U.S. patent application number 12/195702 was filed with the patent office on 2009-01-01 for novel photosensitive resin compositions.
This patent application is currently assigned to Fujifilm Electronic Materials U.S.A., Inc.. Invention is credited to Richard Hopla, Jon Metivier, Ahmad A. Naiini, David B. Powell, Il'ya Rushkin.
Application Number | 20090004444 12/195702 |
Document ID | / |
Family ID | 34465196 |
Filed Date | 2009-01-01 |
United States Patent
Application |
20090004444 |
Kind Code |
A1 |
Naiini; Ahmad A. ; et
al. |
January 1, 2009 |
Novel Photosensitive Resin Compositions
Abstract
A positive-working photosensitive composition containing one or
more polybenzoxazole precursor polymers, a diazonaphthoquinone
photoactive compound which is the condensation product of a
compound containing from 2 to about 9 aromatic hydroxyl groups with
a 5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinone
diazide sulfonyl compound, and at least one solvent, and the use of
such compositions to form a relief pattern on a substrate.
Inventors: |
Naiini; Ahmad A.;
(Greenwich, RI) ; Hopla; Richard; (Cranston,
RI) ; Powell; David B.; (Minnetonka, MN) ;
Metivier; Jon; (Billerica, MA) ; Rushkin; Il'ya;
(Walpole, MA) |
Correspondence
Address: |
FISH & RICHARDSON PC
P.O. BOX 1022
MINNEAPOLIS
MN
55440-1022
US
|
Assignee: |
Fujifilm Electronic Materials
U.S.A., Inc.
East Providence
RI
|
Family ID: |
34465196 |
Appl. No.: |
12/195702 |
Filed: |
August 21, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10966349 |
Feb 18, 2005 |
7416830 |
|
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12195702 |
|
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60511198 |
Oct 15, 2003 |
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Current U.S.
Class: |
428/195.1 ;
430/281.1; 430/325 |
Current CPC
Class: |
Y10T 428/24802 20150115;
G03F 7/022 20130101; G03F 7/023 20130101 |
Class at
Publication: |
428/195.1 ;
430/281.1; 430/325 |
International
Class: |
G03F 7/004 20060101
G03F007/004; G03F 7/20 20060101 G03F007/20 |
Claims
1. A positive photosensitive resin composition, comprising: (a) one
or more polybenzoxazole precursor polymers having structure (II);
##STR00060## wherein Ar.sup.1 is selected from the group consisting
of a tetravalent aromatic group, a tetravalent heterocyclic group,
and mixtures thereof; Ar.sup.2 is selected from the group
consisting of a divalent aromatic group, a divalent heterocyclic
group, a divalent alicyclic group, and a divalent aliphatic group
that optionally contains silicon; Ar.sup.3 is selected from the
group consisting of a divalent aromatic group, a divalent aliphatic
group, a divalent heterocyclic group, and mixtures thereof;
Ar.sup.4 is selected from the group consisting of
Ar.sup.1(OD).sub.k.sup.1(OH).sub.k.sup.2 and Ar.sup.2; x is from
about 10 to about 1000; y is from 0 to about 900; D is selected
from the group consisting of one of the following moieties:
##STR00061## in which R is selected from the group consisting of H,
halogen, C.sub.1-C.sub.4 alkyl group, C.sub.1-C.sub.4 alkoxy group,
cyclopentyl and cyclohexyl; k.sup.1 is any positive value of up to
about 0.5; and k.sup.2 is any value from about 1.5 to about 2 with
the proviso that (k.sup.1+k.sup.2)=2; and (b) a diazonaphthoquinone
photoactive compound which is the condensation product of a
compound containing from 2 to 9 aromatic hydroxyl groups with a
5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinone
diazide sulfonyl compound.
2. The composition of claim 1, wherein diazonaphthoquinone
photoactive compound is selected from the group consisting of
compounds of the following formulas: ##STR00062## ##STR00063## in
which at least one Q is moiety (IX), at least one Q is moiety (X),
and each remainder Q is H, moieties (IX) and (X) being:
##STR00064##
3. The composition of claim 2, wherein the diazonaphthoquinone
photoactive compound is selected from the group consisting of the
compounds of formulas (VII a), (VII b), (VII e), (VII g), (VII h),
(VII i), (VII l), (VII n), (VII o), and (VII p).
4. The composition of claim 2, wherein the diazonaphthoquinone
photoactive compound is the compound of formula (VII p).
5. The composition of claim 2, wherein the molar ratio of moiety
(IX) to moiety (X) is from about 20/80 to 80/20 and from about 2
mol % to about 34 mol % of Q is H.
6. The composition of claim 1, wherein the diazonaphthoquinone
photoactive compound has a solubility of at least about 18 wt % in
gamma-butyrolactone at room temperature.
7. The composition of claim 1, wherein Ar.sup.1 is a moiety
selected from the group consisting of: ##STR00065## in which
X.sup.1 is selected from the group consisting of --O--, --S--,
--C(CF.sub.3).sub.2--, --CH.sub.2--, --SO.sub.2--, --NHCO-- and
--SiR.sup.9.sub.2-- and each R.sup.9 is independently selected from
the group consisting of a C.sub.1-C.sub.7 linear or branched alkyl
and a C.sub.5-C.sub.8 cycloalkyl group.
8. The composition of claim 1, wherein Ar.sup.3 is a moiety
selected from the group consisting of: ##STR00066## in which
X.sup.2 is selected from the group consisting of --O--, --S--,
--C(CH.sub.3).sub.2--, --C(CF.sub.3).sub.2--, --CH.sub.2--,
--SO.sub.2--, and --NHCO--.
9. The composition of claim 1, further comprising an adhesion
promoter.
10. The composition of claim 9, wherein the adhesion promoter is a
compound of formula (XI): ##STR00067## in which each R.sup.10 is
independently selected from the group consisting of a
C.sub.1-C.sub.4 alkyl group and a C.sub.5-C.sub.7 cycloalkyl group;
each R.sup.11 is independently selected from the group consisting
of a C.sub.1-C.sub.4 alkyl group, a C.sub.1-C.sub.4 alkoxy group, a
C.sub.5-C.sub.7 cycloalkyl group and a C.sub.5-C.sub.7 cycloalkoxy
group; d is an integer from 0 to 3; n is an integer from 1 to 6;
and R.sup.12 is a moiety selected from the group consisting of:
##STR00068## in which each R.sup.13 and R.sup.14 are independently
selected from the group consisting of a C.sub.1-C.sub.4 alkyl group
and a C.sub.5-C.sub.7 cycloalkyl group, and R.sup.15 is selected
from the group consisting of a C.sub.1-C.sub.4 alkyl group and a
C.sub.5-C.sub.7 cycloalkyl group.
11. The composition of claim 10, wherein Ar.sup.1 is a moiety
derived from a reactant selected from the group consisting of
2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropanel,
3,3'-dihydroxy-4,4'-diaminodiphenylether, 3,3'-dihydroxybenzidine,
4,6-diaminoresorcinol, and 2,2-bis(3-amino-4-hydroxyphenyl)propane
and mixtures thereof; Ar.sup.3 is a moiety derived from a reactant
selected from the group consisting of
4,4'-diphenyletherdicarboxylic acid, terephthalic acid, isophthalic
acid, isophthaloyl dichloride, phthaloyl dichloride, terephthaloyl
dichloride, 4,4'-diphenyletherdicarboxylic acid dichloride,
dimethylisophthalate, dimethylphthalate, dimethylterephthalate,
diethylisophthalate, diethylphthalate, and diethylterephthalate and
mixtures thereof.
12. The composition of claim 1, further comprising an organic
solvent.
13. The composition of claim 12, wherein the organic solvent
comprises N-methyl-2-pyrrolidone, gamma-butyrolactone,
N,N-dimethylacetamide, dimethyl-2-piperidone,
N,N-dimethylformamide, or a mixture thereof.
14. The composition of claim 1, further comprising a dissolution
inhibitor.
15. The composition of claim 14, wherein the dissolution inhibitor
comprises diphenylsilane diol.
16. A process, comprising: (1) coating on a substrate a
positive-working photosensitive composition, thereby forming a
coated substrate, the composition comprising: (a) one or more
polybenzoxazole precursor polymers having structure (II);
##STR00069## wherein Ar.sup.1 is selected from the group consisting
of a tetravalent aromatic group, a tetravalent heterocyclic group,
and mixtures thereof; Ar.sup.2 is selected from the group
consisting of a divalent aromatic group, a divalent heterocyclic
group, a divalent alicyclic group, and a divalent aliphatic group
that optionally contains silicon; Ar.sup.3 is selected from the
group consisting of a divalent aromatic group, a divalent aliphatic
group, a divalent heterocyclic group, and mixtures thereof;
Ar.sup.4 is selected from the group consisting of
Ar.sup.1(OD).sub.k.sup.1(OH).sub.k.sup.2 and Ar.sup.2; x is from
about 10 to about 1000; y is from 0 to about 900; D is selected
from the group consisting of one of the following moieties:
##STR00070## in which R is selected from the group consisting of H,
halogen, C.sub.1-C.sub.4 alkyl group, C.sub.1-C.sub.4 alkoxy group,
cyclopentyl and cyclohexyl; k.sup.1 is any positive value of up to
about 0.5; and k.sup.2 is any value from about 1.5 to about 2 with
the proviso that (k.sup.1+k.sup.2)=2; and (b) a diazonaphthoquinone
photoactive compound which is the condensation product of a
compound containing from 2 to 9 aromatic hydroxyl groups with a
5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinone
diazide sulfonyl compound; (2) prebaking the coated substrate; (3)
exposing the prebaked coated substrate to actinic radiation; (4)
developing the exposed coated substrate with an aqueous developer,
thereby forming an uncured relief image on the coated substrate;
and (5) baking the developed coated substrate at an elevated
temperature, thereby curing the relief image.
17. A device, comprising a substrate, and a relief pattern formed
by the process of claim 16, the relief pattern being supported by
the substrate.
18. The device of claim 17, wherein the device is a memory device,
a logic device, or a plating stencil.
19. A positive photosensitive resin composition, comprising: (a)
one or more polybenzoxazole precursor polymers having structure
(II); ##STR00071## wherein Ar.sup.1 is selected from the group
consisting of a tetravalent aromatic group, a tetravalent
heterocyclic group, and mixtures thereof; Ar.sup.2 is selected from
the group consisting of a divalent aromatic group, a divalent
heterocyclic group, a divalent alicyclic group, and a divalent
aliphatic group that optionally contains silicon; Ar.sup.3 is
selected from the group consisting of a divalent aromatic group, a
divalent aliphatic group, a divalent heterocyclic group, and
mixtures thereof; Ar.sup.4 is selected from the group consisting of
Ar.sup.1(OD).sub.k.sup.1(OH).sub.k.sup.2 and Ar.sup.2; x is from
about 10 to about 1000; y is from 0 to about 900; D is selected
from the group consisting of one of the following moieties:
##STR00072## in which R is selected from the group consisting of H,
halogen, C.sub.1-C.sub.4 alkyl group, C.sub.1-C.sub.4 alkoxy group,
cyclopentyl and cyclohexyl; k.sup.1 is any positive value of up to
about 0.5; and k.sup.2 is any value from about 1.5 to about 2 with
the proviso that (k.sup.1+k.sup.2)=2; (b) a diazonaphthoquinone
photoactive compound of formula (VIII p): ##STR00073## in which one
Q is moiety (IX) and the other Q is moiety (X), moieties (IX) and
(X) being: ##STR00074## (c) an adhesion promoter.
20. The composition of claim 19, wherein the adhesion promoter is a
compound of formula (XI): ##STR00075## in which each R.sup.10 is
independently selected from the group consisting of a
C.sub.1-C.sub.4 alkyl group and a C.sub.5-C.sub.7 cycloalkyl group;
each R.sup.11 is independently selected from the group consisting
of a C.sub.1-C.sub.4 alkyl group, a C.sub.1-C.sub.4 alkoxy group, a
C.sub.5-C.sub.7 cycloalkyl group and a C.sub.5-C.sub.7 cycloalkoxy
group; d is an integer from 0 to 3; n is an integer from 1 to 6;
and R.sup.12 is a moiety selected from the group consisting of:
##STR00076## in which each R.sup.13 and R.sup.14 are independently
selected from the group consisting of a C.sub.1-C.sub.4 alkyl group
and a C.sub.5-C.sub.7 cycloalkyl group, and R.sup.15 is selected
from the group consisting of a C.sub.1-C.sub.4 alkyl group and a
C.sub.5-C.sub.7 cycloalkyl group.
21. The composition of claim 19, further comprising an organic
solvent.
22. The composition of claim 21, wherein the organic solvent
comprises N-methyl-2-pyrrolidone, gamma-butyrolactone,
N,N-dimethylacetamide, dimethyl-2-piperidone,
N,N-dimethylformamide, or a mixture thereof.
23. The composition of claim 19, wherein the molar ratio of moiety
(IX) to moiety (X) is from about 20/80 to 80/20 and from about 2
mol % to about 34 mol % of Q is H.
24. The composition of claim 19, wherein the diazonaphthoquinone
photoactive compound has a solubility of at least about 18 wt % in
gamma-butyrolactone at room temperature.
25. The composition of claim 19, wherein Ar.sup.1 is a moiety
selected from the group consisting of: ##STR00077## in which
X.sup.1 is selected from the group consisting of --O--, --S--,
--C(CF.sub.3).sub.2--, --CH.sub.2--, --SO.sub.2--, --NHCO-- and
--SiR.sup.9.sub.2-- and each R.sup.9 is independently selected from
the group consisting of a C.sub.1-C.sub.7 linear or branched alkyl
and a C.sub.5-C.sub.8 cycloalkyl group.
26. The composition of claim 19, wherein Ar.sup.3 is a moiety
selected from the group consisting of: ##STR00078## in which
X.sup.2 is selected from the group consisting of --O--, --S--,
--C(CH.sub.3).sub.2--, --C(CF.sub.3).sub.2--, --CH.sub.2--,
--SO.sub.2--, and --NHCO--.
27. The composition of claim 19, further comprising a dissolution
inhibitor.
28. The composition of claim 27, wherein the dissolution inhibitor
comprises diphenylsilane diol.
29. A process, comprising: (1) coating on a substrate a
positive-working photosensitive composition, thereby forming a
coated substrate, the composition comprising: (a) one or more
polybenzoxazole precursor polymers having structure (II);
##STR00079## wherein Ar.sup.1 is selected from the group consisting
of a tetravalent aromatic group, a tetravalent heterocyclic group,
and mixtures thereof; Ar.sup.2 is selected from the group
consisting of a divalent aromatic group, a divalent heterocyclic
group, a divalent alicyclic group, and a divalent aliphatic group
that optionally contains silicon; Ar.sup.3 is selected from the
group consisting of a divalent aromatic group, a divalent aliphatic
group, a divalent heterocyclic group, and mixtures thereof;
Ar.sup.4 is selected from the group consisting of
Ar.sup.1(OD).sub.k.sup.1(OH).sub.k.sup.2 and Ar.sup.2; x is from
about 10 to about 1000; y is from 0 to about 900; D is selected
from the group consisting of one of the following moieties:
##STR00080## in which R is selected from the group consisting of H,
halogen, C.sub.1-C.sub.4 alkyl group, C.sub.1-C.sub.4 alkoxy group,
cyclopentyl and cyclohexyl; k.sup.1 is any positive value of up to
about 0.5; and k.sup.2 is any value from about 1.5 to about 2 with
the proviso that (k.sup.1+k.sup.2)=2; (b) a diazonaphthoquinone
photoactive compound of formula (VII p): ##STR00081## in which one
Q is moiety (IX) and the other Q is moiety (X), moieties (IX) and
(X) being: ##STR00082## (c) an adhesion promoter; (2) prebaking the
coated substrate; (3) exposing the prebaked coated substrate to
actinic radiation; (4) developing the exposed coated substrate with
an aqueous developer, thereby forming an uncured relief image on
the coated substrate; and (5) baking the developed coated substrate
at an elevated temperature, thereby curing the relief image.
30. A device, comprising a substrate, and a relief pattern formed
by the process of claim 29, the relief pattern being supported by
the substrate.
31. The device of claim 30, wherein the device is a memory device,
a logic device, or a plating stencil.
Description
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. Utility patent
application Ser. No. 10/966,349, filed Oct. 15, 2004, which claims
priority from U.S. Provisional Patent Application No. 60/511,198,
filed Oct. 15, 2003. The entire disclosures of the parent
applications are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present disclosure relates to positive photosensitive
resin compositions. More specifically, the present disclosure
relates to a positive-working, aqueous base developable
photosensitive polybenzoxazole (PBO) precursor compositions, a
process of use for said photosensitive composition, and electronic
parts produced by said process of use.
BACKGROUND OF THE INVENTION
[0003] In microelectronic applications, polymers that demonstrate
high temperature resistance are generally well known. Precursors of
such polymers, such as polyimides and polybenzoxazoles can be made
photoreactive with suitable additives. The precursors are converted
to the desired polymer by known techniques such as exposure to high
temperatures. The polymer precursors are used to prepare protective
layers, insulating layers, and relief structures of highly
heat-resistant polymers.
[0004] Conventional positive-working photosensitive
polybenzoxazoles (PBO) contain an alkaline soluble PBO precursor
and a diazoquinone photoactive compound as shown in U.S. Pat. No.
4,371,685. The diazoquinone compound inhibits the solubility of the
PBO precursor in an aqueous base. After exposure to light, the
diazoquinone compound undergoes photolysis and converts to
indenecarboxylic acid, which promotes the aqueous base solubility
of the PBO precursor. U.S. Pat. Nos. 6,177,225 and 6,127,086 teach
the use of a PBO precursor, which contains diazoquinone moieties
attached to its backbone along with a diazoquinone photoactive
compound in positive-working photosensitive polybenzoxazole (PBO)
compositions. Recently U.S. patent application Ser. No. 10/793,337
disclosed a composition containing a polybenzoxazole precursor
backbone mixed with a PBO precursor, which contained diazoquinone
moieties attached to its backbone and at least one photoactive
compound such as a diazoquinone compound. U.S. patent application
Ser. No. 10/796,587 disclosed a composition based on a PBO
precursor, which contained diazoquinone moieties attached to its
backbone and had the amines at the end of the polymer chain capped
by various moieties and a diazoquionone photoactive compound. U.S.
patent application Ser. No. 10/793,341 discloses photosensitive
polybenzoxazole precursor compositions that contained diazoquinone
moieties attached to its backbone and contained diazoquinone
compounds without active hydrogen in their structures. Such
compositions provided light color films upon curing. U.S. patent
application Ser. No. 10/796,587 also disclosed a composition
containing a PBO precursor, which contained diazoquinone moieties
attached to its backbone and had the amines at the end of polymer
chain capped by various moieties and had at least one photoactive
compound (PAC) without active hydrogen to produce a light color
film upon curing. In the art described above, the diazoquinone
moiety employed in the photoactive compound was of a single type.
Mixed diazoquinone compounds were not considered.
[0005] U.S. Pat. No. 4,818,658 disclosed a photoactive compound
that was the reaction product of curcumin with 5-naphthoquinone
diazide sulfonyl compounds and 4-naphthoquinone diazide sulfonyl
compounds. U.S. Pat. No. 5,612,164 disclosed a positive photoresist
including a trihydroxyphenylethane containing both 5-naphthoquinone
diazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group,
and a trihydroxybenzophenone containing both 5-naphthoquinone
diazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group.
German Patent No. DD 289,265 disclosed a photoactive compound
containing both 5-naphthoquinone diazide sulfonyl group and a
4-naphthoquinone diazide sulfonyl group. U.S. Pat. No. 6,524,764
disclosed positive-type photosensitive polyimide and
polybenzoxazole precursor compositions with photoactive compound
containing both 5-naphthoquinone diazide sulfonyl group and
4-naphthoquinone diazide sulfonyl group. The 5-naphthoquinone
diazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group
could be in the same molecule or in a mixture of two photoactive
components.
SUMMARY OF THE INVENTION
[0006] The applicants surprisingly discovered that PBO compositions
including a polybenzoxazole precursor resin and photoactive
compounds containing both 5-naphthoquinone diazide sulfonyl group
and 4-naphthoquinone diazide sulfonyl group have superior
lithographic performance to those compositions including a
polybenzoxazole precursor resin and photoactive compounds
containing only 5-naphthoquinone diazide sulfonyl or only
4-naphthoquinone diazide sulfonyl.
[0007] Photosensitive formulations based on photoactive compounds
containing both 5-naphthoquinone diazide sulfonyl group and
4-naphthoquinone diazide sulfonyl group have good imaging and
mechanical properties as well as superior shelf life stability.
[0008] The present disclosure discloses a positive photosensitive
resin composition including: [0009] (a) one or more polybenzoxazole
precursor polymers having structure (II) or structure (IV);
##STR00001##
[0009] in which Ar.sup.1 is a tetravalent aromatic group, a
tetravalent heterocyclic group, or mixtures thereof; Ar.sup.2 is a
divalent aromatic group, a divalent heterocyclic group, a divalent
alicyclic group, or a divalent aliphatic group that may contain
silicon; Ar.sup.3 is a divalent aromatic group, a divalent
aliphatic group, a divalent heterocyclic group, or mixtures
thereof; Ar.sup.4 is Ar.sup.1 (OH).sub.2 or Ar.sup.2, x is from
about 10 to about 1000; y is from 0 to about 900; D is H or one of
the following moieties:
##STR00002##
in which R is H, halogen, C.sub.1-C.sub.4 alkyl group,
C.sub.1-C.sub.4 alkoxy group, cyclopentyl or cyclohexyl; k.sup.1
can be any positive value of up to about 0.5, k.sup.2 can be any
value from about 1.5 to about 2 with the proviso that
(k.sup.1+k.sup.2)=2, G is a monovalent organic group having a
carbonyl, carbonyloxy or sulfonyl group, [0010] (b) a
diazonaphthoquinone photoactive compound which is the condensation
product of a compound containing from 2 to about 9 aromatic
hydroxyl groups with a 5-naphthoquinone diazide sulfonyl compound
and a 4-naphthoquinone diazide sulfonyl compound, and [0011] (c)
optionally at least one solvent.
[0012] The present disclosure also concerns a process for forming a
relief pattern and electronic parts using the photosensitive
composition. The process includes the steps of: [0013] (a) coating
on a suitable substrate, a positive-working photosensitive
composition including one or more polybenzoxazole precursor
polymers having any of the structures (II) or (IV), a
photosensitive agent which is the condensation product of reaction
of compound containing from 2 to about 9 aromatic hydroxyl groups
with a 5-naphthoquinone diazide sulfonyl compound and a
4-naphthoquinone diazide sulfonyl compound, and at least one
solvent, thereby forming a coated substrate; [0014] (b) prebaking
the coated substrate; [0015] (c) exposing the prebaked coated
substrate to actinic radiation; [0016] (d) developing the exposed
coated substrate with an aqueous developer, thereby forming an
uncured relief image on the coated substrate; and [0017] (e) baking
the developed coated substrate at an elevated temperature, thereby
curing the relief image.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The first embodiment of the present disclosure includes a
positive photosensitive resin composition including:
[0019] (a) one or more polybenzoxazole precursor polymers having
structure (II) or structure (IV)
##STR00003##
in which Ar.sup.1 is a tetravalent aromatic group, a tetravalent
heterocyclic group, or mixtures thereof; Ar.sup.2 is a divalent
aromatic group, a divalent heterocyclic group, a divalent alicyclic
group, or a divalent aliphatic group that may contain silicon;
Ar.sup.3 is a divalent aromatic group, a divalent aliphatic group,
a divalent heterocyclic group, or mixtures thereof; Ar.sup.4 is
Ar.sup.1 (OH).sub.2 or Ar.sup.2, x is from about 10 to about 1000;
y is from 0 to about 900; D is H or one of the following
moieties:
##STR00004##
in which R is H, halogen, C.sub.1-C.sub.4 alkyl group,
C.sub.1-C.sub.4 alkoxy group, cyclopentyl, or cyclohexyl; k.sup.1
can be any positive value of up to about 0.5, k.sup.2 can be any
value from about 1.5 to about 2 with the proviso that
(k.sup.1+k.sup.2)=2, G is a monovalent organic group having a
carbonyl, carbonyloxy or sulfonyl group;
[0020] (b) at least one photoactive compound which is the
condensation product of a compound containing from 2 to about 9
aromatic hydroxyl groups with a 5-naphthoquinone diazide sulfonyl
compound and a 4-naphthoquinone diazide sulfonyl compound, and
[0021] (c) optionally at least one solvent.
[0022] Polymers of Structures (II) and (III) can be prepared from
polymers of Structure (I) in one step.
##STR00005##
[0023] Polymer of Structure (I) can be prepared from monomers
having Structures (V), (VI), (VII). Monomers having Structures (V),
(VI), (VII) are reacted in the presence of a base to synthesize
polybenzoxazole precursor polymers of Structure (I).
##STR00006##
In Structures (I), (V), (VI), and (VII), Ar.sup.1, Ar.sup.2,
Ar.sup.3, x, and y are as previously defined, and W is C(O)Cl, COOH
or C(O)OR.sup.2 and in which R.sup.2 is C.sub.1-C.sub.7 linear or
branched alkyl group or a C.sub.5-C.sub.8 cycloalkyl group.
[0024] In Structures (II), (IV), and (V), Ar.sup.1 is a tetravalent
aromatic or a tetravalent heterocyclic group. Examples of Ar.sup.1
include but are not limited to:
##STR00007##
in which X.sup.1 is --O--, --S--, --C(CF.sub.3).sub.2--,
--C(CH.sub.3).sub.2--, --CH.sub.2--, --SO.sub.2--, --NHCO-- or
--SiR.sup.1.sub.2-- and each R.sup.1 is independently a
C.sub.1-C.sub.7 linear or branched alkyl or C.sub.5-C.sub.8
cycloalkyl group. Examples of R.sup.1 include, but are not limited
to, --CH.sub.3, --C.sub.2H.sub.5, n-C.sub.3H.sub.7,
i-C.sub.3H.sub.7, n-C.sub.4H.sub.9, t-C.sub.4H.sub.9, and
cyclohexyl.
[0025] Examples of monomers having the Structure (V) containing
Ar.sup.1 include but are not limited to
2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,
3,3'-dihydroxy-4,4'-diaminodiphenylether, 3,3'-dihydroxybenzidine,
4,6-diaminoresorcinol, and 2,2-bis(3-amino-4-hydroxyphenyl)propane.
The substitution pattern of the two hydroxy and two amino groups in
the monomer of Structure (V) may be any of the possible
substitution patterns with the proviso that the each amino group
has an ortho relationship with a hydroxyl group in order to be able
to form the benzoxazole ring. Furthermore, the polybenzoxazole
precursor base polymer, may be synthesized using a mixture of two
or more monomers described by generic Structure V.
[0026] In Structures (II), (IV), and (VI), Ar.sup.2 is a divalent
aromatic, a divalent heterocyclic, a divalent alicyclic, or a
divalent aliphatic group that may contain silicon. Examples of
Ar.sup.2 include but are not limited to:
##STR00008##
in which X.sup.1 is as defined before, X.sup.2 is --O--, --S--,
--C(CF.sub.3).sub.2--, --C(CH.sub.3).sub.2--, --CH.sub.2--,
--SO.sub.2--, or --NHCO--, Z=H or C.sub.1-C.sub.8 linear, branched
or cyclic alkyl and p is an integer from 1 to 6. Examples of
suitable Z groups include, but are not limited to, methyl, ethyl,
propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-octyl,
cyclopentyl, cyclohexyl and cyclooctyl.
[0027] Examples of monomers having the Structure (VI) containing
Ar.sup.2 include, but are not limited to,
5(6)-diamino-1-(4-aminophenyl)-1,3,3-trimethylindane (DAPI),
m-phenylenediamine, p-phenylenediamine,
2,2'-bis(trifluoromethyl)-4,4'-diamino-1,1'-biphenyl,
3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
2,4-tolylenediamine, 3,3'-diaminodiphenyl sulfone,
3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone,
3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone,
3,4'-diaminodiphenyl ketone, 1,3-bis(4-aminophenoxy)benzene,
1,3-bis(3-amino-phenoxy)benzene,
1,4-bis(.gamma.-aminopropyl)tetramethyldisiloxane,
2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine,
p-xylylenediamine, methylenediamine, tetramethylenediamine,
pentamethylenediamine, hexamethylenediamine,
2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine,
heptamethylenediamine, 2,5-dimethylheptamethylenediamine,
3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,
octamethylenediamine, nonamethylenediamine,
2,5-dimethylnonamethylenediamine, decamethylenediamine,
ethylenediamine, propylenediamine, 2,2-dimethylpropylenediamine,
1,10-diamino-1,10-dimethyldecane, 2,11-diaminidodecane,
1,12-diaminooctadecane, 2,17-diaminoeicosane,
3,3'-dimethyl-4,4'-diaminodiphenylmethane,
bis(4-aminocyclohexyl)methane, 3,3'-diaminodiphenylethane,
4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide,
2,6-diaminopyridine, 2,5-diaminopyridine,
2,6-diamino-4-trifluoromethylpyridine,
2,5-diamino-1,3,4,-oxadiazole, 1,4-diaminocyclohexane,
4,4'-methylenedianiline, 4,4'-methylene-bis(o-choloroaniline),
4,4'-methylene-bis(3-methylaniline),
4,4'-methylene-bis(2-ethylaniline),
4,4'-methylene-bis(2-methoxyaniline), 4,4'-oxy-dianiline,
4,4'-oxy-bis-(2-methoxyaniline), 4,4'-oxy-bis-(2-chloroaniline),
4,4'-thio-dianiline, 4,4'-thio-bis-(2-methylaniline),
4,4'-thio-bis-(2-methyoxyaniline), 4,4'-thio-bis-(2-chloroaniline).
Furthermore, the polybenzoxazole precursor base polymer, may be
synthesized using a mixture of two or more monomers described by
generic Structure VI.
[0028] In Structures (II), (IV), and (VII), Ar.sup.3 is a divalent
aromatic, a divalent aliphatic, or a divalent heterocyclic group.
Examples of Ar.sup.3 include but are not limited to:
##STR00009##
in which X.sup.2 is --O--, --S--, --C(CF.sub.3).sub.2--,
--C(CH.sub.3).sub.2--, --CH.sub.2--, --SO.sub.2--, or --NHCO--.
[0029] In Structure (VII), W is C(O)Cl, COOH or C(O)OR.sup.2 in
which R.sup.2 is C.sub.1-C.sub.7 linear or branched alkyl group or
a C.sub.5-C.sub.8 cycloalkyl group. Examples of R.sup.2 include,
but are not limited to, --CH.sub.3, --C.sub.2H.sub.5,
n-C.sub.3H.sub.7, i-C.sub.3H.sub.7, n-C.sub.4H.sub.9,
t-C.sub.4H.sub.9, and cyclohexyl.
[0030] Monomers having the Structure VII are diacids, diacid
dichlorides and diesters. Examples of suitable dicarboxylic acids
(W.dbd.COOH) include, but are not limited to,
4,4'-diphenyletherdicarboxylic acid, terephthalic acid, isophthalic
acid and mixtures thereof. Examples of suitable diacid chlorides
(W.dbd.COCl) include, but are not limited to, isophthaloyl
dichloride, phthaloyl dichloride, terephthaloyl dichloride,
1,4-oxydibenzoyl chloride and mixtures thereof. Examples of
suitable dicarboxylic esters (W.dbd.C(O)OR.sup.2) include, but are
not limited to: dimethylisophthalate, dimethylphthalate,
dimethylterphthalate, diethylisophthalate, diethylphthalate,
diethylterphthalate and mixtures thereof.
[0031] Monomers having Structures (V) and (VI) and (VII) react to
produce a polybenzoxazole precursor base polymer of Structure (I).
Any conventional method for reacting a dicarboxylic acid or its
dichloride or diester with at least one aromatic and/or
heterocyclic dihydroxydiamine, and optionally, with at least one
diamine, may be used. Generally, the reaction for diacid
dichlorides (W.dbd.C(O)Cl) is carried out at about -10.degree. C.
to about 30.degree. C. for about 6 to about 48 hours in the
presence of an approximately stoichiometric amount of amine base.
Examples of suitable amine bases include, but are not limited to
pyridine, triethyl amine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
1,5-diazabicyclo[4.3.0]non-5-ene (DBN), dimethylpyridine, and
dimethylaniline. The polybenzoxazole precursor base polymer of
Structure (I) may be isolated by precipitation into water,
recovered by filtration and dried. Descriptions of suitable
syntheses employing diesters or diacids may be found in U.S. Pat.
No. 4,395,482, U.S. Pat. No. 4,622,285, and U.S. Pat. No.
5,096,999, herein incorporated by reference.
[0032] The preferred reaction solvents are N-methyl-2-pyrrolidone
(NMP), gamma-butyrolactone (GBL), N,N-dimethylformamide (DMF),
N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone,
dimethylsulfoxide (DMSO), sulfolane, and diglyme. The most
preferred solvents are N-methyl-2-pyrrolidone (NMP) and
gamma-butyrolactone (GBL).
[0033] Monomers having structure (V), (VI), and (VII) are employed
such that the ratio of [(V)+(VI)]/(VII) is generally from about 1
to about 1.2. Preferably, the ratio of [(V)+(VI)]/(VII) is
generally from about 1 to about 1.1. The monomer having the
Structure (V) is employed from about 10 to about 100 mole % of
[(V)+(VI)] and the monomer having Structure (VI) is employed from
about 0 to about 90 mole % of [(V)+(VI)]. Distribution of the
polymeric units resulting from monomers having the Structures (V)
and (VI) in the polybenzoxazole precursor base polymer may be
random or in blocks within it.
[0034] In Structures (II) to (IV), x is an integer from about 10 to
about 1000, y is an integer from about 0 to about 900 and (x+y) is
about less then 1000. A preferred range for x is from about 10 to
about 300 and a preferred range for y is from about 0 to about 250.
A more preferred range for x is from about 10 to about 100 and a
more preferred range for y is from about 0 to about 100. The most
preferred range for x is from about 10 to about 50 and a most
preferred range for y is from about 0 to about 5.
[0035] The amount of (x+y) can be calculated by dividing the
numeric average molecular weight (Mn) of a polymer of Structure (I)
by the average molecular weight of the repeat unit. The value of Mn
can be determined by such standard methods as membrane osmometry or
gel permeation chromatography as described, for example, in Jan
Rabek, Experimental Methods in Polymer Chemistry, John Wiley &
Sons, New York, 1983.
[0036] It should be noted that molecular weight and inherent
viscosity of the polymers and therefore, x and y at a constant
stoichiometry, can have a wide range depend on the reaction
conditions such as the purity of the solvent, the humidity,
presence or absence of a blanket of nitrogen or argon gas, reaction
temperature, reaction time, and other variables.
[0037] Polybenzoxazole precursor polymer of Structure (II) may be
synthesized by reaction of the polybenzoxazole precursor polymer of
Structure (I) with about 1 mole % to about 40 mole % of a
diazoquinone (based on the number of OH groups from the monomer of
Structure (I)) in the presence of a base to yield the
polybenzoxazole precursor of Structure (II) according to Reaction
1.
##STR00010##
in which Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, D, k.sup.1,
k.sup.2, x and y are as previously defined.
[0038] Examples of the diazoquinone compound DCl that can be
reacted with the PBO polymer (I) include but are not limited to one
of the following:
##STR00011##
in which R is H, a halogen, a C.sub.1-C.sub.4 alkyl group, a
C.sub.1-C.sub.4 alkoxy group, cyclopentyl or cyclohexyl. Examples
of suitable R groups include, but are nor limited to, methyl,
ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, cyclopentyl
to cyclohexyl.
[0039] Generally, the reaction is carried out at about 0.degree. C.
to about 30.degree. C. for about 3 to about 24 hours in a solvent
in the presence of a base. Generally, a slight excess of base to
DCl is employed. Examples of bases include but are not limited to
amine bases such as pyridine, trialkylamine, methylpyridine,
lutidine, n-methylmorpholine, and the like. The most preferred base
is triethylamine. The preferred reaction solvents are
tetrahydrofuran, acetone, N-methyl-2-pyrrolidone (NMP),
gamma-butyrolactone (GBL), N,N-dimethylformamide (DMF),
N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone,
dimethylsulfoxide (DMSO), sulfolane, and diglyme. The most
preferred reaction solvents are tetrahydrofuran and acetone. The
reaction mixture should be protected from actinic rays.
[0040] The molar amount of DCl may range from about 1% to about 40%
of the quantity of OH groups from monomers of Structure (V) to
yield k.sup.1 from 0.01 to about 0.4. A preferred amount of DCl is
from about 1% to about 20% of the quantity of OH groups from
monomers of Structure (V) to produce k.sup.1 from about 0.01 to
about 0.20. A more preferred amount of DCl is from about 1% to
about 10% of the quantity of OH groups from monomers of Structure
(V) to produce k.sup.1 from about 0.01 to about 0.10. A most
preferred amount of DCl is from about 1% to about 5% of the
quantity of OH groups from monomers of Structure (V) to produce
k.sup.1 from about 0.01 to about 0.05.
[0041] Polybenzoxazole precursor polymer of Structure (III):
##STR00012##
in which Ar.sup.1 is a tetravalent aromatic group, a tetravalent
heterocyclic group, or mixtures thereof; Ar.sup.2 is a divalent
aromatic group, a divalent heterocyclic group, a divalent alicyclic
group, or a divalent aliphatic group that may contain silicon;
Ar.sup.3 is a divalent aromatic group, a divalent aliphatic group,
a divalent heterocyclic group, or mixtures thereof; Ar.sup.4 is
Ar.sup.1(OD).sub.k.sup.1(OH).sub.k or Ar.sup.2 and G is a
monovalent organic group having a carbonyl, carbonyloxy, or
sulfonyl group, may be synthesized by reaction of polybenzoxazole
base polymer of Structure (I) with G-M where G is a monovalent
organic group having a carbonyl, carbonyloxy or sulfonyl group and
M is a reactive leaving group. Examples of G include, but are not
limited to the following structures:
##STR00013##
[0042] Examples of M groups include, but are not limited to, Cl,
Br, mesylate, triflate, substituted carbonyloxy groups, and
substituted carbonate groups.
[0043] Examples of suitable classes of G-M compounds includes but
are not is limited to carbon and sulfonic acid chlorides, carbon
and sulfonic acid bromides, linear and cyclic carbon and sulfonic
acid anhydrides, and alkoxy or aryloxy substituted acid chlorides.
Examples of suitable G-M compounds include maleic anhydride,
succinic anhydride, acetic anhydride, propionic anhydride,
norbornene anhydride, phthalic anhydride, camphor sulfonic acid
anhydride, trifluoromethane sulfonic acid anhydride,
methanesulfonic acid anhydride, p-toluenesulfonic acid anhydride,
ethanesulfonic acid anhydride, butanesulfonic acid anhydride,
perfluorobutanesulfonic acid anhydride, acetyl chloride,
methanesulfonyl chloride, trifluoromethanesulfonyl chloride,
benzoyl chloride, norbornene carboxylic acid chloride, di-t-butyl
dicarbonate, dimethyl dicarbonate, diethyldicarbonate,
dibutyldicarbonate, t-butyl chloroformate, ethyl chloroformate,
n-butyl chloroformate, and methyl chloroformate. Further examples
include compounds having the structures shown below.
##STR00014##
[0044] The reaction can be carried out in a suitable solvent by
addition of G-M to a dry solution of the polybenzoxazole precursor
base polymer at a temperature from about -25.degree. C. to about
40.degree. C. The more preferred temperature is from about
0.degree. C. to about 25.degree. C. The most preferred temperature
is from about 5.degree. C. to about 10.degree. C. The reaction time
is from about 1 hour to about 24 hours. The molar amount of GM
employed is a slightly excess (3-6%) of the sum of the molar
amounts of monomer of structures (V) and (VI) less the molar amount
of monomer of structure (VII). Addition of organic or inorganic
base may also be employed. Examples of suitable organic amine bases
include, but are not limited to pyridine, triethyl amine,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
1,5-diazabicyclo[4.3.0]non-5-ene (DBN), dimethylpyridine, and
dimethylaniline. Examples of other suitable bases include sodium
hydroxide, sodium carbonate, and sodium silicate.
[0045] The preferred reaction solvents are
propyleneglycolmethylether acetate (PGMEA), N-methyl-2-pyrrolidone
(NMP), gamma-butyrolactone (GBL), N,N-dimethylformamide (DMF),
N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone,
dimethylsulfoxide (DMSO), tetrahydrofuran (THF), acetone,
sulfolane, and diglyme. The most preferred solvents are diglyme and
PGMEA.
[0046] Polybenzoxazole precursor polymer of Structure (IV) may be
synthesized by reaction of polybenzoxazole precursor polymer of
Structure (III) with about 1% to about 40% mole % of a diazoquinone
(based on the number of OH groups from the monomer of Structure
(II)) in the presence of a base to yield the polybenzoxazole
precursor (IV) according to Reaction 2.
##STR00015##
in which Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, D, k.sup.1,
k.sup.2, x, y, and G are as previously defined.
[0047] Examples of the diazoquinone compound DCl that can be
reacted with the PBO polymer (III) include but are not limited to
one of the following:
##STR00016##
in which R is H, a halogen, a C.sub.1-C.sub.4 alkyl group,
C.sub.1-C.sub.4 alkoxy group, cyclopentyl or cyclohexyl. Examples
of suitable R groups include, but are nor limited to, methyl,
ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, cyclopentyl
ot cyclohexyl.
[0048] The molar amount of DCl may range from about 1% to about 40%
of the quantity of OH groups from monomers of Structure (V) to
yield k.sup.1 from 0.01 to about 0.4. A preferred amount of DCl is
from about 1% to about 20% of the quantity of OH groups from
monomers of Structure (V) to produce k.sup.1 from about 0.01 to
about 0.20. A more preferred amount of DCl is from about 1% to
about 10% of the quantity of OH groups from monomers of Structure
(V) to produce k.sup.1 from about 0.01 to about 0.10. A most
preferred amount of DCl is from about 1% to about 5% of the
quantity of OH groups from monomers of Structure (V) to produce
k.sup.1 from about 0.01 to about 0.05.
[0049] The reaction conditions are identical to that description
for the synthesis of polybenzoxazole precursor polymer of Structure
(II).
[0050] A polybenzoxazole precursor polymer of Structure (IV) can
also be prepared by reaction of a polybenzoxazole precursor polymer
of Structure (II) with G-M. The definition of G and M are as
defined before and the reaction condition is the same as described
for the preparation of polybenzoxazole precursor polymer of
Structure (III).
[0051] The photoactive compound (b) of the photosensitive resin
composition are those of the following compounds (VIII) and
includes one or more diazonaphthoquinone photoactive compounds
which are the condensation products of compounds containing from 2
to about 9 aromatic hydroxyl groups with a 5-naphthoquinone diazide
sulfonyl compound and a 4-naphthoquinone diazide sulfonyl
compound.
[0052] The phenolic compounds (i.e. the backbone) typically
employed in the preparation of a photoactive compound may be
prepared by any suitable method. A common method of synthesis is by
reaction of a suitable phenol derivative with a suitable aldehyde
or ketone in the presence of a solvent such as methanol. The
reaction is most often catalyzed by a strong acid (e.g. sulfuric
acid or p-toluene sulfonic acid). Generally, the reaction is
carried out at about at about 15.degree. C. to about 80.degree. C.
for about 3 hours to about 48 hours.
[0053] The photoactive compounds (VII) are synthesized by reaction
of the backbone with DCl. Generally, the reaction is carried out at
about 0.degree. C. to about 30.degree. C. for about 4 to about 36
hours in a solvent in the presence of a base. Generally, a slight
excess of base to DCl is employed. Examples of bases include but
are not limited to amine bases such as pyridine, trialkylamine,
methylpyridine, lutidine, n-methylmorpholine, and the like. The
most preferred base is triethylamine. The preferred reaction
solvents are tetrahydrofuran (THF), gamma-butyrolactone (GBL),
N,N-dimethylformamide (DMF), acetone, N,N-dimethylacetamide (DMAc),
dimethyl-2-piperidone, dimethylsulfoxide (DMSO), sulfolane, and
diglyme. The most preferred solvents are tetrahydrofuran (THF),
acetone and gamma-butyrolactone (GBL). The reaction mixture should
be protected from actinic rays.
[0054] Examples of compounds (VIII) include, but are not limited
to, one or more of the following compounds:
##STR00017## ##STR00018##
in which at least one Q is (IX) and another Q is (X) with the
remainder being H.
##STR00019##
[0055] The ratio of (IX)/(X) is from about 1/99 to about 99/1. A
preferred ratio of (IX)/(X) is from about 20/80 to about 80/20. In
compound VIII, Q=H may be from about 0% to about 90%. A preferred
compound VII is where Q=H is from about 0 to about 75%. A more
preferred VII is where Q=H is from about 0 to about 50%. A most
preferred VIII is where Q=H is from about 2% to about 34%.
[0056] The diazonaphthoquinone photoactive compound which includes
the condensation product of a compound containing from 2 to about 9
aromatic hydroxyl groups with a 5-naphthoquinone diazide sulfonyl
compound and a 4-naphthoquinone diazide sulfonyl compound may
further contain similar condensation products containing only a
5-naphthoquinone diazide sulfonyl moiety (moieties) or only a
4-naphthoquinone diazide sulfonyl moiety (moieties).
[0057] Suitable solvents of this photosensitive composition are
polar organic solvents. Suitable examples of polar organic solvents
include but are not limited to, N-methyl-2-pyrrolidone (NMP),
gamma-butyrolactone (GBL), N,N-dimethylacetamide (DMAc),
dimethyl-2-piperidone, N,N-dimethylformamide (DMF), and mixtures
thereof. The preferred solvents are gamma-butyrolactone and
N-methyl-2-pyrrolidone. The most preferred solvent is
gamma-butyrolactone.
[0058] The amount of polybenzoxazole precursor polymers of
Structures (II) or (IV) in the photosensitive composition is from
about 5 wt. % to about 50 wt. %. The more preferred amount of
polybenzoxazole precursor polymers of Structures (II) or (IV) is
from about 20 wt. % to about 45 wt. % and the most preferred amount
of polybenzoxazole precursor polymers of Structures (II) or (IV) is
from about 30 wt. % to about 40 wt. %. Polybenzoxazole precursor
polymers of Structures (II) or (IV) can be used singly or be
combined in any ratio. Up to 25% of the amount of the
polybenzoxazole precursor polymer of Structures (II) or (V) may be
replaced by other organic solvent soluble, aqueous base soluble,
aromatic or heterocyclic group polymers or copolymers. Examples of
organic solvent soluble, aqueous base soluble, aromatic or
heterocyclic group polymers or copolymers may include polyimides,
polybenzoimidazoles, polybenzothiazoles, polytrizoles,
polyquinazolones, polyquinazolindiones, polyquinacridones,
polybenxazinones, polyanthrazolines, polyoxadiazoles,
polyhydantoins, polyindophenazines, or polythiadiazoles.
[0059] The amount of photosensitive compound, i.e., diazoquinone
compound (VII), used in this composition is from about 1 wt. % to
about 20 wt. % of the total weight of the composition, preferably,
about 2 wt. % to 10 wt. %, and most preferably, about 3 wt. % to
about 6 wt. %.
[0060] The solvent component (c) includes about 40 wt. % to about
80 wt. % of the photosensitive composition. A preferred solvent
range is from about 45 wt. % to about 70 wt. %. A more preferred
range of solvent is from about 50 wt. % to about 65 wt. %.
[0061] Optionally, an adhesion promoter may be included in the
photosensitive composition. If employed, the amount of adhesion
promoter ranges from about 0.1 wt. % to about 2 wt. % of total
weight of composition. A preferred amount of adhesion promoter is
from about 0.2 wt. % to about 1.5 wt. %. A more preferred amount of
adhesion promoter is from about 0.3 wt. % to about 1 wt. %.
Suitable adhesion promoters include, for example, amino silanes,
and mixtures or derivatives thereof. Examples of suitable adhesion
promoters which may be employed in the present disclosure may be
described by Structure XI
##STR00020##
in which each R.sup.10 is independently a C.sub.1-C.sub.4 alkyl
group or a C.sub.5-C.sub.7 cycloalkyl group and each R.sup.11 is
independently a C.sub.1-C.sub.4 alkyl group, a C.sub.1-C.sub.4
alkoxy group, a C.sub.5-C.sub.7 cycloalkyl group or a
C.sub.5-C.sub.7 cycloalkoxy group; d is an integer from 0 to 3 and
n is an integer from 1 to about 6. R.sup.12 is one of the following
moieties:
##STR00021##
in which each R.sup.13 and R.sup.14 are independently a
C.sub.1-C.sub.4 alkyl group or a C.sub.5-C.sub.7 cycloalkyl group,
and R.sup.15 is a C.sub.1-C.sub.4 alkyl group and a C.sub.5-C.sub.7
cycloalkyl group. Preferred adhesion promoters are those in which
R.sup.12 are
##STR00022##
[0062] More preferred adhesion promoters are those in which
R.sup.12 is
##STR00023##
[0063] The most preferred adhesion promoters are
##STR00024##
[0064] The photosensitive compositions of the present disclosure
may further include other additives. Suitable additives include,
for example, leveling agents, dissolution inhibitors and the like.
Such additives may be included in the photosensitive compositions
in about 0.03 to about 10 wt % of the total weight of
composition.
[0065] The second embodiment of the present disclosure concerns a
process for forming a relief pattern using the photosensitive
composition. The process includes the steps of: [0066] (a) coating
on a suitable substrate, a positive-working photosensitive
composition including one or more polybenzoxazole precursor
polymers having Structures (II) or (IV), a diazonaphthoquinone
photoactive compound which is the condensation product of a
compound containing from 2 to about 9 aromatic hydroxyl groups with
a 5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinone
diazide sulfonyl compound, and at least one solvent, thereby
forming a coated substrate; [0067] (b) prebaking the coated
substrate; [0068] (c) exposing the prebaked coated substrate to
actinic radiation; [0069] (d) developing the exposed coated
substrate with an aqueous developer, thereby forming an uncured
relief image on the coated substrate; and [0070] (e) baking the
developed coated substrate at an elevated temperature, thereby
curing the relief image.
[0071] The process may optionally include the step of post exposure
baking the exposed coated substrate at an elevated temperature,
prior to developing. Still another optional step is rinsing the
developed substrate, prior to curing.
[0072] The positive acting, photoactive resin of this disclosure is
coated on a suitable substrate. The substrate may be, for example,
semiconductor materials such as a silicon wafer or a ceramic
substrate, glass, metal, or plastic. Coating methods include, but
are not limited to spray coating, spin coating, offset printing,
roller coating, screen printing, extrusion coating, meniscus
coating, curtain coating, and immersion coating. The resulting film
is prebaked at an elevated temperature. The bake may be completed
at one or more temperatures within the temperature bake of from
about 70.degree. C. to about 120.degree. C. for several minutes to
half an hour, depending on the method, to evaporate the remaining
solvent. Any suitable baking means may be employed. Examples of
suitable baking means include, but are not limited to, hot plates
and convection ovens. The resulting dry film has a thickness of
from about 3 to about 50 micron or more preferably from about 4 to
about 20 micron or most preferably from about 5 to about 15
micron.
[0073] After the bake, step, the resulting dry film is exposed to
actinic rays in a preferred pattern through a mask. X-rays,
electron beam, ultraviolet rays, visible light, and the like can be
used as actinic rays. The most preferable rays are those with
wavelength of 436 nm (g-line) and 365 nm (1-line).
[0074] Following exposure to actinic radiation, in an optional step
it may be advantageous to heat the exposed and coated substrate to
a temperature between about 70.degree. C. and 120.degree. C. The
exposed and coated substrate is heated in this temperature range
for a short period of time, typically several seconds to several
minutes and may be carried out using any suitable heating means.
Preferred means include baking on a hot plate or in a convection
oven. This process step is commonly referred to in the art as post
exposure baking.
[0075] Next, the film is developed using an aqueous developer and a
relief pattern is formed. The aqueous developer contains aqueous
base. Examples of suitable bases include, but are not limited to,
inorganic alkalis (e.g., potassium hydroxide, sodium hydroxide,
ammonia water), primary amines (e.g., ethylamine, n-propylamine),
secondary amines (e.g. diethylamine, di-n-propylamine), tertiary
amines (e.g., triethylamine), alcoholamines (e.g. triethanolamine),
quaternary ammonium salts (e.g., tetramethylammonium hydroxide,
tetraethylammonium hydroxide), and mixtures thereof. The
concentration of base employed will vary depending on the base
solubility of the polymer employed and the specific base employed.
The most preferred developers are those containing
tetramethylammonium hydroxide (TMAH). Suitable concentrations of
TMAH range from about 1% to about 5%. In addition, an appropriate
amount of a surfactant can be added to the developer. Development
can be carried out by means of immersion, spray, puddle, or other
similar developing methods at temperatures from about 10.degree. C.
to about 40.degree. C. for about 30 seconds to about 5 minutes.
After development, the relief pattern may be optionally rinsed
using deionized water and dried by spinning, baking on a hot plate,
in an oven, or other suitable means.
[0076] The benzoxazole ring is then formed by curing of the uncured
relief pattern to obtain the final high heat resistant pattern.
Curing is performed by baking the developed, uncured relief pattern
at or above the glass transition temperature T.sub.g of the
photosensitive composition to obtain the benzoxazole ring that
provides high heat resistance. Typically, temperatures above about
200.degree. C. are used.
##STR00025##
Preferably, temperatures from about 250.degree. C. to about
400.degree. C. are applied. The curing time is from about 15
minutes to about 24 hours depending on the particular heating
method employed. A more preferred range for the curing time is from
about 20 minutes to about 5 hours and the most preferred range of
curing time is from about 30 minutes to about 3 hours. Curing can
be done in air or preferably, under a blanket of nitrogen and may
be carried by any suitable heating means. Preferred means include
baking on a hot plate or in a convection oven.
BRIEF DESCRIPTION OF DRAWINGS
[0077] FIG. 1 is a graph of exposure versus film thickness loss for
composition of this disclosure and comparative compositions.
[0078] To illustrate the present disclosure, the following examples
are provided. It should be understood that the present disclosure
is not limited to the examples described.
SYNTHESIS EXAMPLE 1
Synthesis of Polybenzoxazole Precursor Polymer of Structure
(Ia)
##STR00026##
[0080] To a 100 mL three-necked round bottom flask equipped with a
mechanical stirrer, nitrogen inlet and addition funnel, 3.66 g (10
mmol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 1.70 g
(21 mmol) of pyridine and 15 g of N-methyl-2-pyrrolidone (NMP) were
added. The solution was stirred at room temperature until all
solids was dissolved and then was cooled in an ice water bath at
0-5.degree. C. To this solution, 1.01 g (5 mmol) of isophthaloyl
chloride and 1.477 g (5 mmol) of 1,4-oxydibenzoyl chloride
dissolved in 10 g of NMP was added drop-wise. After the addition
was completed, the resulting mixture was stirred at room
temperature for 18 hours. The viscous solution was precipitated in
800 mL of vigorously stirred de-ionized water. The polymer was
collected by filtration and washed with de-ionized water and a
water/methanol (50/50) mixture. The polymer was dried under vacuum
at 105.degree. C. for 24 hours. The yield was almost quantitative
and the inherent viscosity of the polymer was 0.36 dL/g measured in
NMP at the concentration of 0.5 g/dL at 25.degree. C.
SYNTHESIS EXAMPLE 2
Synthesis of Polymer of Structure (Ia) with Alternative Monomer
Ratio
[0081] To a 2 L, three-necked, round bottom flask equipped with a
mechanical stirrer, nitrogen inlet and addition funnel, 155.9 g
(426.0 mmol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane,
64.3 g (794.9 mmol) of pyridine, and 637.5 g of N-methylpyrrolidone
(NMP) were added. The solution was stirred at room temperature
until all solids dissolved, then cooled in an ice water bath at
0-5.degree. C. To this solution, 39.3 g (194 mmol) of isophthaloyl
chloride, and 56.9 g (194 mmol) of 1,4-oxydibenzoyl chloride
dissolved in 427.5 g of NMP, were added drop-wise. After the
addition was completed, the resulting mixture was stirred at room
temperature for 18 hours. The viscous solution was precipitated in
10 liters of vigorously stirred de-ionized water. The polymer was
collected by filtration and washed with de-ionized water and a
water/methanol (50/50) mixture. The polymer was dried under vacuum
conditions at 105.degree. C. for 24 hours.
[0082] The yield was almost quantitative and the inherent viscosity
(IV) of the polymer was 0.20 dL/g measured in NMP at a
concentration of 0.5 g/dL at 25.degree. C.
[0083] The number average molecular weight (Mn) was determined by
gel permeation chromatography using four Phenogel 10 columns with
pore sizes of 10.sup.4 A, 500 A, 100 A and 50 A and THF as an
eluent. Polystyrene standards were used for calibration. The
typical Mn for a polymer prepared by the above procedure was 5,800.
The average molecular weight of the repeat unit is about 540, so
the degree of polymerization (x+y) was determined to be about 11
(5800/540). Since y=0, X=11.
SYNTHESIS EXAMPLE 3
Synthesis of Polybenzoxazole Precursor Polymer of Structure
(IIa)
[0084] To a 100 mL three-necked round bottom flask equipped with a
mechanical stirrer, 5.42 g (10.0 mmol) of the polymer obtained in
Synthesis Example 1 and 50 mL of tetrahydrofuran (THF) were added.
The mixture was stirred for ten minutes and the solid was fully
dissolved. 0.81 g (3 mmol) of 5-naphthoquinone diazide sulfonyl
chloride was then added and the mixture was stirred for another 10
minutes. Triethylamine, 0.3 g (3 mmol), was added gradually within
15 minutes and then the reaction mixture was stirred for 5 hours.
The reaction mixture was then added gradually to 500 mL of
vigorously stirred de-ionized water. The precipitated product was
separated by filtration and washed with 200 mL of de-ionized water.
To the product was added another 600 mL de-ionized water and the
mixture vigorously stirred for 30 minutes. After filtration the
product was washed with 100 mL de-ionized water. The isolated
product was dried at 40.degree. C. overnight. The yield was
91%.
SYNTHESIS EXAMPLE 4
Synthesis of Polybenzoxazole Precursor Polymer of Structure (IIa)
Having Alternate Monomer Ratios
[0085] Synthesis Example 3 was repeated except the polymer obtained
in Synthesis Example 2 was reacted with 3 mol % of 5-naphthoquinone
diazide sulfonyl chloride. The inherent viscosity of the polymer
was 0.21 dL/g measured in NMP at the concentration of 0.5 g/dL at
25.degree. C.
SYNTHESIS EXAMPLE 5
Synthesis of a Polybenzoxazole Precursor Polymer of Structure
(IIIa; G=Acetyl)
##STR00027##
[0087] 3 small batches of PBO precursor polymers synthesized
according to Synthesis Example 2 were mixed to obtain 100 g (184.5
mmol) PBO precursor mixture with inherent viscosity of 0.205 dL/g.
The mixture was dissolved in 1,000 g of diglyme. Residual water was
removed as an azeotrope with diglyme using a rotary evaporator at
65.degree. C. (10-12 torr). About 500 g of solvents was removed
during the azeotrope distillation.
[0088] The reaction solution was transferred to a 1,000 mL, three
neck, round bottom flask equipped with N.sub.2 inlet and magnetic
stirrer. The reaction mixture cooled on ice bath down to about
5.degree. C. Acetyl chloride (3.3 ml, 3.6 g) was added via syringe
over the period of 5 minutes keeping reaction solution well
stirred.
[0089] The reaction was held on ice bath for about 10 minutes. Then
the ice bath was removed and the reaction was allowed to warm up
over the period of 1 hour. Then, the mixture was again cooled to
5.degree. C. on the ice bath. Pyridine (3.7 ml, 3.6 g) was added
via syringe over the period of 1 hour. Reaction was kept on the ice
bath for 10 minutes, and then was allowed to warm up over the
period of 1 hour.
[0090] The reaction mixture was precipitated into 6 L of water. The
polymer was collected by filtration and air dried overnight. Then,
the polymer was dissolved in 500-600 g of acetone and precipitated
into 6 L of water/methanol (70/30). The polymer was again collected
by filtration and air-dried for several hours. The wet polymer cake
was dissolved in a mixture 700 g of THF and was precipitated in 7 L
of water, filtered, air-dried overnight followed by 24 hours drying
in vacuum oven at 90.degree. C.
[0091] Terminal NH.sub.2 groups have a chemical shift of 4.5 ppm.
After the reaction of acetyl chloride and polybenzoxazole precursor
polymer was completed, it was observed that this peak was
completely vanished, indicative that all NH.sub.2 groups were
reacted.
SYNTHESIS EXAMPLE 6
Synthesis of a Polybenzoxazole Precursor Polymer of Structure
(IVa); G=Acetyl
##STR00028##
[0093] To a 1 L three-necked round bottom flask equipped with a
mechanical stirrer, 67.5 g (approximately 120 mmol) of a mixture of
two batches of polymer synthesized according to Synthesis Example 5
and 650 g of tetrahydrofuran (THF) were added. The mixture was
stirred for ten minutes and the solid was fully dissolved. 1.01 g
(0.38 mmol) of 2,1-naphthoquinonediazide-5-sulfonyl chloride (IId
R.dbd.H) was then added and the mixture was stirred for another 10
minutes. Triethylamine, 0.39 g (3.9 mmol) mixed with 50 mL THF was
added gradually within 30 minutes and then the reaction mixture was
stirred for overnight. The reaction mixture was then added
gradually to 3 L of vigorously stirred de-ionized water. The
precipitated product was separated by filtration and reslurried
twice, each time with 3 L of de-ionized water. After filtration the
product was washed with 2 L de-ionized water. The isolated product
was dried at 40.degree. C. overnight. The yield of the product was
84%.
SYNTHESIS EXAMPLE 7
Synthesis of a Polymer of Structure (IVb); G=Phthaloyl Via an
Alternative Embodiment
##STR00029##
[0095] To a 1 L three-necked round bottom flask equipped with a
mechanical stirrer, and nitrogen inlet 100 g (165.9 mmol) of the
polymer obtained in Synthesis Example 4 and 290 g of diglyme were
added. The mixture was stirred for about 25 minutes and the solid
was fully dissolved. 6.5 g (43.9 mmol) of phthalic anhydride was
then added portion-wise within an hour at room temperature and the
mixture was stirred for 16 hours. The reaction mixture was then
added gradually to 5,200 mL of vigorously stirred de-ionized water
during a 60 minutes period. The precipitated product was separated
by filtration and washed with 2,000 mL of de-ionized water. To the
product was added another 4,000 mL de-ionized water and the mixture
vigorously stirred for 30 minutes. After filtration the product was
washed with 2,000 mL de-ionized water. The isolated product was
dried at 40.degree. C. overnight. The yield of the product was
90%.
SYNTHESIS EXAMPLE 8
Preparation of Polybenzoxazole Precursor Polymer of Structure
(Ib)
##STR00030##
[0097] To a 20 L reactor equipped with a mechanical agitator,
nitrogen inlet and thermocouple, 1,500 g (4.09 mol) of
hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 622 g (7.86
mol) of pyridine and 7,250 g of N-methyl-2-pyrrolidone (NMP) were
added. The solution was stirred at room temperature until all
solids dissolved and then cooled in an ice water bath at
0-5.degree. C. To this solution, 291 g (1.43 mol) of terephthaloyl
chloride and 634.5 g (2.15 mol) of 1,4-oxydibenzoyl chloride
dissolved in 2,760 g of NMP was added by using a diaphragm pump and
Teflon transfer lines. The pump and Teflon transfer lines were
cleaned by using 200 g of NMP. After the addition was completed,
the resulting mixture was stirred at room temperature for 18 hours.
The viscous solution was precipitated in 140 L of vigorously
stirred de-ionized water. The polymer was collected by filtration
and washed with 35 L of de-ionized water and a water/methanol
(50/50) mixture. The polymer was dried under vacuum at 75.degree.
C. for 24 hours. The yield was almost quantitative and the inherent
viscosity of the polymer was 0.183 dL/g measured in NMP at the
concentration of 0.5 g/dL at 25.degree. C.
SYNTHESIS EXAMPLE 9
Preparation of a Polybenzoxazole Precursor Polymer of Structure
(IIb)
##STR00031##
[0099] Synthesis Example 3 was repeated except the polymer from
Synthesis Example 8 was employed and the ratio of
2,1-naphthoquinonediazide-5-sulfonyl chloride to the total number
of OH groups of the polymer was changed to 0.02. The yield was 96%
and the inherent viscosity of the polymer was 0.201 dL/g measured
in NMP at the concentration of 0.5 g/dL at 25.degree. C.
SYNTHESIS EXAMPLE 10
Synthesis of Polymer of Structure (IIIb) G=Acetyl
##STR00032##
[0101] Synthesis Example 5 was repeated except the polymer employed
was the one prepared in Synthesis Example 8. The yield was 83.7%
and the inherent viscosity of the polymer was 0.205 dL/g measured
in NMP at the concentration of 0.5 g/dL at 25.degree. C.
SYNTHESIS EXAMPLE 11
Synthesis of Polymer of Structure (IVb); G=Acetyl
##STR00033##
[0103] Synthesis Example 4 was repeated except the polymer used was
one synthesized in Synthesis Example 10 and the ratio of
2,1-naphthoquinonediazide-5-sulfonyl chloride (IId R.dbd.H) to OH
groups of the polymer was changed to 2.0/100. The yield was 96% and
the inherent viscosity of the polymer was 0.204 dL/g measured in
NMP at the concentration of 0.5 g/dL at 25.degree. C.
SYNTHESIS EXAMPLE 12
Preparation of a Polybenzoxazole Precursor Polymer of Structure
(Ic)
##STR00034##
[0105] To a 20 L reactor equipped with a mechanical agitator,
nitrogen inlet and thermocouple, 1,500 g (4.09 mol) of
hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 622 g (7.86
mol) of pyridine and 5,000 g of N-methyl-2-pyrrolidone (NMP) were
added. The solution was stirred at room temperature until all
solids dissolved and then cooled in an ice water bath at
0-5.degree. C. To this solution, 212.0 g (1.04 mol) of
terephthaloyl chloride, 212.0 g (1.04 mol) of isophthaloyl chloride
and 411.0 g (1.39 mol) of 1,4-oxydibenzoyl chloride dissolved in
2,960 g of NMP were added by using a diaphragm pump and Teflon
transfer lines. The pump and Teflon transfer lines were cleaned
using 200 g of NMP, which was then added to the solution. After the
addition was completed, the resulting mixture was stirred at room
temperature for 18 hours. The viscous solution was precipitated in
140 L of vigorously stirred de-ionized water. The polymer was
collected by filtration and washed with 35 L of de-ionized water
and a water/methanol (50/50) mixture. The polymer was dried under
vacuum at 75.degree. C. for 24 hours. The yield was almost
quantitative and the inherent viscosity of the polymer was 0.205
dL/g measured in NMP at the concentration of 0.5 g/dL at 25.degree.
C.
SYNTHESIS EXAMPLE 13
Synthesis of a Polybenzoxazole Polymer Precursor of Structure
(IIc)
##STR00035##
[0107] Synthesis Example 3 was repeated except the polymer from
Synthesis Example 12 was employed and the ratio of
2,1-naphthoquinonediazide-5-sulfonyl chloride to the total number
of OH groups of the polymer was changed to 0.025. The yield was 96%
and the inherent viscosity of the polymer was 0.201 dL/g measured
in NMP at the concentration of 0.5 g/dL at 25.degree. C.
SYNTHESIS EXAMPLE 14
Synthesis of Polymer of Structure (IIIc); G=Acetyl
##STR00036##
[0109] Synthesis Example 5 was repeated except the polymer used was
one prepared in Synthesis Example 12. The yield was 93.6% and the
inherent viscosity of the polymer was 0.212 dL/g measured in NMP at
the concentration of 0.5 g/dL at 25.degree. C.
SYNTHESIS EXAMPLE 15
Synthesis of Polymer of Structure (IVc); G=Acetyl
##STR00037##
[0111] Synthesis Example 4 was repeated except the polymer employed
was the one prepared in Synthesis Example 14 and the ratio of
2,1-naphthoquinonediazide-5-sulfonyl chloride (IId R.dbd.H) to OH
groups of the polymer was changed to 3.0/100. The yield was 98.7%
and the inherent viscosity of the polymer was 0.206 dL/g measured
in NMP at the concentration of 0.5 g/dL at 25.degree. C.
SYNTHESIS EXAMPLE 16
Synthesis of a Photoactive Compound (PAC) of Structure (VIII p)
##STR00038##
[0113] To a 500 mL, 3-neck flask equipped with mechanical stirrer,
dropping funnel, pH probe, thermometer and nitrogen purge system
were added 225 mL of THF and 30 g of
(4,4'-(1-phenylethylidene)bisphenol), Bisphenol AP. The mixture was
stirred until bisphenol AP was fully dissolved. To this was added
27.75 g of 4-naphthoquinone diazide sulfonyl chloride and 25 mL of
THF. The reaction mixture was stirred until the solid was fully
dissolved. 10.475 g of triethylamine dissolved in 50 mL THF was
added to the reaction mixture gradually while the pH was kept under
8 during this process. The temperature during this exothermic
reaction was kept under 30.degree. C. Upon completion of addition,
the reaction mixture was stirred for 48 hours. To this was added
27.75 g of 5-naphthoquinone diazide sulfonyl chloride and 25 mL of
THF and the reaction mixture was stirred for 30 minutes. 10.475 g
triethylamine dissolved in 50 mL THF was added to the reaction
mixture gradually while the pH was kept under 8 during this
process. Again during this exothermic reaction the temperature was
kept under 30.degree. C. Upon completion of the addition, the
reaction mixture was stirred for 20 hours. The reaction mixture was
then added gradually to a mixture of 6 L of DI-water and 10 g of
HCl. The product was filtered and washed with 2 L of de-ionized
water. The product was then reslurried by using 3 L of de-ionized
water, filtered and washed with 1 L of de-ionized water. The
product was then dried inside a vacuum oven at 40.degree. C. until
the amount of water dropped below 2%. HPLC analysis revealed that
the product is mixture of several esters as shown in Table 1.
SYNTHESIS EXAMPLE 17
Synthesis of a Photoactive Compound (Pac) of Structure (VIII p)
Using Different Ratio of 4-Naphthoquinone Diazide Sulfonyl Chloride
to 5-Naphthoquinone Diazide Sulfonyl Chloride
[0114] Synthesis example 16 was repeated except the ratio of
4-naphthoquinone diazide sulfonyl chloride to 5-naphthoquinone
diazide sulfonyl chloride was changed from 1/1 to 1/3. HPLC
analysis revealed that the product is mixture of several esters as
shown in Table 1. The total yield of this reaction was 91.7%
SYNTHESIS EXAMPLE 18
Synthesis of a Photoactive Compound (PAC) of Structure (VIII p)
Using Different Ratio of 4-Naphthoquinone Diazide Sulfonyl Chloride
to 5-Naphthoquinone Diazide Sulfonyl Chloride
[0115] Synthesis Example 16 was repeated except the ratio of
4-naphthoquinone diazide sulfonyl chloride to 5-naphthoquinone
diazide sulfonyl chloride was changed from 1/1 to 311. HPLC
analysis revealed that the product is mixture of several esters as
shown in Table 1. The total yield of this reaction was 88.0%.
TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Structure Compound ple 16
ple 17 ple 18 ##STR00039## S214 0.61% 0.12 0.21 ##STR00040## S215
0.53% 0.26 0.11 ##STR00041## S214monoester 1.72% 0.30 2.73
##STR00042## S215monoester 1.4% 0.62 0.68 ##STR00043## S215diester
18.9% 50.3 4.50 ##STR00044## MixedEster PAC 46.7% 39.9 32.6
##STR00045## S214diester 29% 8.00 58.3
[0116] The solubility of this compound on GBL was tested and it was
more than 18%
COMPARATIVE SYNTHESIS EXAMPLE 1
Synthesis of a Photoactive Compound (PAC) of Structure (XII)
##STR00046##
[0118] The reaction was similar to that of Example 7 except only
5-naphthoquinone diazide sulfonyl chloride was used. HPLC analysis
revealed that about 94% of the product was diester and 6% was
monoester. The solubility of this compound in GBL was about 10%
COMPARATIVE SYNTHESIS EXAMPLE 2
Synthesis of a Photoactive Compound (PAC) of Structure (XIII)
##STR00047##
[0120] The reaction was similar to that of Synthesis Example 17
except only 4-naphthoquinone diazide sulfonyl chloride was used.
HPLC analysis revealed that about 87% of the product is diester and
13% is monoester. The solubility of this compound on GBL was tested
and it was only about 2-3%.
EXAMPLE 1
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VIII p)
[0121] 100 parts polymer obtained in Synthesis Example 4, 11.9 part
of bis phenol AP PAC obtained from example 16, 5 parts of
diphenylsilane diol and 3 parts of
gamma-ureidopropyltrimethoxysilane (adhesion promoter) was
dissolved in GBL and filtered. The formulation was spin coated on a
silicon wafer then baked on a hotplate for 4 minutes at 120.degree.
C., resulting in a film thickness of 14.01 .mu.m. The film was then
exposed utilizing an i-line stepper in an open frame exposure
array, which incrementally increased exposure energy 10 mJ/cm.sup.2
with a starting exposure energy of 400 mJ/cm.sup.2. The wafer was
then developed with two 50 second puddles with a 0.262 N aqueous
solution of tetra-methyl ammonium hydroxide, resulting in an array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 495 mJ/cm.sup.2. The
unexposed film thickness decreased 6.15 microns to 7.85 microns
(43.97% film thickness loss).
EXAMPLE 2
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VIII p)
[0122] The photosensitive composition of Example 1 was spin coated
on a silicon wafer and baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 14.05 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 10
mJ/cm.sup.2 with a starting exposure energy of 600 mJ/cm.sup.2. The
wafer was then developed with two 40 second puddles. The
formulation cleared boxes at a dose of 670 mJ/cm.sup.2. The
unexposed film thickness decreased 5.13 microns to 8.92 microns
(36.51% film thickness loss).
EXAMPLE 3
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VIII p)
[0123] The photosensitive composition of Example 1 was spin coated
on a silicon wafer then baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 14.03 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 10
mJ/cm.sup.2 with a starting exposure energy of 800 mJ/cm.sup.2. The
wafer was then developed with two 28 second puddles. The
formulation cleared boxes at a dose of 950 mJ/cm.sup.2. The
unexposed film thickness decreased 3.98 microns to 10.05 microns
(28.37% film thickness loss).
EXAMPLE 4
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VII p)
[0124] The photosensitive composition of Example 1 was spin coated
on a silicon wafer then baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 13.91 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 50
mJ/cm.sup.2 with a starting exposure energy of 300 mJ/cm.sup.2. The
wafer was then developed with two 41.5 second puddles. The
formulation cleared boxes at a dose of 650 mJ/cm.sup.2. The
unexposed film thickness decreased 5.33 microns to 8.58 microns
(38.32% film thickness loss).
COMPARATIVE EXAMPLE 1
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (XII)
[0125] 100 parts polymer obtained in Synthesis Example 4, 11.9 part
of bis phenol AP PAC shown in structure XII (see Comparative
Synthesis Example 1), 5 parts of diphenylsilane diol and 3 parts of
gamma-ureidopropyltrimethoxysilane (adhesion promoter) was
dissolved in GBL and filtered. The formulation was spin coated on a
silicon wafer then baked on a hotplate for 4 minutes at 120.degree.
C., resulting in a film thickness of 14.17 .mu.m. The film was then
exposed utilizing an i-line stepper in an open frame exposure
array, which incrementally increased exposure energy 10 mJ/cm.sup.2
with a starting exposure energy of 400 mJ/cm.sup.2. The wafer was
then developed with two 56 second puddles with a 0.262 N aqueous
solution of tetra-methyl ammonium hydroxide, resulting in a array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 440 mJ/cm.sup.2. The
unexposed film thickness decreased 7.3 microns to 6.87 microns
(51.52% film thickness loss).
COMPARATIVE EXAMPLE 2
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (XII)
[0126] The photosensitive composition of Comparative Example 1 was
spin coated on a silicon wafer then baked on a hotplate for 4
minutes at 120.degree. C., resulting in a film thickness of 14.12
.mu.m. The film was then exposed utilizing an i-line stepper in an
open frame exposure array, which incrementally increased exposure
energy 10 mJ/cm.sup.2 with a starting exposure energy of 600
mJ/cm.sup.2. The wafer was then developed with two 42 second
puddles. The formulation cleared boxes at a dose of 640
mJ/cm.sup.2. The unexposed film thickness decreased 5.68 microns to
8.44 microns (40.23% film thickness loss).
COMPARATIVE EXAMPLE 3
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (XII)
[0127] The photosensitive composition of Comparative Example 1 was
spin coated on a silicon wafer then baked on a hotplate for 4
minutes at 120.degree. C., resulting in a film thickness of 14.07
.mu.m. The film was then exposed utilizing an i-line stepper in an
open frame exposure array, which incrementally increased exposure
energy 10 mJ/cm.sup.2 with a starting exposure energy of 800
mJ/cm.sup.2. The wafer was then developed with two 34 second
puddles. The formulation cleared boxes at a dose of 825
mJ/cm.sup.2. The unexposed film thickness decreased 4.82 microns to
9.25 microns (34.26% film thickness loss).
COMPARATIVE EXAMPLE 4
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (XII)
[0128] The photosensitive composition of Comparative Example 1 was
spin coated on a silicon wafer then baked on a hotplate for 4
minutes at 120.degree. C., resulting in a film thickness of 14.18
.mu.m. The film was then exposed utilizing an i-line stepper in an
open frame exposure array, which incrementally increased exposure
energy 50 mJ/cm.sup.2 with a starting exposure energy of 300
mJ/cm.sup.2. The wafer was then developed with two 41.5 second
puddles. The formulation cleared boxes at a dose of 700
mJ/cm.sup.2. The unexposed film thickness decreased 5.66 microns to
8.62 microns (39.92% film thickness loss).
[0129] The results of Examples 1-4 and comparative Examples of 1-4
are shown in FIG. 1. From these results, it is obvious that the
composition used in Examples 1-4 have a better film thickness
retention at the same energy dose in compare with the composition
used in Comparative Examples 1-4.
EXAMPLE 5
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VII p)
[0130] 100 parts polymer obtained in Synthesis Example 4, 11.9 part
of bis phenol AP PAC obtained from example 17, 5 part of
diphenylsilane diol and 3 parts of
gamma-ureidopropyltrimethoxysilane was dissolved in GBL and
filtered. The formulation was spin coated on a silicon wafer then
baked on a hotplate for 4 minutes at 120.degree. C., resulting in a
film thickness of 14.15 .mu.m. The film was then exposed utilizing
an i-line stepper in an open frame exposure array, which
incrementally increased exposure energy 20 mJ/cm.sup.2 with a
starting exposure energy of 300 mJ/cm.sup.2. The wafer was then
developed with two 45 second puddles with a 0.262N aqueous solution
of tetra-methyl ammonium hydroxide, resulting in an array of
exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 485 mJ/cm.sup.2. The
unexposed film thickness decreased 6.71 microns to 7.43 microns
(47.44% film thickness loss).
EXAMPLE 6
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VII p)
[0131] The photosensitive composition of Example 5 was spin coated
on a silicon wafer and baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 14.11 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 20
mJ/cm.sup.2 with a starting exposure energy of 500 mJ/cm.sup.2. The
wafer was then developed with two 33 second puddles. The
formulation cleared boxes at a dose of 680 mJ/cm.sup.2. The
unexposed film thickness decreased 5.30 microns to 8.81 microns
(37.57% film thickness loss).
EXAMPLE 7
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VIII p)
[0132] The photosensitive composition of Example 5 was spin coated
on a silicon wafer then baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 14.14 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 20
mJ/cm.sup.2 with a starting exposure energy of 800 mJ/cm.sup.2. The
wafer was then developed with two 28 second puddles. The
formulation cleared boxes at a dose of 920 mJ/cm.sup.2. The
unexposed film thickness decreased 4.19 microns to 9.95 microns
(29.63% film thickness loss).
[0133] From the results of Examples 5-7 and comparative Examples of
1-4, it is obvious that the composition used in Examples 5-7 have a
better film thickness retention at the same energy dose in
comparison with the composition used in Comparative Examples
1-4.
EXAMPLE 8
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VII p)
[0134] 100 parts polymer obtained in Synthesis Example 4, 11.9 part
of bis phenol AP PAC obtained from example 18, 5 part of
diphenylsilane diol and 3 parts of
gamma-ureidopropyltrimethoxysilane was dissolved in GBL and
filtered. The formulation was spin coated on a silicon wafer then
baked on a hotplate for 4 minutes at 120.degree. C., resulting in a
film thickness of 14.09 .mu.m. The film was then exposed utilizing
an i-line stepper in an open frame exposure array, which
incrementally increased exposure energy 20 mJ/cm.sup.2 with a
starting exposure energy of 800 mJ/cm.sup.2. The wafer was then
developed with two 22 second puddles with a 0.262 N aqueous
solution of tetra-methyl ammonium hydroxide, resulting in an array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 860 mJ/cm.sup.2. The
unexposed film thickness decreased 4.06 microns to 10.02 microns
(28.84% film thickness loss).
EXAMPLE 9
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VII p)
[0135] The photosensitive composition of Example 8 was spin coated
on a silicon wafer and baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 14.09 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 20
mJ/cm.sup.2 with a starting exposure energy of 500 mJ/cm.sup.2. The
wafer was then developed with two 30 second puddles. The
formulation cleared boxes at a dose of 640 mJ/cm.sup.2. The
unexposed film thickness decreased 5.11 microns to 8.99 microns
(36.23% film thickness loss).
EXAMPLE 10
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VII p)
[0136] The photosensitive composition of Example 8 was spin coated
on a silicon wafer then baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 14.11 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 20
mJ/cm.sup.2 with a starting exposure energy of 300 mJ/cm.sup.2. The
wafer was then developed with two 28 second puddles. The
formulation cleared boxes at a dose of 420 mJ/cm.sup.2. The
unexposed film thickness decreased 6.66 microns to 7.45 microns
(47.21% film thickness loss).
[0137] From the results of Examples 8-10 and comparative Examples
1-4, it is obvious that the composition used in Examples 8-10 have
a better film thickness retention at the same energy dose in
comparison with the composition used in Comparative Examples
1-4.
EXAMPLE 11
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VII p)
[0138] 100 parts polymer obtained in Synthesis Example 4, 14.3
parts of bis phenol AP PAC obtained from Synthesis Example 16, 2.5
parts of diphenylsilane diol and 1.4 parts of
gamma-ureidopropyltrimethoxysilane (adhesion promoter) were
dissolved in GBL and filtered. The formulation was spin coated on a
silicon wafer then baked on a hotplate for 4 minutes at 120.degree.
C., resulting in a film thickness of 14.07 .mu.m. The film was then
exposed utilizing an i-line stepper in an open frame exposure
array, which incrementally increased exposure energy 50 mJ/cm.sup.2
with a starting exposure energy of 300 mJ/cm.sup.2. The wafer was
then developed with two 41.5 second puddles with a 0.262 N aqueous
solution of tetramethyl ammonium hydroxide, resulting in an array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 800 mJ/cm.sup.2. The
unexposed film thickness decreased 4.59 to 9.48 microns (32.62%
film thickness loss).
COMPARATIVE EXAMPLE 5
Composition Based on a PAC with Structure (XIII)
[0139] Attempts to prepare a composition containing 100 parts
polymer obtained in Synthesis Example 4, 11.9 parts of bis phenol
AP PAC shown in structure (XIII; see Comparative Synthesis Example
2), 5 parts of diphenylsilane diol and 3 parts of
gamma-ureidopropyltrimethoxysilane (adhesion promoter) dissolved in
GBL failed due to lack of solubility of PAC (XIII).
EXAMPLE 12
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VIII p)
[0140] 100 parts polymer obtained in Synthesis Example 9, 21 parts
PAC obtained from Synthesis Example 16 and 1.5 part of
gamma-glycidoxypropyltrimethoxysilane was dissolved in NMP and
filtered. The formulation was spin coated on a silicon wafer then
baked on a hotplate for 4 minutes at 120.degree. C., resulting in a
film thickness of 14.21 .mu.m. The film was then exposed utilizing
an i-line stepper in an open frame exposure array, which
incrementally increased exposure energy 25 mJ/cm.sup.2 with a
starting exposure energy of 700 mJ/cm.sup.2. The wafer was then
developed with two 40 second puddles with a 0.262 N aqueous
solution of tetra-methyl ammonium hydroxide, resulting in an array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 1100 mJ/cm.sup.2. The
unexposed film thickness decreased 6.85 microns to 7.36 microns
(48.21% film thickness loss).
EXAMPLE 13
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VII p)
[0141] 100 parts polymer obtained in Synthesis Example 13, 21 parts
of PAC obtained from Synthesis Example 16, 2.5 part of
diphenylsilane diol and 5 part of
gamma-mercaptopropyltriethoxysilane was dissolved in NMP and
filtered. The formulation was spin coated on a silicon wafer then
baked on a hotplate for 4 minutes at 120.degree. C., resulting in a
film thickness of 16.76 .mu.m. The film was then exposed utilizing
an i-line stepper in an open frame exposure array, which
incrementally increased exposure energy 50 mJ/cm.sup.2 with a
starting exposure energy of 100 mJ/cm.sup.2. The wafer was then
developed with two 70 second puddles with a 0.262 N aqueous
solution of tetra-methyl ammonium hydroxide, resulting in an array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 500 mJ/cm.sup.2. The
unexposed film thickness decreased 9.72 microns to 7.04 microns
(57.98% film thickness loss).
EXAMPLE 14
Lithographic Evaluation of a Photosensitive Composition Based on a
PAC with Structure (VIII p)
[0142] 100 parts polymer obtained in Synthesis Example 7, 13.5
parts of PAC obtained from Synthesis Example 16, 1.98 part of
diphenylsilane diol and 1.53 part of
gamma-Ureidopropyltrimethoxysilane was dissolved in GBL and
filtered. The formulation was spin coated on a silicon wafer then
baked on a hotplate for 4 minutes at 120.degree. C., resulting in a
film thickness of 13.99 .mu.m. The film was then exposed utilizing
an i-line stepper in an open frame exposure array, which
incrementally increased exposure energy 10 mJ/cm.sup.2 with a
starting exposure energy of 440 mJ/cm.sup.2. The wafer was then
developed with two 30 second puddles with a 0.262 N aqueous
solution of tetra-methyl ammonium hydroxide, resulting in an array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 520 mJ/cm.sup.2. The
unexposed film thickness decreased 5.70 microns to 8.29 microns
(40.73% film thickness loss).
SYNTHESIS EXAMPLE 19
Synthesis of a Photoactive Compound (PAC) of Structure (VIIIo)
##STR00048##
[0144] To a 500 mL, 3-neck flask equipped with mechanical stirrer,
dropping funnel, pH probe, thermometer and nitrogen purge system
were added 150 mL of THF and 15.14 g of
bis(3,5-dimethyl-4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane.
The mixture was stirred until the backbone was fully dissolved. To
this was added 9.028 g of 4-naphthoquinone diazide sulfonyl
chloride and 10 mL of THF. The reaction mixture was stirred until
the solid was fully dissolved. 3.732 g of triethylamine dissolved
in 10 mL THF was added to the reaction mixture gradually while the
pH was kept under 8 during this process. The temperature during
this exothermic reaction was kept under 30.degree. C. Upon
completion of addition, the reaction mixture was stirred for 24
hours. At this point, HPLC showed that 6.5% of S-214 was not
reacted. To the mixture was added 2.5 g of triethylamine and 10 mL
of THF. Upon completion of addition, the reaction mixture was
stirred for another 24 hours. To this was added 16.76 g of
5-naphthoquinone diazide sulfonyl chloride and 10 mL of THF and the
reaction mixture was stirred for 30 minutes. 5.0 g triethylamine
dissolved in 10 mL THF was added to the reaction mixture gradually
while the pH was kept under 8 during this process. Again during
this exothermic reaction the temperature was kept under 30.degree.
C. Upon completion of the addition, the reaction mixture was
stirred for 20 hours. At this point HPLC showed that 4.9% of S-215
was not reacted. To the mixture was added 2.5 g of triethylamine
and 10 mL of THF. Upon completion of addition, the reaction mixture
was stirred for another 24 hours. The reaction mixture was then
added gradually to a mixture of 4 L of DI-water and 10 g of HCl.
The product was filtered and washed with 1 L of de-ionized water.
The product was then reslurried by using 2.5 L of de-ionized water,
filtered and washed with 1 L Of de-ionized water. The product was
then dried inside a vacuum oven at 40.degree. C. until the amount
of water dropped below 2%. HPLC analysis revealed that the product
was a mixture of esters as shown in Table 2.
TABLE-US-00002 TABLE 2 Structure Amount ##STR00049## 2.41%
##STR00050## 8.11% ##STR00051## 10.48% ##STR00052## 1.04%
##STR00053## 32.09% ##STR00054## 10.57% ##STR00055## 28.1%
##STR00056## 2.66
[0145] The total amount of DNQ on the backbone was about 2.22 mole
per 1 mole of backbone. The composition of the reaction product was
10.5% monoesters, 43.6 diesters, and 41.33% triesters.
EXAMPLE 15
Lithographic Evaluation of a Photosensitive Composition Based on
PAC (VIIIo)
[0146] 100 parts polymer obtained in Synthesis Example 4, 17 parts
of PAC VIIIo obtained in Synthesis Example 19, and 1 part of
triethoxysilanepropyl-ethylcarbamate were dissolved in GBL and
filtered. The formulation was spin coated on a silicon wafer and
then baked on a hotplate for 4 minutes at 120.degree. C., resulting
in a film thickness of 14.02 .mu.m. The film was then exposed
utilizing an i-line stepper in an open frame exposure array, which
incrementally increased exposure energy 20 mJ/cm.sup.2 with a
starting exposure energy of 300 mJ/cm.sup.2. The wafer was then
developed with two 20 second puddles with a 0.262 N aqueous
solution of tetra-methyl ammonium hydroxide, resulting in an array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 664 mJ/cm.sup.2. The
unexposed film thickness decreased 5.04 microns to 8.97 microns
(36.01% film thickness loss).
EXAMPLE 16
Lithographic Evaluation of a Photosensitive Composition Based on
PAC (VIIIo)
[0147] The photosensitive composition of Example 15 was spin coated
on a silicon wafer and then baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 13.89 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 20
mJ/cm.sup.2 with a starting exposure energy of 100 mJ/cm.sup.2. The
wafer was then developed with two 30 second puddles with a 0.262 N
aqueous solution of tetra-methyl ammonium hydroxide, resulting in
an array of exposed boxes that were either clear of or containing
residue. These boxes were visually inspected for what was exposure
energy at which residue were completely cleared from the exposed
area. The formulation cleared boxes at a dose of 364 mJ/cm.sup.2.
The unexposed film thickness decreased 6.82 microns to 7.07 microns
(49.13% film thickness loss).
EXAMPLE 17
Lithographic Evaluation of a Photosensitive Composition Based on
PAC (VIIIo)
[0148] The photosensitive composition of Example 15 was spin coated
on a silicon wafer and then baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 14.00 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 20
mJ/cm.sup.2 with a starting exposure energy of 100 mJ/cm.sup.2. The
wafer was then developed with two 35 second puddles with a 0.262 N
aqueous solution of tetra-methyl ammonium hydroxide, resulting in
an array of exposed boxes that were either clear of or containing
residue. These boxes were visually inspected for what was exposure
energy at which residue were completely cleared from the exposed
area. The formulation cleared boxes at a dose of 292 mJ/cm.sup.2.
The unexposed film thickness decreased 7.52 microns to 6.47 microns
(53.75% film thickness loss).
EXAMPLE 18
Lithographic Evaluation of a Photosensitive Composition Based on
PAC (VIIIo)
[0149] Photosensitive composition of Example 15 was spin coated on
a silicon wafer and then baked on a hotplate for 4 minutes at
120.degree. C., resulting in a film thickness of 13.90 .mu.m. The
film was then exposed utilizing an i-line stepper in an open frame
exposure array, which incrementally increased exposure energy 20
mJ/cm.sup.2 with a starting exposure energy of 600 mJ/cm.sup.2. The
wafer was then developed with two 15 second puddles with a 0.262 N
aqueous solution of tetra-methyl ammonium hydroxide, resulting in
an array of exposed boxes that were either clear of or containing
residue. These boxes were visually inspected for what was exposure
energy at which residue were completely cleared from the exposed
area. The formulation cleared boxes at a dose of 852 mJ/cm.sup.2.
The unexposed film thickness decreased 4.17 microns to 9.73 microns
(30.00% film thickness loss).
COMPARATIVE SYNTHESIS EXAMPLE 3
[0150] Pac XIV was prepared by a method similar to that described
in Comparative Synthesis Example 1. Analysis (see Table 3) showed
that it was mixture composed of the following components.
TABLE-US-00003 TABLE 3 Structure Amount ##STR00057## 2.69%
##STR00058## 27.60% ##STR00059## 62.77%
[0151] The total amount of DNQ was 2.48 mole per 1 mole of backbone
and contained 2.69% monoester, 27.6% diester, and 62.77% triester.
Triesters are more effective in retaining unexposed film during
lithography.
COMPARATIVE EXAMPLE 6
Lithographic Evaluation of a Photosensitive Composition Based on
PAC (XIV)
[0152] 100 parts polymer obtained in Synthesis Example 4, 17 parts
of PAC XIV obtained in Comparative Synthesis Example 3, and 1 part
of triethoxysilane-propylethylcarbamate were dissolved in GBL and
filtered. The formulation was spin coated on a silicon wafer and
then baked on a hotplate for 4 minutes at 120.degree. C., resulting
in a film thickness of 14.31 .mu.m. The film was then exposed
utilizing an i-line stepper in an open frame exposure array, which
incrementally increased exposure energy 20 mJ/cm.sup.2 with a
starting exposure energy of 100 mJ/cm.sup.2. The wafer was then
developed with two 70 second puddles with a 0.262 N aqueous
solution of tetra-methyl ammonium hydroxide, resulting in an array
of exposed boxes that were either clear of or containing residue.
These boxes were visually inspected for what was exposure energy at
which residue were completely cleared from the exposed area. The
formulation cleared boxes at a dose of 300 mJ/cm.sup.2. The
unexposed film thickness decreased 7.75 microns to 6.56 microns
(54.14% film thickness loss).
COMPARATIVE EXAMPLE 7
Lithographic Evaluation of a Photosensitive Composition Based on
PAC(XIV)
[0153] The photosensitive composition prepared in Comparative
Example 6 was spin coated on a silicon wafer and then baked on a
hotplate for 4 minutes at 120.degree. C., resulting in a film
thickness of 14.16 .mu.m. The film was then exposed utilizing an
i-line stepper in an open frame exposure array, which incrementally
increased exposure energy 20 mJ/cm.sup.2 with a starting exposure
energy of 300 mJ/cm.sup.2. The wafer was then developed with two 60
second puddles with a 0.262N aqueous solution of tetra-methyl
ammonium hydroxide, resulting in a array of exposed boxes that were
either clear of or containing residue. These boxes were visually
inspected for what was exposure energy at which residue were
completely cleared from the exposed area. The formulation cleared
boxes at a dose of 384 mJ/cm.sup.2. The unexposed film thickness
decreased 6.87 microns to 7.29 microns (48.51% film thickness
loss).
COMPARATIVE EXAMPLE 8
Lithographic Evaluation of a Photosensitive Composition Based on
PAC(XIV)
[0154] The photosensitive composition obtained in Comparative
Example 6 was spin coated on a silicon wafer and then baked on a
hotplate for 4 minutes at 120.degree. C., resulting in a film
thickness of 14.19 .mu.m. The film was then exposed utilizing an
i-line stepper in an open frame exposure array, which incrementally
increased exposure energy 20 mJ/cm.sup.2 with a starting exposure
energy of 350 mJ/cm.sup.2. The wafer was then developed with two 50
second puddles with a 0.262 N aqueous solution of tetra-methyl
ammonium hydroxide, resulting in an array of exposed boxes that
were either clear of or containing residue. These boxes were
visually inspected for what was exposure energy at which residue
were completely cleared from the exposed area. The formulation
cleared boxes at a dose of 534 mJ/cm.sup.2. The unexposed film
thickness decreased 5.90 microns to 8.29 microns (41.58% film
thickness loss).
COMPARATIVE EXAMPLE 9
Lithographic Evaluation of a Photosensitive Composition Based on
PAC(XIV)
[0155] The photosensitive composition obtained in Comparative
Example 6 was spin coated on a silicon wafer and then baked on a
hotplate for 4 minutes at 120.degree. C., resulting in a film
thickness of 14.11 .mu.m. The film was then exposed utilizing an
i-line stepper in an open frame exposure array, which incrementally
increased exposure energy 20 mJ/cm.sup.2 with a starting exposure
energy of 500 mJ/cm.sup.2. The wafer was then developed with two 40
second puddles with a 0.262 N aqueous solution of tetra-methyl
ammonium hydroxide, resulting in an array of exposed boxes that
were either clear of or containing residue. These boxes were
visually inspected for what was exposure energy at which residue
were completely cleared from the exposed area. The formulation
cleared boxes at a dose of 684 mJ/cm.sup.2. The unexposed film
thickness decreased 4.80 microns to 9.30 microns (34.04% film
thickness loss).
[0156] The results of Examples 15-18 are compared with Comparative
Examples 6-9 and this shows that although the total amount of DNQ
is lower in the mixed ester, surprisingly, the performance of the
two photosensitive compositions are similar. Lower DNQ amounts
decrease costs of manufacture.
[0157] While the present disclosure has been described herein with
reference to the specific embodiments thereof, it will be
appreciated that changes, modification and variations can be made
without departing from the spirit and scope of the inventive
concept disclosed herein. Accordingly, it is intended to embrace
all such changes, modification and variations that fall with the
spirit and scope of the appended claims.
* * * * *