The present invention relates a film member having a concave-convex structure.
Background Art
[0002] Light emitting elements expected as next-generation of displays or illumination
devices include an organic EL element (organic Electro-Luminescence element or organic
light emitting diode). In the organic EL element, a hole injected from an anode via a hole
injecting layer and electron injected from a cathode via an electron injecting layer are
carried to a light emitting layer respectively, then the hole and electron are recombined on
an organic molecule in 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 emitting layer is required to be
efficiently extracted from the surface of the organic EL element. In order to meet this
demand, it is known from PATENT LITERATURE I that a diffraction grating substrate
having a concave-convex structure (uneven structure) is provided on a light extraction
surface of the organic EL element.
[0003] Further, as a base member of the organic EL elernent, a film base member such as
a film base member which is formed of a resin, which is light weight and flexible, and can
be produced in a large size, has started to be adopted, in place of a glass substrate which is
heavy weight, easily broken and hard to be producêd in a large size. The film base
member such as the resin film base membe¡ however, has a problem that the fìhn base
member has a gas barrier property inferior to that of the glass substrate. In some cases,
any moisture and/or oxygen lower the brightness and/or luminous effìcacy (light-emitting
efficiency), etc. of the organic EL element. For this reason, in a case that a resin film
base member is used as the base member of the organic EL element, it is necessary that a
gas banier layer is formed for the purpose of preventing any deterioration due to the
moisture and/or a gas such as oxygen. For example, PATENT LITERATURE 2
describes a film member for an organic EL element in which a gas barrier layer made of
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silicon oxide is formed on a resin film base member, and a concave-convex structure layer
made of polymethyl methacrylate (PMMA) is formed on the gas barrier layer.
t00041 [Citation List]
[Patent Literature]
PATENT LITERATURE l: Japanese Patent Applicarion Laid-open No.
2006-236748
PATENT LITERATURE 2: International Publication No. V/O 20061095612 A1
SUMMARY OF INVENTION
Problem to be Solved by the Invention:
[0005] The Applicant ofthe present application found out, through researches and
investigation conducted by the Applicant, that the adhesion force between the gas barrier
layer and the concave-convex structure layer is weak in a film member such as that
described in PATENT LITERATTIRE 2, and that the concave-convex structure layer is
detached (exfoliated or peeled off) from the gas barrier layer during the manufacture
process of the film member. In view of this situation, an object of the present invention is
to provide a film member which has excellent adhesion property between the
concave-convex structure layer and the gas barrier layer, and which has high gas barrier
property.
Solution to the Problem:
[0006] Aocording to a first aspect of the present invention, there is provided a film
member having a concave-convex structure, the film member comprising:
a base member;
a gas barrier layer formed on the base member; and
a concave-convex structure layer formed on a surface ofthe gas barrier layer,
wherein the surface of the gas barrier layer is formed of an inorganic material
which is same as a material of the concave-convex structure layer, and the concave-convex
structure layer is obtained from a precursor solution applied on the gas barrier layer.
[0007] In the film member, the gas barrier layer may be a single layer firm.
[0008] In the film member, (i) each of a plurality of,convexities and each of a plurality of
concavities of the concave-convex structure layer may have an elongated shape which
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extends while winding (waving) in a plane view; and
(ii) the plurality of convexities may have extending directions, bending directions
and lengths which are non-uniform among the plurality of convexities, and the plurality of
concavities may have extending directions, bending directions and lengths which are
non-uniform among the plurality of concavities.
[00091 In the film member, adhesion force between the gas barrier layer and the
concave-convex structure layer may be greater than 4 N/m.
[0010] In the fìlm member, an average pitch of a plurality of concavities and a plurality
of convexities of the concave-convex structure layer may be in a range of 100 nm to 1500
nm; and
an average value of depth distribution of the plurality of concavities and the
plurality of convexities may be in a range of 20 nm to 200 nm.
[001U According to a second aspect of the present invention, there is provided a method
of producing the film member having the concave-convex structure of the first aspect, the
method including:
forming the gas barrier layer on the base member;
forming a film by applying the precursor solution onto the gas barier layer; and
pressing a mold having a concave-convex pattern against the film while curing the
film so as to transfer the concave-convex pattern of the mold to the film.
[00121 The method of producing the film member may further include producing the
mold having the concave-convex pattern by utilizing self-organization of a block
copolymer. Further, the block copolymer may be self-organized by a solvent annealing.
[00131 According to a third aspect of the present invention, there is provided an organic
EL element formed by successively stacking, on the fîlm member of the first aspect, a first
electrode, an organic layer and a metal elechode.
Effects of Invention:
[00141 Since the film member having the concave-convex structure of the present
invention includes the gas barrier layer and the concave-convex structure layer which are
formed on the base member, the film member has excellent gas banier property and high
light extraction effrciency. Accordingly, a light emitting element produced by using the
film member has a high light emitting ef.ficiency and a long service life due to the
suppression ofthe deterioration caused by the moisture and/or gas such as oxygen.
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Further, since the surface, of the gas barrier layer, which makes contact wjth the
concave-convex structure layer is made of an inorganic material which is same as a
material of the concave-convex structure layer, the adhesion property between the gas
banier layer and the concave-convex structure layer is high, and thus the concave-convex
structure layer does not peel off(exfoliate) from the gas barrier layer. Therefore, the film
member having the concave-convex structure of the present invention is quite effective for
a various kinds of devices such as organic EL elements, solar batteries, etc.
BRIEF DESCRIPTION OF DRAWINGS
[00f5] Fig. 1 is a schematic cross-sectional view of a film member having a
concave-convex structure of an embodiment.
Fig.2(a) is a schematic plane view of a concave-convex pattern of the film
member having the concave-convex structure of the embodiment, and Fig. 2(b) depicts a
cross-sectional profile on a cutting line in the schematic piane view in Fig. 2(a).
Fig. 3 is a view conceptually depicting an example of a situation in a transfer step
in a method for producing the film member of the embodiment.
Figs. 4(a) to 4(c) are each a schematic cross-sectional view of a light-emitting
element of an embodiment, wherein Fig. 4(a) depicts an example of a schematic
cross-sectional view of the light-emitting element wherein a concave-convex pattern of a
film member is maintained in a surface of an organiclayer; Fig. @) depicts an example of
a schematic cross-sectional view of a light-emitting element wherein a surface of an
organic layer is flat; and Fig. a(c) depicts an example of a schematic cross-sectional view
of a light-emitting element provided with an optical functional layer.
Fig. 5 is a table indicating the materials of film members produced in Example
and Comparative Examples, and the results of evaluation therefor.
DESCRIPTION OF EMBODIMENTS
[00161 In the following, an embodiment of a film member having a concave-convex
structure, an embodiment of a method for producing the film member, and an embodiment
of a light-emitting element produced by using the film member having the concave-convex
structure according to the present invention will be explained, with reference to the
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[0017] [Film Member]
A film member 100 having a concave-convex structure (concave-convex pattern)
of an embodiment has such a configuration wherein a gas barrier layer 30 and a
concave-convex structure layer 60 are formed in this order on a film base member 40, as
depicted in Fig. 1.
t001Sl
The film base member 40 is not particularly limited, and it is possible to
appropriately use any publicly known transparent substrate which can be used for the light
emitting element. Those usable as the film base member 40 include, for example,
substrates made of resins such as polyester (polyethylene terephthalate, polybutylene
terephthalate, polyethylene naphthalate, polyarylate, and the like), an acrylic-based resin
(polymethyl methacrylate and the like), polycarbonate, polyvinyl chloride, a styrene-based
resin (ABS resin and the like), a cellulose-based resin (triacetyl cellulose and the like), a
polyimide-based resin (polyimide resin, polyimideamide ¡esin, and the like) and
cycloolefin polymer; and the like. In a case that the film member 100 is used as an
optical substrate of the light-emitting element, the base member 40 is preferably a base
member having the heat-resisting property, the weather resisting property against UV light,
etc. It is allowable to perform a surface treatment for the base member 40 or to provide
an easy-adhesion layer on the base member 40 so as to improve the adhesion property of
the base member 40. Further, it is also allowable to provide a smoothing layer in order to
cover any projection on the surface of the film member. The thickness of the film base
member 40 is preferably in a range of I pm to 2000 pm.
[0019]
The gas barrier layer 30 is a layer for preventing permeation of oxygen and water
vapor; a material constructing the gas barrier layer 30 is preferably an inorganic material
such as a metallic oxide, a metallic nitride, a metallic sulfide, a metal carbide, etc., and is
further preferably an inorganic material such as a silicon oxide, an aluminum oxide, a
silicon nitride, a silicon oxynitride, an aluminum oxynitride, a magnesium oxide, azinc
oxide, an indium oxide, a tin oxide, etc. The gas barrier layer 30 may be a single layer
film of any one of these material, or a multi-layered film formed by stacking a plurality of
kinds of these materials. Alternatively, the gas barrier layer 30 may be a multi-layered
film formed by stacking a plurality of layers including an organic material and at least one
of the above-described inorganic materials. In a case that the gas barrier layer 30 is a
multi-layered film, it is allowable to provide a stress relaxation layer between the layers.
A surface (surface making contact with the concave-convex structure layer 60) 30a of the
gas barrier layer 30 is composed of the materialsame as an inorganic material composing
the concave-convex structure layer 60, which in turn increases the adhesion property
between the gas banier layer 30 and the concave-convex structure layer 60. Further, the
gas barier layer 30 preferably has a light-transmissivify. With this, the film member 100
can be used as an optical substrate for a light-emitting element such as an organic EL
element. The gas barrier layer 30 preferably has a transmissivity of not less than 80o/o at a
tneasurement wavelength of 550 nm, more preferably has a transmissivity of not less than
90o/o at the measurement wavelength of 550 nm. Further, it is allowable to perform, for
the gas barrier layer 30, a surface treatment for enhancing the adhesion property ofthe gas
barrier layer 30 with respect to the concave-convex structure layer 60 such as a plasma
treatment, a corona treatment, etc.
[0020] The thickness of the gas barrier layer 30 is preferably in a range of 5 nm to 2000
nm. In a case that the thickness is less than 5 nm, there are many cases of film defect, and
any sufficient moisture-preventing effect (gas barrier effect) cannot be obtained. On the
other hand, in a case that the thickness exceeds 2000 nm, although the moisture-preventing
effect is theoretically high, the internal stress is high, which in turn makes the bas barier
layer 30 to be brittle. This makes it impossible to obtain any desired moisture-preventing
effect, as well as leads to such a fear that any cracking, etc., might occur in the gas barrier
layer 30 due to any external factor such as bending, pulling, etc. after the film formation.
As a result, it is difficult to impart the flexibility to the film member 100.
[00211
The concave-convex structure layer 60 is a layer having a fine or minute
concave-convex pattern (concave-convex structure) 80 formed on a surface thereof. The
minute concave-convex pattern 80 may be any pattern such as a pattern having a lens
structure, a structure having a light diffi.¡sion function, a light diffraction function, etc.
Fig. 2(a) depicts an example of a schematic plane view of the concave-convex pattern 80
of the concave-convex structure 60 of the embodiment, and Fig. 2(b) depicts a
cross-sectional profile on a cutting line in the schematic plane view in Fig. 2(a). The
cross-sectional shape of the concave-convex structure layer 60 may be formed of relatively
gently inclined surfaces and may construct a waveform (in the present application, referred
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to as "waveform structure", as appropriate) upward from the base member 40, as depicted
in Fig. 2(b). Namely, convexities of the concave-convex pattern 80 have a cross-sectional
shape whiclr is narrowing from the base portion, of each convexity, located on the side of
the base member 40 toward the apex poftion of each convexity. The concave-convex
pattern 80 ofthe concave-convex structure layer 60 may have such a characteristic that, as
in Fig. 2(a) depicting an example of a schematic plane view of the concave-convex pattern
80; a plurality of convexities (white portions) and a pluralify of concavities (black portions)
have an elongated shape extending while winding (waving, meandering), and that the
convexities and the concavities in the concave-convex pattern 80 have the extending
directions, winding direction (bending directions) and extending lengths which are
irregular in a plane view. Accordingly, the concave-convex pattern 80 is clearly different
from a regularly arranged pattern such as stripe, waved stripe, zigzag, etc., or a regularly
arranged pattern such as dot-shaped pattern, etc. The concave-convex pattern 80 does not
include such a regularly arranged pattern, and can be distinguished, in view of this point,
from apattern, such as a circuit pattern, which has a regularity and/or many linear portions
or straight lines, etc. Since the concave-convex structure layer 60 (the concave-convex
pattern 80) has the above-described characteristics, even under a condition that the
concave-convex structure layer 60 is cut in any plane orthogonal to a surface ofthe base
member 40,the concave-convex cross-sectional shape consequently appears repeatedly.
Further, a part (portion) or the entirety of the convexities and the concavities of the
concave-convex pattern 80 may be branched at an intermediate portion thereof in a plane
view (see Fig. 2(a)). Note that in Fig. 2(a), the pitch of the convexities appears to be
uniform as a whole. Furthermore, in the concave-convex pattern 80, the concavities are
defined by the convexities, and extend along the convexities.
I0t22l In order that the concave-convex structure layer 60 functions as a diffraction
grating, the average pitch of concavities and convexities is preferably in a range of 100 nm
to 1500 nm. In a case that the average pitch of the concavities and convexities is less than
the above-described lower limit, the pitch is tôo small with respect to the wavelength of a
visible light, and the diffraction of the light by the concavities and convexities is less likely
to occur. On the other hand, in a case that the average pitch of the concavities and
convexities exceeds the above-described upper limit, the diffraction angle is so small that
functions as the diffraction grating are more likely to be lost. The average pitch of the
concavities and convexities is rnore preferably in a range of 200 nm to 1200 nm, The
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average value of the depth distribution of the concavities and convexities is preferably in a
range of 20 nm to 200 nm. In a case that the average value of the depth distribution of the
concavities and convexities is less than the above-described lower limit, the depth is too
small with respect to the wavelength of the visible light, and thus any necessary diffraction
is less likely to be generated. On the other hand, in a case that the average value of the
depth distribution ofthe concavities and convexities exceeds the above-described upper
lirnit, the intensity of diffracted light is likely to become non-unifonn, which in turn results
in, for example in a case that an organic EL element is produced by using the film member
100, non-unifonn electric field distribution in an organic layer in the organic EL element,
generating such a tendency that the electric field is concentrated in a certain location and
thus easily generating a leakage current, and/or that the service life ofthe organic EL
element is shortened. The average value of the depth distribution of the concavities and
convexities is more preferably in a range of 30 nm to 150 nm. The standard deviation of
the depths of convexities and concavities is preferably in a range of 10 nm to 100 nm. In
a case that the standard deviation of the depths of concavities and convexities is less than
the lower limit, the depth is so short relative to the wavelengths of the visible light that the
required diffraction is less likely to occur. On the other hand, in a case that the standard
deviation of the depths of concavities and convexities exceeds the upper limit, the intensity
of diffracted light is likely to become non-uniform, which in turn results in, for example in
a case that an organic EL element is produced by using the film member 100, non-uniform
electric field distribution in the organic layer in the organic EL element, generating such a
tendency that the electric field is concentrated in a certain location and thus easily
generating a leakage current, and/or that the service life of the organic EL element is
shortened. The standard deviation of the depths of convexities and concavities is more
preferably within a range of 15 nm to 75 nm.
[0023] In the present application, the term "average pitch of concavities and convexities"
means an average value of the pitch of coneavities and convexities in a case of measuring
the pitch ofthe concavities and convexities (spacing distance between adjacent convex
portions or spacing distance between adjacent concave portions) in a surface on which the
convexities and concavities are formed. Such an average value of the pitch of concavities
and convexities can be obtained as follows. Namely, a concavity and convexity analysis
image is obtained by measuring the concavities and convexities on the surface by using a
scanning probe microscope (for example, a scanning probe microscope manufactured by
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HITACHI HIGH-TECH SCIENCE CORPORATION, under the product name of
"E-sweep", etc.), under the following measurement conditions, then the distances between
randomly selected concave portions or convex portions adjacent to each other are
measured at not less than 100 points in the concavity and convexity analysis image, and
then the average of the distances is arithmetically calculated and is determined as the
average pitch of concavities and convexities.
The measurement conditions are as follows:
Measurement mode: cantilever intermittent contact mode
Material of the cantilever: silicon
Lever width of the cantilever: 40 pm
Diarneter of tip of chip of the cantilever: 10 nm
100241 Further, in the present application, the average value of the depth distribution of
concavities and convexities and the standard deviation of the depths of concavities and
convexities can be calculated by the following manner. Namely, a concavity and
convexity analysis image is obtained by measuring the shape of the concavities and
convexities on the surface by using a scanning probe microscope (for example, a scanning
probe microscope manufactured by HITACHI HIGH-TECH SCIENCE CORPORATION,
under the product name of "E-sweep", etc.). When performing the analysis of the
concavities and convexities, the measurement is performed in a randomly selected
measurement region of 3 pm square (vertical: 3 ¡rm, horizontal: 3 pm) or in a randomly
selected measurement region of 10 pm square (vertical: 10 ¡rm, horizontal: l0 pm) under
the above-described conditions. When doing so, data of height of concavities and
convexities at not less than 16,384 points (vertical: 128 points x horizontal: 128 points) are
obtained within the measurement region, each in nanometer scale. Note that although the
number of measurement points is different depending on the kind and/or setting of the
measurement device which is used, for example in a case of using the above-described
scanning probe microscope manufactured by HITACHI HIGH-TECH SCIENCE
CORPORATION, under the product name of "E-sweep" as the measurement device, it is
possible to perform the measurement at measurement points of 65,536 points (vefücal 256
points x horizontal: 256 points; namely, the measurement in a resolution of 256 x256
pixels) within the measurement region of 3 pm square. Then, with respect to the height
of concavities and convexities (unit: nm) measured in such a manner, at first, a
measurement point "P" is determined, among all the rneasurement points, which is the
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highest from the surface of the substrate. Then, a plane which includes the measurement
point P and which is parallel to the surface of the substrate is determined as a reference
plane (horizontal plane), and a depth value from the reference plane (difference obtained
by subtracting, from the value of height from the substrate at the measurement point P, tlre
height from the substrate at each of the measurement points) is obtained as the data of
depth of concavities and convexities. Note that such a depth data of the concavities and
convexities can be obtained, for example, by performing automatic calculation with
software in the measurement device (for example, the above-described scanning probe
microscope manufactured by HITACHI HIGH-TECH SCIENCE CORPORATION, under
the product name of "E-sweep"), and the value obtained by the automatic calculation in
such a manner can be utilized as the data of depth of concavities and convexities. After
obtaining the data of depth of concavity and convexity at each of the measurement points
in this manner, the values, which can be calculated by obtaining the arithmetic average
value and the standard deviation of the obtained data of depths of concavity and convexit¡r,
are adopted as the average value ofthe depth distribution of concavities and convexities
and the standard deviation of the depths of concavities and convexities. In this
specification, the average pitch ofconcavities and convexities and the average value ofthe
depth distribution of concavities and convexities can be obtained via the above-described
measuring method, regardless of the material of the surface on which the concavities and
convexities are formed.
t00251 rhe concave-convex pattern 80 may a quasi-periodic pattern in which a
Fourier-transformed image, obtained by performing a two-dimensional fast
Fourier-transform processing on a concavity and convexity analysis image obtained by
analyzing a concave-convex shape on the surface, shows a circular or annular pattern,
namely, such a quasi-periodic pattern in which, although concavities and convexities have
no particular orientation (directionality), the pattern has the distribution of pitches of
concavities and convexities (pitches of concavities and convexities vary). Therefore, the
film member having such a quasi-periodic pattern is suitable for a diffraction substrate
used in a surface-emitting element, such as the organic EL element, provided that the film
member has concavities and convexities of which pitch distribution or pitch variability
enables the film member to diffract visible light.
[00261 As the material of the concave-convex shucture layer 60, an inorganic material
rn-ay be used. In particular, it is allowable to use an inorganic material exemplified by
silicon-based materials such as silica, SiN, SiON and the like; titanium (Ti)-based
materials (TiO2 and the like); materials based on indium-tin oxide (ITO); and ZnO, ZnS,
ZrOz, AlzOt BaTiO¡, and SrTiOz; and the like. By forming the concave-convex structure
layer 60 of such an inorganic material, it is possible to further suppress the permeation of
the oxygen and the water vapor through the film member 100. Such a concave-convex
structure layer 60 can be formed by: applying a solution (a precursor solution) of a
precursor of the inorganic material on the gas barrier layer so as to form a film; and by
curing the film by means of a reaction, drying, etc., as will be described later on. Further,
as described above, the concave-convex structure layer 60 is preferably formed ofa
material same as the material forming the surface 30a of the gas barrier layer 30 (a surface,
of the gas barrier layer 30, which makes contact with the concave-convex structure layer
60). By doing so, the adhesion property between the gas barier layer 30 and the
concave-convex structure layer 60 is improved.
100211 The thickness ofthe concave-convex structure layer 60 is preferably in a range of
100 nm to l0 pm. In a case that the thickness ofthe concave-convex structure layer 60 is
less than 100 nm, the transfer of the concave-convex shape by imprinting as described later
is difficult. On the other hand in a case that the thickness of the concave-convex
structure layer 60 exceeds 10 pm, any structural defect such as a crack is more likely to
occur. Here, the "thickness ofthe concave-convex structure layer 60" in this context
means an average value ofdistances from the bottom surface ofthe concave-convex
structure layer 60 to the surface in which the concave-convex pattern is formed.
100281 The adhesion force between the concave-convex structure layer 60 and the gas
barrier layer 30 is preferably greater than 4N/m. With this, in a production process of the
film member 100 or in a production process a various kinds of devices such as an optical
element using the film member 100, etc., it is possible to prevent any layer detachment or
exfoliation from occurring between the concave-convex structure layer 60 and the gas
baruier layer 30. The adhesion force between the concave-convex structure layer 60 and
the gas barrier layer 30 can be measured, for example, in the following manner. Namely,
gas baruier la¡rers are formed on two film base members, respectively; and a solution (a
precursor solution) of a precursor of an inorganic material, which is same as the inorganic
material used for forming the concave-convex structure layer, is further applied on one
film base mernber, of the two film base members, so as to form a coating film of the
precursor solution thereon. Then, after overlapping the two film base members such that
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the coating film of the precursor solution formed on the one film member of the two film
base members makes contact with the gas barrier layer formed on the other film member of
the two film base members, the coating film of the precursor solution is cured to thereby
form an inorganic material layer. Namely, a sample having a structure composed of the
fìlm base member/the gas barrier layerlthe inorganic material layer/the gas barrier layer/the
film base member is obtained. In this sample, the inorganic material layer is a layer
which is formed of the inorganic material same as the inorganic material forming the
concave-convex structure layer. The film base members, each of which is the uppermost
layer or the lowermost layer of this sample, are held respectively to be peeled at a constant
speed in a 18O-degree direction (to be peeled in a T-shaped manner). Then, the sample is
divided (torn) into two portions from the weakest interface. The peel strength (peeling
force) at this time is measured by using, for example, a tensile tester (mode name:
Strograph E-L; manufactured by TOYO SEIKI SEISAKU-SHO, LTD.), etc. The
measured peel strength indicates the adhesion force of the peeled interface. The adhesion
force between the gas barrier layer and the concave-convex structure layer can be
appreciated from the measure value of the peel strength in the case that the peeling occurs
at the interface between the gas barrier layer and the concave-convex structure layer.
Note that in such a case that the adhesion force between the respective layers is greater
than the strength of the film base member, the bas barrier layer or the concave-convex
structure layer itself the sample is to be torn (broken) from the base member or from a
location inside the layer, rather than from the interface between the respective layers.
[0029] [Method of Producing Film Member]
Next, a method of producing a film member having the concave-convex structure
of the embodiment will be explained. The film member having the concave-convex
structure of the embodiment can be produced by a nano-imprint method as explained
below. The method of producing such a film member 100 having the concave-convex
structure of the embodiment mainly includes: a gas barier layer forming step of forming a
gas barrier layer on a film base member; a solution preparation step of prep aring a
precursor solution (a solution of a precursor of an inorganic material); a coating step of
coating the gas banier layer with the prepared precursor solution to form a coating film (a
film of the precursor) ; a transfer step of transferring a concave-convex pattern of a mold to
the coating film on the gas barrier layer by pressing the mold against the coating film while
curing (pre-curinglthe coating film; and a main curing step of performing main curing for
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the coating film. In the following, the respective steps wilt be explained in the above
order.
t00301
At first, a gas barrier layer is formed on a film base member. For example, the
gas baruier layer can be formed by a wet method such as the sol-gel method. Specifically,
alkoxide such as silicon alkoxide, titanium alkoxide, etc., is used as a metal compound raw
material to be applied on the base member by means of the spraying method, the spin
coating method, etc., to form a film; and then the formed film is cured (subjected to the
gelation), thereby making it possible to form the gas barrier layer. Alternatively, the gas
barier layer may be formed on the film base member by the sputtering method, the
ion-assisted method, or by the plasma cvD method, the plasma cvD method under
atmospheric pressure or in the vicinity thereof, as will be described later on. Still
altematively, it is allowable to form a multi-layered film, as the gas barier layer, by
stacking a plurality of materials in any of the above-described methods. In any of cases
that the gas barrier layer is a multi-layered fìlm or a single layer film, the uppermost
surface (a surface making contact with the concave-convex structure layer) of the gas
barrier layer is preferably formed of a material same as that forming the concave-convex
structure layer. With this, the adhesion force between the concave-convex structure layer
and the gas barrier layer can be improved.
[0031ì With the wet system (wet method) such as the sol-gel rnethod using the spraying
method and the spin coating method, it is diffìcult to obtain the smoothness (evenness) in
the molecular level (nm level). Further, since the wet system uses a solvent, there is
limitation to usable base members or usable solvents in a case that the base member is
made of an organic material. Accordingly, it is preferred that the gas barrier layer is
formed by the plasma CVD method, the plasma CVD method under atmospheric pressure
or in the vicinity thereof, as will be described later on. Among these methods, in
particular, the forming method by the plasma CVD method under atmospheric pressure is
preferued since this method does not require any decompression chamber, etc., is capable
of performing the film formation at a high speed, and has a high productivity.
[0032] The details of the film forming method by the plasma cVD method under
atmospheric pressure is described, for example, in Japanese Patent Application Laid-open
Nos. 2004-052028, 2004-198902, etc. The method uses an organornetallic compound
as the raw material, and it is allowable to use the raw material compound in either a
fl
,g
I+
gaseous, Iiquid or solid state at normal temperature under normal pressure. ln a case that
the raw material compound is used in its gaseous state, the raw material compound can be
introduced as it is into a discharge space; on the other hand, in a case that the raw material
compound is in a liquid or solid state, the material is used after being gasified once by
means of heating, bubbling, decompression, ultrasonic radiation, etc. In view of such a
situation, preferred organometallic compounds include, for example, a metal alkoxide of
which boiling point is not more than 200"C.
[00331 Examples of such metal alkoxide include a silicon compound such as silane,
tetramethoxysilane, tetraethoxysilane (TEOS), tetra-n-propoxysilane, etc.; a titanium
compound such as titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium
tetraisopropoxide, elc.; azirconium compound such as zirconium-n-propoxide, etc.,; an
aluminum compound such as aluminum ethoxide, aluminum triisopropoxide, aluminum
isopropox ide, etc. ; antym ony ethoxide ; arseni c triethox ide ; zinc acetylacetonate ;
diethylzinc; and the like.
[0034] Further, cracking gas is used together with the gaseous raw material containing
these organometallic compounds to compose a reactive gas, for the purpose of cracking the
organometallic compounds to thereby obtain an inorganic compound. The cracking gas is
exemplified by a hydrogen gas, water vapor, etc.
t00351 In the plasma CVD method, a discharge gas easily turned to a plasma state is
mainly mixed with the reactive gas. As the discharge gas, for example, a nitrogen gas; a
rare gas such as a gas of an element of the eighteenth group ofthe periodic table,
specifically, helium, neon, argon, etc.; and the like, can be used. In particular, the
nitrogen gas is preferred in view ofthe production cost.
[0036] The film formation is performed by mixing the discharge gas with the reactive gas
to thereby obtain a mixed gas, and by supplying the mixed gas to a discharge plasma
generating apparatus (plasma generator). The ratio of the discharge gas relative to the
reactive gas is different depending on the property of a film as an object to be formed, for
example, the percentage of the discharge gas is not less than 50Yo in the entire mixed gas.
[0037] For example, the metal alkoxide or the silicon alkoxide (such as tehaethoxysilane
(TEOS) of which boiling point is not more than 200oC, is used as the raw material
compounds, oxygen is used as the cracking gas, and the rare gas or an inert gas such as
nitrogen is used as the discharge gas, and the plasma discharge is performed. In such a
case, it is possible to form a film of silicon oxide (silicon oxide fihn) as the gas barrier
]'
ì
i: x,ç
layer of the embodiment.
[0038ì Note that for the purpose of forming a concave-convex structure layer having a
desired concave-convex pattern on the gas barrier layer, asurface ofthe gas barrier layer
(including a surface obtained by a surface treatment and/or a surface ofan easy-adhesion
layer as well in a case that any surface treatment is performed and/or any easy-adhesion
layer is provided) may be flat or smooth.
[0039]
In order to form a concave-convex structure layer made of an inorganic material, a
solution of a precursor of the inorganic material is prepared. For example, in a case that
the concave-convex structure layer made of the inorganic material is formed by using the
sol-gel method, a metal alkoxide as a precursor is prepared. For example, in a case that
concave-convex structure layer made of silica is formed on a base member, it is possible to
use, as the precursor of silica (silica precursor): tetraalkoxide monomers represented by
tetraalkoxysilane such as tetramethoxysilane (TMOS), tetraethoxysilane (TEOS),
tetra-i-propoxysilane, tetra-n-propoxysilane, teha-i-butoxysilane, tetra-n-butoxysilane,
tetra-sec-butoxysilane, tetra-t-butoxysilane, etc.; trialkoxide monomers represented by
trialkoxysilane such as methyl trimethoxysilane, ethyl trimethoxysilane, propyl
trimethoxysilane, isopropyl trimethoxysilane, phenyl trimethoxysilane, methyl
triethoxysilane (MTES), ethyl triethoxysilane, propyl triethoxysilane, isopropyl
triethoxysilane, phenyl triethoxysilane, methyl tripropoxysilane, ethyl tripropoxysilane,
propyl tripropoxysilane, isopropyl tripropoxysilane, phenyl tripropoxysilane, methyl
triisopropoxysilane, ethyl triisopropoxysilane, propyl triisopropoxysilane, isopropyl
triisopropoxysilane, phenyl triisopropoxysilane, tolyltriethoxysilane, etc.; dialkoxide
monomers represented by dialkoxysilane such as dimethyl dimethoxysilane, dimethyl
diethoxysilane, dimethyl dipropoxysilane, dimethyl diisopropoxysilane, dimethyl
di-n-butoxysilane, dimethyl di-i-butoxysilane, dimethyl di-sec-butoxysilane, dimethyl
di-t-butoxysilane, diethyl dimethoxysilane, diethyl diethoxysilane, diethyl dipropoxysilane,
diethyl diisopropoxysilane, diethyl di-n-butoxysilane, diethyl di-i-butoxysilane, diethyl
di-sec-butoxysilane, diethyl di-t-butoxysilane, dipropyl dimethoxysilane, dipropyl
diethoxysi lane, dipropyl dipropoxysilane, dipropyl diisopropoxysilane, dipropyl
di-n-butoxysilane, dipropyl di-i-butoxysilane, dipropyl di-sec-butoxysilane, dipropyl
di-t-butoxysilane, diisopropyl dimethoxysilane, diisopropyl diethoxysilane, diisopropyl
dipropoxysilane, diisopropyl diisopropoxysilane, diisopropyl di-n-butoxysilane,
';
v' lL
diisopropyl di-i-butoxysilane, diisopropyl di-sec-butoxysilane, diisopropyl
di-t-butoxysilane, diphenyl dimethoxysilane, diphenyl diethoxysilane, diphenyl
dipropoxysilane, diphenyl diisopropoxysilane, diphenyl di-n-butoxysilane, diphenyl
di-i-butoxysilane, diphenyl di-sec-butoxysilane, diphenyl di-t-butoxysilane, etc. Further,
it is also possible to use alkyltrialkoxysilane and dialkyldialkoxysilane in each of which an
alkyl group has carbon numbers of C4 to C18. It is also allowable to use metal alkoxide
such as: monomers having vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane,
etc.; monomers having epoxy group such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
3-glycidoxypropylmethyldimethoxysiIane, 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.;
monomers having styryl group such as p-styryltrimethoxysilane, etc.; monomers having
methacrylic group such as 3-methacryloxypropylmethyldimethoxysilane,
3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane,
3-methacryloxypropyltriethoxysilane, etc.; monomers having acrylic group such as
3-acryloxypropyltrimethoxysilane, etc.; monomers having amino group such as
N-2-(aminoethyl)-3 -aminopropylmethyldimethoxysilane,
N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, etc.; monomer having ureide group such as
3-ureidepropyltriethoxysilane, etc.; monomers having mercapto group such as
3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.;
monomers having sulf,rde group such as bis(triethoxysilylpropyl) tetrasulfide, etc.;
monomers having isocyanate group such as 3-isocyanatopropyltriethoxysilane, etc. ;
polymers obtained by polymerizing the foregoing monomers in small amounts; and
composite materials characterized in that functional group and/or polymer is/are introduced
into a part of the material as described above. Fufther, a part of or all of the alkyl group
and the phenyl group of each of these compounds may be substituted with fluorine.
Further, examples of the silica precursor include metal acetylacetonate, metal carboxylate,
oxychloride, chloride, and mixtures thereof. The silica precursor, however, is not limited
to these. In addition to Si, examples of the 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, it is possible to use, as
the silica precursor, a silane coupling agent having, in its molecule, a hydrolysis group.
'*rr+
having the afünity and the reactivity with silica and an organic functional group.having the
water-repellence. For example, there are exemplified silane monomer such as
n-octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, etc.; vinylsilane
such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane,
vinylmethyldimethoxysilane, etc.; methacrylsilane such as
3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc.;
epoxysi lane suclr as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysi lane,
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.;
mercaptosiIane such as 3-mercaptopropyltrimethoxysilane,
3 -mercaptopropyltriethoxys ilane, etc. ; sulfursilane such as
3 -octanoylthio- I -propyltriethoxysilane, etc. ; aminosilane such as
3 -aminopropyltriethoxysi lane, 3 -aminopropyltrimethoxysilane,
N-(2-am inoethyl)-3 -aminopropylhimethoxysilane,
N-(2-am inoethyl)-3 -am inopropylmethyldimethoxysilane,
3-(N-phenyl)-aminopropyltrimethoxysilane, etc.; polymers obtained by polymerizingthe
monomers as described above; and the like.
[0040] In a case that a mixture of TEOS and MTES is used as the precursor of the
inorganic material, the mixture ratio thereof can be, for example, I : I in a molar ratio.
The precursor produces amorphous silica by being subjected to the hydrolysis and
polycondensation reaction. An acid such as hydrochloric acid or an alkali such as
ammonia is added in order to adjust the pH of the solution as a synthesis condition. The
pH is preferably not more than 4 or not less than 10. Water may be added to perform the
hydrolysis. The amount of water to be added can be not less than 1.5 times, with respect
to the amount of metal alkoxide species, in the molar ratio.
[004U Examples of a solvent of the precursor solution used in the sol-gel method include
alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol, etc.; aliphatic
hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, etc.; aromatic
hydrocarbons such as benzene, toluene, xylene, mesitylene, etc.; ethers such as diethyl
ether, tetrahydrofuran, dioxane, etc.; ketones such as acetone, methyl ethyl ketone,
isophorone, cyclohexanone, etc.; ether alcohols such as butoxyethyl ether, hexyloxyethyl
alcohol, methoxy-2-propanol, benzyloxyethanol, etc.; glycols such as ethylene glycol,
propylene glycol, etc.; glycol ethers such as ethylene glycol dimethyl ether, diethylene
glycol dimethyl.ether, propylene glycol monomethyl ether acetate, etc.; esters such as ethyl
/1 ,2'lg
ìs
¡1.
acetate, ethyl lactate, y-butyrolactone, etc.; phenols such as phenol, chlorophenol, etc.;
amides such as N,N-dimethylformarnide, N,N-dimethylacetamide, N-methylpyrrolidone,
etc.; halogen-based solvents such as chloroform, methylene chloride, tetrachloroethane,
monoclrlorobenzene, dichlorobenzene, etc.; hetero-element containing compounds such as
carbon disulfide, etc.; water; and mixture solvents thereof. Especially, ethanol and
isopropyl alcohol are preferable. Further, a mixture of water and ethanol, and a mixture
of water and isopropyl alcohol are also preferable.
100421 As an additive of the precursor solution used in the sol-gel method, it is possible
to use polyethylene glycol, polyethylene oxide, hydroxypropylcellulose, and polyvinyl
alcohol for viscosity a-djustment; alkanolamine such as triethanolamine, B-diketone such as
acetylacetone, B-ketoester, formamid, dimetylformamide, and dioxane, etc., as a solution
stabilizer. Further, it is possible to use, as an additive to the precursor solution, a material
which generates an acid or alkali by being irradiated with light such as energy rays
represented by ultraviolet rays such as excimer UV light. By adding such a material, the
precursor solution can be gelled (cured) by being iradiated with light, thereby making it
possible to form the inorganic material.
[00431 Alternatively, a polysilazane solution may be used as the precursor of the
inorganic material. The pol¡lsilazane is oxidized by being irradiated with an energy ray
such as excimer UV light, is thereby ceramized (subjected to silica reforming or
modification) and forms silic4 SiN or SiON. Note that the "polysilazane" 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, Si3Na, or SiOxNv, which is an
intermediate solid solution of such a ceramics. A compound, which is ceramized at
relatively low temperature and is modified into silic4 as that represented by the following
general formula (l) described in Japanese Patent Application Laid-open No. H08-172879,
is more preferable.
[00441 General formula (i):
-si (Rl) (R2)-N (R3)-
In the general formula (l), Rl, R2, and R3 each represent a hydrogen atom, an
alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an
alkylarnino group, or an alkoxy group.
[00451 Among the compounds represented by the general formula (l),
perhydropolysilazane (refened to also as PHPS),in which all of Rl, R2, and R3 are
Fn
hydrogen atoms and organopolysilazane in which a part of the hydrogen bonded to Si
thereof is substituted by, for example, an alkyl group are particularly preferred.
t00461 Other examples of the polysilazane ceramized at low temperature which are
usable include: silicon alkoxide-added polysilazane obtained by reacting polysilazane with
silicon alkoxide (see, for example, Japanese Patent Laid-Open No. H05-23 8827);
glycidol-added polysilazane obtained by reaction with glycidol (see, for example, Japanese
Patent Laid-open No. H06-122852);alcolrol-added polysilazane obtained by reaction with
alcohol (see, for example, Japanese Patent Laid-open No. H06-240208); metal
carboxylate-added polysilazane obtained by reaction with metal carboxylate (see, for
example, Japanese Patent Laid-Open No. H06-2991 l8); acetylacetonato complex-added
polysilazane obtained by reaction with an acetylacetonato complex containing a metal (see,
for example, Japanese Patent Laid-Open No. H06-306329); metallic fine particles-added
polysilazane obtained by adding metallic fine particles (see, for example, Japanese Patent
Laid-Open No. H07-196986), and the like.
[00471 As the solvent ofthe 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
alicyctric ethers. Amine or a metal catalyst may be added in order to promote the
modification into a silicon oxide compound.
[00481 Note that a dispersion liquid of fine particles of an inorganic material may be used,
instead of using the above-described precursor solution of the inorganic material. Further,
it is altowable to form the concave-convex structure layer by a liquid phase deposition
(LPD) method, etc. In the present application, "a layer obtained from the precursor
solution" means a layer formed by curing a film formed by application of the precursor
solution by means of polycondensation reaction, oxidation reaction, drying, etc.; and the
layer obtained from the precursor solution encompasses a layer formed by the application
of the dispersion liquid of the fine particles of the inorganic material and then by the drying,
and a layer formed by the liquid phase deposition method, as well.
[0049]
The precursor solution of the inorganic material prepared as described above is
applied onto the gas barrier layer (the gas barrier layer is coated with the precursor solution
of the inorganic material). It is allowable to perform a surface treatment such as the
plasma treatment, the corona treatment, etc., for, or provide an easy-adhesion layer on, the
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gas baruier layer in order to improve the adhesion property. As the coating method for
coating the gas barier layer with the precursor solution, 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 preferable,
because the base member having a relatively large area can be coated uniformly with the
precursor solution and the coating can be quickly completed prior to curing (gelation) of a
precursor film obtained by the application of the precursor solution.
[0050] After the coating of the gas barrier layer with the precursor solution, the base
member may be kept (held) in the atmospheric air or under reduced pressure in order to
evaporate the solvent contained in the coating film (precursor film). In a case that the
holding time of the base member is short, the viscosity of the coating film is too low to
transfer the concave-convex pattern to the coating film. On the other hand, in a case that
the holding time of the base member is too long, the polymerization reaction of the
precursor proceeds and the viscosit¡r of the coating film becomes too high, which in turn
makes it impossible to transfer the concave-convex pattem to the coating fihn. Further,
after the coating of the gas barrier layer with the precursor solution, the gelation of the
coating film proceeds as the evaporation ofthe solvent proceeds, and the physical properly
such as the viscosity of the coating film also changes in a short time. From the viewpoint
of the stability of concave-convex pattern formation, it is prefened that drying time which
enables a good pattern transfer has a sufficiently wide range. The range of the drying
time which enables a good pattern transfer can be adjusted by the drying temperature
(holding temperature), the drying pressure, the kind of precursor, the ratio of mixture of the
material species of the precursor, the solvent amount used at the time of preparation of the
precursor solution (concentration of precursor), etc. Note that in the drying step, since the
solvent in the coating film (precursor film) is evaporated only by holding the base member
as it is, any active drying operation such as heating and/or blowing is not necessarily
required; raihe., for drying the coating film, it is only required to leave the base member
having the coating film formed thereon as it is for a predetermined time or to transport the
base member for a predetermined time period so as to perform subsequent steps. Namely,
the drying step is not indispensable in the method for producing the film member of the
embodiment.
[0051]
';/
26
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Next, a mold for concave-convex pattern transfer is used to transfer the
concave-convex pattern of the mold to the coating film (precursor film). A film-shaped
mold or metal mold, which can be produced by a method to be described later on, can be
used as the mold, and it is preferred that a flexible film-shaped mold be used as the mold.
In this situation, a pressing roll may be used to press the mold against the precursor fìlm.
The roll process using the pressing roll has the following advantages over the pressing
system. Namely, for example, the period of time during which the mold and the coating
film are brought in contact with each other is short, and hence it is possible to prevent any
deformation or collapse of pattern which would be otherwise caused by the difference in
thermal expansion coefficient among the mold, the base member, and a stage on which the
base member is placed, etc.; it is possible to prevent the generation of bubbles of gas in the
pattern due to the bumping of the solvent in the precursor film or to prevent any trace or
mark of gas from remaining; it is possible to reduce the transfer pressure and the releasing
force (peeling force) owing to the line contact with the base member (coating film),
thereby making it possible to easily handle a base member with larger area; and no bubble
is included during the pressing. Further, the base member may be heated while the mold
is being pressed thereto. Fig. 3 depicts an example in which the mold is pressed against
the coating film (precursor film) by using the pressing roll. As depicted in Fig. 3, the
concave-convex pattern of a film-shaped mold 140 can be transferred to a coatin gfilm 64
on the base member 40 by sending the film-shaped mold 140 between a pressing roll722
and the base member 40 being transported immediately below the pressing roll 122.
Namely, when the film-shaped mold 140 is pressed against the coating film 64 with the
pressing roll 122, the surface of the coatin gfilm 64 on the base member 40 is coated
(covered) with the film-shaped mold 140 while the film-shaped mold 140 and the base
member 40 are synchronously transported. In this situation, by rotating the pressing roll
122 while pressing the pressing roll 122 against the back surface (surface on the side
opposite to the surface in which the concave-convex pattern is formed) of the film-shaped
mold 140, the film-shaped mold 140 moves with the base member 40 while being brought
into tight contact with the base member 40. In order to send the long film-shaped mold
140 to the pressing roll122, such a confìguration is conveniently used wherein the
film-shaped mold 140 is fed directly from a film roll around which the long film-shaped
mold 140 is wound.
[00521 After the mold 140 is pressed against the precursor film, the precursor film may
¿
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'72{2
-:.,r-:,-:-'-j--:- -:_-:J-:::j:j!:-j.l ; i:r. : i:..tt:,
be subjected to pre-baking. The pre-baking converts the precursor film into an inorganic
material and cures the coating film, thereby solidifying the concave-convex pattern, which
in turn allows the concave-convex pattern to be less likely to be collapsed during releasing
or peeling of the mold 140. In a case that the pre-baking is performed, heating is
preferably performed at a temperature in a range of the room temperature to 300"C in the
atmosphere. Note that, however, it is not necessarily required to perform the pre-baking.
On the other hand, in a case that the material generating an acid or alkali by being
irradiated with a light such as ultraviolet ray is added to the precursor solution, it is
allowable for example to irradiate the precursor film with the energy ray represented by
ultraviolet ray including the excimer UV light, rather than performing the pre-baking for
the precursor film, so as to cure the coating fìlm.
[0053] After the pressing with the mold or the pre-baking for the precursor film, the mold
is released or peeled off from the coating film (precursor film, or an inorganic material film
formed by converting the precursor film into the inorganic material). As the method for
releasing the mold, any publicly known releasing method can be adopted. Convexities
and concavities of the concave-convex paffern of the mold used in the producing method of
the embodiment have an elongated shape, and a waveform structure in which inclination is
gentle, thereby providing satisfactory releasing properfy (releasability or peeling property).
Further, since the inorganic material obtained by converting the precursor is made of the
material same as that forming the surface of the gas barrier layer, the coating film is firmly
attached to the gas barrier layer. Accordingly, the coating film is not peeled off or
removed from the gas barrier layer while the coating film is maintaining the tight contact
with the mold. The mold may be released while the coating film being heated. By
doing so, gas generated from the coating film is allowed to escape, thereby preventing any
generation of bubbles in the coating film. In a case that the roll process is used, the
releasing force (peeling force) may be smaller than that in the pressing system using a
plate-shaped mold, and it is possible to easily release the mold from the coating film
without allowing the coating film to remain on the mold. In particular, since the pressing
is performed while the coating film is being heated, the reaction progresses more easily,
which in turn facilitates the releasing of the mold from the coating film immediately after
the pressing. In order to improve the releasing properfy (peeling propelty) of the mold, it
is possible to use a peeling roll (releasing roll). As depicted in Fig. 3, a peeling roll
(releasing roll), 123 is disposed on the downstream side of the pressing roll122, and the
rqfú,
peeling roll 123 rotates and supports the film-shaped mold 14û while urging the
film-shaped mold 140 toward the coating film 64. With this configuration, it is possible
to maintain a state that the film-shaped mold 140 is attached to the coating film 64 as long
as a distance between the pressing roll 722 and the peeling roll 123 (for a certain period of
time). Then, a path of the film-shaped mold 140 is changed so that the fìlm-shaped mold
140 is pulled up above the peeling roll 123 on the downstream side of the peeling roll123,
thereby peeling off (releasing) the film-shaped mold 140 from the coating film in which
concavities and convexities are formed (concave-convex structure layer 60). The
pre-baking or the heating for the coating film 64 may be performed during a period in
which the film-shaped mold 140 is attached to the coating film 64. Note that in a case of
using the peeling roll123,the releasing of the mold 140 becomes easier by releasing the
mold 140 from the coating film while heatingthe coating fil,m 64, for example, at a
temperature in a range of the room temperature to 300"C in the atmosphere.
[0054]
After the mold is released from the coating film formed with the concavities and
convexities (concave-convex structure layer), the concave-convex structure layer may be
cured (subjected to main curing or baking). In the embodiment, the concave-convex
structure layer can be cured by performing main baking therefor. In a case of using a
precursor which is converted into silica by the sol-gel method, the hydroxyl group or the
like contained in silica (amorphous silica) constructing the concave-convex structure layer
is desorbed or eliminated (subjected to the leaving) by the main baking, and the
concave-convex structure layer is further hardened or solidified. The main baking is
preferably performed at a temperature in a range of 200oC to l200oC for a duration of time
in a range of about 5 minutes to about 6 hours. In this situatìon, in a case that the
concave-convex structure layer is made of silica, silica is amorphous, crystalline, or in a
mixture state of the amorphous and the crystalline, depending on the baking temperature
and the baking time. Note that it is not necessarily indispensable that the curing step is
performed. Further, in a case that a material, which generates an acid or alkali by being
irradiated with a light such as ultraviolet ray, is added to the precursor solution, the
concave-convex structure layer can be subjected to the main curing by being irradiated
with an energy ray represented by ultraviolet ray including the excimer UV light, rather
than baking the concave-convex structure layer.
t00d5Ì In the above-describedmanner, it is possible to produce a film member 100 in
'7L{ +
which the gas barrier layer 30 and the concave-convex structure layer 60 are formed on the
film member 40, as depicted in Fig. 1.
[0056ì Note that as the precursor with which the coating is performed in the coating step
as described above, it is allowable to use a precursor such as TiO2, ZnO, ZnS, ZrO2, Al2O3,
BaTiO3, SrTiOz, ITO, etc., other than the silica precursor. It is preferred to use a
precursor of an inorganic rnaterial which is same as the inorganic material forming
(constructing) the uppermost surface (a surface making contact with the concave-convex
structure layer) 30a ofthe gas barrier layer.
[0057] The material for forming the concave-convex structure layer may be a material
obtained by mixing the above-described precursor with an ultraviolet absorbent material.
The ultraviolet absorbent material has the function or effect to prevent deterioration of the
f,rlm by absorbing ultraviolet rays and converting the light energy into something harmless
such as heat. Any publicly known agent may be used as the ultraviolet absorbent material.
Those usable as the ultraviolet absorbent material include, for example,
benzotriazole-based absorbents, triazine-based absorbents, salicylic acid derivative-based
absorbents, benzophenone-based absorbents, etc.
[0058] A covering layer (coating layer) may be formed on the surface of the
concave-convex structure layer. It is preferred thut th" thickness ofthe covering layer be
in a range of25%oto 150%o ofthe standard deviation ofdepth ofconcavities and
convexities ofthe concave-convex structure layer. Such a covering layer can cover any
foreign matter and/or defect which rnight be present on the surface of the concave-convex
structure layer. Thus, in a case that a light emitting element such as an organic EL
element is formed by using this film member, it is possible to effectively prevent any leak
current in the light emitting element. Further, a light emitting element, which is formed
by using the film member provided with the covering layer having a thickness within the
above range, has good light extraction efficiency.
[0059] As the material of the covering layer (covering material (coating material)), it is
possible to use: sol-gel materials which are exemplified above as being usable as the
material for the concave-convex structure layer and including: SiOy, TiO2, ZnO, ZrO2,
Al2O3, ZnS, BaTiO3, STTiO2,ITO (indium-tin oxide), etc.; materials obtained by allowing
any one of these sol-gel materials to contain publicly known fine particles, filler,
ultraviolet absorbent material, etc. In particular, it is preferred that the covering layer is
formed by using a material that is same as the material used as the material for the
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concave-convex structure layer. By forming the covering layer of a material same as the
material of the concave-convex structure layer, it is possible to suppress the reflection of
light at an interface between the covering layer and the concave-convex structure layer.
As a solution of the sol-gel material (sol-gel material solution) used for forming for the
covering layer, it is prefered to use a material obtained by further diluting, with a solvent,
the sol-gel material solution used for forming the concave-convex structure layer. With
this, the covering layer can be easily formed to have a predetermined film thickness
(thickness) which is thinner than the concave-convex structure layer.
[00601 Further, other than using the sol-gel method, it is allowable to form the covering
layer by using, for example, a method using a dispersion liquid of fine particles of the
inorganic material, the liquid phase deposition (LPD), etc.
[006X] Alternatively, polysilazane may be used to form the covering layer. In this case,
it is also allowable to form the covering layer by performing the application and transfer
using the polysilazane, and to cure and thereby ceramicize (perform silica reforming or
modification for) the formed covering layer so as to obtain a covering layer made of silica,
SN or SiON. Note that the "polysilazane" 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 SiO2, Si3Na, or SiOyNy, which is an intermediate solid solution of such a
ceramics. A compound, which is ceramized at relatively low temperature and is modified
into silica, as that represented by the following general formula (l) described in Japanese
Patent Application Laid-open No. H08-l 12879, is more preferable.
[0062] General Formula (l):
-si (R1) (R2)-N (R3)-
In the general formula (1), Rl, R2, and R3 each represent a hydrogen atom, an
alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an
alkylamino group, or an alkoxy group.
[00631 Among the compounds represented by the general formula (l),
perhydropolysilazane (referredto also as PHPS) in which all of Rl, 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 alkyl group are particularly preferred.
[0064] Other examples of the polysilazane ceramized at low temperature which are
usable include: silicon alkoxide-added polysilazane obtained by reacting polysilazane with
silicon alkoxide (see, for example, Japanese Patent Laid-Open No. H05-23 B8Z7\;
+:
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glycidol-added polysilazane obtained by reaction with glycidol (see, for example, Japanese
Patent Laid-open No. H06-122852); alcohol-added polysilazane obtained by reaction with
alcohol (see, for example, Japanese Patent Laid-open No. H06-240208); metal
carboxylate-added polysilazane obtained by reaction with metal carboxylate (see, for
example, Japanese Patent Laid-Open No. H06-2991 I 8); acetylacetonato complex-added
polysilazane obtained by reaction with an acetylacetonato complex containing a metal (see,
for example, Japanese Patent Laid-Open No. H06-306329); metallic fine particles-added
polysilazane obtained by adding metallic fine particles (see, for example, Japanese Patent
Laid-Open No. H07-196986), and the like.
t00651 As the 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.
[0066] The quring of polysilazane may be promoted by heating, or by inadiation with an
energy ray such as excimer UV light, etc.
[0067] Further, it is allowable to use, as the material for the covering layer, acurable
resin material (curable resin), other than the above-described inorganic material. In such
a case of forming the covering layer with the curable resin, for example, the covering layer
may be formed by applying the curable resin onto the concave-convex structure layer, and
then by curing the applied curable resin. The curable resin may be applied after being
diluted with an organic solvent. As the organic solvent used in this case, an organic
solvent, which can dissolve the resin before being cured, can be selected and used. For
example, it is possible to select the organic solvent from among publicly known organic
solvents including, for example, alcohol-based solvents such as methanol, ethanol, and
isopropyl alcohol (IPA); and ketone-based solvents such as acetone, methyl ethyl ketone,
and methyl isobutyl ketone (MIBK). As the method for applying the curable resin, for
example, it is possible to adopt various coating methods such as the spin coating method,
spray coating method, dip coating method, dropping method, gravure printing method,
screen printing method, relief printing method, die coating method, curtain coating method,
ink-jet method, sputtering method, etc. The condition for curing the curable resin
depends on the kind of the resin to be used. For example, the curing temperature is
preferably in a range of room temperature to 250"C, and the curing time is preferably in a
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range of 0.5 minute to 3 hours. Alternatively, a method may be employed in which the
curable resin is cured by being irradiated with an energy ray such as ulhaviolet light or
electron beam. In such a case, the amount of the irradiation is preferably in a range of 20
mJlcm2 to 5 J/cm2.
[0068] Further, a hydrophobization treatment may be performed on the surface of the
concave-convex structure layer (the surface ofthe covering layer in a case that the
covering layer is formed). Any known method for the hydrophobization treatment may
be used. For example, regarding the surface of silica, the hydrophobization treatment can
be performed with dimethyl dichlorosilane, trimethyl alkoxysilan, etc., or with a silicone
oil and a trimethylsilylating agent such as hexamethyl-disilazane. Alternatively, it is also
allowable to employ a surface treatment method for a surface of metal oxide powder with
supercritical carbon dioxide. By allowing the surface of the concave-convex structure
layer to have the hydrophobicity, it is possible to easily remove moisture from the substrate
during a manufacturing process of an optical element such as organic EL element using the
film member of the embodiment thereby making it possible to prevent, in the optical
element, any generation of defect, such as a dark spot, and any deterioration of the device.
[00691
Examples of a mold for concave-convex pattern transfer used for producing a film
member having the concave-convex structure of the embodiment include, for example, a
metal mold or a film-shaped resin mold produced in a method as will be described later on.
The resin forming the resin mold also includes rubber such as natural rubber or synthetic
rubber. The mold has a concave-convex pattern (convexity and concavity pattern) on a
surface thereof.
[0070ì An explanation will be given about an exemplary method for producing the mold
for concave-convex pattern transfer. A master block pattern for forming the
concave-convex pattern of the mold is produced first. For example, in a case that a film
member having a concave-convex pattern composed of curved line-shaped convexities and
concavities extending in non-uniform directions, it is suitable that the master block is
formed by a method of utilizing the selÊorganization or self-assembly (micro phase
separation) of a block copolymer by heating, as described in International Publication No.
WO20121096368 of the applicants of the present invention (hereinafter refered to as "BCP
(Block Copolymer) thermal annealing method" as appropriate), or a method of utilizing the
self-organization or self-assembly of a block copolymer under a solvent atmosphere, as
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described in International Publication No. WOZtl3l161454 of the applicants of the present
invention (hereinafter referred to as "BCP solvent annealing method" as appropriate), or a
method of heating and cooling a vapor deposited film on a polymer film to form
concavities and convexities of wrinkles on a surface of polymer, as disclosed in
International Publication No. WO20l1/007878 Al of the applicants of the present
invention (hereinafter referred to as "BKL (Buckling) method" as appropriate). In a case
that the pattern is formed by the BCP thermal annealing method or the BCP solvent
annealing method, although any material can be used as the material for forming the
pattern, the material is preferably a block copolymer composed of a combination of two
selected from the group consisting of: a styrene-based polymer such as polystyrene;
polyalkyl methacrylate such as polymethyl methacrylate; polyethylene oxide;
polybutadiene; polyisoprene; polyvinylpyridine; and polylactic acid. The pattern formed
by the self-organization of these materials preferably has a horizontal cylinder structure
(structure wherein cylinders are oriented horizontally relative to a base material) as
described in WO2013/161454,or a vertical lamella structure (structure in which lamellae
are oriented vertically relative to a base material) as described in "Macromolecules" 2014,
Y ol. 47 ,Issue 2, among which the vertical lamella structure is more preferred for a case of
forming deeper concavities and convexities. Further, the concave-convex pattern
obtained by the solvent annealing process may be subjected to etching by irradiation with
energy rays represented by ultraviolet rays such as excimer IfV light, or etching by a dry
etching method such as RIE (reactive ion etching), etc. Furthermore, the concave-convex
pattern which has been subjected to such an etching may be subjected to the heating
process. Morêover, based on the concave-convex pattem formed by the BÇP thermal
annealing method or the BCP solvent annealing method, it is possible to form a
concave-convex pattern in which concavities and convexities have further deeper depth,
with a method as descrìbed in "Advanced Materials" 2012,vol.24, pp. 5688-5694,
"Science", vol.322,vol. 429 (2008), etc. Namely, a base material layer formed of SiO2,
Si, etc. is coated with a bloci copolymer, and a self-organ izationstructure of the block
copolymer is formed by the BCP thermal annealing method or the BCP solvent annealing
method. Then, one of the segments of the block copolymer is selectively etched away.
The other segment, as the remaining segment, is used as a mask to perform etching for the
base material layer, thereby forming a groove (concavity or concave portion) having a
desired depth in the base material layer.
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[007U Instead of using the above-described BCP thermal annealing method; the BKL
method and the BCP solvent annealing method, the photolithography method may be used
to form the concave-convex pattern. Other than these, the concave-convex pattern ofthe
master block can be produced, for example, also by 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 a fine-processing method using the selÊorganization or
self-assembly of fine particles, etc. In a case of manufacturing a film member having a
concave-convex pattern composed oflinear or curved-shaped convexities and concavities
extending in a uniform direction, it is allowable to form a master block having the
concave-convex pattern composed ofthe linear or curved-shaped convexities and
concavities extending in the uniform direction, with the these methods.
100721 After forming the master block with the concave-convex pattern by means of the
BCP thermal annealing method, the BKL method or the BCP solvent annealing method,
etc., further, a mold to which the pattern is transferred 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
pattern thereon, by means of non-electrolytic plating, sputtering, vapor deposition, or the
like. The thickness of the seed layer is preferably not less than 10 nm to uniformize a
current density during the subsequent electroforming process, and thereby making the
thickness of a metal layer accumulated by the subsequent electroforming process be
uniform. As the material of the seed layer, it is possible to use, 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, or alloy thereof.
Subsequently, a 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 pm to 30000 pm. As the material of the
metal layer accumulated by the electroforming, it is possible to use any of the metal
species as described above which can be used as the seed layer. Considering ease of the
subsequent processes for forming the mold such as pressing with respect to the resin layer,
releasing (peeling-off), and cleaning (washing), the formed metal layer desirably has
appropriate hardness and thickness.
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[0073] The metal layer including the seed layer obtained as described above is released
(peeled off) from the master block having the concave-convex structure to obtain a metal
substrate. As the releasing method, the metal layer may be peeled off physically, or the
materials composing the paffern of the master block may be dissolved to be removed by
using an organic solvent dissolving them, such as toluene, tetrahydrofuran (THF), and
chloroform. When the metal substrate is peeled off from the master block, a remaining
material component on the metal substrate can be relnoved by cleaning. Aq the cleaning
method, it is possible to use wet cleaning using a surfactant etc., or dry cleaning using
ultraviolet rays and/or plasma. Alternatively, for example, it is allowable to use an
adhesive agent or a bonding agent such that the remaining material component is caused to
attach or adhere to the adhesive agent or the bonding agent then is removed. Accordingly,
the metal substrate (metal mold) which can be obtained in such a manner and to which the
pattern has been transferred from the master block may be used as the mold for
concave-convex pattern hansfer of the embodiment.
100741 Further, a flexible mold such as a film-shaped mold can be produced by using the
obtained metal substrate and by transferring the concave-convex structure (pattern) of the
obtained metal substrate to a film-shaped supporting substrate. For example, after a
curable resin is applied on the supporting substrate (the supporting substrate is coated with
the curable resin) to form a resin layer, the resin layer is cured while the concave-convex
structure of the metal substrate is being pressed against the resin layer. The supporting
substrate is exemplified, for example, by base members made of inorganic materials such
as glass, quartz (quartzglass), silicon, etc.; base members made of organic materials such
as silicone resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN),
polycarbonate (PC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA),
polystyrene (PS), polyimide (PI), polyarylate, etc.; and metallic materials such as nickel,
copper, aluminum, etc. The thickness of the supporting substrate may be in a range of 1
pm to 500 pm.
[0075] The curable resin can be exemplified by various resins including, for example,
monomers, oligomers, and polymers of those based on epoxy, acryl, methacryl, vinyl ether,
oxetane, urethane, melamine, urea, polyester, polyolefin, phenol, cross-linking type liquid
crystal, fluorine, silicone, polyamide, etc. The thickness of the curable resin is preferably
in a range of 0.5 prn to 50O pm. In a case that the thickness is less than the lower limit,
heights of the concavities and convexities formed on the surface of the cured resin layer
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are likely to be insuf'ficient. On the other hand, in a case that the thickness exceeds the
upper limit, the influence of volume change of the resin upon curing is likely to be so large
that there is such a possibility that the formation of the shape of the concavities and
convexities might be unsatisfactory.
[0076] As a method for coating the supporting substrate with the curable resin, it is
possible to adopt, for example, various coating methods such as the spin coating method,
spray coating method, dip coating method, dropping method, gravure printing method,
screen printing method, relief printing method, die coating method, curtain coating method,
ink-jet method, and sputtering rnethod. Further, although the condition for curing the
curable resin varies depending on the kind of the resin to be used, the curing temperature is
preferably for example in a range of the room 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 ray such as ultraviolet
light or electron beam. In such a case, the amount of the irradiation is preferably in a
range of 20 mJ/cm2 to 5 Jlcm2.
[00771 Subsequently, the metal substrate is detached from the curable resin layer after the
curing. The method for detaching the metal substrate is not limited to a mechanical
releasing (exfoliating or peeling off) method, and a publicly known method can be adopted.
Accordingly, a film-shaped resin mold, which can be obtained in such a manner and which
has the cured resin layer having the concavities and convexities and formed on the
supporting substrate, may be used as the mold for concave-convex pattern transfer of the
embodiment
[0078] Furthe¡ it is possible to coat the concave-convex structure (pattern) of the metal
substrate obtained in the above-described manner with a rubber-based resin material, to
cure the coated resin material, and to release the cured resin material from the metal
substrate, so as to manufacture a rubber mold having the concave-convex pattern of the
metal substrate transferred thereto. The obtained rubber mold may be used as the mold
for concave-convex pattern transfer of the embodiment. Silicone rubber or a mixture or
copolymer of silicone rubber and another material is particularly preferably used as the
rubber-based resin material. The usable silicone rubber is exemplified, for example, by
polyorganosiloxane, cross-linking type polyorganosiloxane, a
polyorganosiloxane/polycarbonate copolymer, a polyorganosiloxane/polyphenylene
copolymer, a polyorganosiloxaneþolystyrene copolymer, polytrimethyl-silylpropyne,
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poly-4-methyl pentene, etc. The silicone rubber is more inexpensive than other resin
materials; has superior heat resistance, high heat conductivity, and elasticity; and the
silicone rubber is less likely to be àeformed under a high temperature condition. Thus,
the silicone rubber is suitable for the transfer process for concave-convex pattern under the
high temperature condition. Further, since the silicone rubber-based material has lrigh
perrneability of gas and water vapor, a solvent and water vapor of a material to be
subjected to transfer can go through or permeate the silicone rubber material easily.
Therefore, the silicone rubber-based material is suitable for such a case of using the rubber
mold for the purpose of transferring the concave-convex pattern to a film of the precursor
of the inorganic material as described above. Further, it is preferred that the surface free
energy of rubber-based material be not more than 25 mN/m. With this, it is possible to
obtain a superior mold-releasing properly during the transfer of the concave-convex pattern
of the rubber mold to the coating film on the base member, thereby making it possible to
prevent any transfer failure. The rubber mold may have, for example, a length in a range
of 50 mm to 1000 mm, a width in a range of 50 mm to 3000 mm, and a thickness in a
range of I mm to 50 mm. Further, a mold-release treatment may be performed on the
surface ofthe concave-convex pattern ofthe rubber mold as needed.
[0079] [Light Emitting Element]
Next, an explanation will be given about an embodiment of a light emitting
element produced by using a substrate having the concave-convex structure of the
above-described embodiment. As depicted respectively in Figs. 4(a) and 4(c), light
emitting elements 200,200a and 200b, of the embodiment, each include a first electr ode 92,
an organic layer 94 and a second electrode 98 in this order on a film member 100 having a
concave-convex structure (concave-convex pattern) 80 and formed of a base member 40, a
gas barrier layer 30 and a concave-convex structure layer 60.
[0080]
The first electrode 92 may be a transparent elechode so that the light from the
organic layer 94 formed on the first electrode 92 passes toward the base member 40. It is
preferred that the first electrode 92be stacked such that the surface of the first electrode 92
maintains or shows the concave-convex structure (concave-convex pattern) 80 formed in
the surface of the concave-convex structure layer 60. Note that the arrangement and the
shape of the first electrode 92 inthe XY direction are not particularly limited.
[008U Those usable as the material of the first electrode 92 include, for example, indium
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oxide, zinc oxide, tin oxide, indium-tin oxide (ITO) which is a composite material thereof,
gold, platinum, silver, and copper. Among these materials, ITO is preferable from the
viewpoint of transparency and electrical conductivify. The thickness of the first electrode
92 is preferably within a range of 20 nm to 500 nm.
[0082]
The organic layer 94 is formed on the first electrode 92. The organic layer 94 is
not particularly limited, provided that the organic layer 94 is usable as an organic layer of
the organic EL element. As the organic layer 94, any publicly known organic layer can
be used as appropriate.
t0083ì The surface of the organic layer 94 (interface between the organic layer 94 and the
second electrode 98) may maintain the shape of the concave-convex pattern 80 formed in
the surface ofthe concave-convex structure layer 60, as depicted in Fig. 4(a).
Alternatively, the surface of the organic layer 94 may be flat without maintaining the shape
ofthe concave-convex pattern 80 formed in the surface ofthe concave-convex structure
layer 60, as depicted in Fig. 4(b). In a case that the surface ofthe organ ic layer 94
maintains the shape of the concave-convex pattern 80 formed in the surface of the
concave-convex structure layer 60, the plasmon absorption by the second electrode 98 is
reduced, tlrus improving the light extraction effìciency. Here, those usable as the material
of the hole transporting layer include, for example, aromatic diamine compounds such as
phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives,
N,N'-bis(3-methylphenyl)-( l, 1'-biphenyl)- 4,4' -diamine (TPD), and
4,4'-bisfN-(naphthyl)-N-phenyl-aminolbiphenyl(u-NPD); oxazole; oxadiazole; rriazole;
imidazole; imidazolone; stilbene derivatives;pyrazoline derivatives; tetrahydroimidazole;
polyarylalkane; butadiene; and
4,4',4"-tris(N-(3-methylphenyl)N-phenylamino)triphenylamine (m-MTDATA). The
examples of materials of the hole transporting layer, however, are not limited to the
above-described materials. The light emitting layer is provided in order that a hole
injected from the first electrode 92 and an 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, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline,
bisstyryl, cyclopentadiene, and aluminum-quinolinol complex (Alq3);
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tri-(p{erphenyl-4-yl)amine; I -aryl-2,5 -di(2-thienyl) pyrrole derivatives; pyran;
quinacridone; rubren; distyrylbenzene derivatives; distyryl arylene derivatives; distyryl
amine derivatives; and various fluorescent pigments or dyes. Further, it is also preferred
that lighlemitting materials selected from the above compounds be mixed as appropriate
and then used. Funthermore, it is possible to preferably use a material system generating
emission of light from a spin multiplet, such as a phosphorescence emitting material
generating emission of phosphorescence and a compound including, in a part of the
molecules, a constituent portion formed by the above materials. The phosphorescence
emitting material preferably includes heavy metal such as iridium. A host material
having high camier mobility may be doped with each of the light-emitting materials as a
guest material to generate the light emission using dipole-dipole interaction (Forster
mechanism) or electron exchange interaction (Dexter mechanism). Those usable as the
material of the electron transporting layer include, for example, heterocyclic
tetracarboxylic anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone
derivatives, thiopyran 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 (Alq3).
Further, in the oxadiazole derivatives mentioned above, it is also possible to use, as an
electron transporting material, thiadiazole derivatives in which oxygen atoms of oxadiazole
rings are substituted by sulfur atoms, and quinoxaline derivatives having quinoxaline rings
known as electron athactive 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 macromolecule. Note that the hole
hansporting layer or the electron transporting layer may also function as the light-emitting
layer.
[0084] Further, from the viewpoint of facilitating the electron injection from the second
electrode 98, a layer made of a metal fluoride or metal oxide such as lithium fluoride (LiF)
or Li2O3, a highly active alkaline earth metal such as Ca, Ba, or Cs, an organic insulating
material, or the like may be provided as an electron injection layer befween the organic
layer 94 and the second electrode 98. Furthermore, from the viewpoint of facilitating the
hole injection from the first elechode 92, it is allowable to provide, as a hole injection layer
between the organic layer 94 and the first electrode 92, alayer made of triazol derivatives,
oxadiazole derivative, imidazole derivative, polyarylalkane derivatives, pyrazoline and
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pyrazolone derivatives, pheny'lenediarnine derivative, arylamine derivatives,
amino-substituted calcone derivatives, oxazole derivatives, styrylanthracene derivatives,
fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives,
aniline-based copolymers, or electroconductive high-molecular oligomar, particularly
thiophene oligomer.
t00851 Moreover, in a case that the organic layer 94 is a stacked body formed of the hole
transporting layer, the light emitting layer, and the electron transporting layer, the
thicknesses of the hole transporting layer, the light emitting layer, and the electron
transporting layer are preferably within a range of 1 nm to 200 nm, a range of 5 nm to 100
nm, and a range of 5 nm to 200 nm, respectively.
[00861
The second electrode 98 is formed on the organic layer 94. As the material of
the second electrode 98, a substance having a small work function can be used as
appropriate, although the material of the second electrode 98 is not particularly limited to
this. For example, the second electrode 98 may be a metal electrode using aluminum,
MgAg, MgIn, AlLi, or the like. The thickness of the second electrode 98 is preferably in
a range of 50 nm to 500 nm. The second electrode 98 may be stacked such that the
surface of the second electrode 98 maintains or shows the concave-convex structure
(concave-convex pattern) 80 formed in the surface ofthe concave-convex structure layer
60.
t00871 Further, as depicted in Fig. 4(c), the light emitting element 200b may have an
optical functional layer 22 on a surface (surface serving as a light extraction surface of the
light emitting element), of the base member 40, on a side opposite to the surface thereof
having the gas barrier layer 30 formed thereon. By providing such an optical functional
layer22 on the surface ofthe base film 40, it is possible to suppress any total reflection of
a light passing through the inside of the base member 40 at the interface of the base
member 40 (including the optical functional layer 22) and the air, thereby making it
possible to improve the light extraction efficiency. Such an optical functional layer 22
may be exemplified by a substance usable for extracting light from the light emitting
element, although the optical functional layer 22 is not particularly limited 1o this. It is
possible to use any optical member having a structure capable of controlling the refraction
of light, light condensing, light diffusion (light scattering), light diffraction, light reflection,
etc., and of extracting the light to the outside of the element. As such an optical
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functional layer 22, it is allowable to use, for example, a variety of kinds of lens members
such as a convex lens such as semicircular lens, a concave lens, a Fresnel lens, a prism lens,
a columnar lens, a lenticular-typed lens, a micro lens formed of a concave-convex layer
which can be formed with a method similar to the method for producing the film member
having the concave-convex structure layer as described above, etc.; a diffusion sheet and a
diffusion board each including a transparent body and a dispersing agent kneaded in the
transparent body, a diffusion sheet and a diffusion board each having a concave-convex
structure (concave-convex pattern) formed in a surface thereof; a diffraction grating, a
member having an anti-reflection function; and the like. Among the above-described
members or lenses, the lens member is preferred from the viewpoint of realizing more
efficient light extraction. Further, as such a lens member, a plurality of lens members
may be used; in such a case, fine or minute lens members are aligned to form a so-called
micro lens (anay). Any commercially available product may be used as the optical
functional layer 22.
[0088] Note that although Fig. a(c) depicts the light emitting element 200b wherein the
optical functional layer 22 is provided on an outside surface of the substrate 40 of the light
emitting element 200 depicted in Fig. 4(a), it is also allowable to provide the optical
functional layer22 on an outside surface of the substrate 40 of the light emitting element
200b depicted in Fig. 4(b).
[00891 Further, since the second electrode 98 is a metallic electrode, it is allowable to
provide a polarizing plate on the second electrode 98, as a countermeasure for the mirror
reflection for the second electrode 98. Furthermore, it is also allowable to seal the
surrounding of each of the light emitting elements 200,200a and 200b, with a sealing
material, for the purpose of preventing any deterioration of each of the light emitting
elements 200,200a and 200b due to the moisture and/or oxygen.
[0090] Since the film member 100 used in the light emitting elements 200,200aand 200
of the embodiment includes the gas barrier layer 30 and the concave-convex structure layer
60 which are made of the inorganic material, the film member 100 has excellent
heat-resisting property, mechanical strength and chemical resistance as well. Accordingly,
in the manufacturing process of the light emitting elements 200,200a and 200b, the film
member 100 is capable of sufficiently withstanding the film forming step performed in a
high-temperature atmosphere, a cleaning step using UV/O3 cleaning, brushing or various
kinds of cleaning fluids such as acid, alkaline solvent, etc.; and a patteming step using a
/3É3+
ai
)1:
a{
6
ll
developer (developing solution)' and/or an etchant. Further, since the gas barrier layer 30
and the concave-convex structure layer 60 are made of the inorganic material, it is possible
to prevent the deterioration of the light emitting elements 200,200aand 200b due to the
moisture and/or oxygen, thereby allowing the light emitting elements 200,200a and 200b
to have a long service life. Further, since the surface 30a, ofthe gas barrier layer 30,
which makes contact with the concave-convex structure layer 60, is made of an inorganic
material same as the material of the concave-convex structure layer 60, the adhesion
property between the gas barrier layer 30 and the concaVe-convex structure layer 60 is
particularly excellent, thereby preventing the moisture and/or oxygen from leaking through
the interface between the gas barrier layer 30 and the concave-convex structure layer 60,
allowing the light emitting elements 200,200aand 200b to have a further long service life.
Furthermore, by using the precursor of the inorganic material for forming the
concave-convex structure layer, it is possible to form the concave-convex pattern ofthe
concave-convex structure layer by means ofthe roll process accurately and assuredly,
thereby making it possible to manufacture the fîlm member with a high throughput.
EXAMPLES
t009U In the following description, the film member according to the present invention
will be specifically explained with an example and comparative examples. The present
invention, however, is not limited to the example and comparative examples. In Example
1 and Comparative Examples I and2, film members each having a concave-convex pattern
(concave-convex structure) were manufactured, respectively, and light emitting elements
were manufactured by using the respective film members. Then, deterioration evaluation
in a high humidity environment was conducted for each of the light emitting elements.
Further, test pieces were manufactured to evaluate the adhesion property between the gas
barrier layer and the concave-convex structure layer in Example I and Comparative
Examples 7 and2, respectively.
[00921 Example I
[Evaluation of Adhesion Property]

In order to produce a test piece to be used for the evaluation ofadhesion property
between the gas banier layer and the concave-convex structure layer, acoating liquid
.:
f"z/ s
serving as the raw materialof the gas barrier layer was prepared in the following manner.
Namely, 25 g of ethyl silicate, 25 g of ethanol, 1.86 g of 2N Hydrochloric Acid and 1 .51 g
of water were mixed to obtain a mixture thereof and the mixture was stirred at 80'C for I
hour to 2 hours. In this situation, the molar ratio of the ethyl silicate to the water in the
mixture was I :1.51. 2.5 g of epoxysilane was mixed to the mixture, and was stirred.
Afterwards, 17.4 g of a PVA aqueous solution of which concentration was l0% was added
to the mixture, and was further stirred for t hour to 2 hours; at a point of time when the
mixture became transparent, 0.1 g of an ethanol solution of N,N- dimethylbenzylamine of
which concentration was 32Yo by mass was added to the mixture, w¿¡s further stirred, and a
coating liquid was obtained. As the base member, a PET film (Cosmoshine A-4300
manufactured by TOYOBO CO., LTD.) having a thickness of 100 pm \¡/as used, and was
coated with the coating liquid by using a gravure coater at a running speed of 80 m/minute,
followed by being dried at a temperature of 135oC. In this manner, a SiOx layer having a
thickness of I pm was obtained as the gas barrier layer on the film base member.
[00931 The film base member having the gas barrier layer formed thereon was subjected
to cutting out, and two pieces of a film base member having a size of 100 mm x 180 mm
were produced. One of the two film base members w¿rs adhered, with a kapton tape, to a
glass substrate of which size was 200 mm x 200 mm. The film base member was adhered
to the glas's substrate so that a surface, of the film base member, on the side opposite to
another surface thereof having the gas barrier layer formed thereon faced (was opposite to)
the glass substrate, and that the entirety of the film base member was located on the glass
substrate.
[0094ì In this example, since the concave-convex structure layer was formed by the
sol-gel method, a solution of the precursor of the inorganic material (sol-gel material
solution) was prepared by the following manner. Namely, 0.75 mol of tetraethoxysilane
(TEOS) and0.25 mol of dimethyldiethoxysilane (DMDES) were added by dropping to a
liquid obtained by mixing22mol of ethanol,5 mol ofwater,0.004 mol of concentrated
hydrochloric acid and 4 mol of acetylaceton. Further, as an additive, 0.5 wtolo of a
surfactant 5-386 (manufacture by SEIMI CHEMICAL CO., LTD) was added, followed by
being stirred for two hours at a temperature of 23"C and a humidity of 45Yo, and thus a
precursor of SiOz (sol-gel material solution) was obtained. The sol-gel material solution
was dropped (dripped) onto the film base member adhered to the glass substrate, was
subjected to the spin coating, and a sol-gel material layer having thickness of 300 nm was
/33{ 1
formed. As a spin coater, ACT-3OODII (manufactured by ACTIVE, CO., LTD.) was used.
Note that the thickness of the coating film was evaluated by an automatic thin-film
measuring apparatus Auto SE manufactured by HORIBA, Ltd.
[0095] After leaving the film base member, having the sol-gel material layer formed
thereon, as it is for I minute at a temperature of 25"C, the other (remaining) one of the two
film base members each having the size of 100 mm x 180 mm was overlaid (overlapped)
with a surface of the sol-gel material layer. At this time, the two film base members were
overlaid with each other such that the sol-gel material layer was sandwiched between the
gas barier layers, namely, such that the suràce, of one of the two film base membe¡s, on
which the sol-gel material layer was formed, faced (was opposite to) the surface, of the
other of the two fìlm base members, on which the gas barrier layer was formed. This test
piece was stationarily placed (allowed to stand still) for 1 minute on a hot plate of which
temperature was 100oC, and the sol-gel material layer was thus cured, thereby forming a
SiO* layer. Next, the overlaid two film base members were taken out from the glass
substrate, and were subjected t9 cutting out so that a strip-shaped test piece of which size
was 25mm x 180mm was obtained. In such a manner, the test piece having a
configuration of the film base memberþas barrier layer (SiO¡ layer)/sol-gel material layer
(SiOx layer)/gas barrier layer (SiO¡ layer)/film base member, was obtained.
[0096]
When the obtained test piece was peeled from one end portion thereof at a speed
of 100 mm/min in a 180-degree direction (peeled in a T-shaped manner), the film base
member was torn, but any peeling did not occur between any layers including between the
gas banier layer and the sol-gel material layer. The peel strength at this time was
measured by a tensile tester (model name: Strograph E-L; manufactured by TOYO SEIKI
SEISAKU-SHO, LTD.), and the measured value fluctuated between 50 N/m and 80 N/m.
Accordingly, it was appreciated that the adhesion force between the gas barrier layer and
the sol-gel material layer exceeded 20 N/m.
[0097] [Manufacture of Light Emitting Element]

At first, a film mold having a concave-convex surface was produced by the BCP
solvent annealing method in order to produce a film member provided with a
concave-convex structure and to be used as a diffraction grating of a light emitting element.
There was prepared a block copolymer manufactured by POLYMER SOURCE INC., and
Y+"
made of polystyrene (hereinafter referred to as "PS" in an abbreviated manner as
appropriate) and polymethyl methacrylate (hereinafter referred to as "PMMA" in an
abbreviated manner as appropriate) as described below.
Mn of PS segment:680,000
Mn of PMMA segment:580,000
Mn of block copolymer : 1,260,000
Volume ratio befween PS segment and PMMA segment (PS:PMMA): 5l:43
Molecular weight distribution (Mw/Mn) :1.28
Tg of PS segment: 107'C
Tg of PMMA segment:134"C
[0098ì The volume ratio between the PS segment and the PMMA segment (the PS
segment: the PMMA 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 g/" t . The number average molecular weights (Mn) and the weight average
molecular weights (Mw) of polymer segments or polymers were measured by using a gel
permeation chromatography (Model No.: "GPC-8020" manufactured by TOSOH
CORPORATION, in which TSK-GEL SuperH1000, SuperH2000, SuperH3000, and
SuperH4000 were connected in series). The glass transition temperatures (Tg) of the
polymer 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 temperature rise of 20"C/min over a temperature range
of OoC to 200"C. The solubility parameters of polystyrene and polymethyl methacrylate
were 9.0 and 9.3 respectively (see "Kagaku Binran Ouyou Hen" (Handbook of Chemistry,
Applied Chemistry), Revised 2nd edition)
[0099| Toluene was added to 230 mg of the block copolymer and 57.5 mg of
Polyethylene Glycol2050 (average Mn = 2050) manufactured by SIGMA-ALDRICH Co.
LLC. as polyethylene oxide so that the total amount thereof was 15 g, followed by
dissolving the mixture. Accordingly, a solution of the block copolymer was prepared.
[0100] The solution of the block copolymer was filtered through a membrane filter
having a pore diameter of 0.5 ¡rm to obtain a block copolymer solution. A glass substrate
was coated with a mixed solution containing 1 g of KBM-5103 manufactured by
SHIN-ETSU SIICONE (SHIN-ETSU CIIEMICAL, CO., LTD.), I gof ion-exchanged
water, 0.1 ml of acetic acid, and l9 g of isopropyl alcohol, by means of the spin coating
::
{+,
(which was perfonned for i0 seconds with rotation speed of 50û rpm, and then performed
continuously for 45 seconds with rotation speed of 800 rpm). The glass substrate was
treated for I 5 minutes at 13OoC, and thus a silane coupling treated glass was obtained.
The silane coupling treated glass as the base member was coated with the obtained block
copolymer solution by means of the spin coating to provide a thickness in a range of 140
nm to 160 nm. The spin coating was performed for l0 seconds at a rotation speed of 200
rpm and then was performed for 30 seconds at a rotation speed of 300 rpm.
[0101] 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 on the surface of the thin film after
the solvent annealing process, and it was found that the block copolymer forming the thin
film underwent the micro phase separation. The cross section of the thin film was
observed by using a transmission electron microscope (TElvÐ (H-7100F4 manufactured by
HITACHI, LTD.). As a result, the circular cross section of the PS portion was aligned in
two tiers (stages or rows) in a direction perpendicular to the surface of the substrate (height
direction) while the circular cross sections of the PS portion were separated from each
other in a direction parallel to the surface of the substrate. When considering together
with an analysis image obtained by using an atomic force microscope, it was revealed that
the PS portion was subjected to the phase separation to form a horizontal cylinder structure
from the PMMA portion. A state was given, in which the PS portion existing as the core
(island) was surrounded by the PMMA portion (sea).
[0102] About 20 nm of a thin nickel layer was formed as a current seed layer by
performing the sputtering on the surface of the thin film processed to have the wave-like
shape by means ofthe solvent annealing process as described above. Subsequently, the
base member equipped witlr the thin film was immersed in a nickel sulfamate bath and
subjected to an electroforming process (maximum current density: 0.05 Alcm2) at a
temperature of 50'C so as to precipitate nickel until the thickness thereof became 250 pm.
The base member equipped with the thin 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 tetrahydrofuran solvent for 2 hours, and
!
'{
t:
y'+,
irt
t:
rf
iF$
t;
n
:'ì
,t}'
i:_
then the nickel electrofonning 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
polymer component(s) adhered to a part of the surface of the electroforming body was
(were) removed. After that, the nickel electroforming body was immersed 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 50"C. Thereafter, the UV ozone
treatment was applied to the nickel electroforming body for l0 minutes.
[0103] Subsequently, the nickel electroforming body was immersed in HD-210lTH
manufactured by DAIKIN CHEMICALS SALES, CO., LTD. for about I minute and was
dried, and then stationarily placed overnight. The next day, the nickel electroforming
body was immersed in HDTH manufactured by DAIKIN CHEMICALS SALES, CO.,
LTD. and was subjected to an ultrasonic cleaning (washing) process for about 1 minute.
In such a manner, a nickel mold for which a mold-release treatment had been performed
was obtained.
[0104] Subsequently, a PET substrate (COSMOSHINE A-4100 manufactured by
TOYOBO CO., LTD.) was coated with a fluorine-based UV curable resin. The
fluorine-based UV curable resin was cured by irradiation with ultraviolet light at 600
mJ/cmz while the nickel mold was pressed thereagainst. After curing of the resin, the
nickel mold was exfoliated or peeled offfrom the cured resin. Accordingly, the film mold,
which was composed of the PET substrate with the resin film to which the surface profile
(surface shape) of the nickel mold was transferred, was obtained.
t01051
In a similar lnanner as the manufacture ofthe test þiece for the evaluation test for
the adhesion properfy, a gas barrier layer (SiO¡ layer) was formed on a film base member,
and was coated with the sol-gel material solution. After the elapse of 60 seconds from the
coating of the gas banier layer with the sol-gel material solution, the film mold
manufactured as described above was overlaid to and pressed against a sol-gel material
layer, formed on the base member, by use of the pressing roll heated to 80'C. After the
completion of the pressing with the film mold, the film mold was released or peeled off
from the sol-gel material layer, and then the sol-gel material layer was heated at a
temperature of 300"C for 60 minutes by using an oven, to thereby cure the sol-gel material
layer. In such a manner, a concave-convex structure layer made of the sol-gel material
layer (SiO¡ layer) having the concave-convex pattern of the filrn mold transferred thereto
{+z
was formed, and a filnr member in which the gas barrier layer and the concave-convex
structure layer were provided in this order on the film base member was formed. Note
that as the pressing roll, there was used a roll which included a heater therein and had the
outer circumference covered with heat-resistant silicon of a thickness of 4 mm, the roll
having a diameter (q) of 50 nrm and a length of 350 mrn in an axial direction of the shaft.
[0f 06] An analysis image of the shape of the concavities and convexities on the surface
ofthe concave-convex pattern ofthe concave-convex structure layer was obtained by using
an atomic force microscope (a scanning probe microscope equipped with an environment
control unit "Nanonavi II Station/E-sweep" manufactured by HITACHI HIGH-TECH
SCIENCE CORPORATION). Analysis conditions of the atomic force microscope were
as follows.
Measurement mode: dynamic force mode
Cantilever: SI-DF4O (material: Si, leverwidth: 40 pm, diameter of tip of chip: l0
nm)
Measurement atmosphere: in air
Measurement temperature : 25" C
[01071
A concavity and convexity analysis image was obtained as described above by
performing a measurement in a ra4domly selected measuring region of 10 pm square
(length: 10 pm, width: l0 ¡rm) at an arbitrary position in the concave-convex structure
layer. Distances between randornly selected concave portions and convex portions in the
depth direction were measured at not less than 100 points in the concavity and convexity
analysis image, and the average of the distances was calculated as the average depth of the
concavities and convexities. The average depth ofthe concave-convex pattern ofthe
concave-convex structure layer obtained by the analysis image in this example was 70 nm.
[0f0q
A concavity and convexity analysis image was obtained as described above by
performing a measurement in a randomly selected measuring region of l0 pm square
(length: 10 pm, width: 10 pm) in the concave-convex structure layer. The obtained
concavity and convexity analysis image was subjected to the flat processing including
primary inclination corection, and then subjected to the two-dimensional fast Fourier
transform processing. Thus, a Fourier-transformed image was obtained. It was
confirmed that the Fourier-transformed image showed a circular pattern substantially
{aa
centered at an origin at which an absolute value of wavenumber was 0 pm-I, and that the
circular pattern was present within a region where the absolute value of wavenumber was
in a range of not more than l0 pm-I.
[0109] The circular pattern of the Fourier-transformed image is a pattern observed due to
gathering of bright spots in the Fourier-transformed image. The term "circular" herein
means that the pattern of the gathering of the bright spots looks like a substantially circular
shape, and is a concept further including a case where a part of the contour of the circular
pattern looks like a convex shape or a concave shape. The pattern of the gathering of the
bright spots may look like a substantially annular shape, and this case is expressed as the
term "annular". It is noted that the term "annular" is a concept further including a case
where a shape of an outer circle or inner circle of the ring looks like a substantially circular
shape and a c¿ße where a part of the contour of the outer circle or the inner circle of the
ring looks like a convex shape or a concave shape. Regarding the relationship between
the pattern of the concave-convex structure and the Fourier-transformed image, the
followings have been revealed. Namely, in a case that the concave-convex structure itself
has neither the pitch distribution nor the directivity, the Fourier-transformed image appears
to have a random pattern (no pattern). On the other hand, in a case that the
concave-convex structure is entirely isotropic in an XY direction but has the pitch
distribution, a circular or annular Fourier-transformed image appears. Further, in a case
that the concave-convex structure has a single pitch, the annular shape appeared in the
Fourier-transformed image tends to be sharp.
101101 The two-dimensional fast Fourier transform processing on the concavify and
convexity analysis image can be easily performed by elechonic image processing by using
a computer equipped with software for the two-dimensional fast Fourier transform
processing.
[011U
A concavity and convexity analysis image was obtained as described above by
pelforming a measurement in a randomly selected measuring region of l0 pm square
(length: l0 pm, width: l0 pm) in the concave-convex structure layer. Distances between
randomly selected adjacent convex portions or between randomly selected adjacent
concave portions were measured at not less than 100 points in the concavity and convexity
analysis image, and the average of the distances was calculated as the average pitch of the
concavities and convexities. The average pitch ofthe concave-convex pattern ofthe
¡
f+t
f
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¿,"tff
$
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:I
à
ii,
;
concave-corlvex structure layer calculated using the analysis image obtained in this
example was 900 nm.
[0112]
A concavity and convexity analysis image was obtained by performing a
rneasurement in a randomly selected measuring region of l0 ¡rm square (length: 10 ¡rm,
width: 10 pm) in the concave-convex structure layer. While doing so, the data of the
depth of concavities and convexities was determined at each of not less than 16,384
(vertical: 128 points x horizontal: 128 points) measuring points in the measuring region on
tlre nanometer scale. By using E-sweep in this example, a measurement at 65,536 points
(vertical: 256 points x horizontal: 256 points) (a measurement with a resolution of 256
pixels x 256 pixels) was conducted in the measuring region of 10 pm square. V/ith
respect to the depth of concavities and convexities (unit: nm) measured in such a manner,
at first, a measurement point "P" was determined, among all the measurement points,
which was the highest from the surface of the substrate. Then, a plane which included the
measurement point P and which was parallel to the surface of the substrate was determined
as a reference plane (horizontal plane), and a depth value from the reference plane
(difference obtained by subtracting, from the value of height from the substrate at the
measurement point P, the height from the substrate at each of the measurement points) was
obtained as the data of depth of concavities and convexities. Note that such a depth data
of the concavities and convexities was able to be obtained, for example, by performing
automatic calculation with software in the E-sweep, and the value obtained by the
automatic calculation in such a manner was able to be utilized as the data of depth of
concavities and convexities. After obtaining the data of depth of concavity and convexity
at each of the measurement points in this manner, the average value (m) of the depth
distribution of the concavities and convexities was able to be determined by calculation
according to the following formula (I):
[0113ì [Formula I]
7îe-*Ë*, (t)
i:l
The average value (m) of depth distribution of concavities and convexities of the
concave-convex structure layer obtained in this example was 70 nm.
N+^
[01141
Similar to the method for measuring the average value (m) of the depth
distribution, the data of depth of the concavities and convexities were obtained by
performing a measurement at not less than 16,384 measuring points (vertical: 128 points x
horizontal: 128 points) in a measuring region of l0 pm square of the concave-convex
structure layer. In this example, a measurement was performed adopting 65,536
measuring points (vefical: 256 points x horizontal: 256 points). Thereafter, the average
value (m) of the depth distribution of the concavities and convexities and the standard
deviation (o) of depth of the concavities and convexities were calculated based on the data
of depth of concavities and convexities of the respective measuring points. Note that it
was possible to determine the average value (m) by the calculation according to the
formula (I) as described above. On the other hand, it was possible to determine the
standard deviation (o) of depth of the concavities and convexities by calculation according
to the following formula (II):
[01151 [Formula II]
(r t)
In the formula (II), "N" represents the total number of measuring points (the
number of all the pixels), "x¡" represents the data of depth of the concavities and
convexities at the i{h measuring point, and "m" represents the average value of the depth
distribution of the concavities and convexities. The standard deviation (o1) of depth of
concavities and convexities in the concave-convex structure layer was 48.1 nm.
[0116]
The film member manufactured in the manner as described above was subjected
to cutting out to thereby obtain a film member having a size of 23 mm x 23 mm, and then a
light emitting element was manufactured such that an inner region, of the film member, of
which distance from the outer edge (outer peripheral area) of the film member was 6.5 mm
became a light emitting portion (having a light emitting area of 10 mm x 10 mm), in the
following manner. At first, an ITO film having a thickness of 72t nm was formed on the
concave-convex structure layer by the sputtering method. Then, a hole transporting layer
(4,4',4" his(9-carbazole)hiphenylamine, thickness: 35 nm), a light emitting layer
ìì
+X"-,,ú
/4 ø Ì+-+
rür-:.::.iia:::i;.,1:irì4¡:!,4¿i1-j:ì;'-,:
(tris(2-phenylpyridinato)iridium(III) complex-doped
4,4',4" tris(9-carbazole)tr iphenylam ine, th ickn ess : I 5 nm ;
tris(2-phenylpyridinato)iridium(IIf compl ex-doped
1,3,5-his(N-phenylbenzimidazole-2-yl)benzene, thickness: 1 5 nm), and an electron
transporting layer (1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene, thickness: 65 nm) were
each stacked, as the organic layer, by a vapor deposition method. Further, a lithium
fluoride layer (thickness: 1.5 nm) and a metal electrode (aluminum, thickness: 50 nm) were
deposited on the stacked body (organic layer). Accordingly, there was obtained a light
emitting element 200 in which the gas barrier layer 30, the concave-convex structure layer
60, a transparent electrode as the first electrode 92,The organic layer 94, and a metallic
electrode 98 as the second electrode were respectively formed on the film member 40, as
depicted in Fig. 4(a).
[01171 [Evaluation of Current Efficiency]
Regarding the light emitting element manufactured in Example l, the curent
efficiency at luminance of 1000 cd/m2 was obtained. The result of the current efficiency
is indicated in the table in Fig. 5. Regarding the light emitting element manufactured in
Example l, the curent efficiency was 98 cd/A.
[0118] Note that the current efüciency was measured by the following method. Namely,
voltage was applied to the light emitting element, and applied voltage V and electric
current I flowing through the light emitting element were measured by a voltage monitor
(model name: R6244 manufactured by ADC CORPORATION), and total luminous flux
amount L was measured by a total luminous flux measuring device manufactured by
SPECTRA CO-OP. The value of luminance (luminance value) L'was calculated from
the thus obtained values of the applied voltage V, the electric current I and the total light
flux amount L. Regarding the current efficiency, the following formula (Fl) was used to
calculate the current efficiency of the light emitting element:
Current Efficiency : (L' lI) x S ...(F1)
In the formula (Fl), S represents a light emitting area of the element. Note that
the value of the luminance L'was converted by the following formula (F2) whìle assuming
that the light distribution characteristic of the light emitting element follows the Lambert
law:
L' :LlnlS...(F2)
[01191 [Evaluation ofDeterioration]
/4+/ g
'ìläi
1.
$t' ;:
ij:
t:.
After the film formation of the second electrode, a sealing material (UV Resin
xNR 55162 manufactured by NAGASE CHEMTEX CoRpoRATIoN) \¡ias applied on
the outer peripheral portion (at a region not formed with the light emitting layer) of the
film member so that the width of the applied sealing material was approximately I mm.
The application of the sealing material was performed by using a dispense robot
(SHOTMASTER 300 manufacrured by MUSASHI ENGINEERING,INC.). Then, a
sealing glass manufactured by NSG PRECISION KABUSHIKI KAISHA was placed on
and pressed against the film member and the sealing material, and then the sealing material
was cured by irradiation with uV light at light intensity of 6 Jlcm2 by using a uV
irradiation light source apparatus of which center wavelength was 365 nrn.
[0120] Deterioration test in a high humidity environment was conducted as follows, by
using the light emitting element sealed in the above-described manner in Example l. At
first, voltage of 4 V was applied to the light ernitting element in an initial state, and the
number of dark spot in the light emitting area was counted. Next, the light emitting
element was stored in a thermohygrostat chamber in which the temperature was 50oC and
the humidity was 90%o. The applications of the voltage of 4 V to the light emitting
element were performed after 3 days and after 14 days, respectively, since the light
emitting element had been placed in the thermohygrostat chamber, and each time the
number of the dark spot in the light emitting area was counted. A case that the number of
dark spot was not more than 20 pieces was considered "pass", and a case that the number
of dark spot was more than 20 pieces and a case that the entire light emitting area was
non-luminous \ryere considered "failure". The results of evaluation are indicated in the
table of Fig. 5. Note that in Fig. 5, a case wherein the number of dark spot was 0 (zero)
was indicated by a mark "*"; a case wherein the number of dark spot was greater than 0
and not more than 20 was indicated by "1"; a case wherein the number of dark spot
exceeded 20 and the case wherein the entire light emittin gareawas non-luminous were
indicated by a mark "-". In the light emitting element produced in Example 1, the number
ofdark spot each at the initial state, after 3 days and after 14 days was 0, and passed the
evaluation.
I012Il Comparative Example I
[Evaluation of Adhesion Property]

A test piece used for the evaluation of adhesion property was manufactured in a
ì,
;-
r.i
:J
/4 { ¿Fî
similar manner to that in Example l, except that an AlOy layer was formed as the gas
barrier layer, rather than the SiO¡ layer. This test piece had a configuration composed of:
fìlm base member/gas barier layer (AlOy layer)/sol-gel material layer (SiOy layer)/gas
barrier layer (AlOy layer)ifilm base member. The gas barrier layer (AlOy layer) was
formed by the vapor deposition method as follows. At first, the film base member was
placed in a vacuum chamber, and the vacuum chamber was evacuated up to 3 X 10-4 Pa.
Afterwards, oxygen was introduced into the chamber by using a mass flow meter, and the
pressure inside the chamber was adjusted to 5 X 10-r Pa. An electron beam (EB) was
used to heat and melt an aluminum target. Then, a shutter (deposition shutter) on the
aluminum target was opened so as to start deposition of the AlOx onto the film base
member. During the deposition, the thickness of the film being formed was monitored by
a thickness meter with a crystal oscillator, and the vapor deposition was performed until
the AlOy layer with a 150 nm thickness was formed
I0l22l
The obtained test piece was subjected to the peeling test in,the T-shaped manner,
similarly to the peeling test conducted for Example 1, and the peel strength was measured
for Comparative Example 1. As the result of T-shaped peeling test, peeling occurred at
the interface between the gas barier layer (AlO¡ layer) and the sol-gel material layer
(SiOx layer). -The peel strength at this time was 4 N/m. Accordingly, it was appreciated
that the adhesion force between the gas barrier layer and the sol-gel material layer was 4
N/m, and that the adhesion force in Comparative Example I was weaker than in Example
1.
[0f æ] [Manufacture of Light Emitting Element]
A light emitting element was manufactured in a similar manner to that in
Example 1, except that an AIO¡ layer was formed as the gas barrier layer, rather than SiOy
layer. The gas barrier layer (AlOy layer) in Comparative Example I was formed in a
similar manner as that for forming the gas barrier layer of the test piece used for the
evaluation of adhesion property in the Comparative Example l.
101241 [Evaluation of Current Effrciency]
Regarding the light emitting element manufactured in Comparative F.xample l,
the current efficiency was obtained in a similar manner as in Example 1. The result of the
current efficiency is indicated in the table in Fig. 5. Regarding the light emitting element
manufactured in Comparative Example l, the current efficiency was 95 cdiA.
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[0125] [Evaluation ofDeterioration]
The light emitting element manufactured as described above was sealed in a
similar manner to that in Example 1, and the evaluation of deterioration was conducted for
the light emitting element in a similar manner as that in Example l. The results of
evaluation are indicated in the table of Fig. 5. In the light emitting element manufactured
in Comparative Example l, any dark spot was not present at the initial state, and passed the
evaluation. Although the dark spot occurred after 3 days since the light emitting element
had been placed in the thermohygrostat chamber, the number of dark spot was not more
than 20, and the light emitting element passed the evaluation. However, the dark spot of
which number exceeded 20 occurred afrer 14 days since the light emitting element had
been placed in the thermohygrostat chamber, and thus failed the evaluation.
10126l Comparative Example 2
[Evaluation of Adhesion Properfy]

A test piece used for the evaluation of adhesion property was manufactured in a
similar manner to that in Example 1, except that the gas barrier layer was not formed.
This test piece of Comparative Example 2had aconfiguration composed of: flrlm base
member/sol-gel material layer (SiOx layer)/film base member.
t0l27l
The obtained test piece was subjected to the peeling test in the T-shaped manner,
similarly to the peeling test conducted for Example 1, and the peel strength was measured
for Comparative Example 2. As the result of T-shaped peeling test, the film base member
was torn, but any peeling did not occur befween any layers. The measured value of the
peel strength at this time fluctuated between 50 N/m and 80 N/m. Accordingly, it was
appreciated that the adhesion force between the film base member and the sol-gel material
layer exceeded 20 N/m.
[01281 [Manufacture of Light Emitting Element]
A light emitting element was manufactured in Comparative Example 2, in a
similar manner to that in Example 1, except that the gas barrier layer was not formed.
101291 [Evaluation of Current Efficiency]
Regarding the light emitting element manufactured in Comparative Example 2,
the current efficiency was obtained in a similar manner as in Example 1. The result of the
current efficiency is indicated in the table in Fig. 5. Regarding the light emitting element
F,,
manufactured in Comparative Example 2,the current efficiency was 90cd/4.
[01301 [Evaluation ofDeterioration]
The light emitting element manufactured as described above in Comparative
Example 2 was sealed in a similar manner to that in Example l, and the evaluation of
deterioration was conducted for the light emitting element in a similar manner as that in
Example l. The results of evaluation are indicated in the table of Fig. 5. In the light
emitting element manufactured in Comparative Example 2, any dark spot was not present
at the initial state, and passed the evaluation. However, the entire light emitting area was
non-luminous both after 3 days and 14 days since the light emitting element had been
placed in the thermohygrostat chamber, and thus failed the evaluation.
[013U As indicated in the table of Fig. 5, comparison among the results of evaluation of
deterioration of Example I and Comparative Examples I and2 revealed that the light
emitting element having the gas barier layer formed of SiOx or AlOx had smaller
deterioration than the light emitting element not having the gas barrier layer. Further,
comparison befween the result of evaluation of deterioration of Example I and that of
Comparative Example I revealed that the light emitting element having the gas barrier
layer formed of SiOx had smaller deterioration than the light emitting element having the
gas banier layer formed ofAlOx. Furthermore, comparison between the result of
evaluation of adhesion property of Example I and that of Comparative Example I revealed
that the light emitting element having the gas barrier layer formed of SiOx had a higher
adhesion properly between the gas barrier layer and the sol-gel material layer than that in
the light emitting element having tlre gas banier layer formed of AlOx. From this
comparison, it is considered that in the film member having the concave:cofiv€X structure,
the adhesion property between the concave-convex structure layer and the gas barrier layer
can be improved by forming the surface, of the gas barrier layer, making contact with the
concave-convex structure layer, of SiOx which is the material same as that forming the
concave-convex structure layer. In a case thatthe surface, ofthe gas barrier layer, making
contact with the concave-convex structure layer is formed of the material same as that
forming the concave-convex structure layer, the adhesion force between the gas barrier
layer and the concave-convex structure layer is greater than 20 N/m, and thus the
concave-convex strucfure layer does not peel offfrom the gas barrier layer during
production of the film member, and can sufficiently withstand the producing process of
light emitting elements such as organic EL elements. Further, owing to the improved
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adhesion force between the concave-convex structure layer and the gas barrier layer, it is
possible to prevent any moisture and/or gas such as oxygen, etc., from passing through the
interface between the concave-convex structure layer and the gas barrier layer, and thus the
gas barrier property of the fìlm member is considered to be improved.
t01321 Although the present invention has been explained as above with the embodiment,
the example, and the comparative examples, the film member of the present invention is
not limited to the above-described embodiment and example, and may be appropriately
modified or changed within the range of the technical ideas described in the following
claims. For example, although the gas barrier layer of the film member in the example is
single-layered, the gas barrier layer may be formed of a plurality of layers (may be
multi-layered); also in such a case, the uppermost layer, namely a layer (surface) making
contact with the concave-convex structure layer, is preferably formed of a material same as
the material forming the concave-convex structure layer.
INDUSTRIAL APPLICABILITY
t01331 Since the film member of the present invention has the gas banier layer and the
concave-convex structure layer which are formed the inorganic material, the film member
has excellent gas barrier property and high light extraction efficiency. Accordingly, a
light emitting element using the film member has a high light emitting efficiency and a
long service life due to the suppression of the deterioration caused by the moisture and/or
gas such as oxygen. Further, since the surface, of the gas barrier layer, which makes
contact with the concave-convex structure layer, is made of an material which is same as
the material of the concave-convex structure layer, the adhesion property between the gas
barrier layer and the concave-convex structure layer is high, and thus the concave-convex
structure layer does not peel (exfoliate) from the gas barrier layer. Furthermore, by using
a precursor (solution) of the inorganic material for forming the concave-convex structure
layer, the concave-convex pattern ofthe concave-convex structure layer can be formed
precisely and assuredly by the roll process, thereby making it possible to produce the film
members'with high throughput. Therefore, the film member having the concave-convex
structure of the present invention is quite effective for a various kinds of devices such as
organic EL elements, solar batteries, etc. Further, the film member of the present
invention can be used for various kinds of applications, not being limited to the optical
53
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substrate. For example, the fihn mernber of the present invention can be used also for
producing a condensing film and an anti-reflection film for solar batferies and various
displays; for producing semiconductor chips; for producing paper such as tissue paper (for
example, a drum for compressing web); for producing food such as noodle-making; for
production in the biological field such as production of biochips provided with fine
channels, biochips for analyzing genome and proteome, cell culture sheets (nanopillar
sheets used as a cell culture container), cell separation microchips, etc.; and the like.
Reference Sign List
[01341 22
30
40
optical functional layer
gas banier layer
base member
concave-convex structure layer
concave-convex pattern
first electrode
organic layer
second electrode
film member
mold

We claim:
1. A film member having a concave-convex structure, comprising:
a base member;
a gas barrier layer formed on the base member; and
a concave-coltvex structure layer fonned on a surface ofthe gas barrier layer,
wherein the strrface of the gas barrier layer is formed of an inorganic material
which is same as a material of the concave-convex structure layer, and the concave-convex
structure layer is obtained from a precursor solution applied on the gas barrier layer.
2: The film member according to claim 1, wherein the gas barrier layer is a
single layer film.
3. The fìlm member according to claim I or 2, wherein:
(i) each of a plurality of convexities and each of a plurality of concavities ofthe
concave-convex structure layer has an elongated shape which extends while winding in a
plane view; and ,
(ii) the plurality of convexities have extending directions, bending directions and
lengths which are non-uniform among the plurality of convexities, and the plurality of
concavities have extending directions, bending directions and lengths which are
non-uniform among the plurality of concavities.
4. The film member according to any one of claims I to 3, wherein adhesio¡
force between the gas barrier layer and the concave-convex structure layer is greater than 4
N/m.
5. The film member according to any one of claims I to 4, wþerein an
average pitch of a plurality of concavities and a plurality of convexities of the
concave-convex structure layer is in a range of 100 nm to 1500 nm; and
an average value of depth distribution of the plurality of concavities and the
plurality of convexities is in a range of 20 nm to 200 nm.
6- A method of producing the film member having the concave-convex
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structure as defined in any one of claims 1 to 5, comprising:
forming the gas barrier layer on the base member;
forming a film by applying the'precursor solution onto the gas barrier layer; and
pressing a mold having a concave-convex pattern against the film while curing the
film so as to transfer the concave-convex pattern of the mold to the film.
7. The method of producing the fitm member according to claim 6, further
comprising producing the mold having the concave-convex pattern by utilizing
self-organization of a block copolyrner.
8. The method of producing the fihn member according to clairn 7, wherein
tlre block copolymer is self-organizedby a solvent annealing.
g. An organic EL element formed by successively stacking, on the film
member as defined in any one of claims I to 5, a first electrode, an organic layer and a
metal electrode.