U.S. patent application number 16/133739 was filed with the patent office on 2019-05-16 for silicon-containing underlayers.
The applicant listed for this patent is Rohm and Haas Electronic Materials LLC. Invention is credited to James F. Cameron, Suzanne M. Coley, Li Cui, Charlotte A Cutler, Daniel Greene, Paul J. LaBeaume, Shintaro Yamada.
Application Number | 20190146343 16/133739 |
Document ID | / |
Family ID | 66432760 |
Filed Date | 2019-05-16 |
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United States Patent
Application |
20190146343 |
Kind Code |
A1 |
Cutler; Charlotte A ; et
al. |
May 16, 2019 |
SILICON-CONTAINING UNDERLAYERS
Abstract
Methods of manufacturing electronic devices employing
wet-strippable underlayer compositions comprising a condensate
and/or hydrolyzate of a polymer comprising as polymerized units one
or more first unsaturated monomers having a condensable
silicon-containing moiety, wherein the condensable
silicon-containing moiety is pendent to the polymer backbone, and
one or more condensable silicon monomers are provided.
Inventors: |
Cutler; Charlotte A;
(Hopkinton, MA) ; Cui; Li; (Westborough, MA)
; Yamada; Shintaro; (Shrewsbury, MA) ; LaBeaume;
Paul J.; (Auburn, MA) ; Coley; Suzanne M.;
(Mansfield, MA) ; Cameron; James F.; (Brookline,
MA) ; Greene; Daniel; (Shrewsbury, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Rohm and Haas Electronic Materials LLC |
Marlborough |
MA |
US |
|
|
Family ID: |
66432760 |
Appl. No.: |
16/133739 |
Filed: |
September 18, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62584151 |
Nov 10, 2017 |
|
|
|
Current U.S.
Class: |
430/323 |
Current CPC
Class: |
G03F 7/11 20130101; C09D
143/04 20130101; G03F 7/162 20130101; C08F 230/08 20130101; G03F
7/322 20130101; G03F 7/20 20130101; G03F 7/423 20130101; C08F
220/1804 20200201; G03F 7/0752 20130101; G03F 7/168 20130101; C08F
2800/10 20130101; C08F 220/1804 20200201; C08F 230/08 20130101;
C08F 220/1804 20200201; C08F 230/08 20130101 |
International
Class: |
G03F 7/11 20060101
G03F007/11; C09D 143/04 20060101 C09D143/04; C08F 230/08 20060101
C08F230/08; G03F 7/16 20060101 G03F007/16; G03F 7/32 20060101
G03F007/32; G03F 7/20 20060101 G03F007/20; G03F 7/42 20060101
G03F007/42 |
Claims
1. A composition comprising: (a) one or more solvents; (b) a
condensate and/or hydrolyzate of (i) one or more condensed
silicon-containing polymers comprising as polymerized units one or
more first unsaturated monomers having a condensable
silicon-containing moiety, wherein the condensable
silicon-containing moiety is pendent to the polymer backbone, and
(ii) one or more condensable silicon monomers; and (c) one or more
crosslinkers free of Si--O linkages
2. The composition of claim 1 wherein at least one condensable
silicon monomer has the formula (8) Si(R.sup.50).sub.p(X).sub.4-p
(8) wherein p is an integer from 0 to 3; each R.sup.50 is
independently chosen from a C.sub.1-30 hydrocarbyl moiety and a
substituted C.sub.1-30 hydrocarbyl moiety; and each X is
independently chosen from halogen, C.sub.1-10 alkoxy, --OH,
--O--C(O)--R.sup.50, and --(O--Si(R.sup.51).sub.2).sub.p2--X.sup.1;
X.sup.1 is independently chosen from halogen, C.sub.1-10 alkoxy,
--OH, --O--C(O)--R.sup.50; each R.sup.51 is independently chosen
from R.sup.50 and X; and p2 is an integer from 1 to 10.
3. The composition of claim 2 wherein p=0 or 1.
4. The composition of claim 1 wherein the condensable
silicon-containing moiety has the formula
*-L-SiR.sup.1.sub.bY.sup.1.sub.3-b wherein L is a single bond or a
divalent linking group; each R.sup.1 is independently chosen from
H, C.sub.1-10-alkyl, C.sub.2-20-alkenyl, C.sub.5-20-aryl, and
C.sub.6-20-aralkyl; each Y.sup.1 is independently chosen from
halogen, C.sub.1-10-alkoxy, C.sub.5-10-aryloxy, C.sub.1-10-carboxy;
b is an integer from 0 to 2; and * denotes the point of attachment
to the polymer backbone.
5. The composition of claim 4 wherein L is a divalent linking
group.
6. The composition of claim 5 wherein the divalent linking group is
an organic radical having from 1 to 20 carbon atoms and optionally
one or more heteroatoms.
7. The composition of claim 4 wherein the divalent linking group
has the formula --C(.dbd.O)--O-L.sup.1- wherein L.sup.1 is a single
bond or an organic radical having from 1 to 20 carbon atoms.
8. The composition of claim 1 wherein at least one first
unsaturated monomer has the formula (1) ##STR00035## wherein L is a
single bond or a divalent linking group; each R.sup.l is
independently chosen from H, C.sub.1-10-alkyl, C.sub.2-20-alkenyl,
C.sub.5-20-aryl, and C.sub.6-20-aralkyl; each of R.sup.2 and
R.sup.3 are independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4
haloalkyl, halogen, C.sub.5-20-aryl, C.sub.6-20 aralkyl, and CN;
R.sup.4 is chosen from H, C.sub.1-10 alkyl, C.sub.1-10 haloalkyl,
halogen, C.sub.5-20-aryl, C.sub.6-20 aralkyl, and C(.dbd.O)R.sup.5;
R.sup.5 is chosen from OR.sup.6 and N(R.sup.7).sub.2; R.sup.6 is
chosen from H, and C.sub.1-20 alkyl; each R.sup.7 is independently
chosen from H, C.sub.1-20 alkyl, and C.sub.6-20 aryl; each Y.sup.1
is independently chosen from halogen, C.sub.1-10-alkoxy,
C.sub.5-10-aryloxy, C.sub.1-10-carboxy; and b is an integer from 0
to 2.
9. The composition of claim 1 wherein the condensate and/or
hydrolyzate further comprises as polymerized units one or more
second unsaturated monomers free of a condensable
silicon-containing moiety.
10. The composition of claim 9 wherein at least one second
unsaturated monomer has an acidic proton and having a pKa in water
from -5 to 13.
11. The composition of claim 9 wherein at least one second
unsaturated monomer has the formula (2) ##STR00036## wherein Z is
chosen from an acid decomposable group, a C.sub.4-30 organic
residue bound to the oxygen through a tertiary carbon, a C.sub.4-30
organic residue comprising an acetal functional group, and a
monovalent organic residue having a lactone moiety; and R.sup.10 is
independently chosen from H, C.sub.1-4 alkyl, C.sub.1-4 haloalkyl,
halogen, and CN.
12. The composition of claim 1 wherein the condensate and/or
hydrolyzate further comprises as polymerized units one or more
unsaturated monomers having a chromophore moiety.
13. The composition of claim 12 wherein the chromophore moiety is
pendent from the polymer backbone.
14. A method comprising (a) coating a substrate with the
composition of claim 1 to form a coating layer; (b) curing the
coating layer to form a polymeric underlayer; (c) disposing a layer
of a photoresist on the polymeric underlayer; (d) pattern-wise
exposing the photoresist layer to form a latent image; (e)
developing the latent image to form a patterned photoresist layer
having a relief image therein; (f) transferring the relief image to
the substrate; and (g) removing the polymeric underlayer by wet
stripping.
15. The method of claim 14 wherein the polymeric underlayer is
removed by wet stripping.
Description
[0001] The present invention relates generally to underlayers and
methods of using them, and particularly to wet-strippable
silicon-containing underlayers and their use in the manufacture of
electronic devices.
[0002] In conventional photolithographic processes, the resist
pattern is used as a mask for pattern transfer to the substrate by
suitable etching processes, such as by reactive ion etch (RIE). The
continued decrease in the thickness of the resist used makes the
resist pattern unsuitable as a mask for pattern transfer by RIE
processes. As a result, alternate processes have been developed
using three, four or more layers as a mask for pattern transfer.
For example, in a trilayer process a silicon-containing
antireflective layer is disposed between an underlayer/organic
planarizing layer and the resist layer. Due to the alternating
selectivity towards fluorine and oxygen-containing RIE chemistry
these layers possess, this trilayer scheme provides highly
selective pattern transfer from the resist pattern on top of the
Si-containing layer into the substrate below the underlayer.
[0003] The resistance of the silicon-containing underlayer toward
oxide-etch chemistry allows this layer to function as an etch mask.
Such silicon-containing underlayers are comprised of a crosslinked
siloxane network. The etch resistance of these materials results
from the silicon content, with a higher silicon content providing
better etch resistance. In current 193 nm lithographic processes,
such silicon-containing underlayers contain .gtoreq.30% silicon.
Such high silicon content and siloxane network structure in these
materials makes their removal challenging. Fluorine-containing
plasma and hydrofluoric acid (HF) can both be used to remove (or
strip) these silicon-containing layers. However, both F-plasma and
HF will remove not only these silicon-containing materials but also
other materials that are desired to remain, such as the substrate.
Wet stripping using tetramethylammonium hydroxide (TMAH) in higher
concentrations, such as .gtoreq.5 wt %, can be used to remove at
least some of these silicon-containing layers, but these higher
concentrations of TMAH also risk damaging the substrate.
Silicon-containing layers having a relatively lower amount of
silicon (.ltoreq.17%) can sometimes be removed using "piranha acid"
(concentrated H.sub.2SO.sub.4+30% H.sub.2O.sub.2), but such an
approach has not achieved commercial success with
silicon-containing materials having higher silicon content.
[0004] Cao et al., Langmuir, 2008, 24, 12771-12778, have reported
microgels formed by free radical copolymerization of N-isopropyl
acrylamide and 3-(trimethoxysilyl)propyl methacrylate, followed by
cross-linking via hydrolysis and condensation of the methoxysilyl
groups. Cao et al. describe such materials as being useful in
biological applications, such as controlled drug release materials,
biosensors and in tissue engineering. U.S. Pat. No. 9,120,952
employs materials similar to those disclosed in the Cao et al.
reference for use in chemical mechanical planarization
processing.
[0005] U.S. Pat. No. 8,932,953 B2 discloses compositions for
forming a silicon-containing resist underlayer, wherein the
compositions contain a combination of component (i) and component
(ii). In this patent, component (i) is a polymer having repeating
units of formula (A) and formula (B) and being capable of
generating a phenolic hydroxyl group, and component (ii) is a
silicon-containing compound obtained by hydrolysis-condensation of
a mixture containing at least one or more hydrolysable compounds of
formula (C) and one or more hydrolysable compounds of formula
(D).
##STR00001##
[0006] That is, the compositions in U.S. Pat. No. 8,932,953 are a
combination of (i) certain organic polymers having both pendent
aryl moieties and pendent Si--O linkages and (ii) certain siloxane
polymers, wherein the pendent aryl moieties are capable of
generating a phenolic hydroxyl group. This combination of
components (i) and (ii) is required in U.S. Pat. No. 8,932,953 in
order to achieve a composition capable of forming a resist
underlayer film not only having excellent storage stability and
adhesion but also having patterning properties unchanged in a
positive development and in a negative development. Films formed
from the compositions of this patent are removed by etching
processes.
[0007] Recent advances in the field of underlayers have provided
certain silicon-containing materials that can be readily removed by
wet stripping techniques. One drawback is that underlayers of such
silicon-containing materials tend to suffer from dissolution or
swelling upon exposure to developers such as tetramethylammonim
hydroxide (TMAH) which can lead to collapse of photoresist patterns
formed on these underlayers. There remains a need for
silicon-containing underlayers that can be removed by wet stripping
and that are more resistant to photoresist pattern collapse.
[0008] The present invention provides a composition comprising: (a)
one or more solvents; (b) a condensate and/or hydrolyzate of (i)
one or more condensed silicon-containing polymers comprising as
polymerized units one or more first unsaturated monomers having a
condensable silicon-containing moiety, wherein the condensable
silicon-containing moiety is pendent to the polymer backbone, and
(ii) one or more condensable silicon monomers; and (c) one or more
crosslinkers free of Si--O linkages. The one or more crosslinkers
are capable of reacting to form covalent bonds with the one or more
silicon-containing polymers.
[0009] Also provided by the present invention is a composition
comprising: (a) one or more solvents; (b) one or more condensed
polymers having an organic polymer chain having pendently-bound
siloxane moieties; and (c) one or more crosslinkers free of Si--O
linkages.
[0010] The present invention further provides a method comprising
(a) coating a substrate with any of the compositions described
above, to form a coating layer; (b) curing the coating layer to
form a polymeric underlayer; (c) disposing a layer of a photoresist
on the polymeric underlayer; (d) pattern-wise exposing the
photoresist layer to form a latent image; (e) developing the latent
image to form a patterned photoresist layer having a relief image
therein; (f) transferring the relief image to the substrate; and
(g) removing the polymeric underlayer by wet stripping. The present
polymeric underlayer is a cured coating comprising as polymerized
units one or more condensed polymers having pendent siloxane
moieties and one or more crosslinkers free of Si--O linkages.
[0011] Still further, the present invention provides a coated
substrate having a cured coating layer comprising as polymerized
units: (a) one or more condensates and/or hydrolyzates of (i) one
or more polymers comprising as polymerized units one or more first
unsaturated monomers having a condensable silicon-containing
moiety, wherein the condensable silicon-containing moiety is
pendent to the polymer backbone, and (ii) one or more condensable
silicon monomers; and (b) one or more crosslinkers free of Si--O
linkages. Alternatively, the present invention provides a coated
substrate having a cured coating layer comprising as polymerized
units: (a) one or more condensed polymers having an organic polymer
chain having pendently-bound siloxane moieties; and (b) one or more
crosslinkers free of Si--O linkages.
[0012] It will be understood that when an element is referred to as
being "adjacent" to or "on" another element, it can be directly
adjacent to or on the other element or intervening elements may be
present therebetween. In contrast, when an element is referred to
as being "directly adjacent" or "directly on" another element,
there are no intervening elements present. It will be understood
that although the terms first, second, third, etc. may be used to
describe various elements, components, regions, layers and/or
sections, these elements, components, regions, layers and/or
sections should not be limited by these terms. These terms are only
used to distinguish one element, component, region, layer or
section from another element, component, region, layer or section.
Thus, a first element, component, region, layer or section
discussed below could be termed a second element, component,
region, layer or section without departing from the teachings of
the present invention.
[0013] As used throughout this specification, the following
abbreviations shall have the following meanings, unless the context
clearly indicates otherwise: .degree. C.=degree Celsius; g=gram;
mg=milligram; ppm=part per million by weight unless otherwise
noted; .mu.m=micron=micrometer; nm=nanometer; A=angstrom; L=liter;
mL=milliliter; sec.=second; min.=minute; hr.=hour; and Da=Dalton.
All amounts are percent by weight and all ratios are molar ratios,
unless otherwise noted. All numerical ranges are inclusive and
combinable in any order, except where it is clear that such
numerical ranges are constrained to add up to 100%. "Wt%" refers to
percent by weight, based on the total weight of a referenced
composition, unless otherwise noted. The articles "a", "an" and
"the" refer to the singular and the plural. As used herein, the
term "and/or" includes any and all combinations of one or more of
the associated listed items. M.sub.w refers to weight average
molecular weight and is determined by gel permeation chromatography
(GPC) using polystyrene standards. Reported pKa values are for
aqueous solutions at 25.degree. C. which may be determined
experimentally, for example, by potentiometric titration such as by
using a potentiometric pH meter available from Sirius Analytical
Instruments Ltd., or may be calculated, for example, by using
Advanced Chemistry Development (ACD) Labs Software Version 11.02.
Unless otherwise noted, all measurements reported herein are made
at room temperature.
[0014] As used throughout the specification, the term "alkyl"
includes linear, branched and cyclic alkyl. The term "alkyl" refers
to an alkane radical, and includes alkane monoradicals, diradicals
(alkylene), and higher-radicals. If no number of carbons is
indicated for any alkyl or heteroalkyl, then 1-12 carbons are
contemplated. The term "heteroalkyl" refers to an alkyl group with
one or more heteroatoms, such as nitrogen, oxygen, sulfur,
phosphorus, replacing one or more carbon atoms within the radical,
for example, as in an ether or a thioether. The term "alkenyl"
refers to an alkene radical, and includes alkene monoradicals,
diradicals (alkenylene), and higher-radicals. "Alkenyl" refers to
linear, branched and cyclic alkene radicals unless otherwise
specified. The term "alkynyl" refers to an alkyne radical, and
includes alkyne monoradicals, diradicals, and higher-radicals.
"Alkynyl" refers to linear and branched alkyne radicals. If no
number of carbons is indicated for any alkenyl or alkynyl, then
2-12 carbons are contemplated. "Organic residue" refers to the
radical of any organic moiety, which may optionally contain one or
more heteroatoms, such as oxygen, nitrogen, silicon, phosphorus,
and halogen, in addition to carbon and hydrogen. An organic residue
may contain one or more aryl or non-aryl rings or both aryl and
non-aryl rings. The term "hydrocarbyl" refers to a radical of any
hydrocarbon, which may be aliphatic, cyclic, aromatic or a
combination thereof, and which may optionally contain one or more
heteroatoms, such as oxygen, nitrogen, silicon, phosphorus, and
halogen, in addition to carbon and hydrogen. The hydrocarbyl
moieties may contain aryl or non-aryl rings or both aryl and
non-aryl rings, such as one or more alicyclic rings, or aromatic
rings or both alicyclic and aromatic rings. When a hydrocarbyl
moiety contains two or more alicyclic rings, such alicyclic rings
may be isolated, fused or spirocyclic. Alicyclic hydrocarbyl
moieties include single alicyclic rings, such as cyclopentyl and
cyclohexyl, as well as bicyclic rings, such as dicyclopentadienyl,
norbornyl, and norbornenyl. When the hydrocarbyl moiety contains
two or more aromatic rings, such rings may be isolated or fused. By
the term "curing" is meant any process, such as polymerization or
condensation, that increases the molecular weight of a material or
composition. "Curable" refers to any material capable of being
cured under certain conditions. The term "oligomer" refers to
dimers, trimers, tetramers and other relatively low molecular
weight materials that are capable of further curing. The term
"polymer" includes oligomers and refers to homopolymers,
copolymers, terpolymers, tetrapolymers and the like. As used
herein, the terms "(meth)acrylate" and "(meth)acrylic acid" refer
to both acrylate and methacrylate, and acrylic acid and methacrylic
acid, respectively.
[0015] Compositions useful in the present invention comprise a
condensed silicon-containing polymer (also referred to herein as a
"condensed polymer"). Coatings of the present compositions, and
films and underlayers formed therefrom, are wet strippable, and
have reduced pattern collapse as compared to conventional
wet-strippable silicon-containing underlayers. As used herein, the
term "condensed polymer" refers to a condensate and/or hydrolyzate
of (i) one or more polymers comprising as polymerized units one or
more first unsaturated monomers having a condensable
silicon-containing moiety, wherein the condensable
silicon-containing moiety is pendent to the polymer backbone, and
(ii) one or more condensable silicon monomers, or alternatively, a
polymer having an organic polymer chain having pendently-bound
siloxane moieties. As used herein, the term "condensate and/or
hydrolyzate" refers to a condensation product, a hydrolysis
product, a hydrolysis-condensation product, or a combination of any
of the foregoing. The term "hydrolysis product" refers to both a
product of partial hydrolysis or complete hydrolysis.
[0016] The present condensed polymers have an organic polymer chain
(or backbone) having pendently-bound siloxane moieties. The organic
polymer chain comprises as polymerized units, preferably
free-radically polymerized units, one or more first unsaturated
monomers having a condensable silicon-containing moiety. Upon
polymerization, preferably free-radical polymerization, of the one
or more first unsaturated monomers and any optional second
unsaturated monomers, the resulting organic polymer chain has one
or more pendent condensable silicon-containing moieties. The one or
more pendent condensable silicon-containing moieties of the organic
polymer chain are then condensed and/or hydrolyzed with one or more
condensable silicon monomers to form the present condensed polymers
having pendently-bound siloxane moieties. As used herein, the term
"siloxane moieties" refers to moieties having at least one (Si--O)
unit. The condensed polymers of the invention may optionally, and
preferably do, have a polymer chain comprising as polymerized units
one or more second unsaturated monomers. Preferably, each of the
first unsaturated monomers and any second unsaturated monomers
comprise one radical polymerizable double or triple bond, more
preferably a radical polymerizable carbon-carbon double or triple
bond, and even more preferably one radical polymerizable
carbon-carbon double bond. The present condensed polymers are
preferably free of repeating units of a monomer having two or more
radical polymerizable double bonds.
[0017] Any unsaturated monomer having a condensable
silicon-containing moiety is suitable for use as the first
unsaturated monomer to form the present condensed polymers. One or
more first unsaturated monomers may be used. Ethylenically
unsaturated monomers having a condensable silicon-containing moiety
are preferred. Preferred first unsaturated monomers are those
having a condensable silicon-containing moiety of the formula
(1)
*-L-SiR.sup.1.sub.bY.sup.1.sub.3-b (1)
wherein L is a single bond or a divalent linking group; each
R.sup.1 is independently chosen from H, C.sub.1-10-alkyl,
C.sub.2-20-alkenyl, C.sub.5-20-aryl, and C.sub.6-20-aralkyl; each
Y.sup.1 is independently chosen from halogen, C.sub.1-10-alkoxy,
C.sub.5-10-aryloxy, and C.sub.1-10-carboxy; b is an integer from 0
to 2; and * denotes the point of attachment to the monomer. It is
preferred that L is a divalent linking group. It is further
preferred that the divalent linking group comprises one or more
heteroatoms chosen from oxygen and silicon. A suitable divalent
linking group is an organic radical having from 1 to 20 carbon
atoms and optionally one or more heteroatoms. Preferred divalent
linking groups have the formula --C(.dbd.O)--O-L.sup.1- wherein
L.sup.1 is a single bond or an organic radical having from 1 to 20
carbon atoms. Preferably, each R.sup.1 is independently chosen from
C.sub.1-10-alkyl, C.sub.2-20-alkenyl, C.sub.5-20-aryl, and
C.sub.6-20-aralkyl. It is preferred that each Y.sup.1 is
independently chosen from halogen, C.sub.1-6-alkoxy,
C.sub.5-10-aryloxy, C.sub.1-6-carboxy, and more preferably from
halogen, C.sub.1-6-alkoxy, and C.sub.1-6-carboxy. Preferably, b is
0 or 1, and more preferably b=0.
[0018] It is preferred that at least one first unsaturated monomer
has the formula (2)
##STR00002##
wherein L is a single bond or a divalent linking group; each
R.sup.1 is independently chosen from H, C.sub.1-10-alkyl,
C.sub.2-20-alkenyl, C.sub.5-20-aryl, and C.sub.6-20-aralkyl; each
of R.sup.2 and R.sup.3 are independently chosen from H,
C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, halogen, C.sub.5-20-aryl,
C.sub.6-20-aralkyl, and CN; R.sup.4 is chosen from H,
C.sub.1-10-alkyl, C.sub.1-10-haloalkyl, halogen, C.sub.5-20-aryl,
C.sub.6-20-aralkyl, and C(.dbd.O)R.sup.5; R.sup.5 is chosen from
OR.sup.6 and N(R.sup.7).sub.2; R.sup.6 is chosen from H, C.sub.1-20
alkyl, C.sub.5-20-aryl, and C.sub.6-20-aralkyl; each R.sup.7 is
independently chosen from H, C.sub.1-20-alkyl, and C.sub.5-20-aryl;
each Y.sup.1 is independently chosen from halogen,
C.sub.1-10-alkoxy, C.sub.5-10-aryloxy, C.sub.1-10-carboxy; and b is
an integer from 0 to 2. It is preferred that L is a divalent
linking group. It is further preferred that the divalent linking
group comprises one or more heteroatoms chosen from oxygen and
silicon. A suitable divalent linking group is an organic radical
having from 1 to 20 carbon atoms and optionally one or more
heteroatoms. Preferred divalent linking groups have the formula
--C(.dbd.O)--O-L.sup.1- wherein L.sup.1 is a single bond or an
organic radical having from 1 to 20 carbon atoms. Preferably, each
R.sup.1 is independently chosen from C.sub.1-10-alkyl,
C.sub.2-20-alkenyl, C.sub.5-20-aryl, and C.sub.6-20-aralkyl. It is
preferred that each Y.sup.1 is independently chosen from halogen,
C.sub.1-6-alkoxy, C.sub.5-10-aryloxy, C.sub.1-6-carboxy, and more
preferably from halogen, C.sub.1-6-alkoxy, and C.sub.1-6-carboxy.
Preferably, b is 0 or 1, and more preferably b=0. It is preferred
that each R.sup.2 and R.sup.3 are independently chosen from H,
C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, C.sub.5-20-aryl, and
C.sub.6-20-aralkyl, and more preferably from H, C.sub.1-4-alkyl,
C.sub.5-20-aryl, and C.sub.6-20-aralkyl. Yet more preferably, each
R.sup.2 and R.sup.3 are independently chosen from H, methyl, ethyl,
propyl, butyl, phenyl, naphthyl, benzyl, and phenethyl. R.sup.4 is
preferably chosen from H, C.sub.1-10-alkyl, C.sub.1-10-haloalkyl,
C.sub.5-20-aryl, C.sub.6-20-aralkyl, and C(.dbd.O)R.sup.5, and more
preferably from H, C.sub.1-10-alkyl, C.sub.5-20-aryl,
C.sub.6-20-aralkyl, and C(.dbd.O)R.sup.5. It is preferred that
R.sup.5 is OR.sup.6. R.sup.6 is preferably chosen from H,
C.sub.1-10-alkyl, C.sub.5-10-aryl, and C.sub.6-15-aralkyl.
Preferably, each R.sup.7 is independently chosen from H,
C.sub.1-10-alkyl, and C.sub.6-20-aryl.
[0019] Suitable first unsaturated monomers having a condensable
silicon-containing moiety are generally commercially available from
a variety of sources, such as Sigma-Aldrich (St. Louis, Mo.), or
may be prepared by methods known in the art. Such monomers may be
used as-is, or may be further purified. Exemplary first unsaturated
monomers include, but are not limited to: allyl dimethoxysilane;
allyl dichlorosilane; (trimethoxysilyl)methyl (meth)acrylate;
(trimethoxysilyl)ethyl (meth)acrylate; (trimethoxysilyl)propyl
(meth)acrylate; (trimethoxysilyl)butyl (meth)acrylate;
(triethoxysilyl)methyl (meth)acrylate; (triethoxysilyl)ethyl
(meth)acrylate; (triethoxysilyl)propyl (meth)acrylate;
(triethoxysilyl)butyl (meth)acrylate; (trichlorosilyl)methyl
(meth)acrylate; (trichlorosilyl)ethyl (meth)acrylate;
(trichlorosilyl)propyl (meth)acrylate; (trichlorosilysilyl)butyl
(meth)acrylate; (methyldimethoxyl)silyppropyl (meth)acrylate;
vinyltriacetoxy silane; (triacetoxysilyl)propyl (meth)acrylate;
4-((trimethoxysilyl)propyl)styrene; 4-(trimethoxysilyl)styrene; and
vinyltrimethoxysilane.
[0020] Preferably, the organic polymer chain of the present
condensed polymers further comprises as polymerized units one or
more second unsaturated monomers, where such second monomers are
free of a condensable silicon-containing moiety. Preferred second
unsaturated monomers are ethylenically unsaturated monomers.
Preferably, the condensed polymers have an organic polymer chain
further comprising as polymerized units one or more second
unsaturated monomers of formula (3)
##STR00003##
wherein Z is chosen from an organic residue having from 1 to 30
carbon atoms and an acidic proton having a pKa in water from -5 to
13, an organic residue having from 1 to 30 carbon atoms and an acid
decomposable group, an organic residue having a chromophore moiety,
--C(.dbd.O)R.sup.13 and CN; each of R.sup.10, R.sup.11 and R.sup.12
is independently chosen from H, C.sub.1-4-alkyl,
C.sub.1-4-haloalkyl, optionally substituted C.sub.5-20-aryl,
halogen, --C(.dbd.O)R.sup.14, C.sub.6-10-aryl, and CN; each of
R.sup.13 and R.sup.14 is independently OR.sup.15 or
N(R.sup.16).sub.2; R.sup.15 is chosen from H, C.sub.1-20-alkyl,
optionally substituted C.sub.5-30-aryl, C.sub.6-20-aralkyl and a
monovalent organic residue having a lactone moiety; and each
R.sup.16 is independently chosen from H, C.sub.1-20-alkyl, and
C.sub.6-20-aryl; wherein Z and R.sup.10 may be taken together to
form a 5 to 7-membered unsaturated ring. Preferably, Z is chosen
from an organic residue having from 1 to 30 carbon atoms and an
acidic proton having a pKa in water from -5 to 13, an organic
residue having from 1 to 30 carbon atoms and an acid decomposable
group, an organic residue having from 5 to 40 carbon atoms and
having a chromophore moiety, and --C(.dbd.O)R.sup.13. A preferred
halogen is fluorine. It is preferred that each of R.sup.10,
R.sup.11 and R.sup.12 is independently chosen from H,
C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, halogen, --C(.dbd.O)R.sup.14,
and C.sub.6-10-aryl, and more preferably from H, methyl,
trifluoromethyl, fluorine, and --C(.dbd.O)R.sup.14. Preferably,
each of R.sup.13 and R.sup.14 is OR.sup.15. R.sup.15 is preferably
chosen from H, C.sub.1-20-alkyl, C.sub.6-20-aryl,
C.sub.6-20-aralkyl and a monovalent organic residue having a
lactone moiety. As used herein, the term "aryl" refers to aromatic
carbocycles and aromatic heterocycles. "Optionally substituted"
aryl refers to both unsubstituted and substituted aryl.
"Substituted aryl" refers to any aryl (or aromatic) moiety having
one or more of its hydrogens replaced with one or more substituents
chosen from halogen, C.sub.1-6-alkyl, C.sub.1-6-haloalkyl,
C.sub.1-6-alkoxy, C.sub.1-6-haloalkoxy, phenyl, and phenoxy,
preferably from halogen, C.sub.1-6-alkyl, C.sub.1-6-alkoxy, phenyl,
and phenoxy, and more preferably from halogen, C.sub.1-6-alkyl, and
phenyl. Preferably, a substituted aryl has from 1 to 3
substituents, and more preferably 1 or 2 substituents. It is
preferred that the present condensed polymers have an organic
polymer chain further comprising as polymerized units two or more
different second unsaturated monomers of formula (4). The mole
ratio of the total moles of the first unsaturated monomers of
formula (1)+formula (2) to the total moles of any optional second
unsaturated monomers such as those of formula (3) is from 100:0 to
25:75, preferably from 95:5 to 25:75, and more preferably from
75:25 to 25:75.
[0021] Preferred monomers of formula (3) wherein Z is an organic
residue having from 1 to 30 carbon atoms and an acidic proton
having a pKa in water from -5 to 13 are those of formula (3a)
##STR00004##
wherein L.sup.1 is a single bond or a divalent linking group; AM is
an acidic moiety having an acidic proton and having a pKa in water
from -5 to 13; each of R.sup.10a, R.sup.11a and R.sup.12a is
independently chosen from H, C.sub.1-4-alkyl, C.sub.1-4-haloalkyl,
optionally substituted C.sub.6-20-aryl, halogen,
--C(.dbd.O)R.sup.14a, and CN; R.sup.14a is chosen from OR.sup.15a
and N(R.sup.16a).sub.2; R.sup.15a is chosen from H,
C.sub.1-20-alkyl, C.sub.5-30-aryl, C.sub.6-20-aralkyl and a
monovalent organic residue having a lactone moiety; and each
R.sup.16a is independently chosen from H, C.sub.1-20-alkyl, and
C.sub.6-20-aryl; wherein any two of L.sup.1, R.sup.10a, R.sup.11a
and R.sup.12a may be taken together with the carbons to which they
are attached to form a 5 to 7-membered ring. Preferably, each of
R.sup.11a and R.sup.12a is independently chosen from H,
C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, optionally substituted
C.sub.6-20-aryl, and halogen, and more preferably from H,
C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, and optionally substituted
C.sub.6-10-aryl. A preferred halogen is fluorine. It is preferred
that R.sup.10a is chosen from H, C.sub.1-10-alkyl,
C.sub.1-10-haloalkyl, optionally substituted C.sub.6-20-aryl, and
--C(.dbd.O)R.sup.14a, and more preferably from H, C.sub.1-10-alkyl,
C.sub.1-10-haloalkyl, optionally substituted C.sub.6-10-aryl, and
--C(.dbd.O)R.sup.14a. R.sup.14a is preferably OR.sup.15a. It is
preferred that R.sup.15a is H, C.sub.1-20-alkyl, C.sub.5-30-aryl,
and C.sub.6-20-aralkyl, and more preferably H. Each R.sup.16a is
preferably chosen from H, and C.sub.1-20-alkyl. L.sup.1 is
preferably a single covalent bond or a divalent organic radical
having from 1 to 20 carbon atoms and optionally one or more
heteroatoms, more preferably L.sup.1 is a single covalent bond or a
divalent hydrocarbyl radical having from 1 to 20 carbon atoms and
optionally one or more oxygen atoms, and still more preferably
L.sup.1 is chosen from a single covalent bond, a divalent
C.sub.1-20-aliphatic moiety optionally comprising one or more
oxygen atoms, a divalent optionally substituted C.sub.6-20-aryl
moiety, and a divalent optionally substituted C.sub.7-20-alkylaryl
moiety. Suitable acidic moieties for AM have one or more acidic
groups chosen from carboxylic acid, sulfonic acid, sulfinic acid,
sulfamic acid, phosphonic acid, boronic acid, aromatic hydroxyl,
hydroxy-hexafluoroisopropyl, and combinations and acid salts
thereof, preferably from carboxylic acid, sulfonic acid, phosphonic
acid, boronic acid, and combinations and acid salts thereof, more
preferably from carboxylic acid, sulfonic acid, phosphonic acid,
boronic acid, and combinations thereof, and still more preferably
carboxylic acid. Yet more preferably, AM is chosen from
--C(.dbd.O)--OH, --S(.dbd.O).sub.2--OH, --P(.dbd.O)(OH).sub.2,
--B(OH).sub.2, C.sub.6-20-hydroxyaryl, mercapto, and
C.sub.1-12-hydroxy-perfluroralkyl, and more preferably from
--C(.dbd.O)--OH, --S(.dbd.O).sub.2--OH, --P(.dbd.O)(OH).sub.2,
--B(OH).sub.2, C.sub.6-20-hydroxyaryl, mercapto, and
C.sub.1-6-hydroxy-perfluroralkyl such as hexafluoro-iso-propanolyl,
and more preferably AM is --C(.dbd.O)--OH. L.sup.1 and R.sup.10a or
R.sup.11a and R.sup.12a may be taken together along with the
carbons to which they are attached to form a 5- to 7-membered
unsaturated ring, preferably a 5- to 6-membered unsaturated ring,
and more preferably a 5- to 6-membered unsaturated carbocyclic
ring. R.sup.10a and R.sup.11a or R.sup.12a and L.sup.1 may be taken
together along with the carbons to which they are attached to form
a 5- to 7-membered saturated or unsaturated ring, preferably a 5-
to 6-membered saturated or unsaturated ring, and more preferably a
5- to 6-membered saturated or unsaturated carbocyclic ring.
[0022] Other preferred second unsaturated monomers of formula (3)
are those of formula (4)
##STR00005##
wherein ADG is an acid decomposable group; and R.sup.20 is chosen
from H, C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, halogen, and CN.
R.sup.20 is preferably chosen from H, C.sub.1-4-alkyl,
C.sub.1-4-fluoroalkyl, fluorine, and CN, more preferably from H,
C.sub.1-4-alkyl, trifluoromethyl, fluorine, and CN, even more
preferably from H, methyl, trifluoromethyl, fluorine, and CN, and
most preferably R.sup.20 is H or methyl. In formula (4), ADG is an
acid decomposable group having from 2 to 30 carbon atoms. The term
"acid decomposable group", as used herein, refers to any functional
group capable of being decomposed by acid to form a different
functional group having increased aqueous base solubility as
compared to the acid decomposable group. Suitable acid decomposable
groups include, but are not limited to, --O--C.sub.4-30-hydrocarbyl
moiety where the C.sub.4-30-hydrocarbyl moiety is bonded to the
oxygen atom through a tertiary carbon atom, a
C.sub.2-30-hydrocarbyl moiety having an anhydride moiety, a
C.sub.2-30-hydrocarbyl moiety having an imide moiety, and a
C.sub.4-30-organic residue comprising an acetal functional group.
Preferred acid decomposable groups are --O--C.sub.4-30-hydrocarbyl
moiety where the C.sub.4-30-hydrocarbyl moiety is bonded to the
oxygen atom through a tertiary carbon atom, and a
C.sub.4-30-organic residue comprising an acetal functional group,
and more preferably --O--C.sub.4-30-hydrocarbyl moiety where the
C.sub.4-20-hydrocarbyl moiety is bonded to the oxygen atom through
a tertiary carbon atom, and a C.sub.4-20-organic residue comprising
an acetal functional group. As used herein, the term "acetal" also
embraces "ketal", "hemiacetal", and "hemiketal." Exemplary acid
decomposable groups include, without limitation,
--NR.sup.21R.sup.22, --OR.sup.23, and --O--C(.dbd.O)--R.sup.24,
wherein R.sup.21 and R.sup.22 are each independently chosen from H,
C.sub.1-20-alkyl, and C.sub.5-10-aryl; R.sup.23 is a
C.sub.4-30-organic residue bound to the oxygen through a tertiary
carbon (that is, a carbon that is bound to three other carbons,
respectively) or a C.sub.4-30-organic residue comprising an acetal
functional group; and R.sup.24 is chosen from H, C.sub.1-30-alkyl,
and C.sub.5-30-aryl. Preferably, R.sup.23 has from 4 to 20 carbon
atoms. It is further preferred that R.sup.23 is a branched or
cyclic moiety. When R.sup.23 contains a cyclic moiety, such cyclic
moiety typically has from 4 to 8 atoms in the ring, and preferably
5 or 6 atoms in the ring. R.sup.23 may optionally contain one or
more heteroatoms such as oxygen. Preferably, R.sup.23 is a branched
aliphatic or a cycloaliphatic moiety optionally containing one or
more heteroatoms.
[0023] Preferred second unsaturated monomers of formula (4) are
those of formula (4a)
##STR00006##
wherein R.sup.23 is chosen from a C.sub.4-20-organic residue bound
to the oxygen through a tertiary carbon or a C.sub.4-20-organic
residue comprising an acetal functional group; and R.sup.20 is
chosen from H, C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, halogen, and
CN. More preferably, R.sup.23 has the structure shown in formula
(5a) or (5b)
##STR00007##
wherein each of R.sup.24, R.sup.25 and R.sup.26 is independently an
organic residue having from 1 to 6 carbon atoms; R.sup.24 and
R.sup.25 may be taken together to form a 4 to 8 membered ring;
L.sup.2 is a divalent linking group or a single chemical bond; A
represents an acetal functional group; and * indicates the point of
attachment to the ester oxygen. It is preferred that each of
R.sup.24, R.sup.25 and R.sup.26 is independently chosen from
C.sub.1-6-alkyl. When R.sup.24 and R.sup.25 are taken together to
form a 4 to 8 membered ring, such ring may be a single ring or may
be bicyclic, and may optionally contain one or more heteroatoms
chosen from oxygen, sulfur and nitrogen, preferably oxygen and
sulfur and more preferably oxygen. Preferably, R.sup.24 and
R.sup.25 may be taken together to form a 5 to 8 membered ring.
Suitable 4 to 8 membered rings include, but are not limited to,
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and
oxabicylco[2.2.1]heptyl, preferably cyclopentyl, cyclohexyl,
norbornyl, and oxabicylco[2.2.1]heptyl, and more preferably
cyclopentyl and cyclohexyl. Suitable divalent linking groups
include C.sub.1-10-alkylene, and preferably C.sub.1-5-alkylene.
Preferably, the acetal functional group is a 5 or 6-membered ring
cyclic ketal, and more preferably a cyclic ketal formed from
acetone. Exemplary moieties for R.sup.23 include, without
limitation: tert-butyl; 2,3-dimethyl-2-butyl;
2,3,3-trimethyl-2-butyl; 2-methyl-2-butyl; 2-methyl-2-pentyl;
3-methyl-3-pentyl; 2,3,4-trimethyl-3-pentyl;
2,2,3,4,4-pentamethyl-3-pentyl; 1-methyl-1-cyclopentyl;
1-ethyl-1-cyclopentyl; 1,2-dimethyl-1-cyclopentyl;
1,2,5-trimethyl-1-cyclopentyl; 1,2,2-trimethyl-cyclopentyl;
1,2,2,5-tetramethyl-1-cyclopentyl;
1,2,2,5,5-pentamethyl-1-cyclopentyl; 1-methyl-1-cyclohexyl;
1-ethyl-1-cyclohexyl; 1,2-dimethyl-1-cyclohexyl;
1,2,6-trimethyl-1-cyclohexyl; 1,2,2,6-tetramethyl-1-cyclohexyl;
1,2,2,6,6-pentamethyl-1-cyclohexyl; 2,4,6-trimethyl-4-heptyl;
3-methyl-3-norbornyl; 3-ethyl-3-norbornyl;
6-methyl-2-oxabicylco[2.2.1] hept-6-yl; and
2-methyl-7-oxabicylco[2.2.1]hept-2-yl. Preferably, R.sup.5 is
chosen from tert-butyl; 2,3-dimethyl-2-butyl;
2,3,3-trimethyl-2-butyl; 2-methyl-2-butyl; 2-methyl-2-pentyl;
3-methyl-3-pentyl; 2,3,4-trimethyl-3-pentyl;
2,2,3,4,4-pentamethyl-3-pentyl; 1-methyl-1-cyclopentyl;
1-ethyl-1-cyclopentyl; 1,2-dimethyl-1-cyclopentyl;
1,2,5-trimethyl-1-cyclopentyl; 1,2,2-trimethyl-cyclopentyl;
1,2,2,5-tetramethyl-1-cyclopentyl;
1,2,2,5,5-pentamethyl-1-cyclopentyl; 1-methyl-1-cyclohexyl;
1-ethyl-1-cyclohexyl; 1,2-dimethyl-1-cyclohexyl;
1,2,6-trimethyl-1-cyclohexyl; 1,2,2,6-tetramethyl-1-cyclohexyl;
1,2,2,6,6-pentamethyl-1-cyclohexyl; and 2,4,6-trimethyl-4-heptyl.
L2 is preferably a divalent linking group. Suitable divalent
linking groups for L2 have are organic residues having from 1 to 20
atoms, and more preferably from 1 to 20 carbon atoms. Optionally,
the divalent linking groups of L2 may contain one or more
heteroatoms, such as oxygen, nitrogen or a combination thereof.
Suitable monomers of formulae (3), (4) and (4a) may be available
commercially or made by a variety of methods known in the art, such
as is disclosed in U.S. Pat. Nos. 6,136,501; 6,379,861; and
6,855,475.
[0024] Other preferred monomers of formula (3) are those of formula
(6)
##STR00008##
wherein R.sup.20a is independently chosen from H, C.sub.1-4-alkyl,
C.sub.1-4-haloalkyl, halogen, and CN; and R.sup.30 is a monovalent
organic residue having a lactone moiety. In formula (6), R.sup.30
is a C.sub.4-20-monovalent organic residue comprising a lactone
moiety. R.sup.30 may comprise any suitable lactone moiety, and
preferably comprises a 5 to 7-membered lactone, which may be
optionally substituted. Suitable substituents on the lactone ring
are C.sub.1-10-alkyl moieties. Suitable lactone moieties for
R.sup.30 are those having formula (7)
##STR00009##
wherein E is a 5 to 7-membered ring lactone; each R.sup.31 is
independently chosen from C.sub.1-10-alkyl; r is an integer from 0
to 3; Y is a chemical bond or a divalent linking residue having
from 1 to 10 carbon atoms; and * indicates the point of attachment
to the oxygen atom of the ester. It is preferred that each R.sup.31
is independently chosen from C.sub.1-6-alkyl, and more preferably
C.sub.1-4-alkyl. Examples of R.sup.31 are methyl, ethyl, n-propyl,
iso-propyl, n-butyl, sec-butyl, and iso-butyl. Preferably, r=0 or
1. Suitable divalent linking residues for Y include, but are not
limited to, divalent organic residues having from 1 to 20 carbon
atoms. Suitable divalent organic residues for Y include, without
limitation, C.sub.1-20-hydrocarbyl moieties,
C.sub.1-20-heteroatom-containing hydrocarbyl moieties, and
substituted C.sub.1-20-hydrocarbyl moieties. The term
"C.sub.1-20-heteroatom-containing hydrocarbyl moieties" refers to
hydrocarbyl moieties having one or more heteroatoms, such as
nitrogen, oxygen, sulfur, phosphorus, within the hydrocarbyl chain.
Exemplary heteroatoms include, but are not limited to, --O--,
--S--, --N(H)--, --N(C.sub.1-20-hydrocarbyl)-, --C(.dbd.O)--O--,
--S(.dbd.O)--, --S(.dbd.O).sub.2--, --C(.dbd.O)--NH--, and the
like. "Substituted C.sub.1-20-hydrocarbyl moieties" refers to any
hydrocarbyl moiety having one or more hydrogens replaced with one
or more substituents such as halogen, cyano, hydroxy, amino,
mercapto, and the like. It is preferred that R.sup.30 is chosen
from gamma-butyrolactone (GBLO), beta-butyrolactone,
gamma-valerolactone, delta-valerolactone, and caprolactone, and
more preferably, R.sup.30 is GBLO. Monomers of formula (6) are
generally commercially available or may be prepared by methods
known in the art.
[0025] In one preferred embodiment, the present condensed polymers
have a polymer chain that further comprise as polymerized units,
one or more second unsaturated monomers comprising a chromophore.
Suitable chromophores are any aromatic (aryl) moiety that absorbs
radiation at the wavelength of interest. Such chromophores are
unsubstituted aromatic moieties, such as phenyl, benzyl, naphthyl,
anthracenyl, and the like, or may be substituted with one or more
of hydroxyl, C.sub.1-10-alkyl, C.sub.2-10-alkenyl,
C.sub.2-10-alkynyl, and C.sub.5-30-aryl, preferably is
unsubstituted or hydroxyl-substituted, and more preferably is
unsubstituted. Preferably, the condensed polymer has an organic
polymer chain comprising as polymerized units, one or more second
unsaturated monomers of formula (3) having a chromophore moiety.
Preferred chromophore moieties are chosen from pyridyl, phenyl,
naphthyl, acenaphthyl, fluorenyl, carbazolyl, anthracenyl,
phenanthryl, pyrenyl, coronenyl, tetracenyl, pentacenyl,
tetraphenyl, benzotetracenyl, triphenylenyl, perylenyl, benzyl,
phenethyl, tolyl, xylyl, styrenyl, vinylnaphthyl, vinylanthracenyl,
dibenzothiophenyl, thioxanthonyl, indolyl, acridinyl, biphenyl,
phenoxy-phenyl, binaphthyl, and the like, and more preferably
phenyl, naphthyl, anthracenyl, phenanthryl, benzyl, and the like.
Chromophores used in the present invention are preferably free of
aromatic rings having a substituent of the structure
*--C(Rx).sub.2--O-Lg, wherein each Rx is independently H or a alkyl
group of 1 to 15 carbons, where each Rx may be taken together form
an aliphatic ring; Lg is H, an aliphatic monovalent hydrocarbon
having 1 to 10 carbons, or a monovalent aromatic group, and *
indicates the point of attachment to the aromatic ring.
[0026] Exemplary second unsaturated monomers include, without
limitation: vinyl aromatic monomers such as styrene,
.alpha.-methylstyrene, .beta.-methylstyrene, stilbene,
vinylnaphthylene, acenaphthalene, and vinylpyridine;
hydroxy-substituted vinyl aromatic monomers such as hydroxystyrene,
o-courmaric acid, m-courmaric acid, p-courmaric acid, and
hydroxyvinylnaphthylene; carboxyl-substituted vinyl aromatic
monomers such as vinyl benzoic acid; ethylenically unsaturated
carboxylic acids such as cinnamic acid, maleic acid, fumaric acid,
crotonic acid, citraconic acid, itaconic acid, 3-pyridine
(meth)acrylic acid, 2-phenyl (meth)acrylic acid, (meth)acrylic
acid, 2-methylenemalonic acid, cyclopentenecarboxylic acid,
methylcyclopentenecarboxylic acid, cyclohexenecarboxylic acid, and
3-hexene-1,6-dicarboxylic acid; hydroxyaryl esters of ethylenically
unsaturated carboxylic acids, such as hydroxyphenyl (meth)acrylate,
hydroxybenzyl (meth)acrylate, hydroxynaphthyl (meth)acrylate, and
hydroxyanthracenyl (meth)acrylate; ethylenically unsaturated
anhydride monomers such as maleic anhydride, citraconic anhydride
and itaconic anhudride, ethylenically unsaturated imide monomers
such as maleimide; ethylenically unsaturated carboxylic acid esters
such as crotonic acid esters, itaconic acid esters, and
(meth)acrylate esters; (meth)acrylonitrile; (meth)acrylamides; and
the like. Suitable (meth)acrylate ester monomers include, but are
not limited to, C.sub.7-10-aralkyl (meth)acrylates,
C.sub.1-10-hydroxyalkyl (meth)acrylates, glycidyl (meth)acrylate,
C.sub.1-10-mercaptoalkyl (meth)acrylates, and C.sub.1-10-alkyl
(meth)acrylates. Exemplary (meth)acrylate ester monomers include,
without limitation, benzyl acrylate, benzyl methacrylate,
hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl
acrylate, hydroxypropyl methacrylate, mercaptopropyl methacrylate,
glycidyl methacrylate, methyl acrylate, and methyl
methacrylate.
[0027] It is preferred that the present condensed polymers have an
organic polymer chain comprising as polymerized units one or more
first unsaturated monomers of formula (2) and one or more second
unsaturated monomers of formula (3), preferably one or more first
unsaturated monomers of formula (2) and two or more second
unsaturated monomers of formula (3), even more preferably one or
more first unsaturated monomers of formula (2) and one or more
second unsaturated monomers of formula (6), and still more
preferably one or more first unsaturated monomers of formula (2),
one or more second unsaturated monomers of formula (6), and one or
more second unsaturated monomers of formula (3) having a
chromophore moiety. When the organic polymer chain of the present
condensed polymers comprise as polymerized units one or more first
unsaturated monomers of formula (2) and one or more second
unsaturated monomers of formula (3), such monomers are present in a
mole ratio of 1:99 to 99:1 of total monomers of formula (2) to
total monomers of formula (3). Preferably, the mole ratio of the
total monomers of formula (2) to the total monomers of formula (3)
is from 95:5 to 5:95, more preferably from 90:10 to 10:90, and yet
more preferably from 50:50 to 5:95. The one or more optional second
unsaturated monomers may be used in an amount from 0 to three times
the molar amount of the total first unsaturated monomers of
formulae (1) and (2). When the present condensed polymers comprise
as polymerized units a relatively higher percentage of second
unsaturated monomers containing a chromophore, such polymers show
reduced ability to be removed by wet stripping. It is preferred
that the present condensed polymers comprise as polymerized units
from 0 to 50 mol % of second unsaturated monomers containing a
chromophore.
[0028] Any condensable silicon monomer may be used to form the
present condensed polymers, provided that the condensable silicon
monomer is different from the first unsaturated monomer having a
condensable silicon moiety, and that the condensable silicon
monomer condenses with the condensable silicon moiety
pendently-bound to the organic polymer backbone. As used herein,
the term "backbone" refers to the main polymer chain As used
herein, "condensable silicon monomer" refers to a silicon monomer
having one or more condensable or hydrolyzable moieties. As used
herein, "condensable moiety" or "hydrolyzable moiety" refers to any
moiety capable to being condensed or hydrolyzed under conditions
used to form the present condensed polymers. Exemplary condensable
or hydrolyzable moieties include, but are not limited to, halogens,
alkoxy, carboxylate, hydroxy, enoxy, oximino, amino, and the like.
Suitable condensable silicon monomers are those of formula (8)
Si(R.sup.50).sub.p(X).sub.4-p (8)
wherein p is an integer from 0 to 3; each R.sup.50 is independently
chosen from a C.sub.1-30 hydrocarbyl moiety and a substituted
C.sub.1-30 hydrocarbyl moiety; and each X is independently chosen
from halogen, C.sub.1-10 alkoxy, --OH, --O--C(O)--R.sup.50, and
--(O--Si(R.sup.51).sub.2).sub.p2--X.sup.1; X.sup.1 is independently
chosen from halogen, C.sub.1-10 alkoxy, --OH, --O--C(O)--R.sup.50;
each R.sup.51 is independently chosen from R.sup.50 and X; and p2
is an integer from 1 to 10. Preferably, p is an integer from 0 to
2, more preferably 0 to 1, and yet more preferably p=0. X is
preferably chosen from C.sub.1-10-alkoxy, --OH,
--O--C(O)--R.sup.50, and --(O--Si(R.sup.51).sub.2).sub.p2--X.sup.1,
and more preferably from C.sub.1-10-alkoxy and --OH. X.sup.1 is
preferably chosen from C.sub.1-10-alkoxy and --OH. The substituted
C.sub.1-10-hydrocarbyl moiety of R.sup.50 refers to any C.sub.1-30
hydrocarbyl moiety having one or more of its hydrogens replaced
with one or more substituted moieties chosen from hydroxy,
mercapto, C.sub.1-20 alkoxy, amino, C.sub.1-20-alkylamino,
di-C.sub.1-20-alkylamino, cyano, halogen, epoxide,
--C(.dbd.O)O--R.sup.17, --C(.dbd.O)--N(R.sup.17).sub.2, and
C(.dbd.O)--O--C(.dbd.O)--R.sup.17, wherein each R.sup.17 is chosen
from H and C.sub.1-20-alkyl. Suitable C.sub.1-30-hydrocarbyl
moieties of R.sup.50, without limitation, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.3-30-cycloalkyl, and
C.sub.6-30-aryl, and preferably are C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.3-20-cycloalkyl, and
C.sub.6-25-aryl. Silicon monomers are often referred to by the
number of hydrolyzable moieties bonded to silicon in the monomer.
For example, "M monomer" refers to a silicon monomer having one
hydrolyzable moiety, such as monomers of formula
(R.sup.50).sub.3SiX, "D monomer" refers to a silicon monomer having
two hydrolyzable moieties such as monomers of the formula
(R.sup.50)2SiX.sub.2, "T monomer" refers to a silicon monomer
having three hydrolyzable moieties such as monomers of the formula
R.sup.50SiX.sub.3, and "Q monomer" refers to a to a silicon monomer
having four hydrolyzable moieties such as monomers of the formula
SiX.sub.4, wherein X and R.sup.50 in each monomer are as described
above. Any of M, D, T and Q monomers may be used individually or a
mixture of any of the foregoing may be used to prepare the present
condensed polymers. Preferably, the condensable silicon monomer is
one or more monomers chosen from formulas (8a), (8b), (8c), and
(8d)
R.sup.50.sub.3SiX (8a)
R.sup.50.sub.2SiX.sub.2 (8b)
R.sup.50SiX.sub.3 (8c)
SiX.sub.4 (8d)
wherein each X and R.sup.50 are as described above for formula (8).
It is preferred that one or more Q monomers, that is, monomers of
formula (8d), are used to prepare the present condensed polymers.
Such condensable silicon monomers are generally commercially
available and may be used as is or may be further purified.
[0029] Condensable silicon monomers useful in forming the present
condensed polymers include, without limitation,
methyltrichlorosilane, methyltrimethoxysilane,
emethyltriethoxysilane, methyltriacetoxysilane,
ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane,
ethyltriacetoxysilane, propyltrichlorosilane,
propyltrimethoxysilane, propyltriethoxysilane,
propyltriacetoxysilane, hydroxypropyltrichlorosilane,
hydroxypropyltrimethoxysilane, hydroxypropyltriethoxysilane,
hydroxypropyltriacetoxysilane, mercaptopropyltrichlorosilane,
mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane,
mercaptopropyltriacetoxy-silane, cyclopentyltrichlorosilane,
cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,
cyclopentyltriacetoxysilane, vinyltrichlorosilane,
vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxy
silane, phenyltrichlorosilane, phenyltrimethoxysilane,
phenyltriethoxysilane, phenyltriacetoxysilane,
biphenyltrichlorosilane, biphenyltrimethoxysilane,
biphenyltriethoxysilane, biphenyltriacetoxysilane,
dimethyldichlorosilane, dimethyldimethoxysilane,
dimethyldiethoxysilane, dimethyldiacetoxysilane,
diethyldichlorosilane, diethyldimethoxysilane,
diethyldiethoxysilane, diethyldiacetoxysilane,
diphenyldichlorosilane, diphenyldimethyoxy-silane,
diphenyldiethoxysilane, diphenyldiacetoxysilane,
methylphenyldichlorosilane, methylphenyldimethoxysilane,
methylphenyldiethoxysilane, methylphenyldiacetoxysilane,
methylvinyldichlorosilane, methylvinyldimethoxysilane,
methylvinyldiethoxysilane, methylvinyldiacetoxysilane,
divinyldichlososilane, divinyldimethoxysilane,
divinyldiethoxysilane, divinyldiacetoxysilane, tetrachlorosilane,
tetramethoxysilane, tetraethoxysilane, and tetraacetoxysilane.
Preferred curable silicon monomers are tetramethoxysilane and
tetraethoxysilane.
[0030] Optionally, one or more etch selectivity improving agents
may also be condensed with the one or more condensable silane
monomers and the one or more polymers described above. Suitable
etch selectivity improving agents are those of formula (9)
G(X.sup.2).sub.m4 (9)
wherein, G is an element from Groups 13 to 15 of the periodic table
excluding carbon and silicon; each X.sup.2 is independently halogen
or OR.sup.52; each R.sup.52 is independently H or an organic group
having 1 to 30 carbon atoms; and m4 is equal to the valence of G.
Preferably, R.sup.52 is chosen from H, C.sub.1-10-alkyl,
--C(O)--C.sub.1-10-alkyl, and C.sub.6-10-aryl, and more preferably
from H, C.sub.1-10-alkyl, and --C(O)--C.sub.1-10-alkyl. G is
preferably an element chosen from boron, aluminum, gallium,
yttrium, germanium, titanium, zirconium, hafnium, bismuth, tin,
phosphorous, vanadium, arsenic, antimony, niobium, and tantalum,
more preferably from boron, aluminum, and germanium, and even more
preferably G is boron. Suitable compounds of formula (9) include,
but are not limited to: trimethyl borate, triethyl borate,
tripropyl borate, tributyl borate, tripentyl borate, trihexyl
borate, tricyclopentyl borate, tricyclohexyl borate, triallyl
borate, triphenyl borate, boron methoxyethoxide, boric acid, boron
oxide; aluminum methoxide, aluminum ethoxide, aluminum propoxide,
aluminum butoxide, aluminum amyloxide, aluminum hexyloxide,
aluminum cyclopentoxide, aluminum cyclohexyloxide, aluminum
allyloxide, aluminum phenoxide, aluminum ethoxyethoxide, aluminum
dipropoxyethyl-acetoacetate, aluminum dibutoxyethyl-acetoacetate,
aluminum propoxy-bis-ethyl-acetoacetate, aluminum
butoxy-bis-ethyl-acetoacetate, aluminum 2,4-pentanedionate,
aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate, germanium
methoxide, germanium ethoxide, germanium propoxide, germanium
butoxide, germanium amyloxide, germanium hexyloxide, germanium
cyclopentoxide, germanium cyclohexyloxide, germanium allyloxide,
germanium phenoxide, and germanium ethoxyethoxide. Suitable etch
selectivity improving agents are those disclosed in U.S. Pat. No.
8,951,917.
[0031] Condensed polymers of the invention may be prepared by first
polymerizing the one or more first unsaturated monomers and any
optional second unsaturated monomers according to methods
well-known in the art to form an uncondensed polymer. Preferably,
the present monomers are polymerized by free-radical
polymerization, such as those procedures used for preparing
(meth)acrylate or styrenic polymers. Any of a wide variety of
free-radical initiators and conditions my be used. Other suitable
polymerization methods of preparing the polymers include, without
limitation, Diels-Alder, living anionic, condensation,
cross-coupling, RAFT, ATRP, and the like. Next, one or more
uncondensed polymers are subjected to conditions to condense and/or
hydrolyze the condensable silicon-containing moiety to form the
present condensed polymers. Such condensation and/or hydrolysis
conditions are well-known in the art and typically involve
contacting the one or more uncondensed polymers with aqueous acid
or aqueous base, and preferably aqueous acid. For example, one or
more of the present uncondensed polymers may be contacted with a
composition comprising water, an acid, and optionally one or more
organic solvents, with optional heating. Preferred acids are
mineral acids, such as HCl. The condensed polymers of the invention
may be partially condensed or fully condensed. By "partially
condensed" it is meant that a portion of the condensable
silicon-containing moieties present in the polymer have undergone a
condensation or hydrolysis reaction. By "fully condensed" is meant
that all condensable silicon-containing moieties present in the
polymer have undergone a condensation or hydrolysis reaction. The
present uncondensed polymers typically have a M.sub.w of 1000 to
10000 Da, preferably from 2000 to 8000 Da, and more preferably from
2500 to 6000 Da. The present condensed polymers typically have a
M.sub.w of 5000 to 75000 Da, preferably from 10000 to 50000 Da, and
more preferably from 20000 to 40000 Da. It will be appreciated by
those skilled in the art that mixtures of condensed polymers may
suitably be used in the present process.
[0032] In addition to one or more of the above-described condensed
polymers, the present compositions further comprise one or more
crosslinkers free of Si--O linkages and one or more organic
solvents. Any crosslinker may be suitably used in the present
coating compositions, provided such crosslinker is free of Si--O
linkages and has a plurality of functional groups capable of
reacting with the condensed polymer upon curing. The crosslinker
has at least 2 functional groups, preferably at least 3, and more
preferably at least 4, functional groups capable of reacting with
the condensed polymer upon curing. Exemplary functional groups
capable of reacting with the condensed polymer upon curing include,
without limitation, hydroxyl groups, epoxy groups, oxetane groups,
thiol groups, lactone moieties, isothiocyanate groups, anhydride
moieties, maleimide moieties, carboxylic acid groups, alkynyl
groups, halogens, aldehyde groups, allyl ether moieties, imine
groups, unsaturated ketone moieties, and the like. Preferred
functional groups are hydroxyl groups. Preferably, the crosslinker
has at least 2 of the same functional group, more preferably at
least 3, and even more preferably at least 4 of the same functional
group. When the functional group is a hydroxyl group, such hydroxyl
group may be a primary, secondary or tertiary aliphatic hydroxyl
group or an aromatic hydroxyl group, and more preferably a primary
aliphatic hydroxyl or a secondary aliphatic hydroxyl group.
Suitable crosslinkers may be polymeric or non-polymeric. Polymeric
crosslinkers useful in the present compositions may be linear,
branched, star or dendritic polymers. When the crosslinker is
polymeric, the functional groups capable of reacting with the
condensed polymer upon curing may be terminal groups on the polymer
chain or be pendently-bound to the polymer chain, or a combination
thereof. Preferably, the crosslinker is a non-polymeric aliphatic
polyol, a polymer having pendently bound hydroxyl groups, or a
mixture thereof. As an upper limit, each terminus and/or each
repeating unit of the polymeric crosslinker may have a functional
group capable of reacting with the condensed polymer upon curing.
Preferably, up to 50 mol %, more preferably up to 40 mol %, even
more preferably up to 30 mol %, and yet more preferably from 10 to
30 mol %, of the repeating units of the polymeric crosslinker have
a functional group capable of reacting with the condensed polymer
upon curing. Preferred polymeric crosslinkers useful in the present
invention are hydroxy-terminated alkylene oxide polymers and
polymers having pendently bound hydroxyl groups. In general, weight
ratio of the condensed polymer to the crosslinker is from 95:5 to
60:40, preferably from 90:10 to 70:30, more preferably from 85:15
to 70:30.
[0033] Suitable non-polymeric crosslinkers have at least 2
functional groups, preferably at least 3, more preferably at least
4, and still more preferably 4 to 6, functional groups capable of
reacting with the condensed polymer upon curing. In general,
non-polymeric crosslinkers have 10 or fewer functional groups
capable of reacting with the condensed polymer during curing.
Typical non-polymeric crosslinkers are those having an organic
residue of 2 to 40, preferably 3 to 30, and more preferably 4 to
30, carbon atoms and from 2 to 10 hydroxyl groups, preferably 2 to
8 hydroxyl groups, more preferably 3 to 8 hydroxyl groups, and yet
more preferably 4 to 6 hydroxyl groups. Optionally, the suitable
non-polymeric crosslinkers may be alkoxylated, that is they may be
reacted with, on average, less than or equal to 2 moles of alkylene
oxide, such as ethylene oxide and/or propylene oxide, per hydroxyl
group. By way of example, if the non-polymeric crosslinker has 4
hydroxyl groups, such as pentaerythritol, it may be reacted with up
to 8 moles of alkylene oxide (that is, an average 2 moles of
alkylene oxide per hydroxyl group). Exemplary non-polymeric
crosslinkers are, without limitation, glycerol, trimethylol ethane,
trimethylol propane, erythritol, pentaerythritol,
dipentaerythritol, tripentaerythritol, di(trimethylolpropane),
2-hydroxymethyl-1,3-propanediol, sorbitol, xylitol, ethoxylated
glycercol having 2 to 6 moles of ethylene oxide, propoxylated
glycerol having 2 to 6 moles of propylene oxide, ethoxylated
trimethylol ethane having 2 to 6 moles of ethylene oxide,
propoxylated trimethylol ethane having 2 to 6 moles of propylene
oxide, ethoxylated trimethylol propane having 2 to 6 moles of
ethylene eoxide, propoxylated trimethylol propane having 2 to 6
moles of propylene oxide, ethoxylated erythritol having 3 to 8
moles of ethylene oxide, propoxylated erythritol having 3 to 8
moles of propylene oxide, ethoxylated pentaerythritol having 3 to 8
moles of ethylene oxide, propoxylated pentaerythritol having 3 to 8
moles of propylene oxide, ethoxylated dipentaerythritol having 4 to
12 moles of ethylene oxide, propoxylated dipentaerythritol having 4
to 12 moles of propylene oxide, ethoxylated tripentaerythritol
having 6 to 16 moles of ethylene oxide, propoxylated
tripentaerythritol having 6 to 16 moles of propylene oxide,
ethoxylated di(trimethylolpropane) having 3 to 8 moles of ethylene
oxide, propoxylated di(trimethylolpropane) having 3 to 8 moles of
propylene oxide, and mixtures thereof. Preferred non-polymeric
crosslinkers are trimethylol propane, erythritol, pentaerythritol,
dipentaerythritol, tripentaerythritol,
2-hydroxymethyl-1,3-propanediol, ethoxylated trimethylol ethane
having 2 to 6 moles of ethylene oxide, propoxylated trimethylol
ethane having 2 to 6 moles of propylene oxide, ethoxylated
trimethylol propane having 2 to 6 moles of ethylene eoxide,
propoxylated trimethylol propane having 2 to 6 moles of propylene
oxide, ethoxylated erythritol having 3 to 8 moles of ethylene
oxide, propoxylated erythritol having 3 to 8 moles of propylene
oxide, ethoxylated pentaerythritol having 3 to 8 moles of ethylene
oxide, propoxylated pentaerythritol having 3 to 8 moles of
propylene oxide, ethoxylated dipentaerythritol having 4 to 12 moles
of ethylene oxide, propoxylated dipentaerythritol having 4 to 12
moles of propylene oxide, ethoxylated tripentaerythritol having 6
to 16 moles of ethylene oxide, propoxylated tripentaerythritol
having 6 to 16 moles of propylene oxide, ethoxylated
di(trimethylolpropane) having 3 to 8 moles of ethylene oxide,
propoxylated di(trimethylolpropane) having 3 to 8 moles of
propylene oxide, and mixtures thereof.
[0034] One class of polymeric crosslinkers useful in the present
compositions are alkylene oxide polymers having
C.sub.2-4-alkyleneoxy repeating units and 2 or more terminal
hydroxyl groups, and polymers having pendently bound hydroxyl
groups. Preferred alkylene oxide polymers have 3 or more terminal
hydroxyl groups, and more preferably 4 or more terminal hydroxy
groups. Exemplary alkyleneoxy repeating units are ethyleneoxy,
propyleneoxy, butyleneoxy, and combinations thereof. Preferred
alkylene oxide polymers are glycerol ethoxylate having an average
of 3-30 ethyleneoxy units, glycerol propxylate having an average of
3-30 propyleneoxy units, trimethylolpropane ethoxylate having an
average of 3-30 ethyleneoxy units, trimethylolpropane propxylate
having an average of 3-30 propyleneoxy units, pentaerythritol
ethoxylate having an average of 3-30 ethyleneoxy units,
pentaerythritol propxylate having an average of 3-30 propyleneoxy
units, pentaerythritol ethoxylate/propoxylate having an average of
3-30 ethyleneoxy units and an average of 3-30 propyleneoxy units,
dipentaerythritol ethoxylate having an average of 4-30 ethyleneoxy
units, dipentaerythritol propxylate having an average of 4-30
propyleneoxy units, and combinations thereof
[0035] Preferred polymeric crosslinkers useful in the present
compositions are polymers having pendently bound hydroxyl groups,
and preferably comprise as polymerized units one or more
unsaturated monomers having a hydroxy-substituted moiety of the
formula *-L.sup.3--OH, where * denotes the point of attachment to
the monomer; and L.sup.3 is a C.sub.1-30-divalent linking group.
Preferably, the polymeric crosslinkers having hydroxyl-substituted
pendent groups comprise as polymerized units one or more monomers
of formula (10)
##STR00010##
wherein R.sup.60 and R.sup.61 are independently H,
C.sub.1-10-alkyl, C.sub.6-20-aryl, C.sub.1-10-haloalkyl, halogen,
or -L.sup.3-OH; R.sup.62 is H, C.sub.1-4-alkyl,
C.sub.1-4-haloalkyl, halogen, CN, or -L.sup.3-OH; and L.sup.3 is a
C.sub.1-30-divalent linking group. It is preferred that R.sup.60
and R.sup.61 are independently H or -L.sup.3-OH, and more
preferably H. Preferably, R.sup.62 is H, C.sub.1-4-alkyl,
C.sub.1-4-haloalkyl, halogen, or CN; and more preferably H or
methyl. L.sup.3 is preferably a C.sub.1-30-organic residue
optionally having from 1 to 10 heteroatoms. Preferred monomers of
formula (10) are C.sub.2-10-hydroxyalkyl (meth)acrylates of formula
(10A) and alkyleneoxy (meth)acrylates of formula (10B)
##STR00011##
wherein R.sup.62a is H or methyl; R.sup.63 is C.sub.2-10-alkylene;
R.sup.62b is H or methyl; and p4 is the average number of
O--C.sub.2-3-alkylene units and is an integer from 1 to 10.
Exemplary monomers of formulae (10A) and (10B) are hydroxyethyl
acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
hydroxypropyl methyacrylate, ethoxylated (meth)acrylate having an
average of 1-10 ethyleneoxy units, and propoxylated (meth)acrylate
having an average of 1-10 propyleneoxy units. Preferred polymeric
crosslinkers having pendently bound hydroxy groups are those
comprising as polymerized units one or more monomers of formula
(10) and one or more monomers chosen from (meth)acrylic acid,
C.sub.1-20-alkyl (meth)acrylates, C.sub.6-20-aryl (meth)acrylates,
C.sub.7-20-arylalkyl (meth)acrylates, vinyl aromatic monomers,
monomers of formula (4), and monomers of formula (6)
##STR00012##
wherein ADG is an acid decomposable group as described above; each
of R.sup.20 and R.sup.20a is independently chosen from H,
C.sub.1-4-alkyl, C.sub.1-4-haloalkyl, halogen, and CN; and R.sup.30
is a monovalent organic residue having a lactone moiety as
described above. Preferably, the polymeric crosslinkers comprise as
polymerized units from 5 to 50 mol %, more preferably 5 to 40 mol
%, even more preferably 5 to 30 mol %, and yet more preferably from
10 to 30 mol %, of monomers of formula (10). Other preferred
monomers of formula (10) include hydroxystyrene and
hydroxy(vinylnaphthalene).
[0036] A variety of organic solvents and water may be used in the
present compositions, provided that such solvent dissolves the
components of the composition. Preferably, the present compositions
comprise one or more organic solvents and optionally water. Organic
solvents may be used alone or a mixture of organic solvents may be
used. Suitable organic solvents include, but are not limited to;
ketones such as cyclohexanone and methyl-2-n-amylketone; alcohols
such as 3-methoxybutanol, 3-methyl-3-methoxybutanol,
1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as
propylene glycol methyl ether (PGME), propylene glycol ethyl ether
(PGEE), ethylene glycol monomethyl ether, propylene glycol
monoethyl ether, ethylene glycol monoethyl ether, propylene glycol
dimethyl ether, and diethylene glycol dimethyl ether; esters such
as propylene glycol monomethyl ether acetate (PGMEA), propylene
glycol monoethyl ether acetate, ethyl lactate (EL), methyl
hydroxyisobutyrate (HBM), ethyl pyruvate, butyl acetate, methyl
3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate,
tert-butyl propionate, and propylene glycol mono-tert-butyl ether
acetate; lactones such as gamma-butyrolactone; ionic liquids; and
any combination of the foregoing. Preferred solvents are PGME,
PGEE, PGMEA, EL, HBM, and combinations thereof.
[0037] The present compositions may further comprise one or more
optional components, such as cure catalysts, coating enhancers, one
or more stabilizers, and the like. The amount of such optional
components used in the present compositions is well within the
ability of those skilled in the art.
[0038] Suitable cure catalysts include, but are not limited to,
thermal acid generators, photoacid generators, photobase
generators, and quaternary ammonium salts, preferably thermal acid
generators and quaternary ammonium salts, and more preferably
quaternary ammonium salts. A thermal acid generator is any compound
which liberates acid upon exposure to heat. Thermal acid generators
are well-known in the art and are generally commercially available,
such as from King Industries, Norwalk, Conn. Exemplary thermal acid
generators include, without limitation, amine blocked strong acids,
such as amine blocked sulfonic acids like amine blocked
dodecylbenzenesulfonic acid. A wide variety of photoacid generators
are known in the art and are also generally commercially available,
such as from Wako Pure Chemical Industries, Ltd., and from BASF SE.
Suitable quaternary ammonium salts are: quaternary ammonium
halides; quaternary ammonium carboxylates; quaternary ammonium
sulfonates; quaternary ammonium bisulfates; and the like. Preferred
quaternary ammonium salts include; benzyltrialkylammonium halides
such as benzyltrimethylammonium chloride and benzyltriethylammonium
chloride; tetraalkylammonium halides such as tetramethylammonium
halides, tetraethylammonium halides, and tetrabutylammonium
halides; tetraalkylammonium carboxylates such as
tetramethylammonium formate, tetramethylammonium acetate,
tetramethylammonium triflate, tetrabutylammonium acetate, and
tetrabutylammonium triflate; tetraalkylammonium sulfonates such as
tetramethylammonium sulfonate and tetrabutylammonium sulfonate; and
the like. Preferred cure catalysts are tetraalkylammonium halides,
and more preferably tetraalkylammonium chlorides. Such quaternary
ammonium salts are generally commercially available, such as from
Sigma-Aldrich, or may be prepared by procedures known in the art.
Such optional curing catalysts are used in the present compositions
in an amount of from 0 to 10% of total solids, preferably from 0.01
to 7% of total solids, and more preferably from 0.05 to 5% of total
solids.
[0039] Coating enhancers are optionally added to the present
compositions to improve the quality of a film or layer of the
composition that is coated on a substrate. Such coating enhancers
may function as plasticizers, surface leveling agents, and the
like. Such coating enhancers are well-known to those skilled in the
art, and are generally commercially available. Exemplary coating
enhancers are: long chain alkanols such as oleyl alcohol, cetyl
alcohol, and the like; glycols such as tripropylene glycol,
tetraethylene glycol, and the like; and surfactants. While any
suitable surfactant may be used as a coating enhancer, such
surfactants are typically non-ionic. Exemplary non-ionic
surfactants are those containing an alkyleneoxy linkage, such as
ethyleneoxy, propyleneoxy, or a combination of ethyleneoxy and
propyleneoxy linkages. It is preferred that one or more coating
enhancers are used in the present compositions. The coating
enhancers are typically used in the present compositions in an
amount of 0 to 10% of total solids, preferably from 0.5 to 10% of
total solids, and more preferably from 1 to 8% of total solids.
[0040] One or more stabilizers may optionally be added to the
present compositions. Such stabilizers are useful for preventing
unwanted hydrolysis or condensation of the silicon-containing
moieties during storage. A variety of such stabilizers are known,
and preferably the silicon-containing polymer stabilizer is an
acid. Suitable acid stabilizers for the siloxane polymers include,
without limitation, carboxylic acids, carboxylic acid anhydrides,
mineral acids, and the like, and mixtures of any of the forgoing.
Exemplary stabilizers include acetic acid, oxalic acid, malonic
acid, malonic anhydride, malic acid, maleic acid, maleic anhydride,
fumaric acid, citraconic acid, glutaric acid, glutaric anhydride,
adipic acid, succinic acid, succinic anhydride, nitric acid and
mixtures thereof. Carboxylic acids are preferred stabilizers, and
more preferably the stabilizers are acetic acid, oxalic acid,
malonic acid, malic acid, maleic acid, fumaric acid, citraconic
acid, glutaric acid, adipic acid, succinic acid, and mixtures
thereof. Such stabilizers are used in an amount of 0 to 20% of
total solids, preferably from 0.1 to 15% of total solids, more
preferably from 0.5 to 10% of total solids, and yet more preferably
from 1 to 10% of total solids.
[0041] The compositions of the invention are prepared by combining
the one or more present condensed polymers; one or more solvents;
and any optional components, in any order. The compositions may be
used as is, or may be further purified, such as by filtration.
[0042] The process of the present invention comprises (a) coating a
substrate with the composition described above to form a coating
layer; (b) curing the coating layer to form a polymeric underlayer;
(c) disposing a layer of a photoresist on the polymeric underlayer;
(d) pattern-wise exposing the photoresist layer to form a latent
image; (e) developing the latent image to form a patterned
photoresist layer having a relief image therein; (f) transferring
the relief image to the substrate; and (g) removing the polymeric
underlayer by wet stripping.
[0043] A coating layer comprising the present compositions may be
coated on an electronic device substrate by any suitable means,
such as spin-coating, slot-die coating, doctor blading, curtain
coating, roller coating, spray coating, dip coating, and the like.
Spin-coating is preferred. In a typical spin-coating method, the
present compositions are applied to a substrate which is spinning
at a rate of 500 to 4000 rpm for a period of 15 to 90 seconds to
obtain a desired layer of the condensed polymer on the substrate.
It will be appreciated by those skilled in the art that the
thickness of the condensed polymer mixture layer may be adjusted by
changing the spin speed, as well as the solids content of the
composition.
[0044] A wide variety of electronic device substrates may be used
in the present invention, such as: packaging substrates such as
multichip modules; flat panel display substrates; integrated
circuit substrates; substrates for light emitting diodes (LEDs)
including organic light emitting diodes (OLEDs); semiconductor
wafers; polycrystalline silicon substrates; and the like. Such
substrates are typically composed of one or more of silicon,
polysilicon, silicon oxide, silicon nitride, silicon oxynitride,
silicon germanium, gallium arsenide, aluminum, sapphire, tungsten,
titanium, titanium-tungsten, nickel, copper, and gold. Suitable
substrates may be in the form of wafers such as those used in the
manufacture of integrated circuits, optical sensors, flat panel
displays, integrated optical circuits, and LEDs. As used herein,
the term "semiconductor wafer" is intended to encompass "an
electronic device substrate," "a semiconductor substrate," "a
semiconductor device," and various packages for various levels of
interconnection, including a single-chip wafer, multiple-chip
wafer, packages for various levels, or other assemblies requiring
solder connections. Such substrates may be any suitable size.
Preferred wafer substrate diameters are 200 mm to 300 mm, although
wafers having smaller and larger diameters may be suitably employed
according to the present invention. As used herein, the term
"semiconductor substrate" includes any substrate having one or more
semiconductor layers or structures which may optionally include
active or operable portions of semiconductor devices. A
semiconductor device refers to a semiconductor substrate upon which
at least one microelectronic device has been or is being batch
fabricated.
[0045] After being coated on the substrate, the coating layer is
optionally soft-baked at a relatively low temperature to remove any
solvent and other relatively volatile components from the
underlayer. Typically, the substrate is baked at a temperature of
.ltoreq.200.degree. C., preferably from 100 to 200.degree. C., and
more preferably from 100 to 150.degree. C. The baking time is
typically from 10 seconds to 10 minutes, preferably from 30 seconds
to 5 minutes, and more preferably from 60 to 90 seconds. When the
substrate is a wafer, such baking step may be performed by heating
the wafer on a hot plate. Such soft-baking step may be performed as
part of the curing of the coating layer, or may be omitted
altogether.
[0046] The coating layer comprising the present condensed polymers
and crosslinkers is then cured to form an underlayer. The coating
layer is sufficiently cured such that the film does not intermix
with a subsequently applied organic layer, such as a photoresist or
other organic layer disposed directly on the coating layer, while
still maintaining the desired antireflective properties (n and k
values) and etch selectivity of the underlayer film. The coating
layer may be cured in an oxygen-containing atmosphere, such as air,
or in an inert atmosphere, such as nitrogen and under conditions,
such as heating, sufficient to provide a cured underlayer. This
curing step is conducted preferably on a hot plate-style apparatus,
although oven curing may be used to obtain equivalent results.
Typically, such curing is performed by heating the condensed
polymer layer at a curing temperature of .ltoreq.350.degree. C.,
and preferably 200 to 250.degree. C. Alternatively, a two-step
curing process or a ramped temperature curing process may be used.
Such two-step and ramped temperature curing conditions are
well-known to those skilled in the art. The curing temperature
selected should be sufficient for any thermal acid generator used
to liberate acid to aid in curing of the condensed polymer film.
The curing time may be from 10 seconds to 10 minutes, preferably
from 30 seconds to 5 minutes, more preferably from 45 seconds to 5
minutes, and yet more preferably from 45 to 90 seconds. The choice
of final curing temperature depends mainly upon the desired curing
rate, with higher curing temperatures requiring shorter curing
times. Following this curing step, the underlayer surface may
optionally be passivated by treatment with a passivating agent such
as a disilazane compound, such as hexamethyldisilazane, or by a
dehydration bake step to remove any adsorbed water. Such
passivating treatment with a disilazane compound is typically
performed at 120.degree. C.
[0047] After curing of the coating layer comprising the condensed
polymer and crosslinker to form an underlayer, one or more
processing layers, such as photoresists, hardmask layers, bottom
antireflective coating (or BARC) layers, and the like, may be
disposed on the underlayer. For example, a photoresist layer may be
disposed, such as by spin coating, directly on the surface of the
underlayer. Alternatively, a BARC layer may be coated directly on
the underlayer, followed by curing of the BARC layer, and coating a
photoresist layer directly on the cured BARC layer. In another
alternative, an organic underlayer is first coated on a substrate
and cured, a condensed polymer layer of the invention is then
coated on the cured organic underlayer, the coating layer is then
cured to form an underlayer, an optional BARC layer may be coated
directly on the underlayer, followed by curing of the optional BARC
layer, and coating a photoresist layer directly on the cured BARC
layer. A wide variety of photoresists may be suitably used, such as
those used in 193 nm lithography, such as those sold under the
EPIC.TM. brand available from Dow Electronic Materials
(Marlborough, Mass.). Suitable photoresists may be either positive
tone development or negative tone development resists, or may be
conventional negative resists. The photoresist layer is then imaged
(exposed) using patterned actinic radiation, and the exposed
photoresist layer is then developed using the appropriate developer
to provide a patterned photoresist layer. An advantage of the
present invention is that pattern collapse of the patterned
photoresist layer upon contact with developer is reduced as
compared to conventional wet-strippable silicon-containing
underlayers. The pattern is next transferred from the photoresist
layer to any optional BARC layer, and then to the underlayer by an
appropriate etching technique, such as dry etching with an
appropriate plasma. Typically, the photoresist is also removed
during such etching step. Next, the pattern is transferred to any
organic underlayer present using an appropriate technique, such as
dry etching with O.sub.2 plasma, and then to the substrate as
appropriate. Following these pattern transfer steps, the
underlayer, and any optional organic underlayers are removed using
conventional techniques. The electronic device substrate is then
further processed according to conventional means.
[0048] The coating layers comprising the present condensed polymers
and underlayers described herein are wet strippable. By "wet
strippable" is meant that the coating layers and underlayers of the
invention are removed, and preferably substantially removed
(.gtoreq.95% of film thickness), by contacting the coating layer or
underlayer with conventional wet stripping compositions, such as:
(1) an aqueous base composition, such as aqueous alkali (typically
about 5%) or aqueous tetramethylammonium hydroxide (typically
.gtoreq.5 wt %), (2) aqueous fluoride ion strippers such as
ammonium fluoride/ammonium bifluoride mixtures, (3) a mixture of
mineral acid, such as sulfuric acid or hydrochloric acid, and
hydrogen peroxide, or (4) a mixture of ammonia, water and
optionally hydrogen peroxide. A particular advantage of the present
polymers, and particularly of the present underlayers, is that they
are wet strippable upon contact with a mixture of ammonia and
hydrogen peroxide. A suitable mixture of sulfuric acid and hydrogen
peroxide is concentrated sulfuric acid+30% hydrogen peroxide. A
wide range of ammonia and water mixtures may be used. A suitable
mixture of ammonia, water and hydrogen peroxide is a mixture of
ammonia+hydrogen peroxide+water in a weight ratio of 1:1:5 to
1:10:50, such as ratios of 1:1:10, 1:1:40, 1:5:40 or 1:1:50.
Typically, such mixtures are used at temperatures of from room
temperature to about 75.degree. C. Preferably, .gtoreq.97%, and
more preferably .gtoreq.99%, of the film thickness of the polymer
layer or underlayer is removed by contacting the polymer layer or
siloxane underlayer with either (i) mixture of sulfuric acid and
hydrogen peroxide or (ii) a mixture of ammonium hydroxide and
hydrogen peroxide.
[0049] Another advantage of the present polymer layers is that they
are easily removed to allow re-work of the substrate, such as a
wafer. In such a re-work process, a composition described above
comprising one or more condensed polymers of the invention is
coated on a substrate. The coated polymer layer is then optionally
soft-baked, and then cured to form an underlayer. Next, a
photoresist layer is coated on the underlayer, and the resist layer
is imaged and developed. The patterned resist layer and the
underlayer may then each be removed to allow the wafer to be
re-worked. The underlayer is contacted with any of the
above-described wet stripping compositions, such as aqueous
tetramethylammonium hydroxide compositions (typically .gtoreq.5 wt
%) and aqueous fluoride ion strippers such as ammonium
fluoride/ammonium bifluoride mixtures, at a suitable temperature to
remove the underlayer to provide the substrate free, or
substantially free, of underlayer and readily undergo additional
re-work as may be necessary. Such re-work includes coating another
layer of the present condensed polymers on the substrate and
processing the polymer coating as described above.
[0050] Example 1. A solution of tent-butyl methacrylate (tBMA),
(173 g), gamma butyrolactone (GBLMA), (166 g) and
3-(trimethoxysilyl)propyl methacrylate (TMSPMA), (60.6 g) dissolved
in 1,3-dioxolane (304 g) and a solution of V-65 initiator (60.6 g)
dissolved in 2:1 v/v tetrahydrofurane/acetonitrile (60.6 g) were
both added dropwise over 2 hr. to 3-dioxolane (710 g) at 75.degree.
C. under a nitrogen blanket. After addition the reaction solution
was held at 75.degree. C. for an additional two hours, cooled to
room temperature and precipitated into heptanes:MTBE (1:1 v/v, 14
L). The precipitated polymer was collected by vacuum filtration and
vacuum oven dried for 24 hours to afford Polymer 1
(tBMA/GBLMA/TMSPMA 50/40/10) as a white solid (271 g, 68%). M.sub.w
was determined by GPC relative to polystyrene standard and was
found to be 5700 Da.
[0051] Example 2. Polymers 2 to 12, reported in Table 2 below, were
synthesized according to the procedure of Example 1 using the
monomers listed in Table 1 below. The amount of each monomer used
is reported in Table 2 in mol %. Polymers 2 to 12 were isolated in
20-99% yield and had the M.sub.w reported in Table 2.
TABLE-US-00001 TABLE 1 ##STR00013## Monomer 1 ##STR00014## Monomer
2 ##STR00015## Monomer 3 ##STR00016## Monomer 4 ##STR00017##
Monomer 5 ##STR00018## Monomer 6 ##STR00019## Monomer 7
##STR00020## Monomer 8 ##STR00021## Monomer 9 ##STR00022## Monomer
10 ##STR00023## Monomer 11 ##STR00024## Monomer 12 ##STR00025##
Monomer 13 ##STR00026## Monomer 14
TABLE-US-00002 TABLE 2 Monomer Monomer Monomer Monomer Monomer
Polymer A (mol %) B (mol %) C (mol %) D (mol %) E (mol %) M.sub.w 2
Monomer Monomer Monomer 14000 1 (10) 2 (50) 3 (40) 3 Monomer
Monomer Monomer Monomer 5400 1 (10) 2 (50) 3 (25) 4 (15) 4 Monomer
Monomer Monomer Monomer 5100 1 (10) 2 (55) 4 (20) 6 (15) 5 Monomer
Monomer Monomer Monomer 5400 1 (10) 2 (50) 3 (25) 6 (15) 6 Monomer
Monomer Monomer Monomer Monomer 4300 1 (10) 2 (50) 3 (25) 4 (5) 6
(10) 7 Monomer Monomer Monomer 4000 1 (10) 2 (40) 3 (50) 8 Monomer
Monomer Monomer Monomer 4000 1 (10) 2 (40) 3 (40) 7 (10) 9 Monomer
Monomer Monomer 4300 1 (20) 2 (50) 3 (30) 10 Monomer Monomer
Monomer Monomer Monomer 4900 1 (10) 2 (50) 3 (25) 4 (5) 8 (10) 11
Monomer Monomer Monomer Monomer 5700 1 (10) 2 (50) 5 (25) 6 (15) 12
Monomer Monomer Monomer Monomer Monomer 6800 1 (10) 2 (50) 5 (25) 4
(5) 6 (10)
[0052] Example 3. The procedure of Example 2 is repeated and is
expected to provide Polymers 13-18 reported in Table 3. The monomer
numbers reported in Table 3 refer to the monomers in Table 1 of
Example 2.
TABLE-US-00003 TABLE 3 Monomer A Monomer B Monomer C Monomer D
Monomer E Polymer (mol %) (mol %) (mol %) (mol %) (mol %) 13
Monomer 1 Monomer 2 Monomer 3 Monomer 4 (5) Monomer 9 (10) (50)
(25) (10) 14 Monomer 2 Monomer 3 Monomer 4 Monomer 12 (45) (25)
(15) (15) 15 Monomer 2 Monomer 4 Monomer 5 Monomer 8 Monomer 11
(30) (25) (25) (10) (10) 16 Monomer 4 Monomer 7 Monomer 9 (5)
Monomer 11 Monomer 14 (25) (25) (10) (35) 17 Monomer 2 Monomer 3
Monomer 4 Monomer 13 (50) (25) (15) (10) 18 Monomer 1 (5) Monomer 2
Monomer 4 Monomer 5 Monomer 13 (50) (15) (20) (10)
[0053] Example 4. A solution of hydrochloric acid (37 wt % in
water, 7.76 g) in water (25.9 g) was added over 10 minutes to a
mixture of TEOS (63.5 g, 50 mol %) and Polymer 1 from Example 1
(50.0 g, 50 mol %) in THF (270 g) and stirred at room temperature
for 1 hr. The reaction mixture was heated to 63.degree. C. for 20
hr. and then cooled to room temperature. PGEE (200 g) was added,
the volatile species removed under reduced pressure, and the
resulting solution was diluted with PGEE to provide Condensed
Polymer 1 (10 wt % in PGEE, 600g) as a clear solution. M.sub.w was
determined by GPC relative to polystyrene standards (28,100
Da).
[0054] Example 5. Condensed Polymers 2 to 26, reported in Table 5
below, were synthesized according to the procedure of Example 4
using Polymers 1 to 12 from Examples 1 and 2 and the monomers
listed in Table 4 below. The amount of each monomer used is
reported in Table 5 in mol %. Condensed Polymers 2 to 12 were
isolated in 20-99% yield and had the M.sub.w reported in Table
5.
TABLE-US-00004 TABLE 4 ##STR00027## Monomer 1S ##STR00028## Monomer
2S ##STR00029## Monomer 3S ##STR00030## Monomer 4S ##STR00031##
Monomer 5S ##STR00032## Monomer 6S ##STR00033## Monomer 7S
TABLE-US-00005 TABLE 5 Con- Monomer densed Polymer Monomer A
Monomer B D Polymer (mol %) (mol %) (mol %) (mol %) M.sub.w 2 1
(45) Monomer 1S 22,700 (55) 3 1 (26) Monomer 1S Monomer 2S Monomer
12,400 (50) (9) 3S (15) 4 1 (50) Monomer 1S 52,800 (50) 5 1 (50)
Monomer 1S 40,300 (50) 6 3 (50) Monomer 1S 26,600 (50) 7 2 (50)
Monomer 1S 100,000 (50) 8 2 (50) Monomer 1S 30,000 (50) 9 4 (50)
Monomer 1S 20,000 (50) 10 5 (50) Monomer 1S 22,000 (50) 11 6 (50)
Monomer 1S 20,500 (50) 12 6 (50) Monomer 1S Monomer 2S 11,100 (40)
(10) 13 9 (40) Monomer 1S Monomer 2S 25,000 (50) (10) 14 1 (40)
Monomer 1S 27,700 (60) 15 1 (30) Monomer 1S 25,700 (70) 16 7 (50)
Monomer 1S 29,000 (50) 17 8 (50) Monomer 1S 27,000 (50) 18 1 (60)
Monomer 1S 40,600 (40) 19 9 (50) Monomer 1S 39,900 (50) 20 1 (30)
Monomer 1S Monomer 2S 24,000 (65) (5) 21 11 (50) Monomer 1S 20,200
(50) 22 12 (50) Monomer 1S 18,700 (50) 23 1 (50) Monomer 1S Monomer
4S 25,000 (40) (10) 24 1 (50) Monomer 1S Monomer 5S 25,000 (40)
(10) 25 1 (50) Monomer 1S Monomer 6S 44,000 (40) (10) 26 1 (50)
Monomer 1S Monomer 7S 24,600 (40) (10)
[0055] Example 6. The following components were combined: 1.6 wt %
of Condensed Polymer 1; 0.09 wt % of a 0.1 wt % solution of
tetrabutylammonium chloride in PGEE; 49 wt % of PGEE; 49.2 wt % of
2-hydroxyisobutyric acid methyl ester; 0.009 wt % acetic acid; and
0.2 wt % coating enhancer. The mixture was filtered through 0.2 gm
polytetrafluoroethylene syringe to provide Comparative Formulation
1.
[0056] Example 7. The procedure of Example 6 was repeated to
prepare Comparative Formulations 2 to 8 by replacing Condensed
Polymer 1 with the Condensed Polymers reported in Table 6.
TABLE-US-00006 TABLE 6 Comparative Formulation Condensed Polymer 2
Condensed Polymer 6 3 Condensed Polymer 7 4 Condensed Polymer 23 5
Condensed Polymer 24 6 Condensed Polymer 25 7 Condensed Polymer 10
8 Condensed Polymer 11
[0057] Example 8. The procedure of Example 6 was repeated except
that Condensed Polymer 1 was replaced with a 85/15 w/w mixture of
Condensed Polymer 1 and propoxylated pentaerythritol having on
average 5 moles of propylene oxide (formula (11),
a+b+c+d.apprxeq.5) as a crosslinker to provide Formulation 1.
##STR00034##
[0058] Example 9. The procedure of Example 6 was repeated to
provide Formulations 2 to 15 by replacing Condensed Polymer 1 with
the condensed polymer/crosslinker mixtures reported in Table 7.
Crosslinker C1 is propoxylated pentaerythritol having on average 5
moles of propylene oxide of formula (11). Crosslinker C2 is a
polymer of tert-butyl methacrylate/alpha-gammabutyrolactone
methacrylate/hydroxyethyl methacrylate/methacrylic acid in a mole
ratio of 25/25/25/25. Crosslinker C3 is a polymer of tert-butyl
methacrylate/alpha-gammabutyrolactone methacrylate/hydroxyethyl
methacrylate in a mole ratio of 50/25/25. Crosslinker C4 is polymer
of methacrylic acid and hydroxyethyl methacrylate in a mole ratio
of 60/40.
TABLE-US-00007 TABLE 7 Condensed Condensed Polymer/Crosslinker
Formulation Polymer Crosslinker (w/w) 2 1 C1 85/15 3 1 C2 85/15 4 1
C3 85/15 5 23 C1 85/15 6 24 C1 85/15 7 25 C1 85/15 8 6 C1 85/15 9 7
C1 85/15 10 10 C1 85/15 11 10 C4 85/15 12 11 C4 95/5 13 11 C4 90/10
14 11 C4 85/15 15 11 C1 85/15
[0059] Example 10. Comparative Formulations from Examples 6 and 7
and Formulations of the invention from Examples 8 and 9 were
spin-coated on a bare 200 mm silicon wafers at 1500 rpm and baked
at 240.degree. C. for 60 seconds using an ACT-8 Clean Track (Tokyo
Electron Co.). The thickness of each coated film after baking of
was measured with an OptiProbe.TM. instrument from Therma-wave Co.
Each coated sample was then evaluated for SC-1 wet strippability
using a 1/1/40 wt/wt/wt mixture of 30% NH.sub.4OH/30%
H.sub.2O.sub.2/water. The SC-1 mixture was heated to 60.degree. C.,
and coupons of each coated wafer were immersed into the solution
for 1 min. The coupons were removed from the SC-1 mixture and
rinsed with deionized water, and the film thickness was again
measured. The film thickness loss for each sample was calculated as
the difference in film thickness before and after contact with the
stripping agent. A separate film prepared as described above was
optionally tested for SC-1 strippability after etching. Etching was
performed for 60 seconds using RIE790 from Plasma-Therm Co. with
oxygen gas, 25 sscm flow, 180 W of power, and 6 mTorr of pressure.
The stripping results, obtained as the rate of film removal in
A/min, are reported in Table 8.
[0060] Comparative Formulations from Examples 6 and 7 and
Formulations of the invention from Examples 8 and 9, at either 1.7%
or 3.5% solids, were coated on 200 mm silicon wafers as described
above with a target thickness of 400 .ANG. or 1000 .ANG. and
measured (post cure) as described above. A puddle of commercially
available 0.26N TMAH developer (MF CD-26) was applied to each wafer
for 60 seconds, after which the wafers were rinsed with DI water,
spin dried and the film thickness was re-measured. A final drying
bake of 105.degree. C./60 seconds was applied to each wafer and
final film thickness was measured. The thickness loss of each film,
reported as the rate of film removal in A/min, resulting from this
TMAH strip is reported in Table 8. A negative film strip value
indicates an increase in film thickness.
TABLE-US-00008 TABLE 8 Before Etch After TMAH Strip Formulation
Example (.ANG./min) Etch (.ANG./min) (.ANG./min) Comparative
Formulation 1 >394 >242 -41 1 905 546 -10 2 754 415 -4 3 807
475 -4 4 759 422 -9 Comparative Formulation 2 409 466 -19 8 210 423
-4 Comparative Formulation 3 190 452 -50 9 140 184 -7 Comparative
Formulation 4 110 114 -25 5 38 96 -3 Comparative Formulation 5 87
99 -21 6 64 84 -2 Comparative Formulation 6 90 98 -6 7 74 89 -2
Comparative Formulation 7 113 409 -13 10 41 145 0 11 116 381 -4
Comparative Formulation 8 226 428 -16 12 158 433 -12 13 134 414 -2
14 86 194 0 15 89 395 1
* * * * *