of the first
electrode 92 in which concavities and convexities of the concave-convex stmcture layer
142 are mainlained is exposed without being covered with the organic layer 94.
[01041
Subsequently, the second electrode (metal electrode) 98 is stacked on the organic
Iayer 94- The metal electrode 98 can be stacked by any known method such as an
evaporation method and a sputtering method. It is preferred that the metal electrode 98
be fonned to cover the organic layer 94 entirely. The patterning of the metal electrode
98 can be performed by any known method such as patterning by use of a mask.
[0105]
Subsequently, the adhesive layer 103 is fo¡med and the sealing member 101 is
attached the¡eto, thereby forming the sealed space 105 (see Figs. 1(a) and l(b)). At first,
the adhesive layer 103 is formed to overlap the outer periphery 142c of the minute
concave-convex layer I42. It is preferred that the adhesive layer 103 be formed to have
a predetermined space D from the org anic layer 94 in a state that the adhesive layer 103
is not brought in contact r¡/ith the org anic layer 94. It is preferred that the distance D be,
for example, 1 ¡rm or longer. The adhesive layer 103 can be formed at a predetennined
position by applþg an adhesive by use of a scannable dispenser, a movable stage,
and/or the like. Further, the adhesive layer i03 having a desired line width ca¡ be
formed by controlling the scanning velocity ofthe dispenser and the discharge amount
of the adhesive from the dispenser. Next, the sealing member 1 0 1 is disposed above the
concave-convex structure layer 142, the first electrode 92, the organic layer 94, and the
metal electrode 98 to face the base member 40 and then the sealing member 101 is
allowed to being adhered (connected) to the base member 40 via the adhesive layer 103.
Accordingly, the space 105 between the base member 40 and the sealing membe¡ 101 is
sealed. Then the adhesive layer 103 is cured by being irradiated with energy rays when
the adhesive layer 103 is made of a material which can be cured by being irradiated with
energy rays. For example, when the adhesive layer 103 is made ofthe photocurable
adhesive, the adhesive layer 103 is cured such that the light in a range from an
lÈBultraviolet
region to a visible region which is obtained by a high-pressure mercury vapor
lamp or a halogen lamp is radiated from the side ofthe sealing member or the side ofthe
base member. When the adhesive layer 103 is made of the thermosetting adhesive, the
adhesive layer 103 is cured by heating, for example, at a temperature of 50 to 150'C.
Accordingly, the base member 40 and the sealing menber 101 are fonned integrally and
thus the light emitting element 100, in which the organic layer 94 is disposed in the
sealed space 105, is formed.
[0106] After formation of the organic layer 94, it is preferred that the organc layer 94
be sealed, for example, in a nitrogen atmosphere (e.g. by use of a glove box, the inside
of which is replaced with high-purity nitrogen gas ofnot less than five-nnes (99 -999%o)
purity) without any contact with atmospheric air. In the above-described sealing step,
the sealing member 101 is aranged after the adhesive layer 103 is formed on the base
member 40. The adhesive layer 103, however, may be formed as follows. Namely, the
sealing member 101 is ananged to face the base member 40 with a space intervening
therebetween, and then an adhesive is injected into the space to form tle adhesive layer
103.
[0107] In the sol-gel material coatìng step, the base member 40 may be coated with a
dispersion liquid of fine parlicles such as TiOz, ZnO, ZnS, ZrO,BeíliOz, or SrTiOz. Of
the above materiais, TiOz is preferably used in view ofthe film formation perfonnance
(coating property) and the refractive index. The coating film made of an inorganic
material may be formed by a liquid phase deposition (LPD) or the 1ike.
[0108] Altematively, the base member 40 may be coated with a polysilazane solution in
the sol-gel material coating step. In this case, a concave-convex structure layer made of
silica may be obtained by forming the coating filn made of the polysilazane solution
into ceramic (silica reforming or modifrcation) in the main baking step. It is noted that
"polysiiazane" is a polymer having a silicon-nitrogen bond, is an inorganic polymer
comprising Si-N, Si-H, N-H, or the like, and is a precursor of a ceramics such as SiOz,
Si:N+, or SiO.\ which is an intennediate solid solution of them. A compound, which
is ceramized at relatively low t€mperatue and is modifred into silica, is more preferred.
For example, a compound, which is represented by the following formula (1) described
in Japanese Patent Application Laid-open No. H8-1728'79, is more preferable.
[0109] Formuia (1): -Si (Rl) (R2)-N (R3)-
+q
lr.
t,
In the fonnuÌa (1), R1, R2, and R3 each represent a hydrogen atom, an alþl
group, an alkenyl group, a cycloalkyl group, a:l aryl group, an aþlsilyl group, an
alkyiamino group, or an alkoxy group.
[0110] Of the compounds represented by the formula (1), perhydropolysilazane
(referred to also as PHPS) in which all ofRl, R2, and R3 are hydrogen atoms and
organopolysilazane in which a part of the hydrogen bonded to Si thereof is substituted
by, for example, an alþl group are particularly prefer¡ed.
[0111f Other examples of the polysilazane ceramized at low temperature include:
silicon alkoxide-added polysilazane obtained by reacting polysilazane with silicon
alkoxide (for example, Japanese Patent Laid-Open No. 5-238827); glycidol-added
polysilazane obtained by reaction with gþidol (for example, Japanese Patent Laid-open
No. 6-122852); alcohol-added polysilazane obtained by reaction with alcohol (for
example, Japanese Patent Laid-open No. 6-240208); metal carboxylate-added
polysilazane obtained by reaction with metal carboxylate (for example, Japanese Patent
Laid-Open No. 6-299118); acetylacetonato complex-added polysilazane obtained by
reaction with an acetylacetonato complex containing a metal (for example, Japanese
Patent Laid-Open No. 6-306329); metallic fine parricles-added polysìlazane obtained by
adding metallic fine particles (for example, Japanese Patent Laid-Open No. 1-196986),
and the like.
[0112] As a solvent of the polysilazane solution, it is possible to use hydrocarbon
solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic
hydrocarbons; halogenated hydrocarbon solvents; and ethers such as aliphatic ethers and
alicyclic ethers. Amine or a metal catalyst may be added in order to promote the
modification into a silicon oxide compound.
[0113] The curing ofpolysilazane may be facilitated by heating or by irradiation with
energy rays such as excimer.
[0114] The coating layer may be fomred on the concave-convex structure layer 142.
The coating layer can be formed by any of the methods which can be used to forrn tle
concave-convex sfucture layer 142. For example, the above-described sol-gel method,
a method by use of a dispersion liquid of fine particles of an inorganic material, the
liquid phase deposition (LPD), and a method of curing polysilazane may be used. When
the silane coupling agent is used as the material of the coating layer, the coating layer
9o
may be formed as foilows. Namely, the coatìng material is applied by any of various
coating methods including, for example, a spin coating method, a spray coating method,
a dip coating method, a dropping method, a grawre printing method, a screen printing
method, a relief printing method, a die coating method, a cufain coating method, an
ink-jet method, and a sputtering method. Then, the applied coating material is dried and
cured under a proper condition suitable to the material used. For example, the coating
material may be heat-dried at temperatures of 100'C to 150"C for 15 to 90 minutes.
Examples
[0115] In the following description, the present invention will be specifrcally explained
with Examples and Comparative Examples. The present invention, however, is not
limited to Examples. In each of Examples and Comparative Examples, a light emitting
element was manufactured and then the evaluation of adhesion property of an adhesive
layer of the light emitting element and the evaluation of deterioration under high
humidþ environment were performed.
[0l16l [Example 1]
A mold having a concave-convex surface was manufactured as follows. At fi¡st,
there was prepared a block copollmer produced by Pollmer Source Inc., which was
made ofpolystyrene (hereinafter referred to as "PS" in an abbreviated manner as
appropriate) and pol)'rnethyl methacrylate (hereinafter ¡efer¡ed to as "PMMA" in an
abbreviated ma¡ner as appropriate) as described below.
Mn ofPS segment : 868,000
Mn of PMMA segment : 857,000
Ma of block copolymer: i,725,000
Voiume ratio between PS segment and PMMA segment (PS:PMMA):53:47
Molecular weight distribution (Mw/Mr) : 1.30
Tg ofPS segment : 96oC
Tg of PMMA segnent: 110"C
[0117] The volume ratio between the first pol¡'rner segment and the second pollmer
segment (the first polymer segment: the second poll.rner segment) in the block
copolymer was calculated on the assumption that the density of polystyrene was 1.05
g/cm3 and the density of polymethyl methacrylate was 1.19 {ar}. The number average
molecular weights (Mn) and the weight average molecular weights (Mw) of polyrner
lì
tr
l:
L::..
):.
l
l
I
1
:::l
segments or pol)¿rners were measured by using a gel pemeation chromatography
(Model No. "GPC-8020" manufactured by TOSOH CORPORATION, in which TSKgel
SuperH1000, SuperH2000, SuperH3000, and SuperH4O00 were connected in series).
The glass transition temperahües (Tg) ofthe polyrner segments were measured by using
a differential scanning calorimeter (manufactured by PERKIN-ELMER, INC. under the
product name of "DSC7"), while the temperature was raised at a rate of ternperature rise
of 2o'Clmin over a temperature range of 0 to 200'C. The solubility parameters of
polystyrene and pol¡.rnethyl methacrylate were 9.0 and 9.3 respectively (see "Kagaku
Binran Ouyou Hen" (Handbook of Chemistry, Applied Chemistry), 2nd edition).
[0118] Toluene was added to 150 mg of the block copollaner and 38 mg of
Poþthylene Glycol 4000 manufactured by Toþo Chemical Lrdustry Co., Ltd. (Mw:
3000, Mw,Mn: 1.10) as polyethylene oxide so that the total amount thereof was 10g,
followed by dissolving them. Then, the solution was filtrated or filtered through a
membrane filter having a pore diameter of 0.5 pm to obtain a block copollnner solution.
The obtained block copoll.rner solution was applied, on a polyphenylene sulfrde filn
(TORELINA manufactured by TORAY INDUSTRIRES, INC.) as a base member to
form a thin film having a thickness of 200 to 250 nm, by spin coatìng. The spin coating
was performed at a spin speed of500 rpm for 10 seconds and then a spin speed of800
rpm for 30 seconds. The thin film formed by the spin coating was left at room
temperature fo¡ 10 minutes until the +hin filrn was dried.
[0119] Then, the base member on which the thin film was formed was subjected to a
solvent annealing process by being stationarily placed in a desiccator filled with
chloroform vapor in advance at room temperature for 24 hours. Inside the desiccator
(volume: 5 L), a screw-type container charged with 100 g of chloroform was placed, and
the atmosphere inside the desiccator was filled with chloroform at the saturated vapor
pressure. Concavities and convexities were observed in the surface of the thin film afte¡
the solvent annealing process, and it was found that the block copolyrner forming the
thin film underwent the micro phase separation.
[0120] About 20 nm of a thin nickel layer was fo¡med as a current seed layer by
performing the sputtering on the surface ofthe thin fikn processed to have the wave-like
shape by the solvent annealing p¡ocess as described above. Subsequently, the base
member equipped with the thin film was immersed in a nickel sulfamate bath and
S2-
subjected to an electroforming process (maximum current densit¡r: 0.05 A"/cm2) at a
temperature of 50"C so as to precipitate nickel until the thickness became 250 pm. The
base member equipped with the tbin film was mechanically peeled off or released from
the nickel electroforming body obtained as described above. Subsequently, the nickel
electroforming body was immersed in a tetrahydrofura¡ solvent for 2 hours, and then the
nickel electroforming body was coated with an acrylic-based UV curable resin, followed
by being cured and peeled off. This process was repeated three times, and thus pollmer
component(s) adhered to a part of the sur{ace of the electroforming body was (were)
removed. After that, the nickel electroforming body was inrmersed in Chemisol 2303
manufactured by THE JAPAN CEE-BEE CHEMICAL CO., LTD., and was cleaned or
washed while being stirred or agitated for 2 hours at 50oC. Thereafter, the LfV ozone
treatment'lras applied to the nickel electroforming body for 10 minutes.
[0121] Subsequently, the nickel electroforming body was immersed in OPTOOL HD-
2100TH manufactured by DAIKIN INDUSTRIES, ltd. for about 1 minute and was
dried, and then stationarily placed overnight. The next day, the nickel electroforming
body was immersed in OPTOOL HD-TH manufactured by DAIKIN INDUSTRIES, ltd.
and was subjected to an ultrasonic cleaning (washing) process for about I minute. In
such a manner, a nickel mold (nickel substrate) for which a mold-release treatment had
been performed was obtained.
[0122] Subsequently, a PET subsrrate (COSMOSHINE A-4100, easy adhesion PET
film manufactured by TOYOBO CO., LTD.) was coated with a fluorine-based IIV
curable resin. The fluorine-based lfV curable resin was cured by irradiation with
ultraviolet light at 600 mJlcm2 while the nickel mold was pressed thereagainst. After
curing ofthe resin, the nickel mold was exfoliated orpeeled off from the cured resin.
Accordingly, a diffraction grating mold, which r¡/as composed of the PET subshate with
the ¡esin film to which the surface profile (surface shape) of the nickel mold was
transfered, was obtained.
[0123] The light emitting element was manufactured by usilg the mold thus obtained.
As the base member of the light emitting element, an alkali-free glass of 30 mm x 30
mm x 0.07 (thickness) mm (produced by Nippon Electric Glass Co., Ltd.) was prepared.
The base member was scrubbed and cleaned by using a cleanser (RBS-25, produced by
Junsei Chemical Co., Ltd.) and a sponge sufficientl¡ and then a concave-convex
Á:>'Q
l
structure layer was fonned thereon by the liftoff method as follows. Namely, the base
member was coated with a positive resist (OFPR-800, produced by TOKYO OHKA
KOGYO Co., LTD.) by spin coating such that the positive resist had a thickness of
about I pm, and then predrying was performed at a temperature of 80oC for 30 minutes.
Exposure was performed with UV light (I: 365 nm) for 16 seconds by using the mask
501 as depicted in Fig. 6(a). In Fig. 6(a), the white portion is a light transmissive
portion, the mask 501 is marked with scales, and respective lengths are represented in
numbers to show sizes thereof. Subsequently, the positive resist on the base member
was developed by using an organic developer (MFCD-26, produced by Shipley Co. Llc.)
and was washed with running water for 3 minutes. Then, drying was performed at a
temperature of 100'C for 10 minutes. A resist ¡emained on a porfion, on the base
member, corresponding to a light-shielding portion (black portion) of the mask 501.
[0124] Subsequently, a sol-gel material to be used as the material of the concave-convex
structure layer was prepared as follows. Namely, 2.5 g of tetraethoxysilane (TEOS) and
2.1 g of methyltriethoxysilane (MTES) were added dropwise to a mixture solution of
24.3 g ofethanol,2.16 gof waß4 and 0.0094 g of concentrated hydroclrloric acid,
followed by being stirred or agitated for 2 hours at a temperature of 23'C and a humidity
of 45Yo.
[01251 The surface, on the tra¡sparent sùbstmte, formed with the pattemed resist was
coated with the sol-gel materiai by spin coating. The spin coating was performed for 8
seconds at rotation speed of 500 rpm, and then for 3 seconds wíth rotation speed of 1000
rpm.
[0126] After the elapse of 60 seconds from the spin coating of the sol-gel material, the
mold obtained as described above was pressed against the coating film made of the solgel
material on the base member by use of the pressing ro11 heated to 80'C while the
pressing ro11 was moved and rotated. Then, the surface, of the mold, on which the
minute concave-convex pattern had been formed was pressed against the coating film on
the base member while the pressing roll at 80'C was being rotated from one end to the
other end of the base membe¡. After the pressing with the mold, the mold was manually
released or peeled offfrom the one end to the other end ofthe base member such that
the angle (pee1 angle) of the mold with respect to the base member was about 30". As
the pressing roll, it was used a roll which included a heate¡ therein and had the outer
E+
circumference covered vr'ith heat-resistant silicon of a thickness of 4 mm, the roll having
a diameter (rp) of50 mm and a length of 350 mm in a¡ axial direction of the shaft.
[01271 Subsequently, the concave-convex skucture layer was subjected to the main
baking by being heated for 60 minutes in an oven of 300"C.
[0128] Subsequently, the resist was stripped or peeled offby using a resist stripping
liquid (Resist Strip N-320, produced by Nagase Sangyo K.K.). The resist and the solgel
film on the resist were removed, and the sol-gel film remained on a portion
corresponding to the white portion (light transmissive portion) ofthe mask 501 depicted
in Fig. 6(a). Namely, the concave-convex sûlÌcture layer made of the sol-gel material
was formed in an area inside a rectangle of 22 mmx20 mm, which was apart from two
sides, ofthe base member, facing each other (hereinafter referred to as "left and right
sides" as appropriate) by a distance of4 mm, apart from one of remaining two sides
(hereinafter referred to as "upper side" as appropriate) by a distance of 3 mm, and apart
from the remaining one side (hereinafter referred to as "lower side" as appropriate) by a
distance of 7 mm.
[01291 The base member with the pattern made ofthe concave-convex struch]re layer
obtained as described above was cleaned with a brush to remove foreign matter and the
like adhered thereto, then organic matter and the like was removed by an alkaline
clea¡er and an organic solvent. On the base member cleaned as described above, an
ITO film havíng a thickness of 120 nm was formed at a temperah[e of 300'C by a
sputtering method. Photoresist was applied on the ITO filrn and exposure was
performed with a mask pattem for a transparent electrode (first electrode), and then the
resist was developed with a developer and ITO was etched with an etching solution.
Accordingly, a transparent electrode having a pattem as depicted in the schematic top
view of Fig. 7 was obtained. The obtained transparent electrode was cleaned with a
brush, and organic matter and the like was removed by an alkaline cleaner and an
organic solvent. Then, the transparent electrode was subjected to a tlV-ozone process.
On the transparent electrode processed as described above, a hole transporting layer
(4,4',4" tis(9-carbazole)triphenylamine, thickness: 35 nm), an organic layer (tris(2-
phenylpyridinato)iridium(Itr) complex-doped 4,4' ,4" tris(9-carbazole)triphenylamine,
tlickness: 15 nm; tris(2-phenylpgidinato)iridium0lD complex-doped 1,3,5-tris(Nphenylbenzimidazole-
2-y1)benzene, thickness: lJ nm), an electron transporting layer
(1,3,5{ris(N-phenylberzimidazole-2-yþenzene, thickness: 65 nm), and a lithium
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fluoride layer (thickness: 1.5 nm) were each stacked by a vapor deposition method, and
further a metal electrode (second electrode) (aluminum, thickness: 50 nm) was formed
by the vapor deposition method.
[0130] The base member, in which the concave-convex structure layer, the transparent
electrode, the organic layer, and the metai electrode were formed, was moved fiorn a
vacuum apparatus into a glove box under Nz atmosphere and adhesive (UV RESIN
XNR 55162, produced by Nagase ChemteX Corporation) was applied on the base
member. The adhesive layer was formed by using a dispenser robot
(SHOTMASTER3O0, produced by Musashi Engineering Inc.) while the applying
position of the adhesive, scanning velociry ofthe dispenser robot, and the amount ofthe
applied adhesive were controlled. The adhesive layer was formed to have a belt or band
shape having 4 mm in width and extending along the circumference of the rectangle of
22mmx20 nmas the center (center line), the circumference of the rectangle being
apart from the lefi and right sides of the base member by a distance of 4 mm, apart from
the upper side by a distance of 3 mm, and apart fiom the lower side by a distance of 7
mm. (That is, the adhesive layer was formed to have a 4 mm-wide belt or band shape
extending along the outer periphery ofthe concave-convex structure layer as the center
line.)
[01311 An engraved glass (alkali-free glass, produced by NSG Precision Co., Ltd.) of 26
mm x 30 mm which had a concave portion of 18 mm x 16 mm was processed with UVO¡
for 3 minutes. The engraved glass was piaced on the base member such that the
concave podion of the engraved glass faced the base membe¡ and the center (center line)
of the width of the convex portion ofthe engraved glass overlapped the applied adhesive
line. The base member was pressed against the engraved glass by using a clip (small
binder clip, produced by Lion Corporation) sandwiching them, and then the clip was
¡emoved. The adhesive layer was cured by being irradiated with IIV light at a totalized
light quantity of 600 mJlcm2 by use of a IJV radiation light source (LIGHTNING CURE
LC8, produced by Hamamatsu Photonics K.K.). The engraved glass was designed to
include protrurling part extending beyond the upper side of the base member by 5 mm
when being placed on the base member in the above-described manner.
[0132] The sealed light emitting element was obtained through the above procedure.
Figs. 1(a) and 1(b) schematically depict a planer structure and a cross-sectional structure
of the manufactured light emitting element, respectively.
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[0133] [Example 2]
In Example 1, the resist pattern was formed to perfomr the patteming of the
concave-convex structure layer by means of photolithography using the positive resist.
In Example 2, the method for forming the resist pattern was changed as described
below, and along with this, the method fo¡ stripping the resist was also changed. A light
emitting element was manufactured in a similar marurer to Example 1 except for the
above. Fig. 2 schematically depicts a cross-sectional structure of the light emitting
element manufactured in Example 2.
[0134] A negative resist prepared as described below was used as the resist. Namely,
1 00 parts of methacrylic acid-methyl methacrylate copolymer in which the composition
ratio (molar ratio) of methacrylic acid and methyl methacrylate was 20:80 and the
weight average molecular weight thereof was 30,000; 6 parts ofpentaerlthritol
tetraacrylic ester; 2 parts of Michler's Ketone; and 2 parts of4-(4-
dirnethylaminophenylazo)-phenol were dissolved in 330 pa¡ts ofa mixed solvent in
which ethyl cellosolve acetate/ethyl cellosolve was 60/40. Then, the obtained solution
was filtrated or filtered through a membra¡e filter of 0.22 pm. The base member was
coated with the negative resist by spi¡ s6¿1ing such that the negative resist had a
thickness of about 1 pm, and then predrying was performed at a temperature of90'C for
60 seconds. Exposure was performed by using a mask 503 depicted in Fig. 6(b) and a
contact exposure apparatus (PLA501F, produced by Canon Inc.) in which the
illumination ratio of gJine/i-line was 7/5 (mVr'/cm2) at an intensity of 130 mJ/cm2. In
Fig. 6(b), the white portion is a light transmissive portion, the mask 503 is marked with
scales, and respective lengths are represented in numbe¡s to show sizes thereof.
Subsequently, paddle development with 0.5% NaOH solution was performed for 60
seconds. Further, the resist pattem was baked and hardened by being irradiated with tIV
light(wavelength:21finm,illuminance:1.2mWcm2)byuseofahigh-pressuremercury
vapor lamp for 200 seconds. The resist formed in the part, in which light was blocked
by the mask 503, was removed.
[0135] After performing the preparation of the sol-gel material to be used for the
concave-convex structure layer, coating, the pressing with the mold, and main baking in
a similar manner to Example 1, the resist pattem was stripped by swinging the base
member in a resist stripping liquid which was dimethylsulfoxide warrned or heated to
50"C, cleaning the base member with isopropyl alcohol, and drying the base member.
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Further, the base member was washed with nurning water a:rd dried. The resist and the
sol-gel fihn on the resist were removed, so that the concave-convex struchrre layer made
of the so1-gel material was formed only on the pofion corresponding to the black
portion (1ight shielding poÍion) of the mask 503 depicted in Fig. 6(b). The base
member having the concave-convex structue layer rras observed by SEM (SU1510
manufactured by HITACHI High-Technologies Corporation). As a result, an angle 0,
which was formed by the surface of the base member and the outer periphery (side
surface) ofthe minute concave-convex structue layer, was 70" (see Fig. 2).
[0136] fExample 3]
A light emitting element was manufactured in a similar manner to Example 1
except that the concave-convex structure layer was fonned as described below by the
UV curing method using a IIV curable resin instead of the 1ift-off method. Figs. 1(a)
and 1(b) schematically depict a planer sûucture and a cross-sectional structure ofthe
manufactured light emitting element, respectively.
[0137] 1 g of silane coupling agent (KBM-5103 produced by SHIN-ETSU
CHEMICAL, CO., LTD.) was added dropwise to a mixture of 1 g of water, 19 g of IPA,
and 0.1 ml of acetic acid while the mixture was being stirred. After that, this mixture
s'olutiotr *as stirred for another hour, thereby preparing a solution of the silane coupling
agent. The base member was cleaned in a similar ma:rner to Example 1, and then
moisture on a su¡face of the base member was removed by drying using spin coater.
The surface of the base member after the drying was coated with the solution of the
silane coupling agent by spin coating. The spin coating was performed at a spin speed
of 1000 rpm for 30 seconds. After that, the base member was baked in an oven of
130"C for 15 minutes. The base member to which the easy-adhesion treaûnent had been
performed was obtained, accordingly. The easy-adhesion treahnent sudace of the base
member to which the easy-adhesion treatrnent had been performed was coated with a
(fV curable resin (PAK-02 produced by Toyo Gosei CO., Ltd.) by spin coating. The
spin coating was performed at a spin speed of i000 rpm for 30 seconds. A diffiaction
g¡ating mold, rühich was similar to that used in Example 1, was pressed against the
coated lfV curable resin using a hand roller. Further, the mask 501 depicted in Fig. 6(a)
was superposed on the mold, and the UV curable resin positioned in the light
transmissive porlion of the mask 50 1 was cured by being inadiated with tIV light at 600
mJ/cm2 from the side of the mask. After the mask and mold were released from the base
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member, uncured resin was cleaned ol washed with IPA and the base merrber was dried
by means of a nihogen blow. Accordingly, the concave-convex structure layer made of
the IJV curable resin which had a similar structure as that of the concave-convex
shxcture layer made of the sol-gel material in Example I was fomred.
[0138] lExample 4]
A light emitting element was manufactured in a similar manner to Example 1
except that a gas barrier filrrr was used as the base member and the concave-convex
structure layer was fo¡med as described below by the fIV curing method using a UV
curable resin instead ofthe lift-offmethod. Figs. 1(a) and 1(b) schematically depict a
planer struchrre and a cross-sectional structure ofthe manufachrred light emitting
element, respectively.
[01391 1 g of silane coupling agent (KBM-5103 produced by SHIN-ETSU
CI{EMICAL, CO., LTD.) was added dropwise to a mixh¡re of 1 g of water, 19 g of IPA,
and 0 . 1 mL of acetic acid while the mixture was being stirred. After that this mixture
solution was stirred for another hour, thereby preparing a solution ofthe silane coupling
agent. As the base member, the gas barrier filn obtained in tle following manner was
used. Namely, a SiOxNy (x, y: 0 to 2) film, which was made of an organic-inorganic
hybrid material composed ofan organic constítuent and an inorganic constituent, was
formed as a barrier film on a PEN base member (TeonexQ65F produced by Teijin
DuPont FiLns Japan Limited) having a film thickness of 200 pm. The water vapor
transmission mte of this gas barrier film was not more tha¡ 1 x l0-3 !Ñ/day. lhe
barrier film of the gas barrier fihn was coated with the solution of the silane coupling
agent by spin coating. The spin coating was performed at a spin speed of 1000 rpm for
30 seconds. After that, the base member was baked in an oven of 130"C for 15 minutes.
The base member with the gas barrier film to which the easy-adhesion treatunent had
been performed was obtained, accordingly. The easy-adhesion treatment surface of the
gas barrier filn to which the easy-adhesion treatnent had been performed was coated
with a fIV curable resin (PAK-02 produced by Toyo Gosei Co., Ltd.) by spin coating.
The spin coating was performed at a spin speed of 1000 rpm for 30 seconds. A
diffraction grating mold, which was similar to that used in Example 1, was pressed
against the coated IJV curable resin using a hand roller. Fufher, the mask 501 depicted
in Fig. 6(a) was superposed on the mold, and the UV curable resin positioned in the
light transmissive portion of the mask 501 was cured by being irradiated with UV light
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at 600 mJ/cmz from the side of the mask. After the mask a¡rd mold were released from
the base member, uncured resin was cleaned or washed with IPA and the base member
was dried by means of a nitrogen blow. Accordingly, the concave-convex structure
layer made ofthe fIV curable resin which had a similar structure as that of the concaveconvex
structure layer made of the sol-gel material in Example 1 was formed on the
base member with the gas barrier film.
l0l40l fComparative Example I I
In Example 1, the patteming of the concave-convex structure layer was
performed by photolithography using the positive resist. kr Comparative Example 1, a
light emitting element was manufachJred in a similar manner to Example 1 except that
the photolithography using the positive resist was not performed. As for the light
emitting element manufactured in Comparative Example 1, the concave-convex
structure layer was formed on the entire su¡face on the base member, and thus ä
structure in which the concave-convex structue layer was exposed to the outside ofthe
adhesive layer was obtained. Fig. 8 schematically depicts its cross-sectional structure.
[0141] [Comparative Example 2]
In Example 1, the patteming of the concave-convex structure layer was
performed by photolithography using the mask 501 depicted in Fig. 6(a). ln
Comparative Example 2, photolithography was performed by using a mask 505 depicted
in Fig. 6(c) instead of the mask 501. In Fig. 6(c), the white portion is a light
transmissive portion, the mask 505 is marked with scales, and respective lengths are
represented in numbers to show sizes thereof. A light emitting element was
manufactured in a similar manner to Example 1 except for the above. As for the
manufactured light emitting element, the outer periphery of the concave-convex
structure layer '',¡/as positioned inside the iffier circumference of the adhesive layer. Fig.
9 schematically depicts its cross-sectional structu¡e.
[0142] [Comparative Example 3]
In Example 4, inadiation with UV light by use of the mask 501 depicted in Fig
6(a) was performed. In Comparative Example 3, irradiation with UV light was
performed without the mask 501. Further, in Example 4, uncured resin was clea¡ed
with IPA and the base member was dried by means of the nitrogen blow after the
irradiation with tIV light. In Comparative Example 3, however, those performed after
the irradiation with IJV light in Example 4 were not pedomed. A light emitting
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element was manufactured in a similar manner to Example 4 except for the above. As
for the light emitting element manufactured in Comparative Example 3, the concaveconvex
structure layer was fo¡med on the entire surface on the base member, and thus a
structure in which the concave-convex structure layer was exposed to the outside ofthe
adhesive layer was obtained. Fig. 8 schernatically depicts its cross-sectional structure.
[0143] [Evaluation of adhesion property]
Regarding the light emitting element ma¡ufachr¡ed i¡ each of Examples 1 to 3
and Comparative Examples I and 2, the adhesion property of the adhesion layer was
evaluated as follows. Namely, as depicted in Fig. 10, the light emitting element was
fixed to a stand (base) 500 and a plate-like L-shape tool 560 (20 mm in depth), of
which cross section was L-shape (a short side 560a having a length of 7 mm, a long side
560b having a length of 15 mm), was inserted unde¡ a protruding part 101a of an
engraved glass 1 0 i . Then, the protruding part 1 0 1 a of the engraved glass 1 0 1 was
pushed up by pushing the long side 560b of the L-shape tool downward in the direction
indicated by the anow in Fig. 10 with the comer of the Lshape tool 560 as the point of
action of a lever. When the engraved glass 101 together with the adhesive layer 103
was separated from or peeled offfrom the upper surface of the base member 40, the
light emitting element was evaluated to be unsatisfactory or defective; and when the
engraved glass 101 was broken and the adhesive layer 103 remained adherìng to the
upper surface of the base member 40, the light emitting element was evaluated to be
satisfactory. The test was performed for ten light emitting elements manufactured in
each ofExamples 1 to 3 and Comparative Examples 1 and 2. The number of defective
light emitting elements is indicated in the table of Fig. 1 1 . Regarding Examples 1 to 3
and Comparative Example 1, allof the ten light emitting elements were evaluated as
satisfactory. In Comparative Example 2, five light emitting elements, of the ten light
emitting elements tested, were evaluated as unsatisfactory. From these results, the light
emittiñg element manufactured in each of Examples 1 to 3 and Comparative Example 1
had a better adhesion property of the lower surface of the adhesive layer thân that of the
light emitting element manufactured in Comparative Example 2. The reason thereof is
considered as follows. Namely, the lower surface of the adhesive layer in Comparative
Example 2 was in contact only with the flat surface, but in Examples 1 to 3 and
Comparative Example 1, the lower surface of the adhesive layer was in contact with the
concave-convex surface. Thus, "catching" and the like obtained by concavities and
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convexities made mechanical releasing (mechanical exfoliation) more difficult, and
concavities and convexities increased an interface area. Such effects strengthened the
adhesive force.
[0144] [Deterioration evaluation]
A deterioration test was performed for the light emitting element manufachrred
in.each of Examples 1 to 4 and Comparative Examples 1 to 3 under high humidity
environment as described below. A voltage of 4 V was applied to the light emitting
element in an initial state, and the number ofdark spots in a light emitting area of 14
mm x 14 mm was counted. Next, the light emitting element was kept in a
thermohygrostat with a temperature of 40'C and a humidity of 90%. 10 days and 20
days after the putting ofthe light emitting element in the thermohygrostat, a voltage of4
V was applied to the light emitting element and the number of dark spots in the light
emitting area of 14 mm x 14 mm was counted. Each of the results is shown in the table
of Fig. 1 1 . Regarding ExamFles 1 to 4 and Comparative Example 2, the number of dark
spots did not increase, that is, the number thereofwas zero. Regarding Comparative
Example 1, the number of dark spots increased to 3 in 10 days and increased to 15 in 20
days. Regarding Comparative Example 3, the number of dark spots increased to 5 in 10
days and increased to 20 in 20 days. Frorn these results, it has been revealed that the
light emitting elements mar factured in Examples 1 to 4 and Comparative Example 2
were less likely to deteriorate than the light emitting elements manufactured in
Comparative Examples 1 and 3. The reason the¡eof is considered as follows. Namely,
the concave-convex structue layer of the light emitting element manufactured in each of
Comparative Examples 1 and 3 was exposed to the outside (atmospheric air) ofthe
adhesive layer, and thus moisture ând oxygen entered the sealed space via the concaveconvex
structure layer. The concave-convex structure layer of the light emitting
element manufactured in each of Examples 1 to 4 and Compamtive Example 2 was not
exposed to the outside (atmospheric air) ofthe adhesive layer, and thus moisture and
oxygen were prevented from penetrating through the concave-convex Structure layer and
entering the sealed space.
[0145] Although the present invention has been explained as above with the
embodiment Examples, and Comparative Examples, the light emitting element and the
method for producing the light emitting element of the present invention are not lirnited
to the above-described embodiment etc., and may be appropriately modifred or changed
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wifhiri the range of the technical ideas described in the following claims. For example,
although the transparent electrode (first electrode) is formed to approximately or
substantially cover the concave-convex structu¡e layer in the embodiment and
Examples, the arrangement and shape of the first electrode are not limited to this. The
adhesive layer may adhere to a part ofthe concave-convex struchrre layer instead ofa
part of fhe first electrode, or the adhesive layer may adhere to both ofa part ofthe first
electrode and a part ofthe concave-convex structure layer such that the adhesive layer
extend thereacross. In any case, since the adhesive layer adheres to the concave-convex
st¡ucture of the concave-convex struchrre layer or the concave-convex surface ofthe
first electrode which reflects or shows the concave-convex structure ofthe concaveconvex
struchlre layer, the adhesive force between the adhesive layer and the base
member improves.
Industrial Applicability
[01461 The light emitting element of the present invention includes the concave-convex
structue layer functionìng ¿s the diffraction grating, and thus light-emitting property
thereof is excellent. Fufher, the light emitting part is sealed by the frame sealing having
sufficient sealing performance. Thus, the deterioration of the light emitting part due to
invading moisture and oxygen is prevented, the occurrence of any defect such as da¡k
spots is reduced, and the light emitting element has a long sewice life. Therefore, the
light emitting element of the present invention is very useful in various light-emitting
devices.
Reference Signs List:
l0l47l 20: resist, 40: base membe¡ 80: mold, 92: first electrode,94'. organic layer,98:
second electrode, 100: light emitting element, 101: sealing member, 103: adhesive layer,
105: sealed space, 742: cottcàve-convex structure layer,242: frst concave-convex
structue layet 342: second concave-convex stucture layer
b^95
We claim:
1. A light emitting element comprising:
a base member;
a sealing member disposed to face the base member;
a concave-convex sùuchlre layer;
a first electrode;
an organic layer;
a second electrode; and
an adhesive layer.
wherein the concave-convex structure layer, the first electrode, the
organic layer, a¡d the second electrode are formed on the base member in that order;
the adhesive layer is positioned between the base member and the sealing
member; and
an outer periphery of the concave-convex shucture layer is positioned
between an inner periphery of the adhesive layer and an outer periphery of the adhesive
1ayer.
2. The light emitting element according to claim 1,
wherein at least one of the fust electrode and the second electrode
includes an overlapping part overlapping both ofthe concave-convex structure layer and
the adhesive layer;
the overlapping pa¡t has a concave-convex surface reflecting or showíng
concavities and convexities of the concâve-convex sû'ucture layer; and
the inner periphery of the adhesive layer adheres to the concave-convex
skucture layer or the concave-convex surface reflecting or showing the concavities and
convexities of the concave-convex structure layer.
3. The light emilting element according to claim 1 or 2, wherein the organic
layer is positioned such that a predetermined space is provided between the adhesive
layer and the organic layer.
4. The light emitting element according to any one of claims 1 to 3, wherein
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the outer periphery ofthe concave-convex structure layer is formed as an inclined
surface, and an angle between the outer periphery ofthe concave-convex stmcture layer
and a surface of the base member is not more than 80o.
5. The light emitting element according to any one of claims 1 to 4, whereir
a space, which is sealed by the base member, the sealing member disposed to face the
base member, and the adhesive layer, is filled with infilling.
6. The light emitting element according to any one of claims 1 to 5, wherein
the outer periphery of the concave-convex structure layer is positioned roughly halfiray
between the outer periphery and the inner periphery of the adhesive layer sealing the
space.
7. The light emitting element according to any one of claims 1 to 6, wherein
the concave-convex structue layer is made ofa sol-gel material.
8. The light emitting element according to any one of claims 1 to 7, whe¡ein
a concave-convex pattem, ofthe concave-convex structüe layet which is positioned on
a lower side ofthe organic layer is different from a concave-convex pattern, of the
concave-convex struchlre layer, which is positioned on a lower side ofthe adhesive
layer.
9
steps of:
A method for manufacturing a light emitting element, comprising the
forming a concave-convex struchtre layer on a base member;
forrning a first electrode on the concave-convex structue layer;
forming an organic layer on the first electrode;
forming a second electrode on the organic layer; and
disposing a sealing member to face the base member such that the
concave-convex structure laye¡ the first electrode, the organic layer, and the second
electrode, those of which are formed on the base member, are positioned between the
base member and the sealing member; and forming an adhesive layer between the base
member and the sealing member,
(.5
wherein the adhesive layer is formed such that an outer periphery ofthe
concave-convex skucture layer is positioned between an inner periphery ofthe adhesive
layer and an outer periphery of the adhesive layer.
10. The method for manufacturing the light emitting element according to
claim 9, wherein the adhesive layer is formed in a position in which the adhesive layer
has no contact with the organic layer.
11. The method for manufacturing the light emitting element according to
claim 9 or 10, wherein the concave-convex structure layer is formed such that an angle
between the outer periphery of the concave-convex shucture layer and a surface of the
base member is not more than 80o.
12. A light emitting element comprising:
a base member;
a sealing member disposed to face the base member;
a first concave-convex stnrcttrre layer having a first concave-convex
pattem;
a second concave-convex structure layer having a second concaveconvex
pattern;
a first electrode;
an organic layer;
a second electrode; and
an adhesive layer,
wherein the f,rrst concave-convex structure layer ând the second concaveconvex
structure layer, which is positioned with a predetermined distance from the fust
concave-convex structure layer, are formed on the base member;
a stacked body of the fi¡st electrode, the organic layer, and the second
electrode is formed on the first concave-convex pattem;
the adhesive layer is formed between the base member and the sealing
member to suround the stacked body; and
the second concave-convex structure layer is disposed not to penetrate
the adhesive layer.
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13. The light emitting element according to claim 12, wherein the second
concave-convex pattern is different from the first concave-convex pattem.
14. The light emitting element according to claim 12, wherein the second
concave-convex pattern is identical to the first concave-convex pattern.
15. The light emitting element according to any one of claims 12 to 14,
wherein a side surface of the second concave-convex stnrchne layer is formed as an
inclined surface, and an angle between the side surface of the second concave-convex
structure layer and a surface of the base member is not more than 80o.
16. The light emitting element according to any one of claims 12 to 15,
wherein an outer periphery ofthe first concave-convex structure layer is formed as an
inclined surface, and an angle between the outer periphery ofthe first concave-convex
structure layer and a surface ofthe base member is not more than 80o.
Dated this 23'd day of February,2016.