U.S. patent application number 11/788503 was filed with the patent office on 2007-11-01 for photosensitive resin composition, thin film panel made with photosensitive resin composition, and method for manufacturing thin film panel.
Invention is credited to Kyu-Young Kim, Hi-Kuk Lee, Yuko Yako.
Application Number | 20070254221 11/788503 |
Document ID | / |
Family ID | 36612046 |
Filed Date | 2007-11-01 |
United States Patent
Application |
20070254221 |
Kind Code |
A1 |
Lee; Hi-Kuk ; et
al. |
November 1, 2007 |
Photosensitive resin composition, thin film panel made with
photosensitive resin composition, and method for manufacturing thin
film panel
Abstract
A photosensitive resin composition includes an alkali-soluble
resin, a quinone diazide, a surfactant, and a solvent. The
surfactant includes an organic fluorine compound having the
structure ##STR1## a first silicone compound having the structure
##STR2## a second silicone compound having the structure ##STR3##
The resin composition may be used in display panels.
Inventors: |
Lee; Hi-Kuk; (Gyeonggi-do,
KR) ; Yako; Yuko; (Osaka, JP) ; Kim;
Kyu-Young; (Gyeonggi-do, KR) |
Correspondence
Address: |
MACPHERSON KWOK CHEN & HEID LLP
2033 GATEWAY PLACE
SUITE 400
SAN JOSE
CA
95110
US
|
Family ID: |
36612046 |
Appl. No.: |
11/788503 |
Filed: |
April 20, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11318157 |
Dec 23, 2005 |
|
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11788503 |
Apr 20, 2007 |
|
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Current U.S.
Class: |
430/20 ;
257/E21.169; 257/E21.26 |
Current CPC
Class: |
H01L 21/02282 20130101;
H01L 21/2855 20130101; H01L 21/0212 20130101; H01L 21/02126
20130101; H01L 27/124 20130101; H01L 27/14632 20130101; H01L
27/1248 20130101; G03F 7/0226 20130101; G03F 7/0048 20130101; H01L
21/3121 20130101; G03F 7/0757 20130101; G03F 7/0046 20130101 |
Class at
Publication: |
430/020 |
International
Class: |
C09K 19/40 20060101
C09K019/40 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 24, 2004 |
KR |
10-2004-0112255 |
Claims
1. A photosensitive resin composition comprising: an alkali-soluble
resin; a quinone diazide; a solvent; and a surfactant that
includes: an organic fluorine compound of structure ##STR31## where
R.sub.f is a chained or branched perfluoroalkylene group including
about 5-10 carbon atoms and Z is a hydrogen or a fluorine; a first
silicone compound of structure ##STR32## where R is a chained or
branched alkylene group including about 2-5 carbon atoms and each
of x and y is an integer of about 1-20; and a second silicone
compound of structure ##STR33## where R' is an alkyl group
including about 1-20 carbon atoms or a chained or branched carbonyl
alkyl group including about 2-21 carbon atoms and each of v and w
is an integer of about 1-20, and each of m and 1 is an integer of
about 1-9 wherein (m+1) lies between 2 and 10.
2-19. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority from Korean Patent
Application No. 10-2004-0112255 filed on Dec. 24, 2004, the content
of which is incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
[0002] (a) Field of the Invention
[0003] The present invention relates generally to a photosensitive
resin composition, a thin film panel including a layer made with
the photosensitive resin composition, and method of manufacturing
the thin film panel. In particular, the invention relates to a
photosensitive resin composition for insulation of a display
panel.
[0004] (b) Description of Related Art
[0005] An active type display device such as an active matrix (AM)
liquid crystal display (LCD) and an active matrix organic light
emitting diode (OLED) display includes a plurality of pixels
arranged in a matrix. The pixels in the matrix include switching
elements, and the pixel boundaries are usually formed by a
plurality of signal lines such as gate lines and data lines for
transmitting signals to the switching elements. The switching
elements of the pixels selectively transmit data signals from the
data lines to the pixels in response to gate signals from the gate
lines for displaying images. The pixels of the LCD adjust the
transmittance of incident light according to the data signals,
while those of the OLED display adjust the luminance of light
emission according to the data signals.
[0006] The LCD and the OLED displays include a panel provided with
the TFTs, the field-generating electrodes, the signal lines, etc.
The panel has a layered structure that includes several conductive
layers and insulating layers. The gate lines, the data lines, and
the field-generating electrodes are formed of different conductive
layers and separated by insulating layers.
[0007] The insulating layers are made of inorganic or organic
insulators. Organic insulators have a transmittance higher than the
inorganic insulators, and therefore often result in increased
luminance (and an increased reference viewing angle for an LCD).
Several of these organic insulators have a photosensitivity level
that allows them to be patterned only by lithography without
etching, thereby simplifying the display manufacturing process.
[0008] However, conventional photosensitive organic insulating
layers often have spots or stains. In particular, as the display
devices increase in size, slit coating or spin-and-slit coating is
preferred to spin coating as a method of forming the organic
insulating layers, and the slit coating and the spin-and-slit
coating of the organic insulating layers frequently generate
stains. The stains may be horizontal stains along a direction of a
slit type nozzle of a coating device, vertical stains along a
length direction of the slit type nozzle, and irregular spots over
an entire surface of a substrate. In addition, portions of the
organic layer near the edges of a substrate are sometimes thicker
than other portions of the organic layer. These portions with extra
thickness may not completely dissolve during the development such
that they remain to form stains, degrading the image quality of the
display device.
[0009] A method and device for forming organic insulating layers
with fewer stains is desired.
SUMMARY OF THE INVENTION
[0010] In one aspect, the invention is a photosensitive resin
composition that includes an alkali-soluble resin, a quinone
diazide, a surfactant, and a solvent. The surfactant includes:
[0011] an organic fluorine compound having the structure ##STR4##
where R.sub.f is a chained or branched perfluoroalkylene group
including about 5-10 carbon atoms and Z is a hydrogen or a
fluorine;
[0012] a first silicone compound having the structure ##STR5##
where R is a chained or branched alkylene group including about 2-5
carbon atoms and each of x and y is an integer of about 1-20;
and
[0013] a second silicone compound having the structure ##STR6##
[0014] where R' is an alkyl group including about 1-20 carbon atoms
or a chained or branched carbonyl alkyl group including about 2-21
carbon atoms and each of v and w is an integer of about 1-20, and
each of m and 1 is an integer of about 1-9 wherein (m+1) lies
between 2 and 10.
[0015] In another aspect, the invention is a thin film panel
including: a substrate; a thin film pattern formed on the
substrate; and an insulating layer formed on the thin film pattern
and made from a photosensitive resin composition including an
alkali-soluble resin, a quinone diazide, a surfactant, and a
solvent. The surfactant includes:
[0016] an organic fluorine compound having the structure ##STR7##
where R.sub.f is a chained or branched perfluoroalkylene group
including about 5-10 carbon atoms and Z is a hydrogen or a
fluorine;
[0017] a first silicone compound having the structure ##STR8##
where R is a chained or branched alkylene group including about 2-5
carbon atoms and each of x and y is an integer of about 1-20;
and
[0018] a second silicone compound having the structure ##STR9##
where R' is an alkyl group including about 1-20 carbon atoms or a
chained or branched carbonyl alkyl group including about 2-21
carbon atoms and each of v and w is an integer of about 1-20, and
each of m and 1 is an integer of about 1-9 wherein (m+1) lies
between 2 and 10.
[0019] In yet another aspect, the invention is a method of
manufacturing a thin film panel. The method includes: forming a
thin film pattern on a substrate; coating a photosensitive resin
composition including an alkali-soluble resin, a quinone diazide, a
surfactant, and a solvent; performing a light exposure on the
photosensitive resin composition; and developing the photosensitive
resin composition. The surfactant includes:
[0020] an organic fluorine compound having the structure ##STR10##
where R.sub.f is a chained or branched perfluoroalkylene group
including about 5-10 carbon atoms and Z is a hydrogen or a
fluorine;
[0021] a first silicone compound having the structure ##STR11##
where R is a chained or branched alkylene group including about 2-5
carbon atoms and each of x and y is an integer of about 1-20;
and
[0022] a second silicone compound having the structure ##STR12##
where R' is an alkyl group including about 1-20 carbon atoms or a
chained or branched carbonyl alkyl group including about 2-21
carbon atoms and each of v and w is an integer of about 1-20, and
each of m and 1 is an integer of about 1-9 wherein (m+1) lies
between 2 and 10.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The present invention will become more apparent by
describing embodiments thereof in detail with reference to the
accompanying drawing in which:
[0024] FIG. 1 is a layout view of a TFT array panel according to an
embodiment of the present invention;
[0025] FIG. 2 is a sectional view of the TFT array panel shown in
FIG. 1 taken along the line II-II';
[0026] FIGS. 3A, 4A, 5A and 6A are layout views of the TFT array
panel shown FIGS. 1 and 2 in intermediate steps of a manufacturing
method thereof according to an embodiment of the present
invention;
[0027] FIG. 3B is a sectional view of the TFT array panel shown in
FIG. 3A taken along the line IIIB-IIIB';
[0028] FIG. 4B is a sectional view of the TFT array panel shown in
FIG. 4A taken along the line IVB-IVB';
[0029] FIG. 5B is a sectional view of the TFT array panel shown in
FIG. 5A taken along the line VB-VB';
[0030] FIG. 6B is a sectional view of the TFT array panel shown in
FIG. 6A taken along the line VIB-VIB';
[0031] FIG. 7 is a layout view of a TFT array panel according to
another embodiment of the present invention;
[0032] FIG. 8 is a sectional view of the TFT array panel shown in
FIG. 7 taken along the line VIII-VIII';
[0033] FIGS. 9A and 10A are layout views of the TFT array panel
shown FIGS. 7 and 8 in intermediate steps of a manufacturing method
thereof according to an embodiment of the present invention;
[0034] FIG. 9B is a sectional view of the TFT array panel shown in
FIG. 9A taken along the line IXB-IXB';
[0035] FIG. 10B is a sectional view of the TFT array panel shown in
FIG. 9A taken along the line XB-XB'; and
[0036] FIGS. 11A-11F are photographs illustrating photosensitive
resin films according to examples of the present invention and
comparative examples.
DETAILED DESCRIPTION OF EMBODIMENTS
[0037] The present invention now will be described more fully
hereinafter with reference to the accompanying drawings, in which
preferred embodiments of the invention are shown. The present
invention may, however, be embodied in many different forms and
should not be construed as limited to the embodiments set forth
herein.
[0038] A photosensitive resin composition according to the present
invention includes an alkali-soluble resin, a quinone diazide, a
surfactant, and a solvent.
[0039] The alkali-soluble resin may include a curable copolymer
that includes a compound (a1) derived from an unsaturated
carboxylic acid and a compound (a2) derived from an unsaturated
compound including a cross-linking group, which is not an
unsaturated carboxylic acid.
[0040] The unsaturated carboxylic acid in the compound (a1) may
include a molecule including one or more carboxyl groups and
examples of the unsaturated carboxylic acid include an unsaturated
monocarboxylic acid and an unsaturated dicarboxylic acid. The
unsaturated carboxylic acid may be selected from an acrylic acid, a
methacrylic acid, a crotonic acid, an itaconic acid, a maleic acid,
a fumaric acid, a citraconic acid, a mesaconic acid, and a cinnamic
acid.
[0041] The compound (a2) may include an unsaturated compound
including an epoxy group or preferably an oxetanyl group.
[0042] Examples of the unsaturated compound including an epoxy
group include a glyddyl(meth)acrylate, a .beta.-methyl
glycidyl(meth)acrylate, a .beta.-methyl glycidyl (meth)acrylate, a
3-methyl-3,4-epoxy butyl(meth)acrylate, a 3-ethyl-3,4-epoxybutyl
(meth)acrylate, a 4-methyl-4,5-epoxy pentyl(meth)acrylate, a
2,3-poxy cyclohexyl methyl(meth)acrylate, a 3,4-epoxy cyclohexyl
methyl(meth)acrylate, an o-vinyl benzyl glycidyl ether, an m-vinyl
benzyl glycidyl ether, a p-vinyl benzyl glycidyl ether, a 1-vinyl
cyclohexene oxide, a 3-vinyl cyclohexene oxide, and a 4-vinyl
cyclohexene oxide.
[0043] Examples of the unsaturated compound including an oxetanyl
group include a 3-(meth)acryloyloxymethyl oxetane, a
3-methyl-3-(meth)acryloyloxymethyl oxetane, a
3-ethyl-3-(meth)acryloyloxymethyl oxetane, a
2-phenyl-3-(meth)acryloyloxymethyl oxetane, a
2-trifluoromethyl-3-(meth)acryloyloxymethyl oxetane, a
2-pentafluoroethyl-3-(meth)acryloyloxymethyl oxetane, a
3-methyl-3-(meth)acryloyloxyethyl oxetane, a
3-methyl-3-(meth)acryloyloxyethyl oxetane, a
2-phenyl-3-(meth)acryloyloxyethyl oxetane, a
2-trifluoromethyl-3-(meth)acryloyloxyethyl oxetane, and a
2-pentafluoroethyl-3-(meth)acryloyloxyethyl oxetane. Among the
above-described oxetanes, the 3-ethyl-3-(meth)acryloyloxymethyl
oxetane is preferable.
[0044] The photosensitive resin composition including the oxetanyl
group is advantageous for storage of the photosensitive resin
composition.
[0045] The curable copolymer may further include a compound (a3)
that includes at least one of: a compound (a31) derived from a
carboxylic acid ester having an olefinic double bond; an compound
(a32) derived from an aromatic compound having a polymerizable,
unsaturated carbon-to-carbon bond; a compound (a33) derived from a
vinyl cyanide; and a compound (a34) derived from an N-substituted
maleimide.
[0046] An example of the carboxylic acid ester having an olefinic
double bond and deriving the compound (a31) includes a compound
derived from: an unsaturated carboxylic acid ester such as a
methyl(meth)acrylate, an ethyl(meth)acrylate, a butyl
(meth)acrylate, a 2-hydroxyethyl(meth)acrylate, a
benzyl(meth)acrylate, a cyclohexyl (meth)acrylate, an
isobornyl(meth)acrylate or a dicyclopentanyl(meth)acrylate,
phenyl(meth)acrylate, a diethyl maleate, a diethyl fumarate, and a
diethyl itaconate; an unsaturated carboxylic acid aminoalkyl ester
such as an aminoethyl(meth)acrylate; and a vinyl ester such as a
vinyl acetate and a vinyl propionate.
[0047] Examples of the aromatic compound having a polymerizable,
unsaturated carbon-to-carbon bond and generating the compound (a32)
include a styrene, an .alpha.-methyl styrene, and a vinyl
toluene.
[0048] An example of the vinyl cyanide from which the compound
(a33) is derived includes a compound derived from a vinyl cyanide
such as an acrylonitrile, a methacrylonitrile, and an
.alpha.-chloro(meth)acrylonitrile.
[0049] Examples of the N-substituted maleimide deriving the
compound (a34) include an N-methyl maleimide, an N-ethyl maleimide,
an N-butyl maleimide, an N-cyclohexyl maleimide, an N-benzyl
maleimide, an N-phenyl maleimide, an N-(4-acetylphenyl)maleimide,
an N-(2,6-diethylphenyl)maleimide, an
N-(4-dimethylamino-3,5-dinitrophenyl)maleimide, an
N-succinimidyl-3-maleimide benzoate, an N-succinimidyl-3-maleimide
propionate, an N-succinimidyl-maleimide butylate, an
N-succinimidyl-6-maleimide caproate, an
N-(1-anilinonaphthyl)-4-maleimide, an
N-[4-(2-benzoxazolyl)phenyl]maleimide, and an
N-(9-acridinyl)maleimide.
[0050] Each of the compounds (a1), (a2), (a31), (a32), (a33) and
(a34) may include one or more compounds derived from the
above-described compounds.
[0051] In the copolymer including the compound (a1) derived from
the unsaturated carboxylic acid and the compound (a2) derived from
the unsaturated compound including the cross-linking group, the
content of the compound (a1) is equal to preferably about 5-50 mol
% and more preferably about 15-40 mol % of the copolymer, and the
content of the compound (a2) is equal to about 5-95 mol % and more
preferably about 15-85 mol % of the copolymer.
[0052] The photosensitive resin composition including the copolymer
that includes the compounds (a1) and (a2) in the amounts described
above has an appropriate resolution speed for a developer and has a
high curability.
[0053] In the copolymer further including the compound (a3) as well
as the compounds (a1) and (a2), the content of the compound (a3) in
the copolymer is equal to preferably about 0.01-90 mol % and more
preferably about 0.01-80 mol %.
[0054] The copolymer may be formed by, for example:
[0055] (1) solution polymerization at about 60-300.degree. C. that
mixes monomers and a polymerization initiator in an organic solvent
with or without a chain transfer agent as described in J. Polym.
Sci., Polym. Chem. (1968), 6(2), pp. 257-267;
[0056] (2) suspension or emulsion polymerization at about
60-300.degree. C. using a solvent that does not dissolve monomers
as described in J. Polym. Sci., Polym. Chem.(1983), 21(10), pp.
2949-2960;
[0057] (3) bulk polymerization at about 60-200.degree. C. as
described in Japanese Patent Application Publication No. Hei
6-80735; and
[0058] (4) successively supplying monomers into polymerization
chamber, heating the monomers at about 180-300.degree. C. for about
5-60 minutes with or without a polymerization initiator, and
extracting reaction products out of the chamber as described in
Japanese Patent Application Publication No. 10-195111.
[0059] In addition, the copolymer may be obtained by mixing and
reacting monomers, polymerization initiators, and an organic
solvent. This may be done by successively supplying monomers in an
organic solvent with an additive polymerization initiator, and by
successively adding monomers and an initiator to an organic
solvent. In order to dissipate the heat of reaction, it is
preferable to supply the monomers successively as opposed to all at
once. In order to obtain polymer compounds having a narrow
molecular weight distribution, it is preferable to successively
supply the polymerization initiator.
[0060] The reaction is performed for preferably about 1 to about 20
hours, and more preferably for about 2 to about 10 hours at a
temperature preferably of about 40 to about 200.degree. C., more
preferably of about 50 to about 150.degree. C., and most preferably
of about 60 to about 120.degree. C. When the monomers are
successively supplied, it is preferable that the monomers are
supplied for about 1 to about 5 hours and continuously heated for
about 1 to about 10 hours. In this case, the reaction
concentration, i.e., the weight percentage of the monomers in the
total reaction solution, is preferably about 10 to about 70%, and
more preferably about 20 to about 60%.
[0061] Examples of the organic solvent include:
[0062] alcohols such as a methanol, an ethanol, a propanol, a
butanol, a pentanol, a hexanol, cyclohexanol;
[0063] ketones such as acetone, methyl ethyl ketone, methyl
isobutyl ketone, diisobutyl ketone, cyclopentanone, and
cyclohexanone;
[0064] ethers such as ethylene glycol dimethyl ether, ethylene
glycol diethyl ether, ethylene glycol dipropyl ether, ethylene
glycol dibutyl ether, ethylene glycol ethyl methyl ether,
diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
diethylene glycol dipropyl ether, diethylene glycol dibutyl ether,
diethylene glycol ethyl methyl ether, ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl
ether, diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether, diethylene glycol monobutyl ether, triethylene
glycol dimethyl ether, tetraethylene glycol dimethyl ether,
propylene glycol monomethyl ether, dipropylene glycol monomethyl
ether, dipropylene glycol monoethyl ether, dipropylene glycol
dimethyl ether, dipropylene glycol diethyl ether,
3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol;
[0065] esters such as ethyl acetate, butyl acetate, amyl acetate,
methyl lactate, ethyl lactate, butyl lactate, 3-methoxy butyl
acetate, 3-methyl-3-methoxy-1-butyl acetate, ethylene glycol
monoethyl ether acetate, ethylene glycol monoethyl ether acetate,
diethylene glycol monobutyl ether acetate, propylene glycol
monomethyl ether acetate, propylene glycol monoethyl ether acetate,
dipropylene glycol monomethyl ether acetate, dipropylene glycol
monoethyl ether acetate, 1,3-propanediol diacetate, ethyl 3-ethoxy
propionate, methyl 3-methoxy propionate, methyl 2-hydroxy
isobutanate, ethylene carbonate, propylene carbonate, and
butyrolactone); and
[0066] aromatic hydrocarbons such as toluene and xylene.
[0067] The solvent may include two or more of the above-described
compounds.
[0068] Examples of the copolymer including the compounds (a1) and
(a2) include 3-ethyl-3-methacryloyloxymethyl oxetane/benzyl
methacrylate/methacrylate copolymer,
3-ethyl-3-methacryloyloxymethyl oxetane/benzyl
methacrylate/methacrylate/styrene copolymer,
3-ethyl-3-methacryloyloxymethyl oxetane/methacrylate/styrene
copolymer, 3-ethyl-3-methacryloyloxymethyl
oxetane/methacrylate/cyclohexyl methacrylate copolymer,
3-ethyl-3-methacryloyloxymethyl oxetane/methacrylate/methyl
methacrylate copolymer, 3-ethyl-3-methacryloyloxymethyl
oxetane/methacrylate/methyl methacrylate/styrene copolymer,
3-ethyl-3-methacryloyloxymethyl oxetane/methacrylate/t-butyl
methacrylate copolymer, 3-ethyl-3-methacryloyloxymethyl
oxetane/methacrylate/isobornyl methacrylate copolymer,
3-ethyl-3-methacryloyloxymethyl oxetane/benzyl acetate copolymer,
3-ethyl-3-methacryloyloxymethyl oxetane/methacrylate/cyclohexyl
acrylate copolymer, 3-ethyl-3-methacryloyloxymethyl
oxetane/methacrylate/isobornyl acrylate copolymer,
3-ethyl-3-methacryloyloxymethyl
oxetane/methacrylate/dicyclopentanyl methacrylate copolymer, or
3-ethyl-3-methacryloyloxymethyl oxetane/methacrylate/t-butyl
acrylate copolymer, 3-ethyl-3-methacryloyloxymethyl
oxetane/methacrylate/phenyl maleimide copolymer, and
3-ethyl-3-methacryloyloxymethyl oxetane/methacrylate/cyclohexyl
maleimide copolymer.
[0069] The average molecular weight of the copolymer including the
compounds (a1) and (a2) determined by gel permeation chromatography
(GPC) using a polystyrene standard is preferably from about 2,000
to about 100,000, more preferably from about 2,000 to about 50,000,
and most preferably from about 3,000 to about 20,000. When the
average molecular weight is in the above-described range, the
development speed is increased with maintaining the insoluble
fraction.
[0070] The content of the copolymer including the compounds (a1)
and (a2) is preferably from about 50 to about 98 wt. %, and more
preferably from about 60 to about 95 wt. % relative to the solid
content of the photosensitive resin composition. The lower limit of
50 wt. % is the lowest content for maintaining the photosensitive
characteristic, and the upper limit of 98 wt. % is determined in
consideration of the lowest amount of other moieties including the
quinone diazide and the surfactant.
[0071] The quinone diazide in the photosensitive resin composition
may be selected from 1,2-benzoquinonediazide sulfonate ester,
1,2-naphthoquinonediazide sulfonate ester, 1,2-benzoquinonediazide
sulfonate amide, and 1,2-naphthoquinonediazide sulfonate amide.
[0072] Examples of the quinone diazide include: [0073]
1,2-naphthoquinone diazide sulfonate esters of
trihydroxybenzophenone such as
2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonat-
e ester,
2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonat-
e ester,
2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonat-
e ester, and
2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate
ester; [0074] 1,2-naphthoquinone diazide sulfonate esters of
tetrahydroxybenzophenone such as [0075]
2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate
ester,
2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sul-
fonate ester,
2,2',4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate
ester,
2,2',4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sul-
fonate ester,
2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate
ester,
2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulf-
onate ester,
2,3,4,2'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-sulfonate
ester,
2,3,4,2'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulf-
onate ester,
2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4--
sulfonate ester, and [0076]
2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5--
sulfonate ester; [0077] 1,2-naphthoquinone diazide sulfonate esters
of pentahydroxybenzophenone such as
2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonat-
e ester and [0078]
2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonat-
e ester; [0079] 1,2-naphthoquinone diazide sulfonate esters of
hexahydroxybenzophenone such as [0080]
2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfon-
ate ester,
2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazid- e
sulfonate ester,
3,4,5,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfon-
ate ester, and
3,4,5,3',4',5-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfona-
te ester; [0081] 1,2-naphthoquinone diazide sulfonate esters of
(polyhydroxyphenyl)alkane such as
bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate
ester,
bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfon-
ate ester,
bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfona- te
ester,
bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonat- e
ester,
1,1,1-tri(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-4-sulf-
onate ester,
1,1,1-tri(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-5-sulfonate
ester,
bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sul-
fonate ester,
bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate
ester,
2,2'-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide--
4-sulfonate ester,
2,2'-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfo-
nate ester,
1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquino-
nediazide-4-sulfonate ester, [0082] 1,1,3-tris(2,5-dimethyl
hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonate
ester, [0083]
4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene])bispheno-
l-1,2-naphthoquinonediazide-5-sulfonate ester, [0084]
bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmete-1,2-naphthoquinoned-
iazide-4-sulfonate ester, [0085]
bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquino-
nediazide-5-sulfonate ester, [0086]
3,3,3',3'-tetramethyl-1,1'-spirobindene-5,6,7,5',6',7'-hexanol-1,2-naphth-
oquinonediazide-4-sulfonate ester, [0087]
3,3,3',3'-tetramethyl-1,1'-spirobindene-5,6,7,5',6',7'-hexanol-1,2-naphth-
oquinonediazide-5-sulfonate ester, [0088]
2,2,4-trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinonediazide-sulfon-
ate ester, and
2,2,4-trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulf-
onate ester.
[0089] The photosensitive resin composition may include two or more
of the above-described quinone diazides.
[0090] The content of the quinone diazide is preferably from about
1.7 to about 50 wt. %, and more preferably from about 5 to about 40
wt. % relative to the solid content of the photosensitive resin
composition. In this case, the difference in the resolution speed
between exposed portions and unexposed portions of the
photosensitive resin composition becomes large to increase the
insoluble fraction. On the contrary, when the weight percentage of
the quinone diazide is less than 1.7 wt. % or greater than 50 wt.
%, the contrast is degraded.
[0091] Examples of the solvent include:
[0092] ethylene glycol monoalkyl ethers such as ethylene glycol
monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol
mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene
glycol mono-n-butyl ether, ethylene glycol mono-sec-butyl ether,
ethylene glycol mono-tert-butyl ether, ethylene glycol
mono-n-pentyl ether, ethylene glycol mono-n-hexyl ether, ethylene
glycol mono-n-heptyl ether, and ethylene glycol mono-n-octyl
ether;
[0093] diethylene glycol dialkyl ethers such as diethylene glycol
dimethyl ether, diethylene glycol diethyl ether, diethylene glycol
di-n-propyl ether, diethylene glycol diisopropyl ether, diethylene
glycol di-n-butyl ether, diethylene glycol di-sec-butyl ether,
diethylene glycol di-tert-butyl ether, diethylene glycol
di-n-pentyl ether, diethylene glycol methyl ethyl ether, diethylene
glycol methyl n-propyl ether, diethylene glycol methyl isopropyl
ether, diethylene glycol methyl n-butyl ether, diethylene glycol
methyl sec-butyl ether, diethylene glycol methyl tert-butyl ether,
diethylene glycol methyl n-pentyl ether, diethylene glycol ethyl
n-propyl ether, diethylene glycol ethyl isopropyl ether, diethylene
glycol ethyl n-butyl ether, diethylene glycol ethyl sec-butyl
ether, diethylene glycol ethyl tert-butyl ether, diethylene glycol
ethyl n-pentyl ether, diethylene glycol n-propyl isopropyl ether,
diethylene glycol n-propyl n-butyl ether, diethylene glycol
n-propyl sec-butyl ether, diethylene glycol n-propyl tert-butyl
ether, diethylene glycol n-propyl n-pentyl ether, diethylene glycol
isopropyl n-butyl ether, diethylene glycol isopropyl sec-butyl
ether, diethylene glycol isopropyl tert-butyl ether, diethylene
glycol isopropyl n-pentyl ether, diethylene glycol n-butyl
sec-butyl ether, diethylene glycol n-butyl tert-butyl ether,
diethylene glycol n-butyl n-pentyl ether, and diethylene glycol
sec-butyl tert-butyl ether, and diethylene glycol sec-butyl
n-pentyl ether;
[0094] ethylene glycol alkyl ether acetates such as methyl
cellosolve acetate and ethyl cellosolve acetate;
[0095] propylene glycol monoalkyl ether acetates such as propylene
glycol monomethyl ether acetate, propylene glycol monoethyl ether
acetate, propylene glycol monopropyl ether acetate, dipropylene
glycol monomethyl ether acetate, and dipropylene glycol monoethyl
ether acetate;
[0096] aromatic hydrocarbons such as benzene, toluene, xylene, and
mesitylene;
[0097] ketones such as methyl ethyl ketone, acetone, methyl amyl
ketone, methyl isobutyl ketone, and cyclohexanone;
[0098] alcohols such as ethanol, propanol, butanol, hexanol,
cyclohexanol, ethylene glycol, and glycerin; and
[0099] esters such as methyl 3-ethoxy propionate, methyl 3-methoxy
propionate, methyl 2-hydroxy isobutanate, ethyl lactate, butyl
lactate, butyl acetate, amyl acetate, methylpyrophosphate, and
1,3-butanediol diacetate.
[0100] Two or more of the above-listed materials may be used as the
solvent.
[0101] Among the above-listed solvents, preferred are diethylene
glycol dimethyl ether, diethylene glycol diethyl ether, diethylene
glycol methyl ethyl ether, ethyl 3-ethoxy propionate, ethyl
lactate, butyl lactate, butyl acetate, and combinations
thereof.
[0102] Examples of a preferable combination include: diethylene
glycol dimethyl ether and ethyl 3-ethoxy propionate; diethylene
glycol dimethyl ether and ethyl lactate; diethylene glycol dimethyl
ether and butyl lactate; diethylene glycol dimethyl ether and butyl
acetate; diethylene glycol diethyl ether and ethyl 3-ethoxy
propionate; diethylene glycol diethyl ether and butyl lactate;
diethylene glycol diethyl ether and butyl lactate; diethylene
glycol diethyl ether and butyl acetate; diethylene glycol methyl
ethyl ether and ethyl 3-ethoxy propionate; diethylene glycol methyl
ethyl ether and ethyl lactate; diethylene glycol methyl ethyl ether
and butyl lactate; diethylene glycol methyl ethyl ether and butyl
acetate; ethyl 3-ethoxy propionate and ethyl lactate; ethyl
3-ethoxy propionate and butyl lactate; and ethyl 3-ethoxy
propionate and butyl acetate. Examples of a more preferable
combination include: diethylene glycol methyl ethyl ether, ethyl
3-ethoxy propionate, and butyl lactate; and diethylene glycol
methyl ethyl ether, ethyl 3-ethoxy propionate, and butyl acetate,
and a combination of diethylene glycol methyl ethyl ether, ethyl
3-ethoxy propionate, butyl lactate, and butyl acetate is most
preferable.
[0103] The content of the solvent is preferably about 50 to about
95 wt. %, and more preferably about 70 to about 90 wt. % relative
to the total content of the photosensitive resin composition. In
addition, the content of the solvent used in a coating device
having a slit-type nozzles is preferably about 75 wt. % to about 90
wt. % relative to the total content of the photosensitive resin
composition. Furthermore, the content of the solvent used in a
coating device performing spin coating as well as slit coating is
preferably about 65 to about 80 wt. % relative to the total content
of the photosensitive resin composition. In this case, the
photosensitive resin composition can form a film having reduced
stains.
[0104] The surfactant includes:
[0105] an organic fluorine compound of ##STR13## where R.sub.f is a
chained or branched perfluoroalkylene group including about 5-10
carbon atoms and Z is a hydrogen or a fluorine;
[0106] a first silicone compound of ##STR14##
[0107] where R is a chained or branched alkylene group including
about 2-5 carbon atoms and each of x and y is an integer of about
1-20; and a second silicone compound of ##STR15## where R' is an
alkyl group including about 1-20 carbon atoms or a chained or
branched carbonyl alkyl group including about 2-21 carbon atoms and
each of v and w is an integer of about 1-20, and each of m and 1 is
an integer of about 1-9 wherein (m+1) lies between 2 and 10.
[0108] Examples of R.sub.f of the organic fluorine compound include
perfluoro n-pentylene group, perfluoro n-hexylene group, perfluoro
n-heptylene group, perfluoro n-octylene group, perfluoro n-nonylene
group, perfluoro n-decylene group, and perfluoro 2-ethylhexylene
group. Among the above-described perfluoroalkylene groups,
perfluoro n-hexylene group, perfluoro n-octylene group, and
perfluoro n-decylene group are preferred.
[0109] Examples of the organic fluorine compound include
3-perfluorohexyl-1,2-epoxypropane,
3-perfluorooctyl-1,2-epoxypropane, and
3-perfluorodecyl-1,2-epoxypropane. Among the above-listed examples,
3-perfluorooctyl-1,2-epoxypropane is preferred.
[0110] The content of the organic fluorine compound is preferably
from about 1 to about 1,000 ppm, more preferably from about 10 to
about 500 ppm, and most preferably from about 50 to about 300 ppm
relative to the total content of the photosensitive resin
composition. In this case, the photosensitive resin composition can
form a film having reduced stains.
[0111] The content of the organic fluorine compound is preferably
from about 10 to about 50 wt. % relative to the total content of
the organic fluorine compound and the silicone compounds.
[0112] Examples of R in the chemical formulae 2 and 3 include
ethylene group, n-propylene group, n-butylene group, pentamethylene
group, isopropylene group, 2-methyl n-propylene group, 3-methyl
n-propylene group, 2,2-dimethyl n-propylene group, 2-methyl
n-butylene group, and 3-methyl n-butylene group. Among the
above-listed groups, ethylene group, n-propylene group, and
isopropylene group are preferred.
[0113] The integer x in chemical formula 2 ranges preferably from
two to six, and the integer y ranges preferably from 5 to 10.
[0114] Any combination of x and y in the above-described ranges can
be selected and any combination of x and y range in the
above-described preferable ranges is preferred.
[0115] An example of the first silicone compound having chemical
formula 2 includes a reaction product between methyl hydro
bis(trimethyl siloxy)silane and polyalkylene glycol monoallyl ether
preferably having a molecular weight from about 200 to about
500.
[0116] The content of the first silicone compound is preferably
from about 1 to about 1,000 ppm (i.e., from about 1.times.10.sup.-4
to about 0.1 wt. %), more preferably from about 10 to about 500 ppm
(i.e., from about 1.times.10.sup.-4 to about 0.05 wt. %), and most
preferably from about 50 to about 300 ppm (i.e., from about
5.times.10.sup.-3 to about 0.03 wt. %) relative to the total
content of the photosensitive resin composition, such that a film
made of the photosensitive resin composition has reduced stains. In
addition, the weight percentage of the first silicone compound in
the surfactant is preferably from about 10 to about 50 wt. %.
[0117] Examples of R' in chemical formula 3 include methyl group,
ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl
group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group,
n-dodecyl group, n-undecyl group, n-tetradecyl group, n-hexadecyl
group, n-octadecyl group, isopropyl group, sec-butyl group,
tert-butyl group, 2-methyl hexyl group, carbonyl methyl group,
carbonyl ethyl group, carbonyl n-propyl group, carbonyl n-butyl
group, carbonyl n-pentyl group, carbonyl n-hexyl group, carbonyl
n-heptyl group, carbonyl n-octyl group, carbonyl n-nonyl group,
carbonyl n-decyl group, carbonyl n-dodecyl group, carbonyl
n-undecyl group, carbonyl n-tetradecyl group, carbonyl n-hexadecyl
group, carbonyl n-octadecyl group, carbonyl isopropyl group,
carbonyl sec-butyl group, carbonyl tert-butyl group, and carbonyl
2-methylhexyl group. Among the above-listed groups, methyl group,
ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl
group, n-octyl group, n-decyl group, n-undecyl group, n-tetradecyl
group, n-hexadecyl group, n-octadecyl group, isopropyl group,
sec-butyl group, tert-butyl group, 2-methyl hexyl group, carbonyl
methyl group, carbonyl ethyl group, carbonyl n-propyl group,
carbonyl n-butyl group, carbonyl n-hexyl group, carbonyl n-octyl
group, carbonyl n-decyl group, carbonyl n-undecyl group, carbonyl
n-tetradecyl group, carbonyl n-hexadecyl group, carbonyl
n-octadecyl group, carbonyl isopropyl group, carbonyl sec-butyl
group, carbonyl tert-butyl group, and carbonyl 2-methylhexyl
group.
[0118] The integer v ranges preferably from two to six, and the
integer w ranges preferably from five to ten.
[0119] Any combination of v and w in the above-described ranges can
be selected and any combination of v and w range in the
above-described preferable ranges is preferred.
[0120] The integer m ranges preferably from one to ten, and the
integer 1 ranges preferably from one to ten.
[0121] Any combination of m and 1 in the above-described ranges can
be selected and any combination of m and 1 range in the
above-described preferable ranges is preferred.
[0122] An example of the second silicone compound includes a
reaction product between trimethylsilyl
terminated-(dimethylsiloxane-methylhydrosiloxane) copolymer and
carboxylic acid ester of polyalkylene glycol allyl alkyl ether or
polyalkylene glycol allyl ether, and preferably includes a reaction
product between trimethylsilyl
terminated-(dimethylsiloxane-methylhydrosiloxane) copolymer and
carboxylic acid ester of polyethylene glycol allyl alkyl ether and
polyethylene glycol allyl ether.
[0123] The second silicone compound is preferably from about 1 to
about 1,000 ppm (i.e., from about 1.times.10.sup.-4 to about 0.1
wt. %), more preferably from about 10 to about 500 ppm (i.e., from
about 1.times.10.sup.-4 to about 0.05 wt. %), and most preferably
from about 50 to about 300 ppm (i.e., from about 5.times.10.sup.-3
to about 0.03 wt. %) relative to the total content of the
photosensitive resin composition, such that a film made of the
photosensitive resin composition has reduced stains. In addition,
the weight percentage of the second silicone compound in the
surfactant is preferably about 10 to about 50 wt. %.
[0124] The surfactant in the photosensitive resin is preferably
present in an amount of about 3 to about 3,000 ppm (i.e., from
about 3.times.10.sup.-4 to about 0.3 wt. %). When the amount of the
surfactant is less than about 3 ppm, the surfactant may not serve
its intended function. Conversely, when the amount of the
surfactant is more than about 3,000 ppm, the surfactant may affect
the photosensitive characteristics of the resin. To achieve the
desired level of solubility and photosensitivity, the amount of the
surfactant is more preferably about 5 to about 800 ppm (i.e., from
about 5.times.10.sup.-4 to about 0.08 wt. %), and most preferably
about 10 to about 800 ppm (i.e., from about 1.times.10.sup.-3 to
about 0.8 wt. %). A film made of the photosensitive resin
composition having the above-described amount of the surfactant has
reduced stains.
[0125] The surfactant in the photosensitive resin composition
improves the solubility of solid ingredients such as the
alkali-soluble resin and the quinone diazide in the solvent to make
the photosensitive resin composition deposit uniformly.
[0126] The photosensitive resin composition may further include a
cationic polymerization initiator, a polyphenol, a cross-linking
agent, a polymerizable monomer, and a silane coupling agent as well
as the alkali-soluble resin, the quinone diazide, the surfactant,
and the solvent.
[0127] An example of the cationic polymerization initiator includes
an onium salt that can initiate the cationic polymerization. The
onium salt includes an onium cation and a Lewis acid anion.
[0128] Examples of the onium cation include diphenyl iodonium,
bis(p-tolyl)iodonium, bis(p-t-butylphenyl)iodonium,
bis(p-octylphenyl)iodonium, bis(p-octacecylphenyl)iodonium,
bis(p-octyloxyphenyl)iodonium, bis(p-octadecyloxyphenyl)iodonium,
phenyl(p-octadecyloxyphenyl)iodonium, p-tolyl)(p-isopropyl
phenyl)iodonium, triphenyl sulfonate, tris(p-tolyl)sulfonate,
tris(p-isopropyl phenyl)sulfonate, tris(2,6-dimethyl
phenyl)sulfonate, tris(p-t-butylphenyl)sulfonate,
tris(p-cyanophenyl)sulfonate, tris(p-chlorophenyl)sulfonate,
dimethyl(methoxy)sulfonate, dimethyl(ethoxy)sulfonate,
dimethyl(propoxy)sulfonate, dimethyl(butoxy)sulfonate,
dimethyl(octyloxy)sulfonate, dimethyl(octadecanoxy)sulfonate,
dimethyl(isopropoxy)sulfonate, dimethyl(t-butoxy)sulfonate,
dimethyl(cyclopentyloxy)sulfonate,
dimethyl(cyclohexyloxy)sulfonate, dimethyl(fluoromethoxy)sulfonate,
dimethyl(2-chloroethoxy)sulfonate,
dimethyl(3-bromopropoxy)sulfonate,
dimethyl(4-cyanobutoxy)sulfonate,
dimethyl(8-nitrooctyloxy)sulfonate,
dimethyl(18-trifluoromethyloctadecanoxy)sulfonate,
dimethyl(2-hydroxy isopropoxy)sulfonate, and
dimethyl(tris(trichloromethyl)methyl)sulfonate. Among the
above-listed onium cations, bis(p-tolyl)iodonium,
p-tolyl)(p-isopropyl phenyl) iodonium,
bis(p-t-butylphenyl)iodonium, triphenyl sulfonate, and
tris(p-t-butylphenyl)sulfonate are preferred.
[0129] Examples of the Lewis acid anions include hexafluoro
phosphate and hexafluoro arsenate, and preferably include
hexafluoro antimonate and tetrakis(pentafluorophenyl)borate.
[0130] Any combination of the above-listed onium cations and Lewis
acid anions can be employed.
[0131] Examples of the cationic polymerization initiator include
diphenyliodonium hexafluorophosphate, bis(p-tolyl)iodonium
hexafluorophosphate, bis(p-t-butylphenyl)iodonium
hexafluorophosphate, bis(p-octylphenyl)iodonium
hexafluorophosphate, bis(p-octacecylphenyl)iodonium
hexafluorophosphate, bis(p-octyloxyphenyl)iodonium
hexafluorophosphate, bis(p-octadecyloxyphenyl)iodonium
hexafluorophosphate, phenyl(p-octadecyloxyphenyl)iodonium
hexafluorophosphate, p-tolyl)(p-isopropyl phenyl)iodonium
hexafluorophosphate, methyl naphthyl iodonium hexafluorophosphate,
ethyl naphthyl iodonium hexafluorophosphate, triphenyl sulfonate
hexafluoro phosphate, tris(p-tolyl)sulfonate hexafluoro phosphate,
tris(p-isopropyl phenyl)sulfonate hexafluoro phosphate,
tris(2,6-dimethyl phenyl)sulfonate hexafluoro phosphate,
tris(p-t-butyl phenyl)sulfonate hexafluoro phosphate,
tris(p-cyanophenyl)sulfonate hexafluoro phosphate,
tris(p-chlorophenyl)sulfonate hexafluoro phosphate, dimethyl
naphthyl sulfonate hexafluoro phosphate, diethyl naphthyl sulfonate
hexafluoro phosphate, dimethyl(methoxy) sulfonate hexafluoro
phosphate, dimethyl ethoxy sulfonate hexafluoro phosphate,
dimethyl(propoxy) sulfonate hexafluoro phosphate, dimethyl (butoxy)
sulfonate hexafluoro phosphate, dimethyl(octyloxy)sulfonate
hexafluoro phosphate, dimethyl(octadecanoxy)sulfonate hexafluoro
phosphate, dimethyl(isopropoxy)sulfonate hexafluoro phosphate,
dimethyl(t-butoxy)sulfonate hexafluoro phosphate,
dimethyl(cyclopentyloxy)sulfonate hexafluorophosphate,
dimethyl(cyclohexyloxy)sulfonate hexafluorophosphate,
dimethyl(fluoromethoxy)sulfonate hexafluorophosphate,
dimethyl(2-chloroethoxy)sulfonate hexafluorophosphate,
dimethyl(3-bromopropoxy)sulfonate hexafluorophosphate,
dimethyl(4-cyanobutoxy)sulfonate hexafluorophosphate,
dimethyl(8-nitrooctyloxy)sulfonate hexafluorophosphate,
dimethyl(18-trifluoromethyloctadecanoxy)sulfonate
hexafluorophosphate, dimethyl(2-hydroxyisopropoxy)sulfonate
hexafluorophosphate, dimethyl(tris(trichloromethyl)methyl)sulfonate
hexafluorophosphate, diphenyliodonium hexafluoroarsenate,
bis(p-tolyl)iodonium hexafluoroarsenate, bis(p-octylphenyl)iodonium
hexafluoroarsenate, bis(p-octadecylphenyl)iodonium
hexafluoroarsenate, bis(p-octyloxyphenyl)iodonium
hexafluoroarsenate, bis(p-octadecyloxyphenyl)iodonium
hexafluoroarsenate, phenyl(p-octadecyloxyphenyl)iodonium
hexafluoroarsenate, (p-tolyl)(p-isopropylphenyl)iodonium
hexafluoroarsenate, methyl naphthyl iodonium hexafluoroarsenate,
ethyl naphthyl iodonium hexafluoroarsenate, triphenyl sulphonate
hexafluoroarsenate, tris(p-tolyl)sulphonate hexafluoroarsenate,
tris(p-isopropylphenyl)sulphonate hexafluoroarsenate,
tris(2,6-dimethylphenyl)sulphonate hexafluoroarsenate,
tris(p-t-butylphenyl)sulphonate hexafluoroarsenate,
tris(p-cyanophenyl)sulphonate hexafluoroarsenate,
tris(p-chlorophenyl)sulphonate hexafluoroarsenate, dimethyl
naphthyl sulphonate hexafluoroarsenate, diethyl naphthyl sulphonate
hexafluoroarsenate, dimethyl(methoxy)sulphonate hexafluoroarsenate,
dimethyl(ethoxy)sulphonate hexafluoroarsenate,
dimethyl(propoxy)sulphonate hexafluoroarsenate,
dimethyl(butoxy)sulphonate hexafluoroarsenate,
dimethyl(octyloxy)sulphonate hexafluoroarsenate,
dimethyl(octadecanoxy)sulphonate hexafluoroarsenate,
dimethyl(isopropoxy)sulphonate hexafluoroarsenate,
dimethyl(t-butoxy)sulphonate hexafluoroarsenate,
dimethyl(cyclopentyloxy)sulphonate hexafluoroarsenate,
dimethyl(cyclohexyloxy)sulphonate hexafluoroarsenate,
dimethyl(fluoromethoxy)sulphonate hexafluoroarsenate,
dimethyl(2-chloroethoxy)sulphonate hexafluoroarsenate,
dimethyl(3-bromopropoxy)sulphonate hexafluoroarsenate,
dimethyl(4-cyanobutoxy)sulphonate hexafluoroarsenate,
dimethyl(8-nitrooctyloxy)sulphonate hexafluoroarsenate,
dimethyl(18-trifluoromethyloctadecanoxy)sulphonate
hexafluoroarsenate, dimethyl(2-hydroxyisopropoxy)sulphonate
hexafluoroarsenate, dimethyl(tris(trichloromethyl)methyl)sulphonate
hexafluoroarsenate, diphenyl iodonium hexafluoroantimonate,
bis(p-tolyl)iodonium hexafluoroantimonate,
bis(p-t-butylphenyl)iodonium hexafluoroantimonate,
bis(p-octylphenyl)iodonium hexafluoroantimonate,
bis(p-octadecylphenyl)iodonium hexafluoroantimonate,
bis(p-octyloxyphenyl)iodonium hexafluoroantimonate,
bis(p-octadecyloxyphenyl)iodonium hexafluoroantimonate,
bis(p-octadecyloxyphenyl)iodonium hexafluoroantimonate,
(p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate, methyl
naphthyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium
hexafluoroantimonate, triphenyl sulfonate hexafluoroantimonate,
tris(p-tolyl)sulfonate hexafluoroantimonate,
tris(p-isopropylphenyl)sulfonate hexafluoroantimonate,
tris(2,6-dimethylphenyl)sulfonate hexafluoroantimonate,
tris(p-t-butylphenyl)sulfonate hexafluoroantimonate,
tris(p-cyanophenyl)sulfonate hexafluoroantimonate,
tris(p-chlorophenyl)sulfonate hexafluoroantimonate, dimethyl
naphthyl sulfonate hexafluoroantimonate, diethyl naphthyl sulfonate
hexafluoroantimonate, dimethyl(methoxy)sulfonate
hexafluoroantimonate, dimethyl(ethoxy)sulfonate
hexafluoroantimonate, dimethyl(propoxy)sulfonate
hexafluoroantimonate, dimethyl(butoxy)sulfonate
hexafluoroantimonate, dimethyl(octyloxy)sulfonate
hexafluoroantimonate, dimethyl(octadecanoxy)sulfonate
hexafluoroantimonate, dimethyl(isopropoxy)sulfonate
hexafluoroantimonate, dimethyl(t-butoxy)sulfonate
hexafluoroantimonate, dimethyl(cyclopentyloxy)sulfonate
hexafluoroantimonate, dimethyl(cyclohexyloxy)sulfonate
hexafluoroantimonate, dimethyl(fluoromethoxy)sulfonate
hexafluoroantimonate, dimethyl(2-chloroethoxy)sulfonate
hexafluoroantimonate, dimethyl(3-bromopropoxy)sulfonate
hexafluoroantimonate, dimethyl(4-cyanobutoxy)sulfonate
hexafluoroantimonate, dimethyl(8-nitrooctyloxy)sulfonate
hexafluoroantimonate,
dimethyl(18-trifluoromethyloctadecanoxy)sulfonate
hexafluoroantimonate, dimethyl(2-hydroxyisopropoxy)sulfonate
hexafluoroantimonate,
dimethyl(tris(trichloromethyl)methyl)sulfonate
hexafluoroantimonate, diphenyliodonium
tetrakis(pentafluorophenyl)borate, bis(p-tolyl)iodonium
tetrakis(pentafluorophenyl)borate, bis(p-t-butylphenyl)iodonium
tetrakis(pentafluorophenyl)borate, bis(p-octylphenyl)iodonium
tetrakis(pentafluorophenyl)borate, bis(p-octadecylphenyl)iodonium
tetrakis(pentafluorophenyl)borate, bis(p-octyloxyphenyl)iodonium
tetrakis(pentafluorophenyl)borate,
bis(p-octadecyloxyphenyl)iodonium
tetrakis(pentafluorophenyl)borate,
phenyl(p-octadecyloxyphenyl)iodonium
tetrakis(pentafluorophenyl)borate,
(p-tolyl)(p-isopropylphenyl)iodonium
tetrakis(pentafluorophenyl)borate, methyl naphthyl iodonium
tetrakis(pentafluorophenyl)borate, ethyl naphthyl iodonium
tetrakis(pentafluorophenyl)borate, triphenyl sulfonate
tetrakis(pentafluorophenyl)borate, tri(p-tolyl)sulfonate
tetrakis(pentafluorophenyl)borate, tris(p-isopropylphenyl)sulfonate
tetrakis(pentafluorophenyl)borate,
tris(2,6-dimethylphenyl)sulfonate
tetrakis(pentafluorophenyl)borate, tris(p-t-butylphenyl)sulfonate
tetrakis(pentafluorophenyl)borate, tris(p-cyanophenyl)sulfonate
tetrakis(pentafluorophenyl)borate, tris(p-chlorophenyl)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl naphthyl sulfonate
tetrakis(pentafluorophenyl)borate, diethyl naphthyl sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(methoxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(ethoxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(propoxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(butoxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(octyloxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(octadecanoxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(isopropoxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(t-butoxy)sulfonate
tetrakis(pentafluorophenyl)borate,
dimethyl(cyclopentyloxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(cyclohexyloxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(fluoromethoxy)sulfonate
tetrakis(pentafluorophenyl)borate,
dimethyl(2-chloroethoxy)sulfonate
tetrakis(pentafluorophenyl)borate,
dimethyl(3-bromopropoxy)sulfonate
tetrakis(pentafluorophenyl)borate, dimethyl(4-cyanobutoxy)sulfonate
tetrakis(pentafluorophenyl)borate,
dimethyl(8-nitrooctyloxy)sulfonate
tetrakis(pentafluorophenyl)borate,
dimethyl(18-trifluoromethyloctadecanoxy)sulfonate
tetrakis(pentafluorophenyl)borate,
dimethyl(2-hydroxyisopropoxy)sulfonate
tetrakis(pentafluorophenyl)borate, and
dimethyl(tris(trichloromethyl)methyl)sulfonate
tetrakis(pentafluorophenyl)borate. Among the above-listed cationic
polymerization initiators, preferred are bis(p-tolyl)iodonium
hexafluorophosphate, (p-tolyl)(p-isopropylphenyl)iodonium
hexafluorophosphate, bis(p-t-butylphenyl)iodonium
hexafluorophosphate, triphenyl sulfonate hexafluorophosphate,
tris(p-t-butylphenyl)sulfonate hexafluorophosphate,
bis(p-tolyl)iodonium hexafluoroarsenate,
(p-tolyl)(p-isopropylphenyl)iodonium hexafluoroarsenate,
bis(p-t-butylphenyl)iodonium hexafluoroarsenate, triphenyl
sulfonate hexafluoroarsenate, tris(p-t-butylphenyl) sulfonate
hexafluoroarsenate, bis(p-tolyl)iodonium hexafluoroantimonate,
(p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate,
bis(p-t-butylphenyl)iodonium hexafluoroantimonate, trisphenyl
sulfonate hexafluoroantimonate, tris(p-t-butylphenyl)sulfonate
hexafluoroantimonate, bis(p-tolyl)iodonium
tetrakis(pentafluorophenyl)borate,
(p-tolyl)(p-isopropylphenyl)iodonium
tetrakis(pentafluorophenyl)borate, bis(p-t-butylphenyl)iodonium
tetrakis(pentafluorophenyl)borate, triphenyl sulfonate
tetrakis(pentafluorophenyl)borate, and
tris(p-t-butylphenyl)sulfonate tetrakis(pentafluorophenyl)borate,
and more preferred are bis(p-tolyl)iodonium hexafluoroantimonate,
(p-tolyl)(p-isopropylphenyl)iodonium hexafluoroantimonate,
bis(p-t-butylphenyl)iodonium hexafluoroantimonate, trisphenyl
sulfonate hexafluoroantimonate, tris(p-t-butylphenyl)sulfonate
hexafluoroantimonate, bis(p-tolyl)iodonium
tetrakis(pentafluorophenyl)borate,
(p-tolyl)(p-isopropylphenyl)iodonium
tetrakis(pentafluorophenyl)borate, bis(p-t-butylphenyl)iodonium
tetrakis(pentafluorophenyl)borate, triphenyl sulfonate
tetrakis(pentafluorophenyl)borate, and
tris(p-t-butylphenyl)sulfonate
tetrakis(pentafluorophenyl)borate.
[0132] The content of the cationic polymerization initiator is
preferably from about 0.01 to about 10 wt. %, and more preferably
from about 0.1 to about 5 wt. % relative to the total solid content
of the photosensitive resin composition. The photosensitive resin
composition including the polymerization initiator in the
above-described range has increased thermal curing rate, the
reduction of the resolution during the thermal curing is
suppressed, and the cured film has increased solvent
resistance.
[0133] The polyphenol includes a compound including molecules that
include two or more phenolic hydroxyl group (--OH), a polymer
polymerized from hydroxystyrene at least, or a novolac resin.
[0134] Examples of the compound, which includes molecules including
two or more phenolic hydroxyl group, include
trihydroxybenzophenones, tetrahydroxybenzophenones,
pentahydroxybenzophenones, hexahydroxybenzophenones, and
(polyhydroxyphenyl)alkanes, which are illustrated in the
description of the quinone diazide.
[0135] An examples of the polymer polymerized from hydroxystyrene
at least includes a resin polymerized from hydroxystyrene such as
polyhydroxystyrene, hydroxystyrene/methylmethacrylate copolymer,
hydroxystyrene/cyclohexyl methacrylate copolymer,
hydroxystyrene/styrene copolymer, and hydroxystyrene/alkoxystyrene
copolymer.
[0136] An example of the novolac resin may be obtained by
condensation polymerization of at least one of phenols, cresols,
and catechols and at least one of aldehydes and ketones.
[0137] The polyphenol is preferably from about 0.01 to about 40 wt.
%, and more preferably from about 0.1 to about 25 wt. % relative to
the total solid content of the photosensitive resin composition,
such that the resolution is increased and the reduction of the
transmittance of the visible light is prevented.
[0138] An example of the cross-linking agent includes a methylol
compound. The methylol compound may be an alkoxymethylated amino
resin such as alkoxymethylated melamine resin and alkoxymethylated
urea resin. Examples of alkoxymethylated melamine resin include
methoxymethylated melamine resin, ethoxymethylated melamine resin,
propoxymethylated melamine resin, and butoxymethylated melamine
resin.
[0139] Two or more of the above-listed cross-linking agents may be
employed.
[0140] The cross-linking agent is preferably from about 0.01 to
about 15 wt. % relative to the total solid content of the
photosensitive resin composition such that an obtained film has
increased transmittance of visible light and improved function as
curable resin pattern.
[0141] The polymerizable monomer may be obtained by radical or
cationic polymerization.
[0142] The polymerizable monomer may be a compound having a
polymerizable carbon-to-carbon unsaturated bond that may be
monofunctional, difunctional, or polyfunctional (i.e.,
trifunctional or more).
[0143] Examples of the monofunctional polymerizable monomer include
nonylphenyl carbitol acrylate, nonylphenyl carbitol methacrylate,
2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl
methacrylate, 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol
methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
and N-vinylpyrolidone.
[0144] Examples of the difunctional polymerizable monomer include
1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene
glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol
diacrylate, neopentyl glycol dimethacrylate, triethylene glycol
diacrylate, triethylene glycol dimethacrylate, bis(acryloyloxyethyl
ether of bisphenol A, 3-methylpentanediol diacrylate, and
3-methylpentanediol dimethacrylate.
[0145] Examples of the polyfunctional polymerizable monomer include
trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
pentaerythritol triacrylate, pentaerythritol trimethacrylate,
pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate,
pentaerythritol pentaacrylate, pentaerythritol pentamethacrylate,
di-pentaerythritol hexaacrylate, and di-pentaerythritol
hexamethacrylate.
[0146] Preferably, the difunctional and polyfunctional
polymerizable monomers can be used. In detail, pentaerythritol
tetraacrylate and di-pentaerythritol hexaacrylate are preferable,
and di-pentaerythritol hexaacrylate is more preferable. The
difunctional and polyfunctional polymerizable monomers can be used
in combination with monofunctional monomer.
[0147] The polymerizable monomer obtained by cationic
polymerization may include a cationically polymerizable functional
group such as a vinyl ether group, a propenyl ether group, an epoxy
group, and an oxetanyl group.
[0148] Examples of the monomer including a vinyl ether group
include triethylene glycol divinyl ether, 1,4-cyclohexane
dimethanol divinyl ether, 4-hydroxy butyl vinyl ether, and dodecyl
vinyl ether.
[0149] An example of the monomer including a propenyl ether group
includes 4-(1-propenyloxymethyl)-1,3-dioxolane-2-on.
[0150] Examples of the monomer including an epoxy group include
bisphenol A type epoxy resin, phenol novolac type epoxy resin,
cresol novolac type epoxy resin, cycloaliphatic epoxy resin,
glycidyl ester type epoxy resin, glycidyl amine type epoxy resin,
and heterocyclic epoxy resin.
[0151] Examples of the monomer including an oxetanyl group include
[0152] bis{3-(3-ethyloxetanyl)methyl}ether,
1,4-bis{3-(3-ethyloxetanyl)methoxy}benzene,
1,3-bis{3-(3-ethyloxetanyl)methoxy}benzene, [0153]
1,4-bis{3-(3-ethyloxetanyl)methoxymethyl}benzene, [0154]
1,3-bis{3-(3-ethyloxetanyl)methoxy}benzene, [0155]
1,4-bis{3-(3-ethyloxetanyl)methoxy}cyclohexane, [0156]
1,3-bis{3-(3-ethyloxetanyl)methoxy}cyclohexane, [0157]
1,4-bis{3-(3-ethyloxetanyl)methoxymethyl}cyclohexane, [0158]
1,3-bis{3-(3-ethyloxetanyl)methoxymethyl}cyclohexane, and [0159]
3-(3-ethyloxetanyl)methylated novolac resin.
[0160] Two or more of the above-listed polymerizable monomers can
be used.
[0161] The polymerizable monomer is preferably from about 0.001 to
about 20 wt. %, and more preferably from about 0.01 to about 10 wt.
% relative to the total solid content of the photosensitive resin
composition.
[0162] Examples of the silane coupling agent include methyl
trimethoxy silane, methyl triethoxy silane, vinyl trichloro silane,
vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triacetoxy
silane, vinyl tris(2-methoxyethoxy)silane, 3
chloropropyl-trimethoxy silane, 3-chloropropylmethyl-dichloro
silane, 3-chloropropylmethyl-dimethoxy silane,
3-chloropropylmethyl-diethoxy silane, 3-glycidoxypropyl-trimethoxy
silane, 3-glycidoxypropyl-triethoxy silane,
3-glycidoxypropylmethyl-dimethoxy silane,
3-mercaptopropyl-trimethoxy silane, 3-methacryloxypropyl-trimethoxy
silane, 3-methacryloxypropylmethyl-dimethoxy silane,
2-(3,4-epoxycyclohexyl)ethyl-trimethoxy silane,
N-2-(N-vinylbenzylaminoethyl)-3-aminopropyl-trimethoxy silane
hydrochloride, hexamethyl disilazane, diaminosilane,
triaminopropyl-trimethoxysilane, 3-aminopropyl-trimethoxysilane,
3-aminopropyl-triethoxysilane, 3-aminopropylmethyl-diethoxysilane,
3-aminopropyl-tris(2-methoxyethoxysilane,
3-(2-aminoethyl)-3-aminopropyl-trimethoxysilane,
3-(2-aminoethyl)-3-aminopropylmethyl-trimethoxysilane,
3-ureidopropyl-trimethoxysilane, 3-ureidopropyl-triethoxysilane,
N-aminoethyl-3-aminopropyl-trimethoxysilane,
N-aminoethyl-3-aminopropylmethyl-trimethoxysilane,
N-methyl-3-aminopropyl-trimethoxysilane, and
N-phenyl-3-aminopropyl-trimethoxysilane, preferably include
3-glycidoxypropyl-trimethoxysilane, 3-glycidoxypropyl-triethoxy
silane, 3-glycidoxypropyl-dimethoxysilane, and
3-glycidoxypropylmethyl-dimethoxysilane, which include an epoxy
group, and more preferably, 2-(3,4-epoxycyclohexyl)ethyl-trimethoxy
silane that includes an epoxy ring.
[0163] The silane coupling agent is preferably from about 0.01 to
about 10 wt. %, more preferably from about 0.1 to about 2 wt. %,
and most preferably from about 0.2 to about 1 wt. % relative to the
total content of the photosensitive resin composition, such that a
curable resin pattern made of the photosensitive resin composition
shows improved adhesion with a substrate.
[0164] The photosensitive resin composition may further include
other ingredients such as an antioxidant, a dissolution inhibitor,
a sensitizer, an UV absorbent, a photostabilizer, an adhesion
promoter, and an electron donor.
[0165] The photosensitive resin composition may be formed by mixing
a solution containing an alkali-soluble resin dissolved in a
solvent, another solution containing a quinone diazide in a
solvent, and another solution containing a surfactant in a solvent.
A solvent may be added to a mixture of an alkali-soluble resin, a
quinone diazide, and a surfactant. It is preferable to remove
solids by filtering the mixture, preferably by using a filter
having a pore diameter less than about 3 microns (e.g., about 0.1
to about 2 microns). The alkali-soluble resin and the quinone
diazide may be dissolved in the same solvent or in different
solvents. A plurality of solvents that can be mixed with each other
may be used.
[0166] Now, a method for forming a film pattern from the
photosensitive resin composition is provided.
[0167] A photosensitive film is coated on a substrate such as
transparent glass and subjected to light exposure and development.
One or more thin film patterns such as thin film transistors, color
filters, organic light emitting diodes, etc., may be formed on the
substrate before the photosensitive thin film is coated.
[0168] Examples of the coating of the photosensitive film include
slit coating using a coating device having slit type nozzles,
slit-and-spin coating that first coats using a nozzle and then
coats using a spin coater, die coating, and curtain flow coating.
Of these coating methods, the slit-and-spin coating is preferred.
After the coating, the photosensitive resin composition may be
prebaked to remove volatile ingredients such as solvents, thereby
forming the photosensitive resin film containing substantially no
volatile ingredient. The photosensitive resin film may have a
thickness of about 1.0 microns to about 8.0 microns.
[0169] Next, the photosensitive film is subjected to a first
exposure through a mask. The mask has a pattern suitable for the
function of the hardened resin pattern. The light exposure
illuminates a light such as g line or g line vertically over an
entire surface of the photosensitive resin film, and aligns the
mask with the photosensitive resin film using a mask aligner or a
stepper.
[0170] The photoresist resin film is then developed by puddle
development, immersion development, or spray development.
[0171] The development may be performed by using an alkaline
aqueous solution. The alkaline aqueous solution contains an
inorganic alkaline compound or an organic alkaline compound.
[0172] Examples of the inorganic alkaline compound include sodium
hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium
dihydrogen phosphate, diammonium hydrogen phosphate, ammonium
dihydrogen phosphate, potassium dihydrogen phosphate, sodium
silicate, potassium silicate, sodium carbonate, potassium
carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
sodium borate, potassium borate, and ammonium.
[0173] Examples of the organic alkaline compound include
tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium
hydroxide, monomethylamine, dimethylamine, trimethylamine,
monoethylamine, diethylamine, triethylamine, monoisopropylamine,
diisopropylamine, and ethanolamine.
[0174] Two or more of the above-listed alkaline compounds may be
used. The content of the alkaline compound is from about 0.01 to
about 10 wt. %, and preferably from about 0.1 to about 5 wt. % of
the total content of the developer.
[0175] The developer may contain a surfactant such as a nonionic
surfactant, a cationic surfactant, and an anionic surfactant.
[0176] Examples of the nonionic surfactant include polyoxyethylene
derivatives such as polyoxyethylenealkylether,
polyoxyethyleneallylether, and polyoxyethylenealkylallylether,
oxyethylene/oxypropylene block copolymer, sorbitan fatty acid
ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene
sorbitol fatty acid ester, glycerin fatty acid ester,
polyoxyethylene fatty acid ester, and polyoxyethylene alkyl
amine.
[0177] Examples of the cationic surfactant include an aminium salt
such as stearylamine hydrochloride and a quaternary ammonium salt
such as lauryl trimethyl ammonium chloride.
[0178] Examples of the anionic surfactant include: sulfate esters
of higher alcohols, such as sodium lauryl alcohol sulfate ester and
sodium oleinalcohol sulfate ester; alkyl sulfates such as sodium
lauryl sulfate and ammonium lauryl sulfate; and sodium
dodecylbenzene sulfonate and sodium dodecyl naphthalene
sulfonate.
[0179] Two or more of the above-listed surfactants are used.
[0180] The developer may include an organic solvent including
water-soluble solvents such as methanol and ethanol.
[0181] The developer dissolves exposed portions of the
photosensitive resin film, which are exposed to light, and leaves
unexposed portions of the photosensitive resin film to form a film
pattern.
[0182] Since the photosensitive resin composition includes the
quinone diazide, the exposed portions of the photosensitive resin
film is quickly removed in a short time, while the unexposed
portions thereof is hardly removed even though they are in contact
with the developer for a long time.
[0183] After the development, the substrate with the film pattern
is cleaned with deionized water and dried.
[0184] A portion or an entire portion of the film pattern is then
subjected to a second light exposure preferably using (deep)
ultraviolet (UV) ray. The illumination of UV on unit area in the
second light exposure may be higher than that in the first light
exposure. The second light exposure is conducted in order to
lighten transparency of the film pattern.
[0185] The photosensitive resin pattern is postbaked at about
150.degree. C. to about 250.degree. C., and more preferably at
about 180.degree. C. to about 240.degree. C. for about 5 to about
120 minutes, and more preferably for about 15 to about 90 minutes.
The postbaking is performed by heating the substrate with a hot
plate, a clean oven, etc. The postbaking improves the heat
resistance and the solvent resistance of the cured photosensitive
resin pattern.
Embodiment 1
SYNTHESIS EXAMPLE 1
[0186] Alkali-soluble Resin Synthesis
[0187] Following materials were put into a 200-ml flask provided
with an agitator, a cooled tube, and a thermometer: TABLE-US-00001
methacrylate 6.8 g; N-cyclohexyl maleimide 14.2 g;
3-ethyl-3-methacryloxymethyloxetane 17.8 g; ethyl
3-ethoxypropionate 45.3 g; diethylene glycol methyl ethyl ether
45.3 g; and azobisisobutyronitrile 1.1 g
[0188] The flask was then immersed in an oil bath and agitated for
about three hours under nitrogen (N.sub.2) atmosphere with
maintaining the temperature of the interior of the flask at about
10-110.degree. C. As a result, an alkali-soluble resin Al was
obtained, which had a weight average molecular weight (Mw) of about
8,000 based on polystyrene standards.
[0189] The measurement of the weight average molecular weight was
performed by
[0190] GPC under the following conditions:
[0191] Device: HLC-8120GPC (manufactured by TOSOH Corporation in
Japan)
[0192] Columns: TSK-GELG4000HXL+TSK-GELG2000HXL (serial connection)
(manufactured by TOSOH Corporation in Japan)
[0193] Column Temperature: 40.degree. C.
[0194] Solvent: tetrahydrofuran (THF)
[0195] Flow Rate: 1.0 ml/min
[0196] Injected Amount: 50 .mu.l
[0197] Detector: RI (Refractive Index)
[0198] Concentration of Sample: 0.6 wt. %
[0199] Standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500,
A-500
SYNTHESIS EXAMPLE 2
[0200] First Silicone Compound (Chemical Formula 2) Synthesis
[0201] 204 g of polyoxyethylene having a molecular chain that has
an allyl group at a terminal thereof and an OH group at another
terminal thereof as shown in chemical formula 4,300 g isopropyl
alcohol, 0.5 g isopropyl alcohol containing 2% chloroplatinic acid,
and 1 g potassium acetate were put into a flask and uniformly
mixed. The temperature was then increased up to a reflux
temperature (i.e., 83.degree. C.) of isopropyl alcohol, and 111 g
of methyl siloxane having Chemical Formula 5 was gradually dropped
into the reflux to perform addition reaction. ##STR16##
[0202] After the addition of methyl siloxane, the reaction was
maintained for four hours and terminated after the formation of SiH
group was confirmed. Thereafter, the product was heated for two
hours under 110.degree. C. and 10 mmHg to remove isopropyl alcohol,
and a 310 g compound having Chemical Formula 6. ##STR17##
EXAMPLE 1
Preparation of Photosensitive Resin Composition 1
[0203] 100 parts by weight of alkali-soluble resin A1, 22 parts by
weight of quinone diazide having Chemical Formula 7, two parts by
weight of (p-tolyl)(p-isopropylphenyl)iodonium
tetrakis(pentafluorophenyl)borate as a cationic polymerization
initiator, a surfactant including 0.08 parts by weight of
3-perfluorooctyl-1,2-epoxypropane as a fluorosurfactant, 0.08 parts
by weight of a first silicone compound having Chemical Formula 6,
and 0.15 parts by weight of SH8400 (manufactured by Dow Corning
Toray Silicone Co., Ltd.) as a second silicone compound, and a
solvent including 291 parts by weight of ethyl 3-ethoxy propionate,
291 parts by weight of diethylene glycol methylethyl ether, 32
parts by weight of butyl acetate, and 32 parts by weight of butyl
lactate are mixed at 23.degree. C., and they were filtrated under
pressure through a polytetrafluoroethylene cartridge filter having
a pore diameter of 1.0 micron to obtain a photosensitive resin
composition 1. ##STR18##
COMPARATIVE EXAMPLE 1
Preparation of Photosensitive Resin Composition 2
[0204] Except for the use of a surfactant including 0.08 parts by
weight of 3-perfluorooctyl-1,2-epoxypropane, the conditions and the
materials were the same as those of Example 1 to obtain a
photosensitive resin composition 2.
COMPARATIVE EXAMPLE 2
Preparation of Photosensitive Resin Composition 3
[0205] Except for the use of a surfactant that does not include a
first silicone compound, the conditions and the materials were the
same as those of Example 1 to obtain a photosensitive resin
composition 3.
COMPARATIVE EXAMPLE 3
Preparation of Photosensitive Resin Composition 4
[0206] Except for the use of a surfactant that does not include a
second silicone compound, the conditions and the materials were the
same as those of Example 1 to obtain a photosensitive resin
composition 4.
[0207] Estimation of Stain Generation and Coating Uniformity
[0208] The photosensitive resin composition 1 (Example 1), the
photosensitive resin composition 2 (Comparative Example 1), the
photosensitive resin composition 3 (Comparative Example 2), and the
photosensitive resin composition 4 (Comparative Example 3) were
coated on four glass substrates with Mo films deposited thereon by
using a spin-and-slit coater manufactured by Dainippon Screen
Manufacturing Co. Ltd. Thereafter, the solvents were removed by
prebaking the resin compositions in a hot plate for 135 seconds at
100.degree. C.
[0209] Next, the substrates were subjected to a first light
exposure using an exposer (MPA-2000 manufactured by Canon Inc. in
Japan) and to development by puddle development. The substrates
were then rinsed by pure water and dried, and entire surfaces of
the substrates were exposed to light during a second light
exposure. Subsequently, the resin compositions were postbaked in a
hot plate for 160 seconds at 130.degree. C. to form a transparent
cured resin pattern.
[0210] Observations on stains on the transparent cured resin and
build-up at edges of the substrates gave the results illustrated in
TABLE 1 and FIG. 11.
[0211] Here, it is noted that Example 1 (EX 1) was formed by using
an inventive solvent, Comparative Example 1 (CE 1) was formed by
using a conventional solvent, and Comparative Examples 2-5 (CE 1-5)
were made by using solvents without one or more ingredients of the
inventive solvent.
[0212] FIGS. 11A, 11B, 11C, 11D and 11E are photographs of the
photosensitive resin films for Comparative Example 1, Comparative
Example 2, Comparative Example 3, Comparative Example 4,
Comparative Example 5, and Example 1, respectively. TABLE-US-00002
TABLE 1 Horizontal Vertical Irregular Stripe Stain Stripe Stain
Spot Build-up Adhesion Ex 1 XX XX X X Good CE 1 .DELTA.
.largecircle. .quadrature. .DELTA. Normal CE 2 .DELTA. .DELTA.
.largecircle. X Good CE 3 .largecircle. .largecircle. X
.largecircle. Poor (.quadrature.: entirely, .largecircle.: partly,
.DELTA.: a few, X: rare, XX: none)
[0213] TABLE 1 shows that horizontal stripe stains, vertical stripe
strains and irregular spots generated during the manufacturing
process were remarkably reduced. In addition, the edge build-up was
reduced and the adhesion with an underlying film was remarkably
improved. Also, the uniformity of distribution of the moieties in
the inventive photosensitive resin was shown to be excellent.
[0214] FIGS. 11A-11F are photographs illustrating photosensitive
resin films according to examples of the present invention and
comparative examples. FIGS. 11A and 11B relate to Example 1, FIGS.
11C and 11D relate to Comparative Example 1, FIG. 11E relates to
Comparative Example 2, and FIG. 11F relates to Comparative Example
3.
[0215] FIG. 11A shows no irregular spot, and FIG. 11A shows the
reduced edge build-up (about 34 mm). FIG. 11C shows irregular spots
spread over the substrate, FIG. 11D shows thick edge build-up
(about 6 mm), FIG. 11E shows partially generated irregular spots,
and FIG. 11F shows thicker edge build-up (about 10 mm).
[0216] Accordingly, it is preferable that a photosensitive resin
composition including an organic fluorine compound and first and
second silicone compounds as a surfactant improves horizontal
stripe stains, vertical stripe strains, irregular spots, the edge
build-up, and the adhesion with an underlying film.
[0217] It is preferable that the weight percentage of each of the
organic fluorine compound, the first silicone compound, and the
second silicone compound in the surfactant is about 10 to about 50
wt. %.
[0218] An organic fluorine compound present in an amount less than
10 wt. % in the surfactant may cause an edge build-up, while its
presence in an amount more than 50 wt. % may cause irregular spots.
A first silicone compound present in an amount less than 10 wt. %
in the surfactant may cause irregular spots, while its presence in
an amount more than 50 wt. % may increase edge build-up to degrade
the thickness uniformity. A second silicone compound present in an
amount more than 50 wt. % may weaken the adhesion.
[0219] TABLE 2 shows film properties for various contents of
ingredients in a surfactant. Here, the contents of alkaline resin
and quinone diazide were equal to in Example 1. TABLE-US-00003
TABLE 2 Organic First Second Fluorine Silicone Silicone Irreg- Edge
Com- Com- Com- Stripe ular Build- No. pound pound pound Stain Spot
Up 1 8 46 46 Normal Good Good 2 10 45 45 Normal Normal Normal 3 52
24 24 Good Very Good Poor 4 46 8 46 Normal Poor Normal 5 45 10 45
Good Normal Good 6 24 52 24 Poor Good Poor 7 46 46 8 Poor Normal
Good 8 45 45 10 Normal Good Good 9 24 24 52 Excel- Normal Not lent
Good (Good: good coating property Normal: no failure, but slightly
unstable processibility Poor: poor quality to cause failure)
Embodiment 2
[0220] Now, thin film transistor (TFT) array panels for liquid
crystal display (LCD) including an insulating layer made from the
above-described photosensitive resin composition 1 and
manufacturing methods thereof are described in detail with
reference to accompanying drawings.
[0221] In the drawings, the thickness of layers, films and regions
are exaggerated for clarity. Like numerals refer to like elements
throughout. It will be understood that when an element such as a
layer, film, region or substrate is referred to as being "on"
another element, it can be directly on the other element or
intervening elements may also be present. In contrast, when an
element is referred to as being "directly on" another element,
there are no intervening elements present.
[0222] First, a thin film transistor (TFT) array panel according to
an embodiment of the present invention will be described in detail
with reference to FIGS. 1 and 2.
[0223] FIG. 1 is a layout view of a TFT array panel according to an
embodiment of the present invention and FIG. 2 is a sectional view
of the TFT array panel shown in FIG. 1 taken along line II-II'.
[0224] A plurality of gate lines 121 are formed on an insulating
substrate 110, which may be transparent glass or plastic, among
others.
[0225] The gate lines 121 transmit gate signals and extend
substantially in a first direction. Each gate line 121 includes a
plurality of gate electrodes 124, a plurality of projections 127
projecting downward, and an end portion 129 having a large area for
contact with another layer or an external driving circuit. A gate
driving circuit (not shown) for generating the gate signals may be
mounted on a flexible printed circuit (FPC) film (not shown), which
may be attached to the substrate 110, directly mounted on the
substrate 110, or integrated onto the substrate 110. The gate lines
121 may extend to be connected to a driving circuit that may be
integrated on the substrate 110.
[0226] The gate lines 121 include two conductive films having
different physical characteristics: a lower film and an upper film
disposed on the lower film. The lower film is preferably made of a
low-resistivity metal, for example an Al-containing metal such as
Al and Al alloy, Ag-containing metal such as Ag and Ag alloy, and
Cu-containing metal such as Cu and Cu alloy, for reducing signal
delay or voltage drop. The upper film is preferably made of
material such as Mo containing metal such as Mo and Mo alloy, Cr,
Ta, or Ti, which has good physical, chemical, and electrical
contact characteristics with other materials such as indium tin
oxide (ITO) or indium zinc oxide (IZO). A good example of the
combination of the two films is a lower Al (alloy) film and an
upper Mo (alloy) film.
[0227] However, the lower film may be made of good contact
material, and the upper film may be made of a low-resistivity
material. In this case, the upper film 129q of the end portions 129
of the gate lines 121 may be removed to expose the lower film 129p.
In addition, the gate lines 121 may include a single layer
preferably made of the above-described materials. Otherwise, the
gate lines 121 may be made of various metals or conductors.
[0228] In FIGS. 2A and 2B, for the gate electrodes 124 and the
projections 127, the lower and upper films thereof are denoted by
additional characters p and q, respectively.
[0229] The lateral sides of the gate lines 121 are inclined
relative to a surface of the substrate 110, and the inclination
angle ranges between about 30-80 degrees.
[0230] A gate insulating layer 140 preferably made of silicon
nitride (SiNx) or silicon oxide (SiOx) is formed on the gate lines
121.
[0231] A plurality of semiconductor stripes 151 preferably made of
hydrogenated amorphous silicon (abbreviated to "a-Si") or
polysilicon are formed on the gate insulating layer 140. Each
semiconductor stripe 151 extends substantially in the second
direction and become wide near the gate lines 121 such that the
semiconductor stripes 151 cover large areas of the gate lines 121.
Each semiconductor stripe 151 has a plurality of projections 154
branched out toward the gate electrodes 124.
[0232] A plurality of ohmic contact stripes and islands 161 and 165
are formed on the semiconductor stripes 151. The ohmic contact
stripes and islands 161 and 165 are preferably made of n+
hydrogenated a-Si heavily doped with an n-type impurity such as
phosphorus, or they may be made of silicide. Each ohmic contact
stripe 161 has a plurality of projections 163, and the projections
163 and the ohmic contact islands 165 are located in pairs on the
projections 154 of the semiconductor stripes 151.
[0233] The lateral sides of the semiconductor stripes 151 and the
ohmic contacts 161 and 165 are inclined relative to a surface of
the substrate, and the inclination angles thereof are preferably in
a range of about 30-80 degrees.
[0234] A plurality of data lines 171, a plurality of drain
electrodes 175, and a plurality of storage conductors 177 are
formed on the ohmic contacts 161 and 165 and the gate insulating
layer 140.
[0235] The data lines 171 transmit data signals and extend
substantially in the second direction to intersect the gate lines
121. Each data line 171 includes a plurality of source electrodes
173 projecting toward the gate electrodes 124 and an end portion
179 having a large area for contact with another layer or an
external driving circuit. A data driving circuit (not shown) for
generating the data signals may be mounted on a FPC film (not
shown), which may be attached to the substrate 110, directly
mounted on the substrate 110, or integrated onto the substrate 110.
The data lines 171 may extend to be connected to a driving circuit
that may be integrated on the substrate 110.
[0236] The drain electrodes 175 are separated from the data lines
171 and disposed opposite the source electrodes 173 with respect to
the gate electrodes 124.
[0237] A gate electrode 124, a source electrode 173, and a drain
electrode 175 along with a projection 154 of a semiconductor stripe
151 form a TFT having a channel formed in the projection 154
disposed between the source electrode 173 and the drain electrode
175.
[0238] The storage conductors 177 are disposed on the projections
127 of the gate lines 121.
[0239] The data lines 171, the drain electrodes 175, and the
storage conductors 177 have a triple-layered structure including a
lower film 171p, 175p and 177p, an intermediate film 171q, 175q and
177q, and an upper film 171r, 175r and 177r. The lower film 171p,
175p and 177p is preferably made of refractory metal such as Cr,
Mo, Ta, Ti, or alloys thereof, the intermediate film 171q, 175q and
177q is preferably made of low resistivity metal such as Al
containing metal, Ag containing metal, and Cu containing metal, and
the upper film 171r, 175r and 177r is made of refractory metal or
alloys thereof having a good contact characteristic with ITO or
IZO.
[0240] The data lines 171, the drain electrodes 175, and the
storage conductors 177 may have a double-layered structure
including a refractory-metal lower film (not shown) and a
low-resistivity upper film (not shown) or a single-layer structure
preferably made of the above-described materials. However, the data
lines 171, the drain electrodes 175, and the storage conductors 177
may be made of various metals or conductors.
[0241] In FIGS. 2A and 2B, for the source electrodes 173 and the
end portions 179 of the data lines 179, the lower, the
intermediate, and the upper films thereof are denoted by additional
characters p, q and r, respectively.
[0242] The data lines 171, the drain electrodes 175, and the
storage conductors 177 have inclined edge profiles, and the
inclination angles thereof range about 30-80 degrees.
[0243] The ohmic contacts 161 and 165 are interposed only between
the underlying semiconductor stripes 151 and the overlying
conductors 171 and 175 thereon and reduce the contact resistance
therebetween. Although the semiconductor stripes 151 are narrower
than the data lines 171 in most places, the width of the
semiconductor stripes 151 becomes large near the gate lines 121 as
described above to smooth the profile of the surface, thereby
preventing the disconnection of the data lines 171. The projections
154 of the semiconductor stripes 151 include some exposed portions
that are not covered by the data lines 171, the drain electrodes
175, and the storage conductors 177 such as portions located
between the source electrodes 173 and the drain electrodes 175.
[0244] A passivation layer 180 is formed on the data lines 171, the
drain electrodes 175, the storage conductors 177, and the exposed
portions of the semiconductor stripes 151.
[0245] The passivation layer 180 is preferably made of
photosensitive organic insulator having a dielectric constant
preferably less than about 4.0. The passivation 180 may have a flat
surface and a thickness from about 1.0 to about 8.0 microns.
[0246] The organic insulator for the passivation 180 is a
photosensitive resin composition including an alkali-soluble resin,
a quinone diazide, a surfactant, and a solvent. The surfactant
includes an organic fluorine compound of ##STR19## where R.sub.f is
a chained or branched perfluoroalkylene group including about 5-10
carbon atoms and Z is a hydrogen or a fluorine;
[0247] a first silicone compound of ##STR20## where R is a chained
or branched alkylene group including about 2-5 carbon atoms and
each of x and y is an integer of about 1-20; and
[0248] a second silicone compound of ##STR21## where R' is an alkyl
group including about 1-20 carbon atoms or a chained or branched
carbonyl alkyl group including about 2-21 carbon atoms and each of
v and w is an integer of about 1-20, and each of m and 1 is an
integer of about 1-9 wherein (m+1) lies between 2 and 10. The
photosensitive resin composition may further include one or more of
a cationic polymerization initiator, a polyphenol, a cross-linking
agent, a polymerizable monomer, and a silane coupling agent.
[0249] The surfactant in the photosensitive resin composition has
an improved solubility for solid ingredients such as the
alkali-soluble resin and the quinone diazide to make the
photosensitive resin composition uniformly spread. Accordingly, a
uniformly thick film can be formed. As a result, the build-up near
the edges of the passivation layer 180 is remarkably reduced to
improve the transmissive and reflective characteristics of the
passivation layer 180.
[0250] The passivation layer 180 may include a lower film of
inorganic insulator such as silicon nitride or silicon oxide and an
upper film of the above-described organic insulator such that it
takes the excellent insulating characteristics of the organic
insulator while preventing the exposed portions of the
semiconductor stripes 151 from being damaged by the organic
insulator.
[0251] The passivation layer 180 has a plurality of contact holes
182, 185 and 187 exposing the end portions 179 of the data lines
171, the drain electrodes 175, and the storage conductors 177,
respectively. The passivation layer 180 and the gate insulating
layer 140 have a plurality of contact holes 181 exposing the end
portions 129 of the gate lines 121.
[0252] A plurality of pixel electrodes 190 and a plurality of
contact assistants 81 and 82 are formed on the passivation layer
180. They are preferably made of transparent conductor such as ITO
or IZO or reflective conductor such as Ag, Al, Cr, or alloys
thereof.
[0253] The pixel electrodes 190 are physically and electrically
connected to the drain electrodes 175 through the contact holes 185
and connected to the storage conductors 177 through the contact
holes 177 such that the pixel electrodes 190 receive data voltages
from the drain electrodes 175 and transmit the data voltages to the
storage conductors 177. The pixel electrodes 190 supplied with the
data voltages generate electric fields in cooperation with a common
electrode (not shown) of an opposing display panel (not shown) that
is supplied with a common voltage. The generated electric fields
determine the orientations of liquid crystal molecules (not shown)
of a liquid crystal layer (not shown) disposed between the two
electrodes. A pixel electrode 190 and the common electrode form a
capacitor referred to as a "liquid crystal capacitor," which stores
applied voltages after the TFT turns off.
[0254] A pixel electrode 190 overlaps a projection 127 of a
previous gate line 121. The pixel electrode 190 and a storage
conductor 177 connected thereto and the projection 127 form an
additional capacitor referred to as a "storage capacitor," which
enhances the voltage-storing capacity of the liquid crystal
capacitor.
[0255] The pixel electrodes 190 overlap the gate lines 121 and the
data lines 171 to increase the aperture ratio.
[0256] The contact assistants 81 and 82 are connected to the end
portions 129 of the gate lines 121 and the end portions 179 of the
data lines 171 through the contact holes 181 and 182, respectively.
The contact assistants 81 and 82 protect the end portions 129 and
179 and enhance the adhesion between the end portions 129 and 179
and external devices.
[0257] A plurality of slope members (not shown) may be formed on
the pixel electrodes 190 and the passivation layer 180. Each of the
slope members includes a ridge and inclined surfaces having an
inclination angle of from about 1 to about 10 degrees and
determines tilt directions of the liquid crystal molecules to
reduce the response time of the liquid crystal. Like the
passivation layer 180, the slope members may be made of a
photosensitive resin composition including an alkali-soluble resin,
a quinone diazide, a surfactant, an organic fluorine compound
having Chemical Formula 1, a first silicone compound having
Chemical formula 2, a second silicone compound having Chemical
formula 3, and a solvent. The solvent includes a diethylene glycol
dialkyl ether that includes an alkyl group including one to five
carbon atoms, an ethyl 3-ethoxy propionate, an alkyl acetate that
includes an alkyl group including three to eight carbon atoms, and
an alkyl lactate that includes an alkyl group including one to six
carbon atoms.
[0258] A method for manufacturing the TFT array panel shown in
FIGS. 1 and 2 according to an embodiment of the present invention
will be described with reference to FIGS. 3A-6B as well as FIGS. 1
and 2.
[0259] FIGS. 3A, 4A, 5A and 6A are layout views of the TFT array
panel shown FIGS. 1 and 2 in intermediate steps of a manufacturing
method thereof according to an embodiment of the present invention,
FIG. 3B is a sectional view of the TFT array panel shown in FIG. 3A
taken along the line IIIB-IIIB, FIG. 4B is a sectional view of the
TFT array panel shown in FIG. 4A taken along the line IVB-IVB',
FIG. 5B is a sectional view of the TFT array panel shown in FIG. 5A
taken along the line VB-VB', and FIG. 6B is a sectional view of the
TFT array panel shown in FIG. 6A taken along the line VIB-VIB'.
[0260] Referring to FIGS. 3A and 3B, a conductive layer is
deposited on an insulating substrate 110 by sputtering, etc. The
conductive layer has a lower film preferably made of Al or Al--Nd
alloy and having a thickness of preferably about 2,500 .ANG. and an
upper film preferably made of Mo.
[0261] The lower and the upper films may be co-sputtered using an
Al or Al--Nd target and a Mo target. When the lower film is
deposited, the Al(--Nd) target is powered, while the Mo target is
unpowered. After the deposition of the lower film, the Al(--Nd)
target is unpowered and the Mo target is powered to deposit the
upper film.
[0262] The upper and the lower films are patterned by lithography
and etching to form a plurality of gate lines 121 including gate
electrodes 124, projections 127, and end portions 129.
[0263] Referring to FIGS. 4A and 4B, a gate insulating layer 140
having a thickness of about 2,000 to about 5,000 .ANG. is deposited
at a temperature of about 250 to about 500.degree. C. Subsequently,
an intrinsic amorphous silicon layer and an extrinsic amorphous
silicon layer are sequentially deposited on the gate insulating
layer 140 and patterned by lithography and etching to form a
plurality of extrinsic semiconductor stripes 164 and a plurality of
intrinsic semiconductor stripes 151 including projections 154.
[0264] Referring to FIGS. 5A and 5B, a conductive layer is
deposited by sputtering, etc. The conductive layer includes a lower
film preferably made of Mo, an intermediate film preferably made of
Al, and an upper film preferably made of Mo. The thickness of the
conductive layer is equal to about 4,000 .ANG. and the sputtering
temperature is equal to about 150.degree. C.
[0265] The conductive layer is then patterned by lithography and
wet etch to form a plurality of data lines 171 including source
electrodes 173 and end portions 179, the drain electrodes 175, and
the storage conductors 177. The etchant for the wet etch may
include phosphoric acid of preferably about 63-70%, nitric acid of
preferably about 4-8%, acetic acid of preferably about 8-11%, and
deionized water.
[0266] Thereafter, exposed portions of the extrinsic semiconductor
stripes 164, which are not covered with the data lines 171, the
drain electrodes 175, and the storage conductors 177, are removed
to complete a plurality of ohmic contact stripes 161 including
projections 163 and a plurality of ohmic contact islands 165 and to
expose portions of the intrinsic semiconductor stripes 151. Oxygen
plasma treatment preferably follows in order to stabilize the
exposed surfaces of the semiconductor stripes 151.
[0267] Referring to FIGS. 6A and 6B, surfactant includes an organic
fluorine compound of ##STR22## where R.sub.f is a chained or
branched perfluoroalkylene group including about 5-10 carbon atoms
and Z is a hydrogen or a fluorine;
[0268] a first silicone compound of ##STR23## where R is a chained
or branched alkylene group including about 2-5 carbon atoms and
each of x and y is an integer of about 1-20; and
[0269] a second silicone compound of ##STR24## where R' is an alkyl
group including about 1-20 carbon atoms or a chained or branched
carbonyl alkyl group including about 2-21 carbon atoms and each of
v and w is an integer of about 1-20, and each of m and 1 is an
integer of about 1-9 wherein (m+1) lies between 2 and 10. The
photosensitive resin composition may further include one or more of
a cationic polymerization initiator, a polyphenol, a cross-linking
agent, a polymerizable monomer, and a silane coupling agent.
[0270] The coating is performed by slit coating while moving the
substrate 110 or a nozzle (not shown) of a coater (not shown). The
thickness of the coated resin composition is about 1.0 to about 8.0
microns.
[0271] The surfactant in the photosensitive resin composition has
an improved solubility for solid ingredients such as the
alkali-soluble resin and the quinone diazide to make the coating
uniformly spread. Accordingly, a uniformly thick coating can be
formed.
[0272] After the coating, the substrate 110 coated with the
photosensitive resin composition is put into an oven and prebaked
for about 90 to about 180 seconds at a temperature of about 90 to
about 110.degree. C. The prebaking removes volatile ingredients
such as solvents.
[0273] Next, the photosensitive film is aligned with a mask by
using a mask aligner and subjected to a first exposure through the
mask. The light exposure illuminates light such as g line or g line
vertically over an entire surface of the photosensitive resin
film.
[0274] The photoresist resin film is then developed by puddle
development with a developer of an alkaline aqueous solution
preferably containing 3 wt. % diisopropyl amine. The developer
dissolves exposed portions of the photosensitive resin film, which
are exposed to light, and leaves unexposed portions of the
photosensitive resin film to form a passivation layer 180 having a
plurality of contact holes 182, 185 and 187 and upper portions of a
plurality of contact holes 181 as shown in FIGS. 6A and 6B.
[0275] Since the photosensitive resin composition includes quinone
diazide, the exposed portions of the photosensitive resin film is
quickly removed in a short time, while the unexposed portions are
hardly removed even though they are in contact with the developer
for a long time.
[0276] After the development, the substrate 110 with the
passivation layer 180 is cleaned with deionized water and
dried.
[0277] At least a portion of the passivation layer 180 is then
subjected to a second light exposure preferably using (deep)
ultraviolet (UV) ray. The illumination of UV on unit area in the
second light exposure may be higher than that in the first light
exposure. The second light exposure removes the portions that were
insufficiently exposed to light in the first light exposure to
reduce the remnants.
[0278] The passivation layer 180 is postbaked for about 5 to about
120 minutes and more preferably for about 15 to about 90 minutes at
a temperature of about 150.degree. C. to about 250.degree. C. and
more preferably at a temperature of about 180.degree. C. to about
240.degree. C. The postbaking is performed by heating the substrate
110 with a hot plate (not shown) or a clean oven (not shown). The
postbaking improves the heat resistance and the solvent resistance
of the cured photosensitive resin pattern.
[0279] Subsequently, the gate insulating layer 140 is etched using
the passivation layer 180 as an etch mask to complete the contact
holes 181.
[0280] Finally, a plurality of pixel electrodes 190 and a plurality
of contact assistants 81 and 82 are formed on the passivation layer
180 and on the exposed portions of the drain electrodes 175, the
end portions 129 of the gate lines 121, and the end portions 179 of
the data lines 171 by sputtering, lithography, and etching an IZO
or ITO layer as shown FIGS. 1 and 2.
[0281] The above-described photosensitive resin composition may be
employed to other insulating layers such as the gate insulating
layer 140.
Embodiment 3
[0282] FIG. 7 is a layout view of a TFT array panel according to
another embodiment of the present invention and FIG. 8 is a
sectional view of the TFT array panel shown in FIG. 7 taken along
the line VIII-VIII'.
[0283] A plurality of gate lines 121 are formed on an insulating
substrate 110 such as transparent glass or plastic.
[0284] The gate lines 121 transmit gate signals and extend
substantially in a first direction. Each gate line 121 includes a
plurality of gate electrodes 124, a plurality of projections 127
projecting downward, and an end portion 129 having a large area for
contact with another layer or an external driving circuit. A gate
driving circuit (not shown) for generating the gate signals may be
mounted on a flexible printed circuit (FPC) film (not shown), which
may be attached to the substrate 110, directly mounted on the
substrate 110, or integrated onto the substrate 110. The gate lines
121 may extend to be connected to a driving circuit that may be
integrated on the substrate 110.
[0285] The gate lines 121 include two conductive films with
different physical characteristics: a lower film and an upper film
disposed on the lower film. The lower film is preferably made of a
low-resistivity metal, for example an Al-containing metal such as
Al and Al alloy, an Ag-containing metal such as Ag and Ag alloy,
and a Cu-containing metal such as Cu and Cu alloy, for reducing
signal delay or voltage drop. The upper film is preferably made of
a material such as Mo containing metal such as Mo and Mo alloy, Cr,
Ta, or Ti, which has good physical, chemical, and electrical
contact characteristics with other materials such as indium tin
oxide (ITO) or indium zinc oxide (IZO). A good example of the
combination of the two films is a lower Al (alloy) film and an
upper Mo (alloy) film.
[0286] However, the lower film may be made of a good contact
material, and the upper film may be made of a low-resistivity
material. In this case, the upper film 129q of the end portions 129
of the gate lines 121 may be removed to expose the lower film 129p.
In addition, the gate lines 121 may include a single layer
preferably made of the above-described materials. Otherwise, the
gate lines 121 may be made of various metals or conductors.
[0287] In FIGS. 7 and 8, for the gate electrodes 124 and the
projections 127, the lower and upper films thereof are denoted by
additional characters p and q, respectively.
[0288] The lateral sides of the gate lines 121 are inclined
relative to a surface of the substrate 110, and the inclination
angle is in the range of about 30-80 degrees.
[0289] A gate insulating layer 140 preferably made of silicon
nitride (SiNx) or silicon oxide (SiOx) is formed on the gate lines
121.
[0290] A plurality of semiconductor stripes 151 preferably made of
hydrogenated amorphous silicon (abbreviated to "a-Si") or
polysilicon are formed on the gate insulating layer 140. Each
semiconductor stripe 151 extends substantially in the second
direction and become wide near the gate lines 121 such that the
semiconductor stripes 151 cover large areas of the gate lines 121.
Each semiconductor stripe 151 has a plurality of projections 154
branching out toward the gate electrodes 124.
[0291] A plurality of ohmic contact stripes and islands 161 and 165
are formed on the semiconductor stripes 151. The ohmic contact
stripes and islands 161 and 165 are preferably made of n+
hydrogenated a-Si heavily doped with n-type impurity such as
phosphorus, or they may be made of silicide. Each ohmic contact
stripe 161 has a plurality of projections 163, and the projections
163 and the ohmic contact islands 165 are located in pairs on the
projections 154 of the semiconductor stripes 151.
[0292] The lateral sides of the semiconductor stripes 151 and the
ohmic contacts 161 and 165 are inclined relative to a surface of
the substrate 110, and the inclination angles are preferably in a
range of about 30-80 degrees.
[0293] A plurality of data lines 171, a plurality of drain
electrodes 175, and a plurality of storage conductors 177 are
formed on the ohmic contacts 161 and 165 and the gate insulating
layer 140.
[0294] The data lines 171 transmit data signals and extend
substantially in the second direction to intersect the gate lines
121. Each data line 171 includes a plurality of source electrodes
173 projecting toward the gate electrodes 124 and an end portion
179 having a large area for contact with another layer or an
external driving circuit. A data driving circuit (not shown) for
generating the data signals may be mounted on a FPC film (not
shown), which may be attached to the substrate 110, directly
mounted on the substrate 110, or integrated onto the substrate 110.
The data lines 171 may extend to be connected to a driving circuit
that may be integrated on the substrate 110.
[0295] The drain electrodes 175 are separated from the data lines
171 and disposed opposite the source electrodes 173 with respect to
the gate electrodes 124.
[0296] A gate electrode 124, a source electrode 173, and a drain
electrode 175 along with a projection 154 of a semiconductor stripe
151 form a TFT having a channel formed in the projection 154
disposed between the source electrode 173 and the drain electrode
175.
[0297] The storage conductors 177 are disposed on the projections
127 of the gate lines 121.
[0298] The data lines 171, the drain electrodes 175, and the
storage conductors 177 have a triple-layered structure including a
lower film 171p and 175p, an intermediate film 171q and 175q, and
an upper film 171r and 175r. The lower film 171p and 175p is
preferably made of a refractory metal such as Cr, Mo, Ta, Ti, or
alloys thereof, the intermediate film 171q and 175q is preferably
made of a low-resistivity metal such as an Al-containing metal, a
Ag-containing metal, and a Cu-containing metal, and the upper film
171r and 175r is made of refractory metal or alloys thereof having
a good contact characteristic with ITO or IZO.
[0299] The data lines 171, the drain electrodes 175, and the
storage conductors 177 may have a double-layered structure
including a refractory-metal lower film (not shown) and a
low-resistivity upper film (not shown) or a single-layer structure
preferably made of the above-described materials. However, the data
lines 171, the drain electrodes 175, and the storage conductors 177
may be made of various metals or conductors.
[0300] In FIGS. 7 and 8, for the source electrodes 173, the storage
conductors 177, and the end portions 179 of the data lines 179, the
lower, the intermediate, and the upper films thereof are denoted by
additional characters p, q and r, respectively.
[0301] The data lines 171, the drain electrodes 175, and the
storage conductors 177 have inclined profiles, and the inclination
angles range between about 30-80 degrees with respect to the
substrate 110.
[0302] The ohmic contacts 161 and 165 are interposed only between
the underlying semiconductor stripes 151 and the overlying
conductors 171 and 175 thereon and reduce the contact resistance
therebetween. Although the semiconductor stripes 151 are narrower
than the data lines 171 at most places, the width of the
semiconductor stripes 151 becomes large near the gate lines 121 as
described above to smooth the profile of the surface, thereby
preventing the disconnection of the data lines 171. The projections
154 of the semiconductor stripes 151 include some exposed portions
that are not covered with the data lines 171, the drain electrodes
175, and the storage conductors 177 such as the portions located
between the source electrodes 173 and the drain electrodes 175.
[0303] A lower passivation film 180q is formed on the data lines
171, the drain electrodes 175, the storage conductors 177, and the
exposed portions of the semiconductor stripes 151. The lower
passivation film 180q is preferably made of an inorganic insulator
such as silicon nitride or silicon oxide.
[0304] A plurality of color filter stripes 230 are formed on the
lower passivation film 180p.
[0305] The color filter stripes 230 extend along the second
direction and each of the color filter stripes 230 represent one of
primary colors such as red, green, and blue. Adjacent color filter
stripes 230 represent different colors and they have edges exactly
matching with each other on the data lines 171. However, the
adjacent color filter stripes 230 may overlap each other to block
the light leakage between the pixel electrodes 190, or may be
spaced apart from each other. The color filter stripes 230 do not
exist in the peripheral areas provided with the end portions 129
and 179 of the signal lines 121 and 171.
[0306] When the color filter stripes 230 are disposed on the
substrate 110 along with the TFTs, the aperture ratio can be
increased.
[0307] An upper passivation film 180q is formed on the color filter
stripes 230. The lower and the upper passivation films 180p and
180q prevent pigments in the color filter stripes 230 from
permeating into other layers.
[0308] The upper passivation film 180q is preferably made of a
photosensitive organic insulator having a dielectric constant
preferably less than about 4.0. The passivation 180 may have a flat
surface.
[0309] The organic insulator for the upper passivation 180q is a
photosensitive resin composition including an alkali-soluble resin,
a quinone diazide, a surfactant, and a solvent. The surfactant
includes an organic fluorine compound of ##STR25## where R.sub.f is
a chained or branched perfluoroalkylene group including about 5-10
carbon atoms and Z is a hydrogen or a fluorine;
[0310] a first silicone compound of ##STR26## where R is a chained
or branched alkylene group including about 2-5 carbon atoms and
each of x and y is an integer of about 1-20; and
[0311] a second silicone compound of ##STR27## where R' is an alkyl
group including about 1-20 carbon atoms or a chained or branched
carbonyl alkyl group including about 2-21 carbon atoms and each of
v and w is an integer of about 1-20, and each of m and 1 is an
integer of about 1-9 wherein (m+1) lies between 2 and 10. The
photosensitive resin composition may further include a cationic
polymerization initiator, a polyphenol, a cross-linking agent, a
polymerizable monomer, and a silane coupling agent.
[0312] The surfactant in the photosensitive resin composition has
an improved solubility for solid ingredients such as the
alkali-soluble resin and the quinone diazide to make the
photosensitive resin composition uniformly spread. Accordingly, a
uniformly thick film can be formed. As a result, the build-up at
edges of the passivation layer 180 is remarkably reduced to improve
the transmissive and reflective characteristics of the passivation
layer 180.
[0313] The passivation films 180p and 180q have a plurality of
contact holes 182, 185 and 187 exposing the end portions 179 of the
data lines 171, the drain electrodes 175, and the storage
conductors 177, respectively. The passivation layer 180 and the
gate insulating layer 140 have a plurality of contact holes 181
exposing the end portions 129 of the gate lines 121. Furthermore,
the color filter stripes 230 have a plurality of contact holes 235
and 237 exposing lower portions of the contact holes 185 and 187
and surfaces of the lower passivation film 180q near the contact
holes 185 and 187.
[0314] A plurality of pixel electrodes 190 and a plurality of
contact assistants 81 and 82 are formed on the upper passivation
film 180q. They are preferably made of a transparent conductor such
as ITO or IZO or reflective conductor such as Ag, Al, Cr, or alloys
thereof.
[0315] The pixel electrodes 190 are electrically connected to the
drain electrodes 175 through the contact holes 185 and connected to
the storage conductors 177 through the contact holes 177 such that
the pixel electrodes 190 receive data voltages from the drain
electrodes 175 and transmit the data voltages to the storage
conductors 177. The pixel electrodes 190 supplied with the data
voltages generate electric fields in cooperation with a common
electrode (not shown) of an opposing display panel (not shown)
supplied with a common voltage, which determine the orientations of
liquid crystal molecules (not shown) of a liquid crystal layer (not
shown) disposed between the two electrodes. A pixel electrode 190
and the common electrode form a liquid crystal capacitor.
[0316] A pixel electrode 190 overlaps a projection 127 of a
previous gate line 121. The pixel electrode 190 and a storage
conductor 177 connected thereto and the projection 127 form a
storage capacitor.
[0317] The pixel electrodes 190 overlap the gate lines 121 and the
data lines 171 to increase the aperture ratio.
[0318] The contact assistants 81 and 82 are connected to the end
portions 129 of the gate lines 121 and the end portions 179 of the
data lines 171 through the contact holes 181 and 182, respectively.
The contact assistants 81 and 82 protect the end portions 129 and
179 and enhance the adhesion between the end portions 129 and 179
and external devices.
[0319] Now, a method of manufacturing the TFT array panel shown in
FIGS. 7 and 8 is described in detail with reference to FIGS. 9A-10B
as well as FIGS. 7 and 8.
[0320] FIGS. 9A and 10A are layout views of the TFT array panel
shown FIGS. 7 and 8 in intermediate steps of a manufacturing method
thereof according to an embodiment of the present invention, FIG.
9B is a sectional view of the TFT array panel shown in FIG. 9A
taken along the line IXB-IXB', and FIG. 10B is a sectional view of
the TFT array panel shown in FIG. 9A taken along the line
XB-XB'.
[0321] Referring to FIGS. 9A and 9B, a plurality of gate lines 121
including gate electrodes projections 127, and end portions 129 are
formed on an insulating substrate 110. A gate insulating layer 140,
a plurality of semiconductor stripes 151 including projections 154,
and a plurality of ohmic contacts 161 and 165 including projections
163 are sequentially formed on the gate lines 121 and the substrate
110. A plurality of data lines 171 including source electrodes 173,
a plurality of data lines 171, and a plurality of storage
conductors 177 are formed on the ohmic contacts 161 and 163 and the
gate insulating layer 140. A lower passivation film 180p is formed
by PECVD, etc. A negative photosensitive film including one of
primary color pigments is coated and patterned to form a plurality
of color filter stripes having contact holes 235 and 237. Repeating
the film coating and patterning for other primary colors, a
plurality of color filter stripes 230 representing other primary
colors are also formed.
[0322] Next, a photosensitive resin film including an
alkali-soluble resin, a quinone diazide, a surfactant, and a
solvent is coated on the color filter stripes 230. The surfactant
includes an organic fluorine compound of ##STR28## where R.sub.f is
a chained or branched perfluoroalkylene group including about 5-10
carbon atoms and Z is a hydrogen or a fluorine;
[0323] a first silicone compound of ##STR29## where R is a chained
or branched alkylene group including about 2-5 carbon atoms and
each of x and y is an integer of about 1-20; and
[0324] a second silicone compound of ##STR30## where R' is an alkyl
group including about 1-20 carbon atoms or a chained or branched
carbonyl alkyl group including about 2-21 carbon atoms and each of
v and w is an integer of about 1-20, and each of m and 1 is an
integer of about 1-9 wherein (m+1) lies between 2 and 10. The
photosensitive resin composition may further include one or more of
a cationic polymerization initiator, a polyphenol, a cross-linking
agent, a polymerizable monomer, and a silane coupling agent.
[0325] The coating is performed by slit coating while moving the
substrate 110 or a nozzle (not shown) of a coater (not shown). The
thickness of the coated resin composition is about 1.0 to about 8.0
microns.
[0326] The surfactant in the photosensitive resin composition has
an improved solubility for solid ingredients such as the
alkali-soluble resin and the quinone diazide to make the coating
deposit uniformly. Accordingly, a uniformly thick coating can be
formed.
[0327] After the coating, the substrate 110 coated with the
photosensitive resin composition is put into an oven and prebaked
for about 90 to about 180 seconds at a temperature of about 90 to
about 110.degree. C. The prebaking removes volatile ingredients
such as solvents.
[0328] Next, the photosensitive film is aligned with a mask by
using a mask aligner and subjected to a first exposure through the
mask. The light exposure illuminates a light such as g line or g
line vertically over an entire surface of the photosensitive resin
film.
[0329] The photoresist resin film is then developed by puddle
development with a developer of an alkaline aqueous solution
preferably containing 3 wt. % diisopropyl amine. The developer
dissolves the light-exposed portions of the photosensitive resin
film and leaves the unexposed portions of the photosensitive resin
film to form an upper passivation film 180q having upper portions
of a plurality of contact holes 181, 182, 185 and 187 as shown in
FIGS. 10A and 10B.
[0330] Since the photosensitive resin composition includes the
quinone diazide, the exposed portions of the photosensitive resin
film is quickly removed in a short time, while the unexposed
portions are hardly removed even though they are in contact with
the developer for a long time.
[0331] After the development, the substrate 110 with the upper
passivation film 180q is cleaned with deionized water and
dried.
[0332] A portion or an entire portion of the upper passivation film
180q is then subjected to a second light exposure preferably using
(deep) ultraviolet (UV) ray. The illumination of UV on unit area in
the second light exposure may be higher than that in the first
light exposure. The second light exposure removes the portions that
may be insufficiently exposed to light in the first light exposure
to reduce the remnants.
[0333] The upper passivation film 180q is postbaked for about 5 to
about 120 minutes and more preferably from about 15 to about 90
minutes at a temperature from about 150.degree. C. to about
250.degree. C. and more preferably from about 180.degree. C. to
about 240.degree. C. The postbaking is performed by heating the
substrate 110 with a hot plate (not shown). The postbaking improves
the heat resistance and the solvent resistance of the cured
photosensitive resin pattern.
[0334] Subsequently, the lower passivation film 180p and the gate
insulating layer 140 are etched using the upper passivation film
180q as an etch mask to complete the contact holes 181, 182, 185
and 187.
[0335] Finally, a plurality of pixel electrodes 190 and a plurality
of contact assistants 81 and 82 are formed on the upper passivation
film 180q and on the exposed portions of the drain electrodes 175,
the end portions 129 of the gate lines 121, and the end portions
179 of the data lines 171 by sputtering, lithography, and etching
an IZO or ITO layer as shown FIGS. 7 and 8.
[0336] The above-described photosensitive resin composition may be
employed to other insulating layers such as the gate insulating
layer 140 and the lower passivation film 180p.
[0337] Many of the above-described features of the TFT array panel
and the manufacturing method thereof shown in FIGS. 1-6B may be
appropriate to the TFT array panel and the manufacturing method
thereof shown in FIGS. 7A-10B.
[0338] The above-described photosensitive resin composition may be
also employed to insulating layers or slope members on the other
panel facing a TFT panel. In addition, the above-described
photosensitive resin composition may be employed to other display
devices such as organic light emitting diode (OLED) display.
[0339] While the present invention has been described in detail
with reference to the preferred embodiments, those skilled in the
art will appreciate that various modifications and substitutions
can be made thereto without departing from the spirit and scope of
the present invention as set forth in the appended claims.
* * * * *