DESCRIPTION
Title of Invention
MANUFACTURING METHOD AND MANUFACTURING DEVICE FOR OPTICAL
SUBSTRATE HAVING CONCAVO-CONVEX PATTERN USING FILM-SHAPED
MOLD, AND MANUFACTURING METHOD FOR DEVICE PROVIDED WITH
OPTICAL SUBSTRATE
Technical Field
[0001] The present invention relates to a manufacturing method for manufacturing an
optical substrate having a minute or fine concave and convex pattern (concavo-convex
pattern) for scattering or diffracting light, by using a long film-shaped mold; an apparatus
performing the manufacturing method; and a method for manufacturing a device provided
with the optical substrate produced by the manufacturing method.
Background Art
[0002] There has been known a lithography method as a method for forming a minute
pattern such as a semiconductor integrated circuit. The resolution of the pattern formed
by the lithography method is dependent on the wavelength of a light source and the
numerical aperture of an optical system, and the light source is expected to have shorter
wavelength in order to meet demand for miniaturized devices in recent years. However,
the light source having the short wavelength is expensive, development thereof is not easy,
and the development of an optical material transmitting such a short-wavelength light is
also needed. Further, manufacturing a large-area pattern through a conventional
lithography method needs a large-size optical element, and thus there are difficulties in
technical and economic aspects. Therefore, a novel method for forming a desired pattern
on a large area has been studied.
[0003] There has been known a nanoimprint method as a method for forming a minute
pattern without using any conventional lithography apparatus. The nanoimprint method
is a technique such that a pattern of an order of nanometer can be transferred by
sandwiching a resin between a mold and a substrate. A thermal nanoimprint method, a
photonanoimprint method, and the like have been studied depending on the employed
material. Of the above methods, the photonanoimprint method includes four steps of: i)
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resin coating (application of a resin layer); ii) pressing by use of the mold; iii)
photo-curing; and iv) mold-releasing. The photonanoimprint method is excellent in that
processing on a nanoscale can be achieved by the simple process as described above.
Especially, since a photo-curable resin curable by being irradiated with light is used as the
resin layer, a period of time for a pattern transfer step is short and high throughput is
promised. Thus, the photonanoimprint method is expected to come into practical use in
many fields including, for example, an optical member such as an organic EL element
(Organic Electro-Luminescence element or organic light emitting diode) and LED, MEMS,
and a biochip, in addition to a semiconductor device.
[0004] For example, in the organic EL element (organic light emitting diode), a hole
injected from a hole injecting layer and electron injected from 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, and
thereby light emission occurs. Therefore, in a case that the organic EL element is used as
a display device and/or an 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, PATENT LITERATURE 1 discloses that a diffraction-grating
substrate is provided on a light extraction surface of the organic EL element.
Citation List
Patent Literature
[0005] PATENT LITERATURE 1: Japanese Patent Application Laid-open No.
2006-236748
PATENT LITERATURE 2: PCT International Publication No.
WO2011/007878A1
[0006] The applicant of the present invention discloses the following method in PATENT
LITERATURE 2 in order to manufacture a concave and convex pattern of the diffraction
grating substrate for the organic EL element. That is, a solution obtained by dissolving a
block copolymer satisfying a predetermined condition into a solvent is applied on a base
member to form a micro phase separation structure of the block copolymer by using a
self-organizing phenomenon of the block copolymer, and thereby obtaining a master block
(metal substrate) in which a minute or fine and irregular concave and convex pattern is
formed. A mixture of a silicon-based polymer and a curing agent is dripped onto the
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obtained master block and then cured to obtain a transferred pattern as a mold. Then, a
glass substrate coated with a curable resin is pressed against the transferred pattern and the
curable resin is cured by irradiation with ultraviolet rays. In this way, a diffraction grating
in which the transferred pattern is duplicated is manufactured. The organic EL element
can be obtained by stacking a transparent electrode, an organic layer, and a metal electrode
on the diffraction grating.
[0007] However, in order to mass-produce the above-mentioned diffraction grating for
the organic EL element, it is necessary to efficiently perform the pattern transfer (pattern
formation) onto the material such as the curable resin by using the transferred pattern a of
the mold.
[0008] Thus, it is expected to develop a new transfer process and transfer apparatus
which are capable of mass-producing the optical substrate, such as the diffraction-grating
substrate, used for the organic EL element and the like with high throughput by using the
nanoimprint method.
[0009] The photo-curable resin described above generally has low heat resistance, and is
decomposed and/or turns into yellow at high temperature. Thus, there is fear that a film
having the minute pattern might be broken in a case that a high-temperature treatment is
included in subsequent steps. Further, the photo-curable resin has a low adhesion
property to a glass substrate. Furthermore, in a case that the resin layer to which the
pattern has been transferred is used for an element such as the organic EL element, there is
fear that impurities are eluted from the resin layer to cause adverse effect on the element.
Therefore, in order to mass-produce the optical substrate, such as the diffracting-grating
substrate, for the organic EL element with high throughput by using the nanoimprint
method, the material for forming the concave and convex pattern on the glass substrate
and/or mold material are required to be optimized.
Summary of Invention
Technical Problem
[0010] In view of the above, an object of the present invention is to provide a novel
manufacturing method and manufacturing apparatus capable of mass-producing an optical
substrate and a device provided with the optical substrate with high throughput, the optical
substrate including a minute or fine concave and convex pattern which has a high adhesion
property to a substrate, heat resistance, and weather resistance.
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Solution to the Problem
[0011] According to a first aspect of the present invention, there is provided a method for
manufacturing an optical substrate having a concave and convex pattern, including:
a step of preparing a long film-shaped mold having a surface of the concave and
convex pattern;
a step of forming a coating film made of a sol-gel material on a substrate;
a step of transferring the surface of the concave and convex pattern of the
film-shaped mold to the coating film by arranging the surface of the concave and convex
pattern to face the coating film and pressing a pressing roll against a surface of the
film-shaped mold on a side opposite to the surface of the concave and convex pattern;
a step of releasing the film-shaped mold from the coating film; and
a step of curing the coating film to which the concave and convex pattern has been
transferred.
[0012] In the method for manufacturing the optical substrate, the step of curing the
coating film may include curing the coating film by baking the coating film.
[0013] In the method for manufacturing the optical substrate, the step of preparing the
long film-shaped mold may include:
coating a long film-shaped base member with a concave-convex forming material;
performing a roll transfer of the concave and convex pattern to the
concave-convex forming material by pressing a transfer roll having the concave and
convex pattern against the concave-convex forming material coating the long film-shaped
base member while rotating the transfer roll; and
curing the concave-convex forming material to which the concave and convex
pattern has been transferred through the roll transfer so as to obtain the long film-shaped
mold in a roll shape. Further, the film-shaped base member having the cured
concave-convex forming material may be wound around a film winding roll, and/or the
concave and convex pattern of the transfer roll may be transferred while the film-shaped
base member is transported by using a film feeding roll feeding the film-shaped base
member and the film winding roll winding or rolling up the film-shaped base member. In
any case, the long film-shaped mold in the roll shape wound around the film winding roll
may move with being fed to the pressing roll. The released long film-shaped mold may
be wound around a mold winding roll.
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[0014] In the method for manufacturing the optical substrate, the pressing roll may be
pressed against the surface of the film-shaped mold on the side opposite to the surface of
the concave and convex pattern while the concave-convex forming material being heated.
By doing so, the pre-baking of the sol-gel material is performed simultaneously with the
pressing, which makes it possible to form the concave and convex pattern reliably and to
facilitate the releasing of the surface of the concave and convex pattern from the coating
film after the pressing. Further, it is possible to further facilitate the releasing of the
surface of the concave and convex pattern from the coating film after the pressing by
heating the pressed concave-convex forming material in the releasing step or between the
transfer step and the releasing step.
[0015] In the method for manufacturing the optical substrate, the surface of the concave
and convex pattern of the long film-shaped mold may be successively pressed against
coating films on a plurality of substrates with the pressing roll while continuously feeding
the long film-shaped mold under or below the pressing roll and transporting each of the
substrates to the pressing roll at a predetermined time interval with the coating film made
of the sol-gel material being formed. The use of the long film-shaped mold enables the
continuous process of each of the substrates, thereby making it possible to improve the
throughput of manufacture of the optical substrate. The length of the film-shaped mold
can be adjusted to a length enough to produce the optical substrate in amount of one lot, for
example, hundreds to thousands of optical substrates. For example, the length of the
film-shaped mold can be adjusted in a range of several hundreds of meters to several
thousands of meters.
[0016] The concave and convex pattern of the film-shaped mold used in the method for
manufacturing the optical substrate may be, for example, an irregular concave and convex
pattern in which an average pitch of concavities and convexities is in a range of 100 to
1500 nm and an average value (average height) of a depth distribution of the concavities
and convexities is in a range of 20 to 200 nm.
[0017] According to a second aspect of the present invention, there is provided an
apparatus for manufacturing an optical substrate, including:
a coating-film forming section configured to form a coating film made of a sol-gel
material on a substrate;
a substrate transporting section configured to transport the substrate on which the
coating film is formed to a predetermined position;
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a mold transporting section which includes a mold feeding roll configured to feed
a long film-shaped mold having a surface of a concave and convex pattern and a mold
winding roll configured to wind or roll up the long film-shaped mold, and is configured to
transport the film-shaped mold to the predetermined position by continuously feeding the
film-shaped mold from the mold feeling roll to the predetermined position and winding the
film-shaped mold around the mold wining roll; and
a pressing roll rotatably arranged at the predetermined position and configured to
press a part of the surface of the concave and convex pattern of the long film-shaped mold,
which is fed to the predetermined position by the mold transporting section, against the
coating film on the substrate which is transported to the predetermined position by the
substrate transporting section.
[0018] The apparatus for manufacturing the optical substrate may further include a
peeling roll configured to peel (release) the part of the surface of the concave and convex
pattern of the long film-shaped mold pressed with the pressing roll from the coating film
on the substrate.
[0019] The apparatus for manufacturing the optical substrate may further include a
heating means configured to heat the coating film on the substrate against which the part of
die surface of the concave and convex pattern of the film-shaped mold is pressed. The
heating means may be provided in the pressing roll. The apparatus for manufacturing the
optical substrate may further include a heating means configured to heat the coating film
when the film-shaped mold is released (peeled off) from the coating film.
[0020] The apparatus for manufacturing the optical substrate may further include a
supporting roll provided at a position to face the pressing roll and configured to support the
substrate from a lower side of the substrate. The coating-film forming section may
include a substrate stage configured to move the substrate while holding the substrate.
[0021] The concave and convex pattern of the film-shaped mold used in the apparatus for
manufacturing the optical substrate may be, for example, an irregular concave and convex
pattern used for scattering or diffracting light in which an average pitch of concavities and
convexities is in a range of 100 to 1500 nm and an average value (average height) of a
depth distribution of the concavities and convexities is in a range of 20 to 200 nm.
[0022] The apparatus for manufacturing the optical substrate may further include a roll
process apparatus configured to form the long film-shaped mold, the roll process apparatus
including: a transporting system configured to transport a substrate film; a coating unit
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configured to coat the substrate film being transported with a concave-convex forming
material; a transfer roll provided on a downstream side of the coating unit and configured
to transfer the concave and convex pattern to the concave-convex forming material; and a
radiation light source configured to emit light to the substrate film. The transporting
system may include a film feeding roll configured to feed the substrate film; a nip roll
configured to urge the substrate film toward the transfer roll; a releasing roll configured to
facilitate releasing of the substrate film from the transfer roll; and a film winding roll
configured to wind or roll up the substrate film to which the concave and convex pattern
has been transferred. In this case, the film winding roll around which the substrate film is
wound may be used as the mold feeding roll configured to feed the film-shaped mold.
[0023] According to a third aspect of the present invention, there is provided a method
for manufacturing a device provided with an optical substrate having a concave and
convex pattern, including:
a substrate formation step of forming a substrate with a predetermined concave
and convex pattern by coating the substrate with a sol-gel material and transferring the
concave and convex pattern to the sol-gel material coating the substrate;
a cleaning step of cleaning the substrate with the concave and convex pattern;
a first electrode formation step of forming a first electrode on the cleaned
substrate by patterning;
an annealing step of annealing the substrate in which the first electrode is formed;
a thin film formation step of forming a thin film on the first electrode; and
a second electrode formation step of forming a second electrode on the thin film.
[0024] In the method for manufacturing the device of the present invention, the so-gel
material as a transfer-target material of the concave and convex pattern has corrosion
resistance and high strength as compared with resin material. Thus, ultrasonic cleaning,
cleaning with a brush, and/or UV/O3 cleaning may be performed in the cleaning step.
[0025] In the method for manufacturing the device of the present invention, the
patterning may be performed by using an acid solvent or an alkaline solvent, and the
patterning may include formation of a first electrode layer, resist coating (application of a
resist), exposure and development, etching of the first electrode layer, and stripping
(removing) of the resist. The sol-gel material also has the corrosion resistance to the
solvent used for each of the processes.
[0026] In the method for manufacturing the device of the present invention, since the
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sol-gel material as the transfer-target material of the concave and convex pattern has heat
resistance, the annealing may be performed at a temperature in a range of 160 degrees
Celsius to 360 degrees Celsius.
[0027] The method for manufacturing the device of the present invention is suitable for
the manufacture of an organic EL element as the device. In this case, the first electrode
may be a transparent electrode, the thin film may include an organic layer, and the second
electrode may be a metal electrode. Further, the method for manufacturing the device of
the present invention is suitable for the manufacture of a solar cell as the device. In this
case, the first electrode may be a transparent electrode, the thin film may include a
semiconductor layer, and the second electrode may be a metal electrode.
[0028] The concave and convex pattern used in the method for manufacturing the device
of the present invention may be an irregular concave and convex pattern used for scattering
or diffracting light in which an average pitch of concavities and convexities is in a range of
100 to 1500 nm and an average value of a depth distribution of the concavities and
convexities is in a range of 20 to 200 nm. The substrate may be a glass substrate and the
sol-gel material may include a silica precursor. The method for manufacturing the device
of the present invention may further include baking of the sol-gel material at a temperature
of 300 degrees Celsius or more after coating the substrate with the sol-gel material and
transferring the predetermined concave and convex pattern to the so-gel material coating
the substrate.
[0029] In the method for manufacturing the device of the present invention, the substrate
formation step may include:
a step of preparing a long film-shaped mold having a surface of the concave and
convex pattern;
a step of forming a coating film made of the sol-gel material on the substrate;
a step of transferring the surface of the concave and convex pattern of the
film-shaped mold to the coating film by arranging the surface of the concave and convex
pattern of the film-shaped mold to face the coating film and pressing a pressing roll against
a surface of the film-shaped mold on a side opposite to the surface of the concave and
convex pattern;
a step of releasing (peeling) the film-shaped mold from the coating film; and
a step of baking the coating film to which the concave and convex pattern has
been transferred.
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Advantageous Effects of Invention
[0030] In the method for manufacturing the optical substrate of the present invention,
since the sol-gel material is used as the concave-convex pattern forming material and the
roll process with the long film-shaped mold is utilized to form the concave and convex
pattern made of the sol-gel material, it is possible to manufacture the optical substrate with
high throughput while performing the pattern transfer accurately and reliably. Since the
concave and convex pattern of the optical substrate manufactured by the method for
manufacturing the optical substrate of the present invention is made of the sol-gel material,
the optical substrate with the concave and convex pattern is excellent in heat resistance,
weather resistance (of which concept includes light resistance), and corrosion resistance.
Further, the optical substrate with the concave and convex pattern is also resistant to the
manufacturing process of an element in which the optical substrate is incorporated, which
makes it possible to extend the service life of the element.
[0031] Since the long film-shaped mold is utilized in the present invention, there are
advantages as follows. That is, regarding a hard mold made of metal, silica, and the like,
in a case that any defect has been found in a concave, and convex pattern of the hard mold,
it is possible to clean and/or repair the defect. Thus, any failure can be avoided which
would be otherwise caused by the transfer of the defect to the so-gel material layer.
However, in the film-shaped mold, the cleaning and the repair as described above are less
likely to be performed easily. In the meanwhile, the mold made of metal, silica, and the
like is in a roll shape, and when any defect such as clogging occurs in the mold, a transfer
device is required to be immediately stopped to exchange the mold. However, since the
transfer using the film-shaped mold is performed while each of the parts of the film-shaped
mold being made to correspond to each single glass substrate, a part having the defect such
as the clogging is marked at an inspection stage, and the transport of the glass substrate can
be suspended until the defect part passes through the glass substrate. Therefore, on the
whole, the use of the film-shaped mold can reduce the occurrence of defective product and
thereby making it possible to improve the throughput. In a case that the concave and
convex pattern of the hard mold made of metal, silica, and the like is tried to be directly
transferred to the sol-gel material layer, various limitations as described below arise and
thereby a desired performance can not be given sufficiently in some cases. For example,
in a case that a hard substrate such as glass is used as the substrate on which the sol-gel
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material layer is formed, the adjustment of the pressure applied to the mold is difficult.
For example, if the pressure applied to the mold is high, the substrate is damaged, for
example, to have a crack since both of the substrate and the mold are hard; or if the
pressure applied to the mold is low, the concave and convex pattern is transferred
insufficiently. Therefore, a soft material must be used for the substrate or the mold.
Even when the film-shaped mold (soft mold) is used, a material to which the concave and
convex pattern is transferred is required to have a superior mold-releasing property, a
superior adhesion property to the substrate, and a superior transferability of the concave
and convex pattern. Thus, the material must be selected from among limited materials.
Accordingly, by dividing the method for manufacturing the optical substrate into two steps
including the first step of manufacturing the film-shaped mold from the metal mold and the
second step of performing the transfer to the sol-gel material layer with the film-shaped
mold, and by selecting a material suitable for each of the steps, a desired material can be
used on a desired substrate in the optical substrate. Consequently,, the transfer can be
performed to have a satisfactory mold-releasing property without causing any pattern
defect, while satisfying necessary characteristics.
[0032] In the method for manufacturing the device of the present invention, since the
concave and convex pattern of the optical substrate is made of the sol-gel material, the
optical substrate has the resistance to the cleaning with the brush and the UV/O3 cleaning
in the cleaning step of cleaning the substrate with the concave and convex pattern, the
corrosion resistance to the acid solvent or alkali solvent used in the first electrode
formation step, and the heat resistance to high temperature in the subsequent annealing step.
Therefore, it is possible to produce the device without inhibiting optical characteristics of
the optical substrate with the concave and convex pattern and/or an adhesion property to
the thin film, which is formed as a working layer, on the optical substrate. Further, the
method for manufacturing the device of the present invention also contributes to improve
the heat resistance, the weather resistance, and the corrosion resistance of the device itself
manufactured by the method for manufacturing the device of the present invention.
Accordingly, the method for manufacturing the device of the present invention is
extremely useful when manufacturing various devices such as the organic EL element and
the solar cell with high throughput.
Brief Description of Drawings
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[0033]
Fig. 1 is a flowchart showing a method for manufacturing a device of the present
invention.
Fig. 2 is a flowchart showing manufacturing steps of an optical substrate used for
the method for manufacturing the device of the present invention.
Fig. 3 is a conceptual view of a roll process apparatus for manufacturing a
film-shaped mold used for manufacture of the optical substrate.
Fig. 4 is a conceptual view for illustrating a roll process using the film-shaped
mold.
Figs. 5(a) to 5(f) conceptually show a process for manufacturing an ITO
transparent electrode.
Fig. 6 shows a cross-section structure of an organic EL element.
Fig. 7 is a conceptual view of an optical substrate manufacturing apparatus for
performing a method for manufacturing the optical substrate of the present invention.
Fig. 8 is a conceptual view illustrating a modified embodiment of the optical
substrate manufacturing apparatus, in which no peeling roll is utilized.
Fig. 9 is a conceptual view illustrating another modified embodiment of the
optical substrate manufacturing apparatus, in which the film-shaped mold as an endless
belt is utilized.
Fig. 10 is a conceptual view illustrating still another modified embodiment of the
optical substrate manufacturing apparatus, in which a heat zone as a heating means of a
sol-gel material layer is provided in a pressing section.
Fig. 11 is a conceptual view illustrating an apparatus for inspecting unevenness of
a diffraction grating substrate.
Fig. 12(a) is a photograph showing an image from the surface of the substrate
observed in Example 1, and Fig. 12(b) is a graph showing profile of pixel positions on the
line LI in the photograph of Fig. 12(a) and pixel values at the pixel positions.
Description of Embodiments
[0034] In the following, embodiments of the present invention will be described with
reference to the drawings. As shown in Fig. 1, a method for manufacturing a device
provided with an optical substrate having a concave and convex pattern according to the
present invention mainly includes: a substrate formation step PI for forming a substrate in
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which the concave and convex pattern is formed; a cleaning step P2 for cleaning the
substrate in which the concave and convex pattern is formed; a first electrode formation
step P3 for forming a first electrode on the cleaned substrate by patterning using an acid
solvent or alkaline solvent; an annealing step P4 for annealing the substrate, on which the
patterned first electrode is formed, at a predetermined temperature; a thin film formation
step P5 for forming a thin film on the annealed substrate; and a second electrode formation
step S6 for forming a second electrode on the thin film. The substrate formation step PI
for forming the substrate in which the concave and convex pattern is formed includes a
method for manufacturing the optical substrate having the concave and convex pattern
according to the present invention. As shown in Fig. 2, the method for manufacturing the
optical substrate having the concave and convex pattern mainly includes a step SO for
preparing a film-shaped mold; a solution preparation step SI for preparing a sol-gel
material; a coating step S2 for coating a substrate with the prepared sol-gel material
(applying the prepared sol-gel material on a substrate); a drying step S3 for drying the
coating film of the sol-gel material coating the substrate; a transfer step S4 for pressing the
film-shaped mold in which a transfer pattern is formed against the dried coating film with a
pressing roll; a releasing step (peeling step) S5 for releasing (peeling off) the mold from
the coating film; and a main baking step S6 in which the coating film is subjected to main
baking.
[0035] Hereinbelow, the method for manufacturing the optical substrate and the method
for manufacturing the device including the optical substrate manufactured by this
manufacturing method according to the present invention will be explained by citing a
manufacturing process of an organic EL element 200 as shown in Fig. 6, as an example,
the organic EL element 200 including a stacked structure on a substrate (diffraction grating
substrate) 40 having a sol-gel material layer 42 in which a concave and convex pattern is
formed.
[0036]
[Substrate formation step]
At first, an explanation will be made about a method for manufacturing the
substrate 40 including the sol-gel material layer 42 in which the concave and convex
pattern is formed using the method for manufacturing the optical substrate of the present
invention by citing, as an example.
[0037]
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The film-shaped mold used for manufacturing an optical member of the present
invention is a film-shaped or sheet-shaped mold which is long, flexible, and has a concave
and convex transfer pattern on a surface thereof. The mold is made, for example, 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), and polyarylate. The concave
and convex pattern may be formed directly in each of the materials, or may be formed in
(on) a concave-convex forming material with which a base material (substrate sheet)
formed of the above-mentioned materials is coated. It is possible to use photo-curable
resin, thermosetting resin, and thermoplastic resin as the concave-convex forming material.
[0038] The film-shaped mold is, for example, a long mold which may have 10 meter or
more in length, 50 to 3000 mm in width, and 1 to 500 um in thickness. The size of the
film-shape mold, in particular, the length thereof can be set appropriately based on the size
of the optical substrate to be mass-produced, the number of optical substrates (the number
of lots) continuously produced in a single manufacturing process. A surface treatment or
an easy-adhesion treatment may be performed to improve an adhesion property between
the substrate and the coating material (concave-convex forming material). Further, a
mold-release treatment may be performed on each surface of the concave and convex
pattern as needed. The concave and convex pattern may be formed to have any profile by
arbitrary method.
[0039] The concave and convex pattern of the film-shaped mold varies in uses of the
optical substrate finally obtained. The concave and convex pattern, for example, may be
an irregular concave and convex pattern in which pitches of concavities and convexities
are ununiform and orientations of the concavities and convexities have no directivity. In
a case that the optical substrate is used for scattering or diffracting visible light, for
example, the average pitch of the concavities and convexities can be within a range from
100 to 1500 nm, and is more preferably within a range from 200 to 1500 nm. In a case
that the average pitch of the concavities and convexities is less than the lower limit, the
pitches are so small relative to wavelengths of the visible light that the diffraction of light
by the concavities and convexities is likely to be insufficient. In a case that the average
pitch exceeds the upper limit, a diffraction angle is so small that functions as an optical
element such as the diffracting grating are more likely to be lost. In similar uses, the
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average value (average height) of a depth distribution of the concavities and convexities is
preferably in a range of 20 to 200 nm, and more preferably in a range of 50 to 150 nm.
[0040] The light scattered and/or diffracted by such a concave and convex pattern is not
light having single wavelength or wavelength having a narrow band. The light scattered
and/or diffracted by such a concave and convex pattern has a range of wavelength
relatively broad, has no directivity, and is directed in various directions. However, the
"irregular concave and convex pattern" includes a quasi-periodic structure such as that in
which a Fourier-transformed image, which is obtained by performing a two-dimensional
fast Fourier-transform processing on a concavity and convexity analysis image obtained by
analyzing a concave and convex shape on the surface, shows a circular or annular pattern,
that is, such as that in which, although the concavities and convexities have no particular
orientation, the pitches of the concavities and convexities vary. Therefore, the substrate
having such a quasi-periodic structure is suitable for a diffraction substrate used in a
surface-emitting element and the like such as the organic EL element; a transparent
conductive substrate of a solar cell; and the like, provided that the substrate has the
concavities and convexities of which pitch distribution or pitch variability enables the
substrate diffract visible light.
[0041] An exemplary method for manufacturing the long film-shaped mold used in the
present invention will be explained by referring to Fig. 3. A roll process apparatus (first
unit) 70 shown in Fig. 3 is an apparatus for manufacturing the film-shaped mold by
forming a concave and convex pattern on a coating film formed on a long substrate film.
The roll process apparatus 70 mainly includes a transporting system 86 which transports a
substrate film (base material) 80, a die coater 82 which coats the substrate film 80 being
transported with the material for forming the concavities and convexities, a transfer roll
(metal mold) 90 which is positioned on the downstream side of the die coater 82 and
transfers a pattern, and a radiation light source 85 which is provided to face the transfer roll
90 with the substrate film 80 intervening therebetween and emits UV light to the substrate
film 80. The transporting system 86 for transporting the substrate film 80 includes a film
feeding roll 72 which feeds the substrate film 80, a nip roll 74 which is arranged to face the
transfer roll 90 with the substrate film 80 intervening therebetween, a releasing roll
(peeling roll) 76 which facilitates the releasing (peeling) of the substrate film 80 from the
transfer roll 90, a film winding roll 87 which winds or rolls up a substrate film 80a
(film-shaped mold) having the pattern transferred thereon, and a plurality of transporting
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rolls 78 which transport the substrate film 80 while maintaining the tension of the substrate
film 80.
[0042] The film-shaped mold is manufactured through the following manufacturing
process by using the roll process apparatus 70. The substrate film 80 wound on the film
feeding roll 72 in advance is fed to the downstream side by the rotations of the film feeding
roll 72, the film winding roll 87, etc. When the substrate film 80 passes through the die
coater 82, a concave-convex forming material 84 is applied on a surface of the substrate
film 80 by the die coater 82 to form a coating film having a predetermined thickness.
Then, the coating film on the substrate film 80 is pressed against the outer circumferential
surface of the transfer roll 90 by the nip roll 74 so as to transfer a pattern of the outer
circumferential surface of the transfer roll 90 to the coating film. At the same time or
immediately after the above, UV light is emitted from the radiation light source 85 to the
coating film so as to cure the concave-convex forming material 84. Although the
wavelength of the UV light varies according to the concave-convex forming material 84,
the wavelength of the UV light is generally in a range of 200 to 450 nm. The amount of
irradiation may be in a range of 10 mJ/cm to 5 J/cm . After releasing (peeling off) the
substrate film 80 with the concave-convex forming material having the cured pattern from
the transfer roll 90 by using the releasing roll (peeling roll) 76, the substrate film 80 is
wound around the film winding roll 87. Accordingly, a long film-shaped mold 80a is
obtained. Since the long film-shaped mold 80a is obtained in a roll shape, it is suitable
for a mass-producing process of the optical substrate using a pressing roll which will be
described later. Further, the shape of the long film-shaped mold 80a is suitable to be
transported to an apparatus performing the mass-producing process of the optical substrate
by use of the pressing roll. Additionary, since the film-shaped mold is rolled up it in a
roll shape after being manufactured, storage and aging processes can be easily performed.
[0043] In the manufacturing process described above, the substrate film 80 is exemplified,
for example, by base members made of inorganic materials such as glass; and
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), and
polyarylate. The thickness of the substrate film may be, for example, in a range of 1 to
500 um.
[0044] The concave-convex forming material 84 is exemplified by curable resins such as
16
various kinds of UV curable resins including, for example, epoxy resin, acrylic resin,
methacrylic resin, vinyl ether resin, oxetane resin, urethane resin, melamine resin, urea
resin, polyester resin, phenol resin, cross-linking type liquid crystal resin, fluorine resin,
and silicone resin. The thickness of the curable resin is preferably in a range of 0.5 to 500
um. In a case that the thickness is less than the lower limit, heights of the concavities and
convexities formed on the surface of a cured resin layer are likely to be insufficient. 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 the formation of the shape of the concavities and
convexities is liable to be unsatisfactory.
[0045] In the above manufacturing process, a die coating method by the die coater is used
to coat the substrate film 80 with the concave-convex forming material 84 (apply the
concave-convex forming material 84 on the substrate film 80). Instead of this, it is
possible to adopt various coating methods such as a spin coating method, a spray coating
method, a dip coating method, a dropping method, a gravure printing method, a screen
printing method, a relief printing method, a curtain coating method, an ink-jet method, and
a sputtering method. The condition for curing the concave-convex forming material 84
such as the curable resin varies depending on the kind of the resin used. For example, a
curing temperature is preferably within a range from room temperature to 250 degrees
Celsius, and an UV light irradiation amount is preferably within a range from 10 mJ/cm2 to
5 J/cm2. The concave-convex forming material 84 may be cured by irradiation with
energy rays such as electron beams other than the UV light.
[0046] The transfer roll 90 used in the above-mentioned manufacturing process may be,
for example, a roll having a pattern directly formed on a surface thereof such as a metal
roll; a roll in which a substrate having a pattern such as a metal substrate is wound on the
roll and then fixed thereto; or a roll formed by manufacturing a cylindrical substrate having
a pattern and fitting and fixing it to the roll. The transfer roll 90 may be made of a hard
material other than the metal.
[0047] Here, an explanation will be made about a method for forming a concave and
convex pattern provided on the surface of the transfer roll 90. It is preferred that the
concave and convex pattern be formed by a method of utilizing self-organization or
assembly (micro phase separation) of a block copolymer described in Japanese Patent
Application Laid-open No. 2011-006487 of the applicants of the present invention
(hereinafter referred to as "BCP (Block Copolymer) method" as appropriate), a method of
17
heating and cooling a polymer film on a vapor-deposited film to form concavities and
convexities of wrinkles on a surface of polymer disclosed in PCT International Publication
No. WO2011/007878Al of the applicants of the present invention (hereinafter referred to
as "BKL (Buckling) method" as appropriate), or the like. A photolithography method
may be utilized instead of the BCP and BKL methods. In a case that the pattern is formed
by the BCP method, the pattern can be made of any material, and the material is preferably
a block copolymer composed of combinations of two selected from the group consisting of
a styrene-based polymer such as polystyren; polyalkyl methacrylate such as polymethyl
methacrylate; polyethylene oxide; polybutadiene; polyisoprene; polyvinylpyridine; and
polylactic acid.
[0048] Pitches and heights of concavities and convexities of the pattern are arbitrary.
For example, in a case that the pattern is used as the diffraction grating scattering or
diffracting light in a visible region, the average pitch of the concavities and convexities is
preferably in a range of 100 nm to 1500 nm, more preferably in a range of 200 nm to 1500
nm. In a case that the average pitch of the concavities and convexities is less than the
lower limit, the pitches are so small relative to wavelengths of the visible light that the
diffraction of the light by the concavities and convexities is less likely to occur. In a case
that the average pitch exceeds the upper limit, a diffraction angle is so small that functions
as an optical element such as the diffraction grating are more likely to be lost. The
average value of the depth distribution of the concavities and convexities is preferably in a
range of 20 nm to 200 nm, and more preferably in a range of 50 nm to 150 nm. In a case
that the average value of the depth distribution of the concavities and convexities is less
than the lower limit, the height is so short relative to the wavelengths of the visible light
that the required diffraction is less likely to occur. In a case that the average value
exceeds the upper limit, the intensity of diffracted light becomes non-uniform, and as a
result, the following tendency is found. When the concave and convex pattern is used, for
example, as the optical element for light extraction of the organic EL element, the electric
field distribution in an EL layer becomes non-uniform, and electric fields concentrate on a
certain position or area, thereby a leak current is more likely to arise and/or the service life
of the optical element is shortened.
[0049] After forming the master block with the pattern by the BCP or BKL method, 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
18
electroforming process can be formed on the master block, which has the pattern to be
transferred, formed by 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 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-mckel-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 to 3000 um. As the material of the metal layer accumulated by the
electroforming, it is possible to use any of metal species as described above which can be
used as the seed layer. It is preferable to use nickel as the material of the metal layer in
view of the wear resistance, the releasing property, and the like of a metal substrate to be
obtained as the mold. In this case, nickel is preferably used also for the seed layer.
Considering ease of the subsequent processes for forming the mold such as pressing to the
resin layer, releasing, and cleaning, the formed metal layer desirably has appropriate
hardness and thickness.
[0050] The metal layer including the seed layer obtained as described above is released
(peeled off) from the master block having the concave and convex structure to obtain a
metal substrate. In order to release the metal layer easily and reliably, it is preferred that
an annealing process be performed by heating the master block with the pattern before the
electroforming. As the releasing method, the metal layer may be peeled off physically, or
the materials composing the pattern of the master block may be dissolved to be removed
by using an organic solvent dissolving them, such as toluene, tetrahydrofuran (THF), and
chloroform. In a case that the metal substrate is peeled off from the master block, a
remaining material component on the metal substrate can be removed by cleaning. As the
cleaning method, it is possible to use wet cleaning using a surfactant etc., or dry cleaning
using ultraviolet rays and/or plasma. Alternatively, for example, the remaining material
component may be attached to an adhesive agent or a bonding agent then be removed.
Accordingly, the metal substrate to which the pattern has been transferred from the master
block can be obtained. The transfer roll 90 having the concave and convex pattern can be
19
obtained by winding or putting the metal substrate obtained as described above around the
surface of a roll body. It is possible to form the film-shaped mold by using the transfer
roll 90 by the above manufacturing process. It is needless to say that the long
film-shaped mold is not required to be self-manufactured and a long film-shaped mold
manufactured by a manufacturer such as a film manufacturer may be used. The step for
preparing the film-shaped mold may be performed at any time, provided that the step is
performed before the transfer step S4 which will be described later. Thus, it is not
indispensable to perform the step for preparing the film-shaped mold before the sol-gel
material preparation step SI.
[0051]
In the method for manufacturing the optical substrate of the present invention, the
sol-gel material is prepared to form the coating film to which the pattern is transferred by a
sol-gel method (step S1 of Fig. 2). For example, in a case that silica is synthesized on a
substrate by the sol-gel method, a sol-gel material of metal alkoxide (silica precursor) is
prepared. The silica precursor is exemplified by metal alkoxides including, for example,
tetraalkoxide monomers such as tetramethoxysilane (TMOS), tetraethoxysilane (TEOS),
tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-i-butoxysilane, tetra-n-butoxysilane,
tetra-sec-butoxysilane, and tetra-t-butoxysilane; trialkoxide monomers 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; a polymer obtained by polymerizing the above monomers in small
amounts; and a composite material characterized in that functional group and/or polymer
is/are introduced into a part of the above material. Further, the silica precursor is
exemplified, for example, by metal acetylacetonate, metal carboxylate, oxychloride,
chloride, and mixtures thereof. The silica precursor, however, is not limited thereto.
Examples of metal species include, in addition to Si, 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.
20
[0052] In a case that a mixture of TEOS and MTES is used, the mixture ratio thereof can
be 1:1, for example, in a molar ratio. The sol-gel material produces amorphous silica by
performing hydrolysis and polycondensation reaction. An acid such as hydrochloric acid
or an alkali such as ammonia is added in order to adjust 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 1.5 times or
more with respect to metal alkoxide species in the molar ratio. It is possible to use, as the
sol-gel material, a material other than the silica. For example, a titanium-based material,
a material based on indium tin oxide (ITO), ZnO, Zr02, AI2O3, and the like may be used.
[0053] Examples of the solvent of the sol-gel material include alcohols such as methanol,
ethanol, isopropyl alcohol (IPA), and butanol; aliphatic hydrocarbons such as hexane,
heptane, octane, decane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene,
xylene, and mesitylene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; ketones
such as acetone, methyl ethyl ketone, isophorone, and cyclohexanone; ether alcohols such
as butoxyethyl ether, hexyloxyethyl alcohol, methoxy-2-propanol, and benzyloxyethanol;
glycols such as ethylene glycol and propylene glycol; glycol ethers such as ethylene glycol
dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether
acetate; esters such as ethyl acetate, ethyl lactate, and y-butyrolactone; phenols such as
phenol and chlorophenol; amides such as N,N-dimethylformamide,
N,N-dimethylacetamide, and N-methylpyrrolidone; halogen-containing solvents such as
chloroform, methylene chloride, tetrachloroethane, monochlorobenzene, and
dichlorobenzene; hetero-element containing compounds such as carbon disulfide; 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.
[0054] As an additive of the sol-gel material, it is possible to use polyethylene glycol,
polyethylene oxide, hydroxypropylcellulose, and polyvinyl alcohol for viscosity
adjustment; alkanolamine such as triethanolamine, P-diketone such as acetylacetone,
P-ketoester, formamid, dimetylformamide, and dioxane, and the like, as a solution
stabilizer.
[0055]
The substrate is coated with the sol-gel material prepared as described above (step
21
S2 of Fig. 2). From a viewpoint of mass-production, it is preferred that the substrate be
coated with the sol-gel material (the sol-gel material be applied on the substrate) at a
predetermined position while a plurality of substrates are continuously transported. As
the coating method, it is possible to use any coating method such as 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 die coating method, the bar coating method, and the spin
coating method are preferable, because the substrate having a relatively large area can be
coated uniformly with the so-gel material and the coating can be quickly completed prior
to gelation of the sol-gel material.
[0056] As the substrate, substrates made of inorganic materials such as glass, silica glass,
and silicon substrates or substrates of resins such as polyethylene terephthalate (PET),
polyethylene terenaphthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP),
polymethyl methacrylate (PMMA), polystyrene (PS), polyimide (PI), and polyarylate may
be used. The substrate may be transparent or opaque. A relatively hard substrate is
preferable from the perspective that the sol-gel material layer is formed on this substrate
and further a functional layer is formed on this substrate when the optical substrate is
incorporated into the device. Further, if a substrate having a concave and convex pattern
obtained from this substrate is used for production of the organic EL element as will be
described later, this substrate desirably has the heat resistance and the weather resistance to
ultraviolet (UV) light and the like. In these respects, substrates made of inorganic
materials such as glass, silica glass, and silicon substrates are more preferable. Since the
inorganic materials are used as the sol-gel material coating the substrates, in a case that the
substrate is made of the inorganic materials, the difference in refractive index between the
substrate and the sol-gel material layer is small and unintended refraction and/or reflection
in the optical substrate can be prevented. Thus, the substrates made of the inorganic
materials are preferable also in these respects. It is allowable to perform a surface
treatment or provide an easy-adhesion layer on the substrate in order to improve an
adhesion property, and to provide a gas barrier layer in order to keep out moisture and/or
gas such as oxygen. It is noted that, since a sol-gel material layer with a desired concave
and convex pattern is formed in subsequent steps, the surface of the substrate (including
the surface treatment or the easy-adhesion layer in case that the surface treatment or the
easy-adhesion layer is present) may be flat, and the substrate itself does not have the
desired concave and convex pattern. It is preferred that each substrate coated with the
22
sol-gel material be transported as it is for the subsequent drying step and transfer step.
[0057]
After the coating step, the substrate is dried by being held or kept in the
atmosphere or under reduced pressure so as to evaporate the solvent in the coating film
(hereinafter also referred to as "sol-gel material layer" as appropriate) (step S3 of Fig. 2).
In a case that the holding time of the substrate is short, the viscosity of the coating film is
too low to transfer the pattern in the subsequent transfer step. In a case that the holding
time of the substrate is too long, the polymerization reaction of the precursor proceeds too
much and thereby the transfer cannot be performed in the transfer step. In case that the
optical substrate is mass-produced, the holding time can be controlled as a time for
transporting the substrate from the sol-gel material coating to the subsequent transfer step
using the film-shaped mold. A holding temperature of the substrate in the drying step
desirably stays constant in a range of 10 to 100 degrees Celsius, and more desirably stays
constant in a range of 10 to 30 degrees Celsius. In a case that the holding temperature is
higher than this range, the gelation reaction of the coating film proceeds rapidly before the
transfer step, which is not preferable. In a case that the holding temperature is lower than
this range, the gelation reaction of the coating film proceeds slowly before the transfer step,
which reduces the productivity and is not preferable. After the sol-gel material coating,
the polymerization reaction of the precursor proceeds as the evaporation of the solvent
proceeds, and the physical property such as the viscosity of the sol-gel material also
changes in a short time. The amount of vaporization of the solvent depends also on the
amount of the solvent (concentration of the sol-gel material) used at the time of preparing
the sol-gel material. For example, in a case that the sol-gel material is the silica precursor,
the hydrolysis and condensation polymerization reaction of the silica precursor occurs as
the gelation reaction and alcohol is generated in the sol-gel material through
dealcoholization reaction. A volatile solvent such as the alcohol is used in the sol-gel
material as the solvent. That is, the alcohol generated in the hydrolysis process and the
alcohol existing as the solvent are included in the sol-gel material, and sol-gel reaction
proceeds by removing them in the drying step. Therefore, it is desirable that the holding
time and holding temperature be adjusted by taking the gelation reaction and the solvent
used in the sol-gel material into consideration. In the drying step, the solvent in the
sol-gel material evaporates simply by holding the substrate as it is. Thus, it is not
23
indispensable to actively perform a drying operation such as heating and blowing.
Leaving the substrate with the coating film as it is for a predetermined time or transporting
said substrate in a predetermined time for subsequent steps are enough for drying the
substrate. That is, the drying step is not indispensable for the substrate formation step.
[0058]
After the time set as described above has elapsed, the film-shaped mold prepared
in the step SO is pressed against the coating film with the pressing roll (laminate roll) to
transfer the concave and convex pattern of the film-shaped mold to the coating film on the
substrate (step S4 of Fig. 2). For example, as shown in Fig. 4, it is possible to transfer the
concave and convex pattern of the film-shaped mold 80a to the coating film (sol-gel
material) 42 on the substrate 40 by sending the film-shaped mold 80a between the pressing
roll 22 and the substrate 40 being transported immediately below the pressing roll 22.
That is, in a case that the film-shaped mold 80a is pressed against the coating film 42 with
the pressing roll 22, the film-shaped mold 80a is coated on the surface of the coating film
42 on the substrate 40 while the film-shaped mold 80a and the substrate 40 are
synchronously transported. In this situation, by rotating the pressing roll 22 while
pressing the pressing roll 22 against the back surface (surface on the side opposite to the
surface in which the concave and convex pattern is formed) of the film-shaped mold 80a,
the film-shaped mold 80a moves with the substrate 40 to adhere to the substrate 40. In
order to send the long film-shaped mold 80a to the pressing roll 22, it is advantageous that
the film-shaped mold 80a is fed directly from the film winding roll 87 (see Fig. 3) around
which the long film-shaped mold 80a is wound in the step SO.
[0059] A roll process using such a pressing roll has the following advantages as
compared with a pressing system: i) the period of time during which the mold and the
coating film are brought in contact with each other in the roll process is shorter than that in
the pressing system, and thus it is possible to prevent deformation of the pattern caused by
the difference among coefficients of thermal expansion of the mold, the substrate, a stage
on which the substrate is provided, and the like; ii) productivity is improved by the roll
process and the productivity is further improved by use of the long film-shaped mold; iii) it
is possible to prevent generation of bubbles of gas in the pattern caused by bumping of the
solvent in the gel solution and/or it is possible to prevent a trace or mark of gas from being
left; iv) it is possible to reduce transfer pressure and releasing force (peeling force) because
24
of line contact with the substrate (coating film), and thereby making it possible to deal with
a larger substrate readily; and v) no bubble is involved during the pressing. Since the
flexible film-shaped mold is used as the mold in the manufacturing method of the present
invention, when the concave and convex pattern of the mold is transferred to the sol-gel
material layer 42 formed on the relatively hard substrate 40, the pattern of the mold can be
uniformly pressed against the sol-gel material layer formed on the entire surface of the
substrate. Accordingly, the concave and convex pattern of the mold can be faithfully
transferred to the sol-gel material layer, thereby making it possible to suppress the
occurrence of transfer omission and/or transfer failure.
[0060] In the transfer step, the film-shaped mold may be pressed against the coating film
while the coating film is heated. As the method for heating the coating film, for example,
the heating through the pressing roll may be performed, or the coating film may be heated
directly or from the side of the substrate. In a case that the heating is performed through
the pressing roll, a heating means may be provided in the pressing roll (transfer roll), and
any heating means can be used. Although it is preferred that a heater be included in the
pressing roll, the heater may be provided separately from the pressing roll. In any case,
arbitrary pressing roll may be used provided that the coating film can be pressed while
being heated. The pressing roll is preferably a roll of which surface is coated with a resin
material with heat resistance, such as ethylene propylene diene rubber (EPDM), silicone
rubber, nitrile rubber, fluororubber, acrylic rubber, and chloroprene rubber. A supporting
roll may be provided to face the pressing roll while sandwiching the substrate
therebetween in order to resist the pressure applied by the pressing roll. Alternatively, a
support base supporting the substrate may be provided.
[0061] The heating temperature of the coating film at the time of the pressing may be in a
range of 40 degrees Celsius to 150 degrees Celsius. In a case that the heating is
performed by use of the pressing roll, the heating temperature of the pressing roll may be
also in a range of 40 degrees Celsius to 150 degrees Celsius. By heating the pressing roll
as described above, the mold can be easily released (peeled off) from the coating film
against which the mold has been pressed, and thereby making it possible to improve the
productivity. In a case that the heating temperature of the coating film or the pressing roll
is less than 40 degrees Celsius, the mold can not be expected to be released (peeled off)
from the coating film quickly. In a case that the heating temperature of the coating film
or the pressing roll exceeds 150 degrees Celsius, the solvent used evaporates so rapidly
25
mat there is fear that the concave and convex pattern is not transferred sufficiently. By
performing the pressing while heating the coating film, an effect similar to that obtained in
pre-baking of the sol-gel material layer which will be described later can be expected.
[0062] After the mold is pressed against the coating film (sol-gel material layer), the
coating film may be subjected to the pre-baking. In a case that the pressing is performed
without heating the coating film, it is preferred that the pre-baking be performed. The
pre-baking promotes gelation of the coating film to solidify the pattern, and thereby the
pattern is less likely to be collapsed during the releasing. That is, the pre-baking has two
roles of the reliable pattern formation and the improvement of releasing property (peeling
property) of the mold. In a case that the pre-baking is performed, the heating is
preferably performed at temperatures of 40 degrees Celsius to 150 degrees Celsius in the
atmosphere.
[0063]
The mold is released or peeled off from the coating film (sol-gel material layer)
after the transfer step or the pre-baking step (step S5). Since the roll process is used as
described above, the releasing force (peeling force) may be smaller than that of a
plate-shaped mold used in the pressing system, and it is possible to easily release the mold
from the coating film without remaining the coating film on the mold. In particular, since
the pressing is performed while the coating film is heated, the reaction is more likely to
progress, which facilitates the releasing the mold from the coating film immediately after
the pressing. In order to promote the releasing property (peeling property) of the mold, it
is possible to use a peeling roll (releasing roll). As shown in Fig. 4, by providing a
peeling roll (releasing roll) 23 on the downstream side of the pressing roll 22 and
supporting the film-shaped mold 80a while urging the film-shaped mold 80a toward the
coating film 42 with the rotating peeling roll 23, a state in which the film-shaped mold 80a
is attached to the coating film can be maintained by a distance between the pressing roll 22
and the peeling roll 23 (for a certain period of time). Then, by changing a path of the
film-shaped mold 80a such that the film-shaped mold 80a is pulled up above the peeling
roll 23 on the downstream side of the peeling roll 23, the film-shaped mold 80a is peeled
off (released) from the coating film 42. The pre-baking or the heating may be performed
during a period in which the film-shaped mold 80a is attached to the coating film. In a
case that the peeling roll 23 is used, by peeling the coating film from the mold 80a while
26
heating the coating film, for example, at temperatures of 40 degrees Celsius to 150 degrees
Celsius, the coating film can be peeled more easily.
[0064]
After the mold is released (peeled off) from the coating film (sol-gel material
layer) 42 on the substrate 40, the coating film is subjected to the main baking (step S6 of
Fig. 2). Hydroxyl group and the like contained in the layer of sol-gel material such as
silica, which forms the coating film, is desorbed or eliminated by the main baking to
further harden (solidify) the coating film. It is preferred that the main baking be
performed at temperatures of 200 degrees Celsius to 1200 degrees Celsius for about 5
minutes to 6 hours. Accordingly, the coating film is cured, and thereby the substrate with
the concave and convex pattern film which corresponds to the concave and convex pattern
of the mold, that is, the substrate in which the sol-gel material layer having the concave
and convex pattern is directly formed on the flat substrate, is obtained. In this situation,
in a case that the sol-gel material layer is made of the silica, depending on a baking
temperature and a baking time, the silica is amorphous, crystalline, or in a mixture state of
the amorphous and the crystalline.
[0065]
The substrate 40 (light extraction substrate), in which the sol-gel material layer 42
having the concave and convex pattern is formed through the roll process, is cleaned.
The cleaning is performed to remove foreign substances and the like adhering to the
substrate. For example, the substrate is mechanically cleaned in pure water by using a
brush such as a roll-brush which is constructed by implanting, in the periphery of a
rotational shaft, polypropylene, vinyl chloride, or the like processed to have a linear-shape
or a strip-shape, and then an alkaline cleaner and an organic solvent are used to eliminate
organic substances and the like. As the alkaline cleaner, it is possible to use, for example,
an alkaline organic compound solution which is commercially available as Semico Clean
(trade name), ethylamine, diethylamine, ethanolamine, and (2-hydroxyethyl)
trimethyl-ammonium hydroxide (choline). As the organic solvent, it is possible to use,
for example, acetone and isopropyl alcohol (IPA).
[0066] In addition to or instead of the above cleaning methods, ultrasonic cleaning may
be performed. The ultrasonic cleaning can be performed, for example, for a few minutes
27
to several tens of minutes by immersing the substrate in alcohols such as isopropyl alcohol,
acetone, or the alkaline organic compound solution known, for example, as Semico Clean
(trade name). In addition to or instead of the above cleaning methods, a UV/O3 process
may be performed.
[0067] In the present invention, since the concave and convex pattern of the optical
substrate is made of the sol-gel material, the concave and convex pattern is relatively hard,
has the resistance to the mechanical cleaning with the brush, and has the corrosion
resistance to the alkaline cleaner and the organic solvent. Further, the concave and
convex pattern of the sol-gel material 42 is more insusceptible to the ultrasonic cleaning or
the UV/O3 process as compared with the curable resin.
[0068]
Subsequently, a transparent electrode 92 as the first electrode is stacked on the
sol-gel material layer 42 on the cleaned substrate 40 to maintain the concave and convex
structure formed on the surface of the sol-gel material layer 42 as shown in Fig. 6 (first
electrode formation step P2 of Fig. 1). The formation process of the transparent electrode
92 will be explained while referring to Fig. 5(a)-(f). At first, as shown in Fig. 5(a), the
film of an electrode material layer 32 forming the transparent electrode 92 is formed on the
substrate 40. As the method for forming the film, any conventionally known method such
as a vapor deposition method, a sputtering method, a CVD method, and a spray method
can be employed as appropriate. Of these methods, the sputtering method is preferably
employed from the viewpoint of improving the adhesion property. As the electrode
material, for example, indium oxide, zinc oxide, tin oxide, indium-tin oxide (ITO) which is
a composite material thereof, gold, platinum, silver, or copper can be used. Of these
materials, ITO is preferable from the viewpoint of transparency and electrical conductivity.
The thickness of the electrode material layer 32 (therefore, transparent electrode 92) is
preferably in a range of 20 to 500 nm. In a case that the thickness is less than the lower
limit, the electrical conductivity is more likely to be insufficient. In a case that the
thickness exceeds the upper limit, there is possibility that the transparency is so insufficient
that emitted EL light cannot be extracted to the outside sufficiently.
[0069] After forming the film of the electrode material layer 32 by the sputter method or
the like, a photoresist 34 is applied on the electrode material layer 32 (the electrode
material layer 32 is coated with a photoresist 34), as shown in Fig. 5(b), in order to form a
28
desired electrode pattern by using a photolithography process (photoetching method).
Next, as shown in Fig. 5(c), the photoresist 34 is exposed with UV light etc., via a mask 44
in which the electrode pattern is formed. Next, as shown in Fig. 5(d), the etching is
performed on the photoresist 34 by a developer to remove a part of the photoresist 34,
thereby exposing a part 32a of the electrode material layer 32. Next, as shown in Fig.
5(e), the exposed part 32a of the electrode material layer 32 is removed by wet etching
with an etching liquid (etchant) such as hydrochloric acid to obtain a patterned electrode
material layer 32b. Then, by removing the photoresist remaining on the electrode
material layer 32b with a resist stripper, the patterned transparent electrode 92 can be
obtained as shown in Fig. 5(f). The substrate is exposed to a high temperature of about
300 degrees Celsius at the time of the sputtering. It is desired that the UV/O3 process be
performed after cleaning the obtained transparent electrode with the brush and eliminating
organic substances and the like by the alkaline cleaner and the organic solvent. The
patterned transparent electrode 92 may be obtained by performing the step for forming the
film of the electrode material layer 32 after the step for developing the photoresist shown
in Fig. 5(d) and then removing the photoresist layer by lift-off (lift-off method).
[0070] In the transparent electrode formation step by using the photolithography process,
a composition composing the photoresist includes organic substances such as ethyl lactate
and propylene glycol methyl ether acetate (PGMEA) as a solvent. As the resist developer,
it is used a solution and the like, of which major component is an organic base such as
tetramethylammonium hydroxide (TMAH) solution and trimethyl (2-hydroxyethyl)
ammonium hydroxide. In the wet etching of the electrode material, it is used an acid
solution such as hydrochloric acid and oxalic acid. As the resist stripper,
N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), diethylene glycol
monobuthyl ether, monoethanolamine, or the like is used. As described above, since the
optical substrate with the concave and convex pattern is exposed to the organic solvent and
the acid solvent such as the developer and the etching liquid in the transparent electrode
formation step, the concave and convex pattern formed in the optical substrate should have
the corrosion resistance thereto. In the present invention, since the concave and convex
pattern is made of the sol-gel material, even when the organic solvent and the acid solvent
are used in the electrode formation step, the concave and convex pattern is not corroded by
the solvents. Further, no color deterioration occurs in the concave and convex pattern.
The first electrode in the present invention is not limited to the transparent electrode, and
29
the first electrode may be an electrode such as a metal electrode having no permeability to
visible light etc., depending on the type of device and/or the use of device.
[0071]
After the photolithography process, the patterned transparent electrode is
subjected to the annealing, so that the crystallinity is increased to reduce a resistance value
and improve a transmittance (annealing step P4 of Fig. 1). The annealing is generally
performed in a heating furnace for about 10 minutes to 3 hours, and the annealing
temperature generally ranges from 160 to 360 degrees Celsius, for example, the annealing
temperature is 250 degrees Celsius. In the annealing step, although the optical substrate
is exposed to an annealing process at a high temperature of about 250 degrees Celsius,
since the sol-gel material layer 42 is usually made of the inorganic materials to have heat
resistance, the annealing process has no effect on the sol-gel material layer 42. Finally,
the annealed substrate is cleaned. A cleaning method similar to the above-mentioned
cleaning method of the optical substrate can be used. For example, the cleaning with the
brush and UV/O3 process may be used.
[0072]
Subsequently, an organic layer 94 as shown in Fig. 6 is stacked on the transparent
electrode 92 (thin film formation step P5 of Fig. 1). 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 known organic layer can be used as
appropriate. The organic layer 94 may be a stacked body of various organic thin films.
For example, the organic layer 94 may be a stacked body of a hole transporting layer 95, a
light-emitting layer 96, and an electron transporting layer 97 as shown in Fig. 6. Here,
examples of materials of the hole transporting layer 95 include aromatic diamine
compounds such as phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin
derivatives, N,N'-bis(3-methylphenyl)-(l,r-biphenyl)-4,4'-diamine (TPD), and
4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl(a-NPD); oxazole; oxadiazole; triazole;
imidazole; imidazolone; stilbene derivatives; pyrazoline derivatives; tetrahydroimidazole;
polyarylalkane; butadiene; and
4,4',4"-tris(N-(3-methylphenyl)N-phenylamino)triphenylamine (m-MTDATA). The
materials of the hole transporting layer, however, are not limited thereto.
30
[0073] By providing the light emitting layer 96, a hole injected from the transparent
electrode 92 and electron injected from a metal electrode 98 are recombined to occur light
emission. Examples of materials of the light emitting layer 96 include 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); tri-(p-terphenyl-4-yl)amine; l-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
preferred that light-emitting materials selected from the above compounds be mixed as
appropriate and then are used. Furthermore, 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 carrier 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). Examples of
materials of the electron transporting layer 97 include 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
derivarives, oxadiazole derivatives, and aluminum-quinolinol complex (Alq3). Further,
in the oxadiazole derivatives mentioned above, it is also possible to use, as the 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 attractive group. Furthermore, it is also possible to use a polymeric
material in which the above materials are introduced into a macromolecular chain or the
above materials are made to be a main chain of the macromolecular chain. It is noted that
the hole transporting layer 95 or the electron transporting layer 97 may also function as the
light-emitting layer 96. In this case, there are two organic layers between the transparent
electrode 92 and the metal electrode 98.
[0074] From the viewpoint of facilitating the electron injection from the metal electrode
31
98, it is allowable to provide, between the organic layer 94 and the metal electrode 98, as
an electron injecting layer, a layer made of a metal fluoride such as lithium fluoride (LiF),
a metal oxide such as Li2C>3, a highly active alkaline earth metal such as Ca, Ba, or Cs, an
organic insulating material, or the like. In addition, from the viewpoint of facilitating the
hole injection from the transparent electrode 92, it is allowable to provide, between the
organic layer 94 and the transparent electrode 92, as the hole injecting layer, a layer made
of triazole derivatives; oxadiazole derivatives; imidazole derivatives; polyarylalkane
derivatives; pyrazoline derivatives and pyrazolone derivatives; phenylenediamine
derivatives; arylamine derivatives; amino-substituted chalcone derivatives; oxazole
derivatives; styrylanthracene derivatives; fluorenon derivatives; hydrazone derivatives;
stilbene derivatives; silazane derivatives; aniline copolymer; or a conductive polymer
oligomer, in particular, thiophene oligomer, or the like.
[0075] In a case that the organic layer 94 is a stacked body formed of the hole
transporting layer 95, the light-emitting layer 96, and the electron transporting layer 97, the
thicknesses of the hole transporting layer 95, the light-emitting layer 96, and the electron
transporting layer 97 are preferably in a range of 1 to 200 nm, in a range of 5 to 100 nm,
and in a range of 5 to 200 nm, respectively. As a method for stacking the organic layer 94,
any known method such as a vapor deposition method, a sputtering method, a spin coating
method, and a die coating method can be employed as appropriate.
[0076]
Subsequently, as shown in Fig. 6, the metal electrode 98 as the second electrode is
stacked on the organic layer 94 (second electrode formation step P6 of Fig. 1). Materials
of the metal electrode 98 are not particularly limited, and a substance having a small work
function can be used as appropriate. Examples of the materials include aluminum, MgAg,
Mgln, and AlLi. The thickness of the metal electrode 98 is preferably in a range of 50 to
500 nm. In a case that the thickness is less than the lower limit, the electrical
conductivity is more likely to be decreased. In a case that the thickness exceeds the upper
limit, there is possibility that the repair or restoration is difficult when a short circuit
between electrodes occurs. Any known method such as a vapor deposition method and a
sputtering method can be adopted to stack the metal electrode 98. Accordingly, the
organic EL element 200 having the structure as shown in Fig. 6 can be obtained.
[0077] After the second electrode formation step, it is allowable to perform a step of
32
sealing the organic EL element 200 by using a sealing material to prevent deterioration due
to moisture and/or oxygen; a step of cutting a panel of the organic EL element 200 as
appropriate (scribe-and-break step); and/or a step of putting a polarizing plate to take a
measure against specular reflection of the metal electrode.
[0078] In the above embodiment, the explanation has been given by citing the
manufacture of the organic EL element as an example. The present invention, however,
can be applied to a method for manufacturing another device such as a solar cell. For
example, in a case that the solar cell is manufactured, the steps PI to P4 (i.e., the substrate
formation step PI, the cleaning step P2, the first electrode formation step S3, and the
annealing step P4) may be substantially the same as those of the manufacturing process of
the organic EL element. However, in the film formation step P5, depending on the type
of the solar cell, it is formed a thin film including, for example, thin-film silicon using
polysilicon and/or compound semiconductor; organic semiconductor; and a dye-sensitized
structure in which an electrolyte layer is provided for semiconductor. In the second
electrode formation step P6, the transparent electrode and/or metal electrode is/are formed.
[0079] Although the sol-gel material curable by heating is used in the method for
manufacturing the optical substrate of the above embodiment, instead of this, it is
allowable to use a photo-curable sol-gel material. In such a case, it is possible to adopt,
for example, a method in which photo-acid generator such as hexafluorophosphate
aromatic sulfonium salt which generates acid by light is used, or a method in which
chemical modification (chelation) is caused by adding P-diketone represented by
acetylacetone to a sol solution and the chemical modification is removed by being
irradiated with light. In a case that the photo-curable sol-gel material is used for the
sol-gel material layer, after the mold is pressed against the coating film (sol-gel material
layer) in the transfer step, the coating film may turn into a gel (be cured) by being
irradiated with light instead of the pre-baking of the coating film. Further, in the main
baking step, after the mold is released from the coating film on the substrate, the coating
film can be cured by being irradiated with light instead of the main-baking of the coating
film.
[0080] In addition to the manufacture of the organic EL and the solar cell, the method for
manufacturing the device of the present invention can be applied to any device, provided
that the device is manufactured through the steps PI to P6 (i.e., the substrate formation step
PI, the cleaning step P2, the first electrode formation step S3, the annealing step P4, the
33
thin film formation step P5, and the second electrode formation step S6). For example,
the method for manufacturing the device of the present invention can be applied to the
manufacture of a liquid crystal display and a touch panel.
[0081]
It was prepared a block copolymer produced by Polymer Source Inc., which was
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= 868,000
Mn of PMMA segment= 857,000
Mn of block copolymer = 1,725,000
Volume ratio between PS segment and PMMA segment (PS:PMMA)= 53:47
Molecular weight distribution (Mw/Mn)= 1.30
Tg of PS segment= 96 degrees Celsius
Tg of PMMA segment= 110 degrees Celsius
[0095] The volume ratio of the first polymer segment and the second polymer segment
(first polymer segment: second polymer segment) in each block copolymer was calculated
on the assumption that the density of polystyrene was 1.05 g/crn , the density of
polymethyl methacrylate was 1.19 g/ cm . The number average molecular weights (Mn)
and the weight average molecular weights (Mw) of polymer segments or polymers were
measured by using gel permeation chromatography (Model No: "GPC-8020" manufactured
by Tosoh Corporation, in which TSK-GEL SuperHlOOO, SuperH2000, SuperH3000, and
SuperH4000 were connected in series). The glass transition temperatures (Tg) of
polymer segments were measured by use of a differential scanning calorimeter
(manufactured by Perkin-Elmer under the product name of "DSC7"), while the temperature
was raised at a rate of temperature rise of 20 degrees Celsius/min over a temperature range
of 0 degrees Celsius to 200 degrees Celsius. 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), 2nd edition).
[0096] Toluene was added to 150 mg of the block copolymer and 38 mg of Polyethylene
Glycol 4000 manufactured by Tokyo Chemical Industry Co., Ltd. (Mw= 3000, Mw/Mn=
1.10) as polyethylene oxide so that the total amount thereof was lOg, followed by
dissolving them. Then, the solution was filtrated or filtered through a membrane filter
having a pore diameter of 0.5 um to obtain a block copolymer solution. The obtained
block copolymer solution was applied, on a polyphenylene sulfide film (TORELINA
40
manufactured by TORAYINDUSTRIRES, INC.) as a base member, in a film thickness of
200 to 250 nm, by spin coating. The spin coating was performed at a spin speed of 500
rpm for 10 seconds, and then performed at a spin speed of 800 rpm for 30 seconds. The
thin film formed by the spin coating was left at room temperature for 10 minutes until the
thin film was dried.
[0097] Subsequently, the base member on which the thin film was formed was heated for
5 hours in an oven of 170 degrees Celsius (first annealing process). Concavities and
convexities were observed on a surface of the heated thin film, and it was found out that
micro phase separation of the block copolymer forming the thin film was caused.
[0098] The thin film heated as described above was subjected to an etching process as
described below to selectively decompose and remove PMMA on the base member. The
tfiin film was irradiated with ultraviolet rays at an irradiation intensity of 30J/cm
(wavelength of 365 nm) by use of a high pressure mercury lamp. Then, the thin film was
immersed in acetone, and was subjected to cleaning with ion-exchanged water, followed
by being dried. As a result, there was formed, on the base member, a concave and convex
pattern clearly deeper than the concavities and convexities which appeared on the surface
of the thin film by the heating process.
[0099] Next, the base member was subjected to a heating process (second annealing
process) for 1 hour in an oven of 140 degrees Celsius so that the concave and convex
pattern formed by the etching process was deformed to have a chevron-shaped structure
(process for forming a shape of chevrons).
[0100] A thin nickel layer of about 10 nm was formed as a current seed layer by
sputtering on the surface of the thin film, for which the process for forming the shape of
chevrons had been performed. Subsequently, the base member with the thin film was
subjected to an electroforming process (maximum current density: 0.05A/cm2) in a nickel
sulfamate bath at a temperature of 50 degrees Celsius to precipitate nickel until the
thickness of nickel became 250 um. The base member with the thin film was
mechanically peeled off from the nickel electroforming body obtained as described above.
Subsequently, the nickel electroforming body was immersed in Chemisol 2303
manufactured by The Japan Cee-Bee Chemical Co., Ltd., followed by being cleaned while
being stirred for 2 hours at 50 degrees Celsius. Thereafter, polymer component(s)
adhering to a part of the surface of the electroforming body was(were) removed by
repeating the following process three times. That is, the nickel electroforming body was
41
coated with an acrylic-based UV curable resin; and the acrylic-based UV curable resin
coating the nickel electroforming body was cured; and then the cured resin was peeled off.
[0101] Subsequently, the nickel electroforming body was immersed in OPTOOL
HD-2100TH manufactured by Daikin Industries, Ltd. for about 1 minute and was dried,
and then stationarily placed overnight. The next day, the nickel electroforming body was
immersed in OPTOOL HD-TH manufactured by Daikin Industries, Ltd. to perform an
ultrasonic cleaning process for about 1 minute. Accordingly, a nickel mold (nickel
substrate) for which a mold-release treatment had been performed was obtained.
[0102] Subsequently, a PET substrate (easily-adhesion PET film manufactured by Toyobo
Co., Ltd., product name: COSMOSHINE A-4100) was coated with a fluorine-based UV
curable resin. Then, the fluorine-based UV curable resin was cured by irradiation with
ultraviolet rays at 600 mJ/cm2, with the obtained nickel mold being pressed against the
PET substrate. After curing of the resin, the nickel mold was peeled off from the cured
resin. Accordingly, a diffraction grating mold made of the PET substrate with the resin
film to which the surface profile of the nickel mold was transferred was obtained.
[0103]
The glass substrate with the pattern made of the sol-gel material layer as the
diffraction grating obtained as described above was cleaned with a brush in pure water to
remove foreign matter and the like adhering thereto. Then, organic matter and the like
adhering to the glass substrate was removed by ultrasonic cleaning by use of Semico Clean
as an alkaline cleaner and IPA as an organic solvent. A transparent electrode was formed
on the cleaned substrate by patterning as follows (see Fig. 5(a)-(f)). At first, a film of
ITO having a thickness of 120 nm was formed by a sputtering method at a temperature of
300 degrees Celsius. Then, the ITO film was coated with a photoresist (produced by
TOKYO OHKA KOGYO CO., LTD., TFR-H) by the spin coating method, and exposure
was performed with light having the wavelength of 365 nm via a mask pattern for the
transparent electrode. Thereafter, the exposed portion of the photoresist was removed by
etching by use of 2.5 % concentration TMAH solution as a developer, so that a part of ITO
is exposed. Next, the exposed area of ITO was removed by using 18 % concentration
hydrochloric acid as an etching liquid. Finally, the residual photoresist was removed by
using a mixed solution of DMSO and NMP (DMSO:NMP = 1:1) as stripper. Accordingly,
the transparent electrode having the predetermined pattern was obtained. After cleaning
the obtained substrate having the transparent electrode with the brush and then removing
the organic matter and the like adhering to the substrate by the ultrasonic cleaning using
the organic solvent (IPA), the UV/O3 process was performed and the substrate was put in
the heating furnace heated to 250 degrees Celsius to perform the annealing process for 20
45
minutes in the ambient atmosphere.
[0111] On the transparent electrode processed as described above, a hole transporting
layer (4,4',4" tris(9-carbazole)triphenylamine, thickness: 35 nm), a light emitting layer
(tris(2-phenylpyridinato)iridium(ni) complex-doped
4,4',4"tris(9-carbazole)triphenylamine, thickness: 15 nm;
tris(2-phenylpyridinato)iridium(ni) complex-doped
l,3,5-tris(N-phenylbenzimidazole-2-yl)benzene, thickness: 15 nm), an electron
transporting layer (l,3,5-tris(N-phenylbenzimidazole-2-yl)benzene, thickness: 65 nm), and
a lithium fluoride layer (thickness: 1.5 nm) were each stacked by a vapor deposition
method. Further, a metal electrode (aluminum, thickness: 50 nm) was formed as the
uppermost layer by a vapor deposition method. Accordingly, the organic EL element as
shown in Fig. 6 was obtained.
[0112] The directivity of light emission of the organic EL element obtained in this
example was evaluated by the following method. That is, the organic EL element in a
luminescent state was visually observed in all the directions (directions of all around 360°).
Neither particularly bright sites nor particularly dark sites were observed when the organic
EL element obtained in this Example was observed in any of the directions of all around
360°, and the brightness was uniform in all the directions. In this way, it was shown that
the directivity of light emission of the organic EL element of the present invention was
sufficiently low.
[0113] In Example 1, the temperature at the time of forming the film of the transparent
electrode (ITO) of the organic EL element was 300 degrees Celsius. Although it is
allowable that the temperature at the time of forming the film of the transparent electrode
is lower than 300 degrees Celsius, the transparent electrode is desired to have low
resistivity, and the film formation is preferably performed at high temperature to increase
crystallinity. In a case that the temperature during the film formation is low, which is
about 100 degrees Celsius, the ITO film formed on the substrate is relatively amorphous
and has inferior specific resistance, and an adhesion property between the substrate and the
ITO thin film is inferior. Although the concave and convex pattern formed of a general
UV curable resin and the like has difficulty in withstanding a film formation process at
high temperature, the use of sol-gel material which is an example of ceramic allows the
concave and convex pattern go through the film formation process at high temperature.
Therefore, the method of the present invention is also suitable for the manufacture of the
46
substrate (diffraction grating) for the organic EL element. Further, in a case that the
curable resin as described above is kept for a long period under high temperature because
of, for example, the generation of heat at the time of emitting light, there is fear that the
curable resin deteriorates to cause yellow discoloration and/or generate gas. Thus, it is
difficult to use the organic EL element using the resin substrate for a long period of time.
In contrast, the organic EL element provided with the substrate made of the sol-gel
material is less likely to deteriorate.
[0114]
[Example 2]
A diffraction grating substrate was manufactured in the same manner as Example
1, except that the pressing roll, which was heated to 150 degrees Celsius, was used. As a
result, the pattern transfer could be performed similarly to Example 1, and it was
confirmed that the average value of the depth distribution of the concave and convex
pattern in the diffraction grating substrate was 56 run and the average pitch was 420 nm.
[0115]
[Example 3]
In this Example, a diffraction grating substrate in which the concave and convex
pattern was formed of the sol-gel material (hereinafter referred to as "sol-gel pattern
substrate") and a diffraction grating substrate in which the same concave and convex
pattern was formed of resin (hereinafter referred to as "resin pattern substrate") were
prepared respectively. Then, the sol-gel pattern substrate was compared with the resin
pattern substrate with respect to the resistance to cleaning, chemicals, and heat in the
manufacturing process of the organic EL element, and results thereof were verified. As
the sol-gel pattern substrate, the diffraction grating substrate manufactured in Example 1
was used. The resin pattern substrate was manufactured as follows. A soda-lime glass
substrate of 15 x 15 x 0.11 cm was coated with a fluorine-based UV curable resin. Then,
the fluorine-based UV curable resin was cured by irradiation with ultraviolet rays at 600
mJ/cm2, with the diffraction grating mold manufactured in Example 1 being pressed
against the substrate. After curing of the resin, the diffraction grating mold was peeled
off from the cured resin. Accordingly, the resin pattern substrate to which the surface
profile of the diffraction grating mold was transferred was obtained.
[0116] The sol-gel pattern substrate and the resin pattern substrate prepared as described
above were subjected to processes simulating the cleaning process, the photolithography
47
process, the ITO etching process, the photoresist stripping step, and the annealing step,
those of which were performed before the thin film formation step in the manufacturing
process of the organic EL element. Then, the concave and convex pattern on each of the
substrates before and after each of the processes was observed. Although the transparent
electrode layer, etc., is stacked on the substrate in the actual manufacturing process of the
organic EL element, in order to examine the effects of chemicals and environmental
temperature on the substrate in each of the processes, no layer was stacked on the substrate
and the substrate was exposed to various environments in the following processes.
[0117]
(1) Cleaning step
In order to evaluate the resistance of each of the diffraction grating substrates (the
sol-gel pattern substrate and the resin pattern substrate) in the cleaning step performed
before the thin film formation step, the following three cleaning experiments were
performed on the sol-gel pattern substrate and the resin pattern substrate.
[0118]
An ultrasonic washer or cleaner (produced by Kokusai Denki LTec:KK) was
filled with isopropyl alcohol (EPA), and each of the sol-gel pattern substrate and the resin
pattern substrate was immersed in the isopropyl alcohol to be cleaned for 20 minutes at
output power of 200 W under room temperature. Subsequently, acetone was used as a
cleaning liquid instead of the isopropyl alcohol to perform the ultrasonic cleaning of each
of the sol-gel pattern substrate and the resin pattern substrate under the similar conditions
of those of the case using the isopropyl alcohol. Further, Semico Clean 56 was used as
the cleaning liquid instead of the isopropyl alcohol, and each of the sol-gel pattern
substrate and the resin pattern substrate was immersed in Semico Clean 56 to be subjected
to the ultrasonic cleaning for 10 minutes at output power of 200 W under room
temperature.
[0119]
The sol-gel pattern substrate and the resin-pattern substrate were each cleaned by
using a small single-substrate brush cleaner (produced by IMAI SEISAKUSHO Co., Ltd.).
A roll brush in which nylon having diameter of 100 jam was put into the surface of a roll
was used as the brush. The cleaning with the brush was performed under the following
48
conditions: rotation speed of the roll brush of 500 rprn; pressure of the roll brush against
the substrate of 0.2 MPa; and a substrate transport speed of 1 m/min. Pure water was
used as cleaning water and two roll brushes were used.
[0120]
The sol-gel pattern substrate and the resin pattern substrate were each
accommodated in a UV/03 cleaner (PL16-110: SEN LIGHTS CORPORATION). Then,
ozone was generated by UV light (wavelengths: 184.9 nm, 253.7 nm) by use of a low
pressure mercury lamp and each of the substrates was irradiated with UV light at 15
mW/cm2 for 10 minutes.
[0121]
(2) Photolithography step
In order to examine the resistance of the sol-gel pattern substrate and the resin
pattern substrate in the photolithography step, a beaker was filled with ethyl lactate
included in the photoresist, and each of the sol-gel pattern substrate and the resin pattern
substrate was immersed in the ethyl lactate for 20 minutes under room temperature.
Further, a similar experiment was carried out by using PGMEA instead of the ethyl lactate.
Furthermore, in order to examine the resistance of the sol-gel pattern substrate and the
resin pattern substrate to a photoresist developer, each of the sol-gel pattern substrate and
the resin pattern substrate was immersed in 2.5% of TMAH as the developer for 20
minutes under room temperature.
[0122]
(3) ITO etching step
In order to examine the resistance of the sol-gel pattern substrate and the resin
pattern substrate in the step of etching and patterning an ITO electrode material, each of
the substrates was immersed in 18% of hydrochloric acid for 20 minutes at ordinary
temperature.
[0123]
(4) Resist stripping step
In order to examine the resistance of the sol-gel pattern substrate and the resin
pattern substrate to the stripper used in the step of stripping the remaining photoresist in
the lithography step, each of the substrates was immersed in NMP for 20 minutes at
ordinary temperature. A similar experiment was carried out by using DMSO instead of
49
NMP.
[0124]
(5) Annealing step
In order to examine the resistance of the sol-gel pattern substrate and the resin
pattern substrate in the annealing step performed after the patterning of the transparent
electrode, each of the substrates was placed in the heating furnace heated to 250 degrees
Celsius for 20 minutes in the ambient atmosphere.
[0125]
In order to evaluate the resistance of the sol-gel pattern substrate and the resin
pattern substrate in each of the processes of the five steps, an inspection of unevenness and
a SPM inspection were performed on each of the substrates before and after each of the
processes. As the inspection of unevenness, the following method was adopted to
observe the overall state of the concave and convex pattern on the surface of each of the
substrates before and after each of the experiments.
[0126] An inspection apparatus 300 shown in Fig. 11 was provided in a dark room, and a
substrate 101 (each of the sol-gel pattern substrate and the resin pattern substrate) before
and after each of the processes in the above five steps was attached to the inspection
apparatus 300 to observe the intensity distribution of scattered light of the substrate under
the following conditions. The inspection apparatus 300 includes a stage device 104 on
which the substrate 101 is placed; a pair of highly directional LED bar illuminations 122
(produced by CCS Inc., LDL2-119 x 16BL) irradiating the substrate 101 with light; a
digital camera 125 taking the image of light reflected from the substrate; and an image
processing device 126 performing image processing and analysis of the obtained image.
The substrate 101 having a size of 30 mm x 30 mm and a thickness of 0.7 mm was
arranged to bridge between extend over a pair of black blocks 102 of the stage device 104,
each of black blocks 102 having a rectangular parallelepiped shape. The height of the
blocks 102 was 40 mm and the distance between the blocks 102 was 27 mm. The pair of
LED bar illuminations 122 had a light-emission central wavelength of 470 nm and an area
of light-emitting section of 119 mm x 160 mm. The pair of LED bar illuminations 122
was provided at a position having a height of 160 mm from the floor surface in a state of
being inclined toward the floor surface at 10° from a horizontal state. The distance
between the two LED bar illuminations 122 was 307 mm. The digital camera 125 was
50
arranged at a position having a distance of 770 mm from the surface of the substrate.
Light emission of the pair of LED bar illuminations was performed at a maximum output
(each 5.7 W) and an image of the substrate 101 was obtained. The type of the digital
camera 125 and the imaging conditions were as follows:
Camera: Canon EOS Kiss X3
Lens: EF-S18-55 mm F3.5-5.6 IS
Shutter speed: 1/100 seconds
ISO sensitivity: 3200
Aperture value: F5.6
White balance: Standard
Picture style: Standard
Pixel value: 0 to 255
[0127] Blue pixel values were sampled or extracted from the image obtained by the
digital camera, and the blue pixel values were displayed as a gray scale. Further, as
shown in Fig. 12(a), only the pixel values on a line LI, which extended in an X direction at
a substantially central position of the image in a Y direction, were sampled to be outputted
as profile of the pixel values with respect to pixel positions in the X direction. Only the
pixel values in the portion to be made into the organic EL element (within the frame
depicted by broken lines in Fig. 12(a)) were outputted as the cross-section profile. Fig.
12(b) shows an example of profile of the pixel values obtained from the sol-gel pattern
substrate with respect to the pixel positions in the X direction. In the example shown in
Fig. 12(b), the average pixel value was 113. It has been found out through preliminary
test(s) that unevenness of luminance was conspicuous when the diffraction grating
substrate, in which the change in average pixel value was 20 % before and after each of the
resistance tests, was used in the organic EL element. Therefore, a case in which the
change in average pixel value was less than 20 % before and after each of the resistance
tests was evaluated as "+" (satisfactory), and a case in which the change in average pixel
value was 20 % or more before and after each of the resistance tests was evaluated as "-"
(unsatisfactory). The evaluation results are shown in TABLE 1.
[0128] In the SPM inspection, the surface condition and depths of concavities and
convexities of the concave and convex pattern on the surface of each of the substrates were
inspected by use of a scanning microscope. In the SPM inspection, it was used the atomic
force microscope (the scanning probe microscope equipped with the environment control
51
unit "Nanonavi II Station/E-sweep" manufactured by Hitachi High-Tech Science
Corporation.) used in Example 1. Analysis conditions of the atomic force microscope
were the same as those in Example 1. A concavity and convexity analysis image was
obtained as described above by performing a measurement in a randomly selected
measuring region of 3 um square (length: 3 urn, width: 3 um) in the substrate. Distances
between randomly selected concave portions and convex portions in the depth direction
were measured at 100 points or more in the concavity and convexity analysis image, and
the average of the distances was calculated as the average value (average height) of depth
distribution of the concavities and convexities. In a case that the change in average value
of depth distribution of the concavities and convexities was 20 % or less as compared with
the substrate before each of the resistance tests, the substrate was evaluated to be
satisfactory or acceptable. In a case that the change in average value of depth distribution
of the concavities and convexities was 20% or more, the substrate was evaluated to be
unsatisfactory or defective. Further, in a case that abnormal projections and/or surface
roughness, which had not been observed before each of the resistance tests, was/were
observed in the image for evaluation, the substrate was evaluated to be unsatisfactory or
defective. In a case that no abnormality or defect was observed in the image for
evaluation, the substrate was evaluated to be satisfactory or acceptable. The case in
which both the average value of depth distribution of the concavities and convexities and
the image for evaluation were evaluated to be satisfactory or acceptable, the substrate was
evaluated to be satisfactory, which is expressed as "+" and cases other than the above case
were evaluated to be satisfactory, which is expressed as "-". The evaluation results are
shown in TABLE 1.
52
[0129] Regarding the resin pattern substrate processed by the UV/O3 cleaning in the
cleaning step, there were observed that the change in average pixel value was 20 % or
more in the observation of unevenness, and that the average value of depth distribution of
the concavities and convexities decreased by 20 % or more in the SPM observation. It is
assumed that these results were brought about by erosion of the concave and convex
pattern of the resin during the UV/O3 cleaning. On the other hand, regarding the sol-gel
pattern substrate, no significant difference was found out between observation results
before and after the UV/O3 cleaning. In the ITO etching process, it was observed in the
SPM observation that the resin pattern substrate had abnormal projections on the concave
and convex surface thereof. It is assumed that this result was brought about by generation
of abnormal precipitate generated by reaction between the resin and the hydrochloric acid
in the ITO etching process. On the other hand, regarding the sol-gel pattern substrate, no
significant difference was found out between observation results before and after the ITO
etching process. Further, regarding the resin pattern substrate after the annealing process,
. there were observed that the change in average pixel value was 20 % or more in the
observation of unevenness, and that the average value of depth distribution of the
concavities and convexities on the concave and convex surface decreased by 20 % or more
in the SPM observation. It is assumed that there results were brought about by melting of
a part of the concave and convex pattern of the resin owing to high temperature in the
annealing process. On the other hand, regarding the sol-gel pattern substrate, no
significant difference was found out between observation results before and after the
annealing process.
[0130]
[Comparative Example 1]
The resin pattern substrate manufactured in Example 3 was used as the diffraction
grating substrate to produce the organic EL element in the same manner as Example 1.
[0131]
[Evaluation of light emission efficiency of organic EL element]
The light emission efficiency of the organic EL element obtained in each of
Example 1 and Comparative Example 1 was measured by the following method. That is,
voltage was applied to the obtained organic EL element, and then the applied voltage V
and a current I flowing through the organic EL element were measured with a source
measurement instrument (manufactured by ADC CORPORATION, R6244), and a total
54
luminous flux amount L was measured with a total flux measurement apparatus
manufactured by Spectra Co-op. From the thus obtained measured values of the applied
voltage V, the current I, and the total luminous flux amount L, a luminance value L' was
calculated. Here, for the current efficiency, the following calculation formula (Fl) was
used:
Current efficiency = (L'II) x S (Fl)
and, for the power efficiency, the following calculation formula (F2) was used:
Power efficiency = (L'IW) x S (F2)
Accordingly, the current efficiency and the power efficiency of the organic EL element
were calculated. In the above formulae, S is a light-emitting or luminescent area of the
element. Noted that the value of the luminance L' was calculated on the assumption that
light distribution characteristic of the organic EL element followed Lambert's law, and the
following calculation formula (F3) was used:
L' = LIdS (F3)
[0132] The current efficiency of the organic EL element of Example 1 at a luminance of
1000 cd/m2 was 11 1.1 cd/A. Further, the power efficiency of the organic EL element of
Example 1 at a luminance of 1000 cd/m2 was 97.7 1mAN. The organic EL element of
Comparative Example 1 could not be evaluated as the element, because the resin pattern
was broken by mechanical damage at the time of the cleaning with the brush, damage at
the time of the UV/03 cleaning, and/or damage caused by heat at the time of the IT0 film
formation. ' An organic EL element manufactured on a glass substrate having no pattern
was prepared as a comparative sample, and the current efficiency and power efficiency of
the organic EL element were measured. As a result, the current efficiency at a luminance
of 1000 cd/m2 was 74.5 cd/A, and the power efficiency at the same luminance of 1000
cd/m2 was 58.4 lm/W.
[0133] As described above, since the concave and convex pattern of the optical substrate
used for the method for manufacturing the device according to the present invention is
made of the sol-gel material, this optical substrate has various advantages as compared
with the substrate having the concave and convex pattern made of the curable resin, as wil
be described below. The sol-gel material has a superior mechanical strength. Thus,
even when the cleaning with the brush is performed on the substrate and the surface of the
concave and convex pattern after formation of the transparent electrode in the
manufacturing process of the organic EL element, damage, the adhesion of foreign matter,
the projection on the transparent electrode, and the like are less likely to occur, and it is
possible to suppress any element failure (defect of an optical element) which would be
otherwise caused by the damage and the like. Therefore, the organic EL element, as the
device obtained by the method of the present invention is superior to the organic EL
element in which the curable resin substrate is used, in terms of the mechanical strength of
the substrate with the concave and convex pattern.
[0134] The substrate made of the sol-gel material produced according to the method of
the present invention has satisfactory chemical resistance. Therefore, the substrate of the
present invention is relatively corrosion-resistant to the alkaline fluid and the organic
solvent used in the cleaning steps of the substrate and the transparent electrode, which
makes it possible to use various cleaning liquids. Further, the alkaline developer or the
acidic etching liquid is sometimes used at the time of the patterning of the transparent
substrate as described above, and the substrate of the present invention is also corrosionresistant
to such developer and etching liquid. In this respect, the substrate of the present
invention has an advantage over the curable resin substrate having relatively low resistance
to the alkaline fluid and the acid solution.
[0135] The substrate made of the sol-gel material produced according to the method of
the present invention has superior heat resistance. Thus, it is also possible to resist a
high-temperature atmosphere of the sputtering step in the process for forming the
transparent electrode of the organic EL element. Further, the substrate made of the
sol-gel material produced according to the method of the present invention is superior to
the curable resin substrate in terms of the UV resistance and the weather resistance.
Therefore, the substrate of the present invention is also resistant to the UV/O3 cleaning
process after the formation of the transparent electrode. Accordingly, by using the
substrate made of the sol-gel material, no influence is exerted on the substrate in the
processes forming the semiconductor film and the organic film.
[0136] In a case that the organic EL element, as the device produced by the method of the
present invention, is used outside or outdoors, it is possible to suppress the deterioration
due to sunlight as compared with the case in which the curable resin substrate is used.
Further, in a case that the curable resin as described above is kept for a long period under
high temperature because of, for example, the generation of heat at the time of emitting
light, there is fear that the curable resin deteriorates to cause yellow discoloration and/or
generate gas. Thus, it is difficult to use the organic EL element using the resin substrate
56
for a long period of time. In contrast, the organic EL element provided with the substrate
made of the sol-gel material is less likely to deteriorate.
[0137] In the above description, the present invention was explained by using Examples.
The manufacturing method and manufacturing apparatus for the optical substrate and the
method for manufacturing the device according to the present invention, however, are not
limited to the above embodiments, and can be appropriately modified within the range of
technical ideas described in the claims. In the above Examples, for example, although the
diffraction grating substrate was manually manufactured by using the bar coater, the oven,
and the like, the diffraction grating substrate, however, may be manufactured by using the
optical substrate manufacturing apparatus as shown in Fig. 4. Further, although the
sol-gel material cured by heat was used in the above Examples, instead of mis, the
photo-curable sol-gel material may be used. In this case, the coating film (sol-gel
material) can be cured by being irradiated with light other than the baking of the coating
film.
Industrial Applicability
[0138] The manufacturing method and manufacturing apparatus for the optical substrate
according to the present invention are capable of manufacturing the optical substrate with
high throughput while performing the minute pattern transfer accurately and reliably. The
method for manufacturing the device according to the present invention utilizes the optical
substrate with the minute concave and convex pattern, which is manufactured by the
manufacturing method and the manufacturing apparatus according to the present invention
and is resistant to the process for manufacturing the element (device) into which the optical
substrate is incorporated because the optical substrate with the minute concave and convex
pattern has excellent in the heat resistance, the weather resistance, and the corrosion
resistance. Therefore, the method for manufacturing the device according to the present
invention makes it possible to extend the service life of the element. Accordingly, the
method for manufacturing the device according to the present invention can produce, with
high throughput, various devices, such as the organic EL element and the solar cell, which
are excellent in the heat resistance, the weather resistance, and the corrosion resistance.
Reference Signs List:
[0139]
57
21: mold feeding roll; 22: pressing roll; 23: peeling roll; 24: mold winding roll; 26:
supporting roll; 29: transporting roll; 30: die coater; 32: electrode material layer; 34:
photoresist; 35: heat zone; 40: substrate; 42: coating film (sol-gel material layer); 44:
mask; 70: roll process apparatus; 72: film feeding roll; 74: nip roll; 76: releasing roll; 78:
transporting roll; 80: substrate film; 80a: film-shaped mold; 82: die coater; 85: UV
radiation light source; 86: substrate film transporting system; 87: film winding roll; 90:
transfer roll; 92: transparent electrode; 94: organic layer; 95: hole transporting layer; 96:
light-emitting layer; 97: electron transporting layer; 98: metal electrode; 100: optical
substrate manufacturing apparatus; 101: diffraction grating substrate; 102: block; 104:
stage device; 120: coating section; 122: LED bar illumination; 125: digital camera; 126:
image processing device; 130: substrate transporting section; 140: mold transporting
section; 142,144,146: electricity-removing unit; 150: pressing section; 160: releasing
section; 200: organic EL element; 300: inspection apparatus
58
We claim:
1. A method for manufacturing an optical substrate having a concave and
convex pattern, comprising:
a step of preparing a long film-shaped mold having a surface of the concave and
convex pattern;
a step of forming a coating film made of a sol-gel material on a substrate;
a step of transferring the surface of the concave and convex pattern of the
film-shaped mold to the coating film by arranging the surface of the concave and convex
pattern to face the coating film and pressing a pressing roll against a surface of the
film-shaped mold on a side opposite to the surface of the concave and convex pattern;
a step of releasing the film-shaped mold from the coating film; and
a step of curing the coating film to which the concave and convex pattern has been
transferred.
2. The method for manufacturing the optical substrate according to claim 1,
wherein the step of curing the coating film includes curing the coating film by baking the
coating film.
3. The method for manufacturing the optical substrate according to claim 1
or 2, wherein the step of preparing the long film-shaped mold includes:
coating a long film-shaped base member with a concave-convex forming material;
performing a roll transfer of the concave and convex pattern to the
concave-convex forming material by pressing a transfer roll having the concave and
convex pattern against the concave-convex forming material coating the long film-shaped
base member while rotating the transfer roll; and
curing the concave-convex forming material to which the concave and convex
pattern has been transferred through the roll transfer so as to obtain the long film-shaped
mold in a roll shape.
4. The method for manufacturing the optical substrate according to claim 3,
wherein the film-shaped base member having the cured concave-convex forming material
is wound around a film winding roll.
59
5. The method for manufacturing the optical substrate according to claim 3,
wherein the concave and convex pattern of the transfer roll is transferred while the
film-shaped base member is transported by using a film feeding roll feeding the
film-shaped base member and a film winding roll winding or rolling up the film-shaped
base member.
6. The method for manufacturing the optical substrate according to claim 4
or 5, wherein the long film-shaped mold in the roll shape wound around the film winding
roll moves with being fed to the pressing roll.
7. The method for manufacturing the optical substrate according to any one
of claims 1 to 6, wherein the released long film-shaped mold is wound around a mold
winding roll.
8. The method for manufacturing the optical substrate according to any one
of claims 1 to 7, wherein the pressing roll is pressed against the surface of the film-shaped
mold on the side opposite to the surface of the concave and convex pattern while the
concave-convex forming material being heated.
9. The method for manufacturing the optical substrate according to any one
of claims 1 to 8, wherein the pressed concave-convex forming material is heated in the
releasing step or between the transfer step and the releasing step.
10. The method for manufacturing the optical substrate according to any one
of claims 1 to 9, wherein the surface of the concave and convex pattern of the long
film-shaped mold is successively pressed against coating films on a plurality of substrates
with the pressing roll while continuously feeding the long film-shaped mold under the
pressing roll and transporting each of the substrates to the pressing roll at a predetermined
time interval with the coating film made of the sol-gel material being formed.
11. The method for manufacturing the optical substrate according to any one
of claims 1 to 10, wherein the concave and convex pattern of the film-shaped mold is an
60
irregular concave and convex pattern in which an average pitch of concavities and
convexities is in a range of 100 to 1500 nm and an average value of a depth distribution of
the concavities and convexities is in a range of 20 to 200 nm.
12. An apparatus for manufacturing an optical substrate, comprising:
a coating-film forming section configured to form a coating film made of a sol-gel
material on a substrate;
a substrate transporting section configured to transport the substrate on which the
coating film is formed to a predetermined position;
a mold transporting section which includes a mold feeding roll configured to feed
a long film-shaped mold having a surface of a concave and convex pattern and a mold
winding roll configured to wind or roll up the long film-shaped mold, and is configured to
transport the film-shaped mold to the predetermined position by continuously feeding the
film-shaped mold from the mold feeling roll to the predetermined position and winding the
film-shaped mold around the mold wining roll; and
a pressing roll rotatably arranged at the predetermined position and configured to
press a part of the surface of the concave and convex pattern of the long film-shaped mold,
which is fed to the predetermined position by the mold transporting section, against the
coating film on the substrate which is transported to the predetermined position by the
substrate transporting section.
13. The apparatus for manufacturing the optical substrate according to claim
12, further comprising a peeling roll configured to peel the part of the surface of the
concave and convex pattern of the long film-shaped mold pressed with the pressing roll
from the coating film on the substrate.
14. The apparatus for manufacturing the optical substrate according to claim
12 or 13, further comprising a heating means configured to heat the coating film on the
substrate against which the part of the surface of the concave and convex pattern of the
film-shaped mold is pressed.
15. The apparatus for manufacturing the optical substrate according to claim
14, wherein the heating means is a heater provided in the pressing roll.
61
16. The apparatus for manufacturing the optical substrate according to any
one of claims 12 to 15, further comprising a heating means configured to heat the coating
film when the film-shaped mold is released from the coating film.
17. The apparatus for manufacturing the optical substrate according to any
one of claims 12 to 16, further comprising a supporting roll provided at a position to face
the pressing roll and configured to support the substrate from a lower side of the substrate.
18. The apparatus for manufacturing the optical substrate according to any
one of claims 12 to 17, wherein the coating-film forming section includes a substrate stage
configured to move the substrate while holding the substrate.
19. The apparatus for manufacturing the optical substrate according to any
one of claims 12 to 18, wherein the concave and convex pattern of the film-shaped mold is
an irregular concave and convex pattern in which an average pitch of concavities and
convexities is in a range of 100 to 1500 nm and an average value of a depth distribution of
the concavities and convexities is in a range of 20 to 200 nm.
20. The apparatus for manufacturing the optical substrate according to any
one of claims 12 to 19, further comprising a roll process apparatus configured to form the
long film-shaped mold, the roll process apparatus including: a transporting system
configured to transport a substrate film; a coating unit configured to coat the substrate film
being transported with a concave-convex forming material; a transfer roll provided on a
downstream side of the coating unit and configured to transfer the concave and convex
pattern to the concave-convex forming material; and a radiation light source configured to
emit light to the substrate film.
21. The apparatus for manufacturing the optical substrate according to claim
20, wherein the transporting system includes a film feeding roll configured to feed the
substrate film; a nip roll configured to urge the substrate film toward the transfer roll; a
releasing roll configured to facilitate releasing of the substrate film from the transfer roll;
and a film winding roll configured to wind or roll up the substrate film to which the
62
concave and convex pattern has been transferred.
22. The apparatus for manufacturing the optical substrate according to claim
21, wherein the film winding roll around which the substrate film is wound is used as the
mold feeding roll configured to feed the film-shaped mold.
23. A method for manufacturing a device provided with an optical substrate
having a concave and convex pattern, comprising:
a substrate formation step of forming a substrate with a predetermined concave
and convex pattern by coating the substrate with a sol-gel material and transferring the
concave and convex pattern to the sol-gel material coating the substrate;
a cleaning step of cleaning the substrate with the concave and convex pattern;
a first electrode formation step of forming a first electrode on the cleaned
substrate by patterning;
an annealing step of annealing the substrate on which the first electrode is formed;
a thin film formation step of forming a thin film on the first electrode; and
a second electrode formation step of forming a second electrode on the thin film.
24. The method for manufacturing the device according to claim 23, wherein
at least one of ultrasonic cleaning, cleaning with a brush, and UV/O3 cleaning is performed
in the cleaning step.
25. The method for manufacturing the device according to claim 23 or 24,
wherein the patterning is performed by using an acid solvent or an alkaline solvent, and the
patterning includes formation of a first electrode layer, resist coating, exposure and
development, etching of the first electrode layer, and stripping of the resist.
26. The method for manufacturing the device according to any one of claims
23 to 25, wherein the annealing is performed at a temperature in a range of 160 degrees
Celsius to 360 degrees Celsius.
27. The method for manufacturing the device according to any one of claims
23 to 26, wherein the device is an organic EL element, the first electrode is a transparent
63
electrode, the thin film includes an organic layer, and the second electrode is a metal
electrode.
28. The method for manufacturing the device according to any one of claims
23 to 27, wherein the device is a solar cell, the first electrode is a transparent electrode, the
thin film includes a semiconductor layer, and the second electrode is a metal electrode.
29. The method for manufacturing the device according to any one of claims
23 to 28, wherein the concave and convex pattern formed on the substrate is an irregular
concave and convex pattern used for scattering or diffracting light in which an average
pitch of concavities and convexities is in a range of 100 to 1500 nm and an average value
of a depth distribution of the concavities and convexities is in a range of 20 to 200 nm.
30. The method for manufacturing the device according to any one of claims
23 to 29, wherein the substrate is a glass substrate and the sol-gel material includes a silica
precursor.
31. The method for manufacturing the device according to any one of claims
23 to 30, further comprising baking of the sol-gel material at a temperature of 300 degrees
Celsius or more after coating the substrate with the sol-gel material and transferring the
predetermined concave and convex pattern to the so-gel material coating the substrate.
32. The method for manufacturing the device according to any one of claims
23 to 31, wherein the substrate formation step includes:
a step of preparing a long film-shaped mold having a surface of the concave and
convex pattern;
a step of forming a coating film made of the sol-gel material on the substrate;
a step of transferring the surface of the concave and convex pattern of the
film-shaped mold to the coating film by arranging the surface of the concave and convex
pattern of the film-shaped mold to face the coating film and pressing a pressing roll against
a surface of the film-shaped mold on a side opposite to the surface of the concave and
convex pattern;
a step of releasing the film-shaped mold from the coating film; and
64
a step of baking the coating film to which the concave and convex pattern has
been transferred.
65