U.S. patent application number 11/439455 was filed with the patent office on 2006-09-28 for methods for producing a dielectric, dielectric having self-generating pores, monomer for porous dielectrics, process for preparing poly-o-hydroxyamides, process for preparing ploybenzoxazoles, and processes for producing an electronic component.
This patent application is currently assigned to Infineon Technologies AG. Invention is credited to Robert Banfic, Klaus Lowack, Anna Maltenberger, Recai Sezi, Andreas Walter.
Application Number | 20060214139 11/439455 |
Document ID | / |
Family ID | 29264862 |
Filed Date | 2006-09-28 |
United States Patent
Application |
20060214139 |
Kind Code |
A1 |
Sezi; Recai ; et
al. |
September 28, 2006 |
Methods for producing a dielectric, dielectric having
self-generating pores, monomer for porous dielectrics, process for
preparing poly-o-hydroxyamides, process for preparing
ploybenzoxazoles, and processes for producing an electronic
component
Abstract
Poly-o-hydroxyamides include binaphthyl substituents as
repeating units. The poly-o-hydroxyamides can be cyclized to give
the polybenzoxazole by heating. Pore formation occurs, so that a
dielectric having a very low dielectric constant k of less than 2.5
is obtained.
Inventors: |
Sezi; Recai; (Rottenbach,
DE) ; Walter; Andreas; (Egloffstein, DE) ;
Lowack; Klaus; (Erlangen, DE) ; Maltenberger;
Anna; (Leutenbach, DE) ; Banfic; Robert;
(Nurnberg, DE) |
Correspondence
Address: |
LERNER GREENBERG STEMER LLP
P O BOX 2480
HOLLYWOOD
FL
33022-2480
US
|
Assignee: |
Infineon Technologies AG
|
Family ID: |
29264862 |
Appl. No.: |
11/439455 |
Filed: |
May 23, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10424376 |
Apr 28, 2003 |
|
|
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11439455 |
May 23, 2006 |
|
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Current U.S.
Class: |
252/576 ;
257/E21.259; 257/E21.273; 257/E23.167; 528/332 |
Current CPC
Class: |
H01L 23/5329 20130101;
C08G 73/22 20130101; H01L 21/312 20130101; H01L 2924/0002 20130101;
C08G 69/26 20130101; H01L 21/02282 20130101; H01L 2924/0002
20130101; H01L 2924/00 20130101; H01L 21/02205 20130101; H01L
21/31695 20130101; H01L 21/02118 20130101; H01L 21/02304 20130101;
H01L 21/02203 20130101; H05K 1/0346 20130101; C08G 69/44 20130101;
H01L 2924/3011 20130101 |
Class at
Publication: |
252/576 ;
528/332 |
International
Class: |
H01B 3/20 20060101
H01B003/20; C08G 69/26 20060101 C08G069/26 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 26, 2002 |
DE |
102 18 788.6 |
Claims
1. A method for producing a dielectric, which comprises: using a
poly-o-hydroxyamides of Formula I ##STR33## where E.sup.1 and
E.sup.2, in each case independently, are substituents selected from
the group consisting of hydrogen, a hydroxyl group, a saturated
monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;
Y.sup.1 and Y.sup.2, in each case independently for each position,
are a divalent hydrocarbon; Z.sup.1, in each case independently for
each position, is a structural unit having a formula selected from
the group consisting of Formula IIa and IIb ##STR34## the bond (-*)
and the substituent -GR.sup.5 being disposed in the ortho position
relative to one another, ##STR35## Z.sup.2, in each case
independently for each position, is a tetravalent hydrocarbon
composed of groups linked to one another and selected from the
group consisting of alkyl and aryl groups; R.sup.1, R.sup.2,
R.sup.3, and R.sup.4, in each case independently, are substituents
selected from the group consisting of H, --C.sub.6H.sub.5,
--(CH.sub.2).sub.n--CH.sub.3, -G-(CH.sub.2).sub.n--CH.sub.3,
--CH((CH.sub.2).sub.nCH.sub.3).sub.2, --CH(CH.sub.3).sub.2,
-G-CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, -G-C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, -G-(CF.sub.2).sub.n--CF.sub.3,
--CF((CF.sub.2).sub.nCF.sub.3).sub.2, --CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --N(CH.sub.3).sub.2, --N(CF.sub.3).sub.2,
##STR36## R.sup.5, in each case independently, is a substituent
selected from the group consisting of H,
--CO(CH.sub.2).sub.n--CH.sub.3, --COO--(CH.sub.2).sub.n--CH.sub.3,
--(CH.sub.2).sub.n--CH.sub.3, --CH((CH.sub.2).sub.nCH.sub.3).sub.2,
--CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, --CF((CF.sub.2).sub.nCF.sub.3).sub.2,
--CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CH.sub.2).sub.n--C.sub.6H.sub.5,
--COO--(CH.sub.2).sub.n--C.sub.6H.sub.5; G is a heteroatom selected
from the group consisting of oxygen and sulfur; a is an integer
from 0 to 1; b has a value from 1 to 200; c has a value from 0 to
200; d is an integer from 0 to 1; n is an integer from 0 to 5;
R.sup.6 is a divalent substituent selected from the group
consisting of: ##STR37## R.sup.7 is a substituent selected from the
group consisting of an alkyl group having from 1 to 10 carbon atoms
and an aryl group having from 5 to 22 carbon atoms; and e is an
integer from 1 to 10.
2. The method according to claim 1, wherein, in E.sup.1 and
E.sup.2, the saturated monovalent hydrocarbon contains a
heteroatom.
3. The method according to claim 1, wherein, in E.sup.1 and
E.sup.2, the unsaturated monovalent hydrocarbon contains a
heteroatom.
4. The method according to claim 1, wherein at least one of the
Y.sup.1 substituents has a heteroatom.
5. The method according to claim 1, wherein at least one of the
Y.sup.2 substituents has a heteroatom.
6. The method according to claim 1, wherein, in Z.sup.2, one of the
groups has a heteroatom.
7. A monomer for the preparation of a poly-o-hydroxyamide usable in
dielectrics, comprising a backbone having a formula selected from
the group consisting of Formula IVa and IV ##STR38## where R.sup.1,
R.sup.2, R.sup.3, and R.sup.4, in each case independently, are
selected from the group of substituents selected from the group
consisting of H, --C.sub.6H.sub.5, --(CH.sub.2).sub.n--CH.sub.3,
-G-(CH.sub.2).sub.n--CH.sub.3,
--CH((CH.sub.2).sub.nCH.sub.3).sub.2, --CH(CH.sub.3).sub.2,
-G-CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, -G-C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, -G-(CF.sub.2).sub.n--CF.sub.3,
--CF((CF.sub.2).sub.nCF.sub.3).sub.2, --CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --N(CH.sub.3).sub.2, --N(CF.sub.3).sub.2,
##STR39## R.sup.5, in each case independently, is a substituent
selected from the group consisting of H,
--CO(CH.sub.2).sub.n--CH.sub.3, --COO--(CH.sub.2).sub.n--CH.sub.3,
--(CH.sub.2).sub.n--CH.sub.3, --CH((CH.sub.2).sub.nCH.sub.3).sub.2,
--CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, --CF((CF.sub.2).sub.nCF.sub.3).sub.2,
--CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CH.sub.2).sub.n--C.sub.6H.sub.5,
--COO--(CH.sub.2).sub.n--C.sub.6H.sub.5; and G is a heteroatom
selected from the group consisting of oxygen and sulfur.
8. A process for preparing poly-o-hydroxyamides, which comprises:
reacting the monomer according to claim 7 with a dicarboxylic acid
having a formula selected from the group consisting of Formulae Va
and Vb ##STR40## where L is a substituent selected from the group
consisting of a hydroxyl group and an activating group; and Y.sup.1
and Y.sup.2, in each case independently for each position, are a
divalent hydrocarbon.
9. A process for preparing poly-o-hydroxyamides, which comprises:
reacting the monomer according to claim 7 with an activated
dicarboxylic acid derivative having a formula selected from the
group consisting of Formulae Va and Vb ##STR41## where L is a
substituent selected from the group consisting of a hydroxyl group
and an activating group; and Y.sup.1 and Y.sup.2, in each case
independently for each position, are a divalent hydrocarbon.
10. The process according to claim 8, which further comprises
carrying out the reacting step with a base.
11. The process according to claim 9, which further comprises
carrying out the reacting step with a base.
12. A process for preparing polybenzoxazoles having a Formula III
##STR42## where Z.sup.1 has a formula selected from the group
consisting of ##STR43## E.sup.1 and E.sup.2, in each case
independently, are substituents selected from the group consisting
of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon,
and an unsaturated monovalent hydrocarbon; Y.sup.1 and Y.sup.2, in
each case independently for each position, are a divalent
hydrocarbon; Z.sup.2, in each case independently for each position,
is a tetravalent hydrocarbon composed of groups linked to one
another and selected from the group consisting of alkyl and aryl
groups; R.sup.1, R.sup.2, R.sup.3, and R.sup.4, in each case
independently, are substituents selected from the group consisting
of H, --C.sub.6H.sub.5, --(CH.sub.2).sub.n--CH.sub.3,
-G-(CH.sub.2).sub.n--CH.sub.3,
--CH((CH.sub.2).sub.nCH.sub.3).sub.2, --CH (CH.sub.3).sub.2,
-G-CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, -G-C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, -G-(CF.sub.2).sub.n--CF.sub.3,
--CF((CF.sub.2).sub.nCF.sub.3).sub.2, --CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --N(CH.sub.3).sub.2, --N(CF.sub.3).sub.2,
##STR44## R.sup.5, in each case independently, is a substituent
selected from the group consisting of H,
--CO(CH.sub.2).sub.n--CH.sub.3, --COO--(CH.sub.2).sub.n--CH.sub.3,
--(CH.sub.2).sub.n--CH.sub.3, --CH((CH.sub.2).sub.nCH.sub.3).sub.2,
--CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, --CF((CF.sub.2).sub.nCF.sub.3).sub.2,
--CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CH.sub.2).sub.n--C.sub.6H.sub.5,
--COO--(CH.sub.2).sub.n--C.sub.6H.sub.5; G is a heteroatom selected
from the group consisting of oxygen and sulfur; a is an integer
from 0 to 1; b has a value from 1 to 200; c has a value from 0 to
200; and d is an integer from 0 to 1; the method which comprises:
heating poly-o-hydroxyamides having a Formula I ##STR45## where
E.sup.1 and E.sup.2, in each case independently, are substituents
selected from the group consisting of hydrogen, a hydroxyl group, a
saturated monovalent hydrocarbon, and an unsaturated monovalent
hydrocarbon; Y.sup.1 and Y.sup.2, in each case independently for
each position, are a divalent hydrocarbon; Z.sup.1, in each case
independently for each position, is a structural unit having a
formula selected from the group consisting of Formula IIa and IIb
##STR46## in which the bond (-*) and the substituent -GR.sup.5 are
disposed in the ortho position relative to one another, ##STR47##
Z.sup.2, in each case independently for each position, is a
tetravalent hydrocarbon composed of groups linked to one another
and selected from the group consisting of alkyl and aryl groups;
R.sup.1, R.sup.2, R.sup.3, and R.sup.4, in each case independently,
are substituents selected from the group consisting of H,
--C.sub.6H.sub.5, --(CH.sub.2).sub.n--CH.sub.3,
-G-(CH.sub.2).sub.n--CH.sub.3,
--CH((CH.sub.2).sub.nCH.sub.3).sub.2, --CH(CH.sub.3).sub.2,
-G-CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, -G-C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, -G-(CF.sub.2).sub.n--CF.sub.3,
--CF((CF.sub.2).sub.nCF.sub.3).sub.2, --CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --N(CH.sub.3).sub.2, --N(CF.sub.3).sub.2,
##STR48## R.sup.5, in each case independently, is a substituent
selected from the group consisting of H, --CO
(CH.sub.2).sub.n--CH.sub.3, --COO--(CH.sub.2).sub.n--CH.sub.3,
--(CH.sub.2).sub.n--CH.sub.3, --CH((CH.sub.2).sub.nCH.sub.3).sub.2,
--CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, --CF((CF.sub.2).sub.nCF.sub.3).sub.2,
--CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CH.sub.2).sub.n--C.sub.6H.sub.5,
--COO--(CH.sub.2).sub.n--C.sub.6H.sub.5; G is a heteroatom selected
from the group consisting of oxygen and sulfur; a is an integer
from 0 to 1; b has a value from 1 to 200; c has a value from 0 to
200; d is an integer from 0 to 1; n is an integer from 0 to 5;
R.sup.6 is a divalent substituent selected from the group
consisting of: ##STR49## R.sup.7 is a substituent selected from the
group consisting of an alkyl group having from 1 to 10 carbon atoms
and an aryl group having from 5 to 22 carbon atoms; and p1 e is an
integer from 1 to 10.
13. A process for producing an electronic component, which
comprises: preparing a solution of a poly-o-hydroxyamide having a
Formula I in a solvent ##STR50## where E.sup.1 and E.sup.2, in each
case independently, are substituents selected from the group
consisting of hydrogen, a hydroxyl group, a saturated monovalent
hydrocarbon, and an unsaturated monovalent hydrocarbon; Y.sup.1 and
Y.sup.2, in each case independently for each position, are a
divalent hydrocarbon; Z.sup.1, in each case independently for each
position, is a structural unit having a formula selected from the
group consisting of Formula IIa and IIb ##STR51## in which the bond
(-*) and the substituent -GR.sup.5 are disposed in the ortho
position relative to one another, ##STR52## Z.sup.2, in each case
independently for each position, is a tetravalent hydrocarbon
composed of groups linked to one another and selected from the
group consisting of alkyl and aryl groups; R.sup.1, R.sup.2,
R.sup.3, and R.sup.4, in each case independently, are substituents
selected from the group consisting of H, --C.sub.6H.sub.5,
--(CH.sub.2).sub.n--CH.sub.3, -G-(CH.sub.2).sub.n--CH.sub.3,
--CH((CH.sub.2).sub.nCH.sub.3).sub.2, --CH(CH.sub.3).sub.2,
-G-CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, -G-C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, -G-(CF.sub.2).sub.n--CF.sub.3,
--CF((CF.sub.2).sub.nCF.sub.3).sub.2, --CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --N(CH.sub.3).sub.2, --N(CF.sub.3).sub.2,
##STR53## R.sup.5, in each case independently, is a substituent
selected from the group consisting of H,
--CO(CH.sub.2).sub.n--CH.sub.3, --COO--(CH.sub.2).sub.n--CH.sub.3,
--(CH.sub.2).sub.n--CH.sub.3, --CH((CH.sub.2).sub.nCH.sub.3).sub.2,
--CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, --CF((CF.sub.2).sub.nCF.sub.3).sub.2,
--CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CH.sub.2).sub.n--C.sub.6H.sub.5,
--COO--(CH.sub.2).sub.n--C.sub.6H.sub.5; G is a heteroatom selected
from the group consisting of oxygen and sulfur; a is an integer
from 0 to 1; b has a value from 1 to 200; c has a value from 0 to
200; d is an integer from 0 to 1; n is an integer from 0 to 5;
R.sup.6 is a divalent substituent selected from the group
consisting of: ##STR54## R.sup.7 is a substituent selected from the
group consisting of an alkyl group having from 1 to 10 carbon atoms
and an aryl group having from 5 to 22 carbon atoms; and e is an
integer from 1 to 10; applying the solution to a substrate;
evaporating the solvent to obtain a film; heating the film to
cyclize the poly-o-hydroxyamide having the Formula I to yield a
polybenzoxazole having a Formula III ##STR55## where Z.sup.1 has a
formula selected from the group consisting of ##STR56## E.sup.1 and
E.sup.2, in each case independently, are substituents selected from
the group consisting of hydrogen, a hydroxyl group, a saturated
monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;
Y.sup.1 and Y.sup.2, in each case independently for each position,
are a divalent hydrocarbon; Z.sup.2, in each case independently for
each position, is a tetravalent hydrocarbon composed of groups
linked to one another and selected from the group consisting of
alkyl and aryl groups; R.sup.1, R.sup.2, R.sup.3, and R.sup.4, in
each case independently, are substituents selected from the group
consisting of H, --C.sub.6H.sub.5, --(CH.sub.2).sub.n--CH.sub.3,
-G-(CH.sub.2).sub.n--CH.sub.3,
--CH((CH.sub.2).sub.nCH.sub.3).sub.2, --CH(CH.sub.3).sub.2,
-G-CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, -G-C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, -G-(CF.sub.2).sub.n--CF.sub.3,
--CF((CF.sub.2).sub.nCF.sub.3).sub.2, --CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --N(CH.sub.3).sub.2, --N(CF.sub.3).sub.2,
##STR57## R.sup.5, in each case independently, is a substituent
selected from the group consisting of H, --CO
(CH.sub.2).sub.n--CH.sub.3, --COO--(CH.sub.2).sub.n--CH.sub.3,
--(CH.sub.2).sub.n--CH.sub.3, --CH((CH.sub.2).sub.nCH.sub.3).sub.2,
--CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, --CF((CF.sub.2).sub.nCF.sub.3).sub.2,
--CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CH.sub.2).sub.n--C.sub.6H.sub.5,
--COO--(CH.sub.2).sub.n--C.sub.6H.sub.5; G is a heteroatom selected
from the group consisting of oxygen and sulfur; a is an integer
from 0 to 1; b has a value from 1 to 200; c has a value from 0 to
200; and d is an integer from 0 to 1; structuring the film to
obtain a resist structure having trenches; depositing a conductive
material on the resist structure so that the trenches are filled
with a conductive material; and removing excess of the conductive
material.
14. A process for producing an electronic component, which
comprises: preparing a solution of a poly-o-hydroxyamide in a
solvent, the poly-o-hyroxyamide having a Formula I ##STR58## where
E.sup.1 and E.sup.2, in each case independently, are substituents
selected from the group consisting of hydrogen, a hydroxyl group, a
saturated monovalent hydrocarbon, and an unsaturated monovalent
hydrocarbon; Y.sup.1 and Y.sup.2, in each case independently for
each position, are a divalent hydrocarbon; Z.sup.1, in each case
independently for each position, is a structural unit having a
formula selected from the group consisting of Formula IIa and IIb
##STR59## in which the bond (-*) and the substituent -GR.sup.5 are
disposed in the ortho position relative to one another, ##STR60##
Z.sup.2, in each case independently for each position, is a
tetravalent hydrocarbon composed of groups linked to one another
and selected from the group consisting of alkyl and aryl groups;
R.sup.1, R.sup.2, R.sup.3, and R.sup.4, in each case independently,
are substituents selected from the group consisting of H,
--C.sub.6H.sub.5, --(CH.sub.2).sub.n--CH.sub.3,
-G-(CH.sub.2).sub.n--CH.sub.3,
--CH((CH.sub.2).sub.nCH.sub.3).sub.2, --CH (CH.sub.3).sub.2,
-G-CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, -G-C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, -G-(CF.sub.2).sub.n--CF.sub.3,
--CF((CF.sub.2).sub.nCF.sub.3).sub.2, --CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --N(CH.sub.3).sub.2, --N(CF.sub.3).sub.2,
##STR61## R.sup.5, in each case independently, is a substituent
selected from the group consisting of H,
--CO(CH.sub.2).sub.n--CH.sub.3, --COO--(CH.sub.2).sub.n--CH.sub.3,
--(CH.sub.2).sub.n--CH.sub.3, --CH((CH.sub.2).sub.nCH.sub.3).sub.2,
--CH(CH.sub.3).sub.3).sub.2, --C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, --CF((CF.sub.2).sub.nCF.sub.3).sub.2,
--CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CH.sub.2).sub.n--C.sub.6H.sub.5,
--COO--(CH.sub.2).sub.n--C.sub.6H.sub.5; G is a heteroatom selected
from the group consisting of oxygen and sulfur; a is an integer
from 0 to 1; b has a value from 1 to 200; c has a value from 0 to
200; d is an integer from 0 to 1; n is an integer from 0 to 5;
R.sup.6 is a divalent substituent selected from the group
consisting of: ##STR62## R.sup.7 is a substituent selected from the
group consisting of an alkyl group having from 1 to 10 carbon atoms
and an aryl group having from 5 to 22 carbon atoms; and e is an
integer from 1 to 10; applying the solution to a substrate having a
surface with metallic structures and trenches formed between the
metallic structures; evaporating the solvent to fill the trenches
with the poly-o-hydroxyamide of the Formula I; and heating the
substrate to cyclize the poly-o-hydroxyamide of the formula I to
yield the polybenzoxazole having a Formula III.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a divisional application of application Ser. No.
10/424,376, filed Apr. 28, 2003; the application also claims the
priority, under 35 U.S.C. .sctn.119, of German patent application
DE 102 18 788.6, filed Apr. 26, 2002; the prior applications are
herewith incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The invention relates to poly-o-hydroxyamides, a process for
their preparation, polybenzoxazoles, and a process for their
preparation, monomers for the preparation of the
poly-o-hydroxyamides, an electronic component that contains the
polybenzoxazoles as a dielectric, and a process for the production
of such electronic components.
[0003] In order to avoid cross-talk of signals which is caused by
capacitive coupling, adjacent conductor tracks in microchips are
insulated from one another by a dielectric disposed between the
conductor tracks. Compounds that are to be used as a dielectric
must meet various requirements. Thus, the signal transit time in
microchips depends both on the material of the conductor track and
on the dielectric that is disposed between the conductor tracks.
The lower the dielectric constant of the dielectric, the shorter
too is the signal transit time. The dielectrics used to date are
based on silica and have a dielectric constant of about four (4).
These materials are gradually being replaced by organic dielectrics
that have a substantially lower dielectric constant. The dielectric
constant of these materials is generally below three (3).
[0004] In the microchips customary at present, the conductor tracks
preferably are formed from aluminum, AlCu, or AlCuSi. With
increasing integration density of the memory chips, there is a
changeover to copper as conductor track material, owing to its
lower electrical resistance in comparison with aluminum. Copper
permits shorter signal transit time and hence a reduction in the
conductor track cross section. In contrast to the techniques
customary to date, in which the dielectric is introduced into the
trenches between the conductor tracks, in the copper damascene
technique, the dielectric is first structured. The resulting
trenches are first coated with a very thin barrier that is
composed, for example, of titanium, titanium nitride, tantalum,
tantalum nitride, silicon carbide, silicon nitride, or silicon
carbonitride. The trenches are then first filled with copper and
then excess copper is ground off mechanically. The dielectric must
therefore be stable to the materials used for the grinding and must
have sufficient adhesion to the substrate in order to avoid
becoming detached during the mechanical grinding process.
Furthermore, the dielectrics must also have sufficient stability in
the following process steps in which further components of the
microchips are produced. For this purpose, they must, for example,
have sufficient thermal stability and must not undergo
decomposition even at temperatures of more than 400.degree. C.
Moreover, the dielectric must be stable to process chemicals, such
as solvents, strippers, bases, acids or aggressive gases. Further
requirements are good solubility and a sufficient shelf-life of the
intermediates from which the dielectrics are produced.
[0005] With unfluorinated polymers that have sufficient thermal
stability, dielectric constants down to about 2.5 are obtainable.
By fluorination of the polymers, it is true that the dielectric
constant can be further reduced. However, these materials have poor
adhesion to the substrate and, at high temperatures, eliminate
fluorine-containing decomposition products, which may damage the
chip.
[0006] In order to be able to provide materials having a dielectric
constant of <2.5, porous materials are currently being
investigated in more detail. Owing to the air-filled nanopores, the
dielectric constant decreases to values of two (2) or less.
However, the porosity of the materials must not be chosen too high
because their mechanical stability otherwise greatly decreases and
the dielectric does not withstand mechanical loads as occur in
chemical mechanical planarization (CMP). Furthermore, the
processing of the currently available porous dielectric is very
difficult because both the process conditions and the solvent used
have a great influence on pore size and pore size distribution. In
most cases, the production of pores is effected by thermal
decomposition reactions that have to be very exactly controlled.
The decomposition products enter the air or ovens and, in addition
to soiling and damaging the apparatuses, can also constitute a
health hazard.
[0007] U.S. Pat. No. 5,776,990 to Hedrick, et al. describes a
porous polymer having a mean pore size of less than 100 nm. The
copolymer is formed from thermally stable and thermally labile
blocks. If a film of such a polymer is heated above the
decomposition temperature of the labile block, a porous dielectric
forms. In order to obtain the desired pore size, however, exact
control of the process conditions is required, such as the sequence
of temperature steps or the solvent used. Furthermore, gaseous
byproducts that can soil or damage the apparatuses used and that
are hazardous to health form.
[0008] Polybenzoxazoles (PBO) are polymers that have very high heat
stability. The substances are already used for the production of
protective and insulating layers. Polybenzoxazoles can be prepared
by cyclization of poly-o-hydroxyamides. The poly-o-hydroxyamides
have good solubility in organic solvents and good film formation
properties. They can easily be applied to electronic components by
using the spin coating technique. After a thermal treatment in
which the poly-o-hydroxyamide is cyclicized to give the
polybenzoxazole, a polymer that has the desired properties is
obtained. Polybenzoxazoles can also be processed directly in their
cyclized form. In this case, however, there are as a rule
difficulties with the solubility of the polymer. Building blocks of
poly-o-hydroxyamides are described, for example, in commonly-owned
German Patent Application DE 100 11 608, which corresponds to U.S.
Pat. No. 6,531,632 B2.
[0009] The mechanism taking place in the cyclization of
poly-o-hydroxyamides to polybenzoxazoles is shown schematically
below: ##STR1##
[0010] Upon heating, the o-hydroxyamide undergoes cyclization to
give the oxazole; water is liberated.
SUMMARY OF THE INVENTION
[0011] It is accordingly an object of the invention to provide
methods for producing a dielectric, a dielectric having
self-generating pores, a monomer for porous dielectrics, a process
for preparing poly-o-hydroxyamides, a process for preparing
polybenzoxazoles, a processes for producing an electronic
component, and a method for forming a dielectric that overcome the
hereinafore-mentioned disadvantages of the heretofore-known devices
of this general type and that provide and involve polymers that can
be easily applied to electronic components and that have a good
electrical insulating effect after their cyclization and exhibit
sufficient thermal stability and very good adhesive and filling
properties.
[0012] With the foregoing and other objects in view, there is
provided, in accordance with the invention, a poly-o-hydroxyamide
having a Formula I: ##STR2## in which
[0013] E.sup.1 and E.sup.2, in each case independently, are
hydrogen, a hydroxyl group or a saturated or unsaturated monovalent
hydrocarbon substituents that may also contain one or more hetero
atoms;
[0014] Y.sup.1 and Y.sup.2, in each case independently for each
position, are a divalent hydrocarbon substituent which may also
contain one or more hetero atoms;
[0015] Z.sup.1, in each case independently for each position, is a
structural unit of the Formula IIa or IIb ##STR3## in which the
bond (-*) and the substituent -GR.sup.5 are configured in the ortho
position relative to one another, ##STR4##
[0016] Z.sup.2, in each case independently for each position, is a
tetravalent hydrocarbon substituent which is composed of alkyl
and/or aryl substituents linked to one another and may also include
one or more hetero atoms;
[0017] R.sup.1, R.sup.2, R.sup.3, and R.sup.4, in each case
independently, are H, --C.sub.6H.sub.5,
--(CH.sub.2).sub.n--CH.sub.3, -G-(CH.sub.2).sub.n--CH.sub.3,
--CH((CH.sub.2).sub.nCH.sub.3).sub.2, --CH(CH.sub.3).sub.2,
-G-CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3, -G-C(CH.sub.3)3,
--(CF.sub.2).sub.n--CF.sub.3, -G-(CF.sub.2).sub.n--CF.sub.3,
--CF((CF.sub.2).sub.nCF.sub.3).sub.2, --CF(CF.sub.3).sub.2,
--C(CF.sub.3).sub.3, --N(CH.sub.3).sub.2, --N(CF.sub.3).sub.2,
[0018] R.sup.5, in each case independently, is H,
--CO(CH.sub.2).sub.n--CH.sub.3, --COO--(CH.sub.2).sub.n--CH.sub.3,
--(CH.sub.2).sub.n--CH.sub.3, --CH((CH.sub.2).sub.nCH.sub.3).sub.2,
--CH(CH.sub.3).sub.2, --C(CH.sub.3).sub.3,
--(CF.sub.2).sub.n--CF.sub.3, --CF((CF.sub.2).sub.nCF.sub.3).sub.2,
--CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CH.sub.2).sub.n-C.sub.6H.sub.5,
--COO--(CH.sub.2).sub.n--C.sub.6H.sub.5,
[0019] G is oxygen or sulfur,
[0020] a is 0 or 1,
[0021] b has a value of from 1 to 200,
[0022] c has a value of from 0 to 200,
[0023] d is 0 or 1, and
[0024] n is an integer from 0 to 10.
[0025] For reasons of simplicity, both the poly-o-hydroxyamides
(G=0) and the poly-o-thioamides (G=S) of the Formula I are referred
to below as poly-o-hydroxyamides. Statements made in connection
with the polymer groups described above apply in context to both
classes of compounds. Formula I represents a polymer having a
continuous polymer backbone. For reasons of simplicity, however,
the molecule in Formula I was represented in two parts.
[0026] The poly-o-hydroxyamides of the Formula I, according to the
invention, form, on cyclization to give the polybenzoxazole, pores
having a magnitude of a few ten nanometers without it being
necessary to provide a component, for example a thermally labile
block or an additive, in the polymer material. The pore size is
influenced primarily by the structure of the poly-o-hydroxyamide of
the Formula I and only to a small extent by the process conditions,
i.e. the solvent used and the temperature program. It is not
necessary to provide additional components that are decomposed to
give gaseous products, in order to produce pores. Consequently,
during pore formation, no impurities form and no damage is done to
the microchip structures already produced. After the cyclization,
the polybenzoxazoles obtained have dielectric constants of less
than 2.5, owing to the porosity of the material, which corresponds
to the lower limit of the fluorine-free polybenzoxazoles having
high thermal stability. The adhesion of the polybenzoxazole
prepared from the poly-o-hydroxyamide of the Formula I to surfaces
relevant for chip technology, such as silicon, silicon carbide,
silicon carbonitride, silicon nitride, silica, titanium, tantalum,
titanium nitride, tantalum nitride or silicon oxynitride, is very
good. Furthermore, the polybenzoxazoles have high stability to
chemicals as used in the production of microchips, such as
solvents, strippers, bases, acids, or aggressive gases. The polymer
materials are therefore very suitable for microelectronic
applications. Moreover, the materials are also outstandingly
suitable for the copper damascene technique. During the copper
grinding process, no disadvantageous effects occur, such as
delamination, cracking or blister formation. The
poly-o-hydroxyamides of the Formula I, according to the invention,
are very readily soluble in many organic solvents. Solvents that
may be used are, for example, acetone, cyclohexanone, diethylene
glycol monoethyl or diethyl ether, N-methylpyrrolidone,
y-butyrolactone, ethyl lactate, methoxypropyl acetate,
tetrahydrofuran, ethyl acetate and mixtures of said solvents. The
solutions can be very readily applied to surfaces of electronic
components e.g. by spin coating, spraying or dip methods and have a
very good film quality. Trenches having a width of less than 100 nm
and an aspect ratio of >4 can also be filled without
difficulties. The poly-o-hydroxyamides according to the invention
can be cyclized by heating to temperatures of 200 to 500.degree. C.
Apart from the desired pore formation, there is no formation of
defects, such as cracks in the filled trenches.
[0027] The poly-o-hydroxyamides of the Formula I are prepared from
bis-o-aminophenols and dicarboxylic acids or their derivatives. The
substituents derived from the dicarboxylic acids can have a wide
variety of structures. They may include saturated, unsaturated or
aromatic hydrocarbon substituents, combinations of these
substituents also being possible. Saturated substituents may be
straight-chain or branched. Furthermore, one or more carbon atoms
may also be replaced by heteroatoms, or the substituents Y.sup.1
and Y.sup.2 may also have groups formed from a plurality of
heteroatoms. Heteroatoms are understood here as meaning atoms which
are not carbon or hydrogen. Particularly preferred heteroatoms are
O, N, S, Si, and P. The chain length determined by the indices a,
b, c, and d can be controlled by the reaction conditions, for
example by using the rate of addition of the starting materials or
by controlling the temperature at which the reaction is performed.
Of course, a distribution of chain lengths is obtained in such a
polymerization, the reaction being carried out in such a way that
the average chain length is within the range of values indicated
above for the indices a, b, c, and d. A narrow molecular weight
distribution of the polymers is desirable. For the index b, the
reaction is controlled in such a way that values in the range of 1
to 200, preferably 4 to 80, result. For the index c, the reaction
is performed in such a way that values in the range of 0 to 200,
preferably 0 to 50, result. The molecular weights or averaged chain
lengths can be determined by customary methods, e.g. gel permeation
chromatography (GPC).
[0028] The properties of the polymer are substantially determined
by the group Z.sup.1. In the group Z.sup.1, the substituents
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are particularly preferably
hydrogen atoms and the substituents GR.sup.5 are particularly
preferably a hydroxyl group or acetyl group. These groups Z.sup.1
permit cyclization to give the benzoxazole under comparatively mild
conditions. Particularly preferred structures for the group Z.sup.1
(formulae IIa and IIb) are shown below: ##STR5##
[0029] In addition to the groups Z.sup.1, the polymer may also
include further groups Z.sup.2 which do not include any binaphthyl
substituents. The groups Z.sup.2 may have a very varied range of
structures. The groups Z.sup.2 preferably include 6 to 30 carbon
atoms. The group Z.sup.2 preferably includes one or two phenyl
groups on which the group GR.sup.5 and the nitrogen atom continuing
the polymer chain are bonded. The group GR.sup.5 and the nitrogen
atom are preferably disposed in the ortho position relative to one
another in order also to permit cyclization to give the oxazole in
the case the groups Z.sup.2. The part-structures of the group
Z.sup.2, in particular phenyl groups, which carry the groups
GR.sup.5 can be linked via alkylene and/or arylene groups or via
groups formed from hetero atoms. The groups Z.sup.2 can be
substituted by monovalent groups, in particular alkyl groups. In
particular, Z.sup.2 is a structural unit which is selected from the
group: ##STR6## in which R.sup.6 is a divalent substituent that is
selected from the following group: ##STR7## in which
[0030] R.sup.7 is an alkyl substituent having 1 to 10 carbon atoms
or an aryl substituent having 5 to 22 carbon atoms; and
[0031] e is an integer from 1 to 10.
[0032] G in groups Z.sup.1 and Z.sup.2 is preferably an oxygen
atom.
[0033] Among the abovementioned substituents R.sup.5, the following
substituents are particularly preferred: ##STR8## in which m is an
integer from 0 to 10, in particular from 0 to 5.
[0034] The groups Y.sup.1 and Y.sup.2 may likewise have a very
large variety of structures and preferably include 5 to 30 carbon
atoms. The groups Y.sup.1 and Y.sup.2 may include saturated and
unsaturated hydrocarbon groups as part-structures, aromatic
hydrocarbon groups being preferred.
[0035] Examples of suitable divalent substituents of the groups
Y.sup.1 and Y.sup.2 are shown below. ##STR9## ##STR10## in
which:
[0036] f is an integer from 1 to 10; and
[0037] g is an integer from 1 to 10.
[0038] Poly-o-hydroxyamide of the Formula I may carry, as terminal
groups E.sup.1 and E.sup.2, a hydrogen atom or a hydroxyl group or
a saturated or unsaturated monovalent hydrocarbon substituent which
may also contain one or more hetero atoms. The hydrocarbon
substituent preferably includes 1 to 30 carbon atoms. Some examples
of suitable terminal groups E.sup.1 and E.sup.2 are shown
below.
[0039] If, in formula I, a=0 and/or d=0, i.e. if E.sup.1 and/or
E.sup.2 are bonded to NH, E.sup.1 and E.sup.2, in each case
independently of one another, are preferably selected from the
following group: ##STR11##
[0040] If, in Formula I, a=1 and/or d=1, i.e. the substituents
E.sup.1 and E.sup.2 are bonded to CO, E.sup.1 and E.sup.2, in each
case independently of one another, are preferably selected from the
following group: ##STR12## in which R.sup.8 is selected from the
following group: ##STR13## in which
[0041] h is 0-10, and
[0042] q is *--O--*, *--S--*, or *--NH--*.
[0043] The terminal groups E.sup.1 and E.sup.2 can be introduced
into the poly-o-hydroxyamides of the Formula I by corresponding
active precursors, for example acid chlorides.
[0044] The structures shown for the substituents Y.sup.1, Y.sup.2,
E.sup.1, and E.sup.2 represent only a selection of preferred
structures. However, this list should not be considered as being
definitive.
[0045] As already mentioned, the polybenzoxazoles obtained from the
poly-o-hydroxyamides of the Formula I by cyclization have
advantageous properties with respect to the thermal stability, the
mechanical strength and the electrical insulating effect. The
invention therefore also relates to polybenzoxazoles of the Formula
III ##STR14## in which ##STR15## and a, b, c, d, R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, Y.sup.1, Y.sup.2, E.sup.1, E.sup.2, and
G have the meaning stated in the case of Formula I.
[0046] For reasons of simplicity, both polybenzoxazoles (G=0) and
polybenzothiazoles (G=S) of the Formula III are referred to as
polybenzoxazoles. The structures of the groups shown in the Formula
III are equally applicable to both classes of compounds. Formula
III represents a polymer having a continuous polymer backbone. For
reasons of simplicity, however, the molecule in Formula III has
been shown in two parts.
[0047] The poly-o-hydroxyamides of Formula I can be prepared by
reacting bis-o-aminophenols or bis-o-aminothiophenols with
dicarboxylic acids or their activated derivatives. The invention
therefore also relates to monomers of the Formulae IVa and IVb:
##STR16## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and
G have the meanings stated in the case of Formula I.
[0048] The monomers of the Formulae IVa and IVb are prepared by
customary synthesis processes, as described, for example, in
Organikum, Wiley-VCH, 1999, page 228 et seq., page 324 et seq. and
page 340 et seq. Similar monomers are described, for example, in
U.S. Pat. No 4,525,539 or in European Patent No. EP 0 317 942.
[0049] The monomers of the Formulae IVa and IVb can be reacted with
dicarboxylic acids or their activated derivatives to give the
desired poly-o-hydroxyamides of the Formula I. The invention
therefore also relates to a process for the preparation of
poly-o-hydroxyamides of the Formula I, monomers of the Formula IVa
and/or IVb being reacted with a dicarboxylic acid or an activated
dicarboxylic acid derivative of the Formulae Va and/or Vb.
##STR17## in which L is a hydroxyl group or an activating group and
Y.sup.1 and Y.sup.2 have the meaning stated in the case of Formula
I. For example, acid chlorides or activated esters, for example
sulfonic acid esters, can be used as an activating group for the
dicarboxylic acid derivatives of the formula V. The reaction of the
monomers of the Formula IVa or IVb and of the dicarboxylic acids of
the Formulae Va and Vb can, however, also be effected in the
presence of a compound that activates the carboxylic acid, such as,
for example, carbonyldiimidazole or dicyclohexylcarbodiimide. In
principle, all reagents which bind the water formed in the reaction
to themselves are suitable. For the preparation of the
poly-o-hydroxyamides of the Formula I, the monomers of the Formula
IVa or IVb and the dicarboxylic acid(s) or optionally the
dicarboxylic acid derivatives of the Formula Va or Vb are reacted
in an organic solvent at -20 to 150.degree. C. in the course of 5
to 20 hours. If required, terminal groups of the polymer can be
blocked with a suitable reagent in order thus to introduce the
terminal groups E.sup.1 and E.sup.2. Suitable-reagents have already
been described in the explanation of the compounds of the Formula
I. The poly-o-hydroxyamide of the formula I which has formed after
the reaction is precipitated by dropwise addition of the reaction
solution to a precipitating agent, washed and dried. Suitable
precipitating agents are water and alcohols, such as isopropanol,
butanol, or ethanol. Mixtures of these precipitating agents may
also be used. It is also suitable for the precipitating agent to
contain from 0.1% to 10% of ammonia. After filtration and drying,
the precipitated polymer can be directly further processed and, for
example for application to a semiconductor substrate, can be
dissolved in one of the solvents mentioned further above.
[0050] The polymerization to give the poly-o-hydroxyamide of the
Formula I can be carried out in the presence of a base in order to
trap acid liberated. Suitable basic acid acceptors are, for
example, pyridine, triethylamine, diazabicyclooctane, or
polyvinylpyridine. However, other basic acid acceptors may also be
used. Compounds that are readily soluble in the solvent used for
the synthesis, for example N-methylpyrrolidone, and in the
precipitating agent, for example water or water/alcohol mixtures,
are those that are completely insoluble in the solvent, such as,
for example, crosslinked polyvinylpyridine, are particularly
preferred. The acid acceptors can then easily be separated from the
resulting poly-o-hydroxyamide during the working up of the reaction
product.
[0051] Particularly suitable solvents for the polymer synthesis are
.gamma.-butyrolactone, tetrahydrofuran, N-methylpyrrolidone, and
dimethylacetamide. However, any solvent in which the starting
components are readily soluble can in principle be used.
[0052] The invention furthermore relates to a process for the
preparation of polybenzoxazoles of the Formula III,
poly-o-hydroxyamides of the Formula I being heated. Heating results
in the formation of an oxazole ring or thiazole ring with
elimination of a small molecule, in general water, the
polybenzoxazoles of the Formula III, according to the invention,
being obtained. The pore formation that occurs is influenced only
to a slight extent by the reaction conditions. The pores have a
diameter in the region of a few ten nanometers and a narrow pore
distribution. The process therefore permits large tolerances in the
production of the dielectric, which substantially simplifies the
reaction procedure.
[0053] The polybenzoxazole of Formula III, which is prepared by the
process according to the invention, has a very low dielectric
constant of k.ltoreq.2.5, owing to the pores enclosed in the
dielectric. It adheres very well to surfaces relevant to chip
technology, such as silicon, silicon carbide, silicon carbonitride,
silicon nitride, silica, titanium, tantalum, titanium nitride,
tantalum nitride, or silicon oxynitride. The invention therefore
also relates to an electronic component that contains the
polybenzoxazole of Formula III described above. Polybenzoxazole of
Formula III may be disposed, for example, as a dielectric between
conductor tracks or conductor track planes or as a buffer layer
between the microchip and the housing surrounding it. The
dielectrics according to the invention are outstandingly suitable
for the copper damascene technique. During the grinding process, no
disadvantageous effects, such as delamination, cracking or blister
formation, occur.
[0054] The invention therefore also relates to a process for the
production of an electronic component, a solution of a
poly-o-hydroxyamide of the Formula I in a solvent first being
prepared. This solution is applied to a substrate and the solvent
is evaporated so that a film is obtained. The film is then heated
in order to cyclize the poly-o-hydroxyamide and convert it into the
polybenzoxazole of Formula III. The film is then structured in
order to obtain a resist structure which has trenches. A conductive
material, for example copper, is then deposited on the resist
structure so that the trenches are filled with a conductive
material. Finally, excess conductive material is removed.
[0055] For example, lithographic processes can be used for
structuring the polybenzoxazole film, an etch-resistant mask being
produced on the film. The structure of the mask is then transferred
into the film of the polybenzoxazole according to the invention by
etching. Copper is preferably used as conductive material. A
barrier can be provided between dielectric and conductive material.
For example, the materials already mentioned further above are
suitable as material for the barrier. Excess conductive material is
removed, for example, by chemical mechanical planarization.
[0056] The invention furthermore relates to a process for the
production of an electronic component, a solution of a
poly-o-hydroxyamide of Formula I described above first being
prepared in a solvent. The solution is then applied to a substrate
that already has on its surface metallic structures between which
trenches are formed. Such structures are, for example, conductor
tracks. The solvent is evaporated so that the trenches are filled
with the poly-o-hydroxyamide. Finally, the substrate is heated in
order to cyclize the poly-o-hydroxyamide to give a
polybenzoxazole.
[0057] The adhesion of the polyhydroxyamides to surfaces relevant
in microelectronics, such as, for example, silicon, silica, silicon
nitride, tantalum nitride, glass or quartz, can be improved by
adding adhesion promoters.
[0058] For example, the following compounds can be used as adhesion
promoters: ##STR18## Other features that are considered as
characteristic for the invention are set forth in the appended
claims.
[0059] Although the invention is illustrated and described herein
as embodied in methods for producing a dielectric, a dielectric
having self-generating pores, a monomer for porous dielectrics, a
process for preparing poly-o-hydroxyamides, a process for preparing
polybenzoxazoles, a processes for producing an electronic
component, and a method for forming a dielectric, it is
nevertheless not intended to be limited to the details shown, since
various modifications and structural changes may be made therein
without departing from the spirit of the invention and within the
scope and range of equivalents of the claims.
[0060] The construction and method of operation of the invention,
however, together with additional objects and advantages thereof
will be best understood from the following description of specific
embodiments when read in connection with the accompanying
drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0061] FIG. 1 is a partial diagrammatic and partial schematic
drawing showing a setup according to the invention for determining
an dielectric constant; and
[0062] FIG. 2 is a photograph showing a shadow mask as used in
example 25 for the production of electrodes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
EXAMPLE 1
Bis-o-aminophenols having Oxygen Bridges:
[0063] Stage 1
[0064] The corresponding bishydroxybinaphthyl and
3-fluoro-6-nitrobenzyloxyphenol are initially introduced under
inert gas (nitrogen or argon) into a three-necked flask that is
provided with a stirrer and an inert gas connection, and
N,N-dimethylformamide is added to these at room temperature. The
mixture is stirred for about 10 to 20 minutes at room temperature.
Thereafter, potassium carbonate is added in portions to the
solution under inert gas. The solution is stirred at an elevated
temperature for a few hours. The reaction temperature is suitably
chosen from 60 to 140.degree. C. The reaction occurs over course of
1 to 10 hours. In addition to N,N-dimethylformamide, for example,
N-methylpyrrolidone, dimethyl sulfoxide, .gamma.-butyrolactone, or
dimethylacetamide can also be used. The concentrations of the
starting materials are suitably chosen in a range from 5 to 50% by
weight.
[0065] The suspension formed is cooled to room temperature and
poured into a cooled (2-10.degree. C.), aqueous potassium hydroxide
solution. The product is precipitated in crystalline form. The
precipitation can be accelerated by adding ethyl acetate. The
product is filtered, washed with water, and then added to a 10%
strength solution of acetic acid in water. The solution is stirred
for 15 to 30 minutes, filtered, washed with water and dried under
inert gas at 40.degree. C./100 mbar in a drying oven until the
weight remains constant. The crude product obtained in this manner
is recrystallized from a solution in tetrahydrofuran and petroleum
ether and dried again under reduced pressure.
[0066] Stage 2 (Hydrogenation and Simultaneous Elimination of the
Benzyl Protective Group):
[0067] The hydrogenation is effected by known hydrogenation
processes for nitro compounds, as described, for example, in
European Patent No. EP 905 121, example 8. For this purpose, the
nitro compound obtained in stage 1 can be dissolved, for example,
in tetrahydrofuran, palladium on active carbon added and
hydrogenation effected with hydrogen at superatmospheric pressure
in an autoclave.
[0068] The bis((3-benzyloxy-4-nitro)phenoxy)binaphthyl prepared in
stage 1 is dissolved in tetrahdyrofuran, and palladium on active
carbon is added under inert gas. The amount of Pd/C is about 10% of
the amount of the compound to be hydrogenated. The suspension is
introduced into a previously heated hydrogenation reactor under
argon inert gas and hydrogenated with hydrogen at room temperature
under pressure. The hydrogenation time is in general 10 to 50
hours. The hydrogen pressure is suitably chosen from 0.5 to 5 bar.
The concentration of the compound to be hydrogenated in
tetrahydrofuran is 5 to 30% by weight. Instead of tetrahydrofuran,
for example, dioxane, halogenated hydrocarbons or toluene can also
be used as the solvent.
[0069] After the hydrogenation, the suspension is transferred under
inert gas into pure ethanol, and concentrated hydrochloric acid is
added with stirring until a clear solution forms. After the product
has completely dissolved, the solution is filtered over a Butchner
funnel in order to remove the Pd catalyst. Thereafter, about 70% of
the amount of solvent is distilled off under reduced pressure and
the concentrated solution is added to a solution of diethyl ether
and acetone (volume ratio 7:3) with rapid stirring. During this
procedure, the product is precipitated in crystalline form. The
suspension is stored for 12-24 hours at 0.degree. C. to 18.degree.
C. The product is then filtered off with suction and dried. The
aminophenol is present as the hydrochloride. In contrast to the
free aminophenol the form is not so greatly sensitive to oxidation
by atmospheric oxygen.
EXAMPLE 2
Bis-o-aminophenols Without Oxygen Bridges
[0070] Stage 1
[0071] Moistened silica is initially introduced into a three-necked
flask provided with a stirrer, a reflux condenser and an inert gas
connection, and 10% strength sulfuric acid is added. The ratios are
chosen at about 10 parts by weight of silica per 6 parts by weight
of 10% strength sulfuric acid. 200 parts by weight of
dichloromethane and 10 parts by weight of dihydroxybinaphthyl are
then added in this sequence. About 10 parts by weight of 65%
strength nitric acid are then added at a temperature of 2 to
10.degree. C. in the course of 15 to 60 minutes. After the end of
the addition, the suspension is stirred until quantitative
conversion of the starting material at room temperature. The
abovementioned ratio can be changed in a range of up to about 20%.
Instead of dichloromethane, other halogenated hydrocarbons may also
be used as the solvent.
[0072] After complete conversion, the suspension is filtered. The
product, which is present adsorbed onto the SiO.sub.2 surface, is
dissolved in a suitable solvent, such as, for example, acetone or
ethyl acetate, and filtered. This procedure is repeated twice. The
organic fractions are combined and evaporated down. The
concentrated solution is slowly poured into dimethyl ether while
stirring, and the precipitated product is filtered off with
suction. The product is then dried under inert gas at 40.degree.
C./100 mbar in a drying oven until the weight remains constant.
[0073] Stage 2:
[0074] The hydrogenation of the compound obtained in stage 1 is
carried out in the same manner as described in example 1.
EXAMPLE 3
Synthesis of 2,2'-diacetoxy-3,3'-diamino-1,1'-binaphthyl as the
hydrochloride
[0075] Stage 1: 2,2'-Diacetoxy-3,3'-dinitro-1,1'-binaphthyl
[0076] 4.088 g (14.29 mmol) of 2,2'-dihydroxy-1,1'-binaphthyl in 50
ml of acetic anhydride are initially introduced into a 250 ml
three-necked flask provided with a reflux condenser, a KPG stirrer
and an inert gas connection and are dissolved. A solution of 4.35
ml (42.80 mmol) of nitric acid (62%) in 25 ml of acetic anhydride
is then added dropwise to the solution at 0.degree. C. in the
course of 30 min. At the same temperature, stirring is carried out
for 4 h and the precipitated orange-red solid is filtered off with
suction on a frit. After the end of the reaction, the mixture is
carefully poured in 500 ml of ice water and thoroughly stirred. The
solid nitro product is filtered off with suction and thoroughly
washed with water.
[0077] The crude product is dissolved in toluene at room
temperature (2 ml/g) and heated to 90.degree. C. and petroleum
ether (4 ml/g) is added until crystallization begins. Thereafter,
the suspension is slowly cooled to room temperature, and the
suspension is stored for a further 4 h in a freezer at -18.degree.
C. and then filtered. The product obtained is dried for 24 h at 200
mbar and 55.degree. C.
[0078] Yield 5.72 g (87% of theory)
[0079] Stage 2: 2,2'-Diacetoxy-3,3'-diamino-1,1'-binaphthyl
hydrochloride
[0080] The hydrogenation is effected according to known processes
for the hydrogenation of nitro compounds, as described, for
example, in European Patent No. EP 905 121, example 8.
[0081] 31.09 g (67.57 mmol) of
2,2'-diacetoxy-3,3'-dinitro-1,1'-binaphthyl are dissolved in 600 ml
of tetrahydrofuran, and 5.00 g of 5% Pd/C are added under inert
gas. The suspension is introduced under Ar inert gas into a
previously heated hydrogenation reactor and hydrogenated at room
temperature for 24 h and under 2 bar H.sub.2 pressure.
[0082] The suspension is then transferred under inert gas into 200
ml of ethanol. 10 ml of concentrated HCl are added with stirring
and, when the product has completely dissolved, filtration is
effected three times over a Buchner funnel to remove the Pd
catalyst. The solution thus obtained is evaporated down to about 20
ml of ethanol at 70.degree. C. and 300 mbar and then added to a
solution of 700 ml of diethyl ether and 30 ml of acetone with rapid
stirring. The suspension is stored for 24 h at -18.degree. C. and
the solid is filtered off and dried.
[0083] Yield: 28.65 g (90% of theory)
[0084] Preparation of the polymers
[0085] Chemicals used
[0086] Bisaminophenols:
2,21-Di(4-amino-3-hydroxyphenyloxy)-1,1l'-binaphthyl--(bisaminophenol
1)
[0087] ##STR19##
3,3'-Diamino-2,2'-dihydroxy-1,1'-binaphthyl--(bis-amino-phenol
2)
[0088] ##STR20##
9,9'-Bis(3-amino-4-hydroxyphenyl)fluorene--(bisamino-phenol 3)
[0089] ##STR21##
4,4'-Diamino-3,3'-dihydroxybiphenyl--(bisaminophenol 4)
[0090] ##STR22##
2,2'-Diacetoxy-3,3'-diamino-1,1'-binaphthyl--(bis-amino-phenol
5)
[0091] ##STR23##
[0092] Dicarboxylic acid chlorides
Naphthalene-2,6-dicarboxylic acid chloride--(dicarboxylic acid
chloride 1)
[0093] ##STR24##
Biphenyl-4,4'-dicarboxylic acid chloride (dicarboxylic acid
chloride 2)
[0094] ##STR25##
phenyl-4,4'-dicarboxylic acid chloride--(dicarboxylic acid chloride
3)
[0095] ##STR26##
Terephthaloyl chloride (dicarboxylic acid chloride 4)
[0096] ##STR27##
5-Phenylethynylisophthoyl chloride--(dicarboxylic acid chloride
5)
[0097] ##STR28##
5-Allyloxyisophthaloyl dichloride--(dicarboxylic acid chloride
6)
[0098] ##STR29##
[0099] Endcaps (E.sup.1, E.sup.2):
Methacryloyl chloride--(Endcap 1)
[0100] ##STR30##
5-Norbornene-2-carboxylic acid chloride--(Endcap 2)
[0101] ##STR31##
5-Norbornene-2,3-dicarboxylic acid anhydride (Endcap 3)
[0102] ##STR32##
EXAMPLE 4
Synthesis of polymer 1
[0103] 50 g (0.1 mmol) of bisaminophenol 1 are dissolved in 400 ml
of distilled N-methylpyrrolidone (NMP). A solution of 23.93 g
(0.095 mol) of dicarboxylic acid chloride 1, dissolved in 200 ml of
distilled NMP is added dropwise to this solution at 10.degree. C.
while stirring. Stirring is continued for a further hour at
10.degree. C. and then for one hour at 20.degree. C. After further
cooling to 10.degree. C., 1.64 g (0.01 mol) of endcap 3, dissolved
in 50 ml of distilled y-butyrolactone (.gamma.-BL) are added
dropwise to the reaction mixture, and stirring is carried out for
one hour at 10.degree. C. and then for one hour at 20.degree. C.
The reaction solution is cooled to 10.degree. C., after which 19.76
g (0.25 mol) of pyridine, dissolved in 30 ml of distilled
.gamma.-BL, are added to said reaction solution and the latter is
warmed up to room temperature and stirred for 2 hours.
[0104] In order to isolate the polymer, the reaction mixture is
filtered and the filtrate is added dropwise to a mixture of 1 1 of
demineralized water and 200 ml of isopropanol while stirring, a
further 3 l of demineralized water being added during the dropwise
addition. The precipitated polymer is filtered off with suction and
washed with 2 l of cold demineralized water. After the filtration
with suction, the polymer is stirred twice for 1 hour at room
temperature in 2.5 portions of a 3% strength ammonia solution and
then filtered off with suction. The polymer is washed neutral with
demineralized water, filtered off, and dried for 72 hours at
50.degree. C./10 mbar.
[0105] The polymer prepared in this manner is readily soluble in
solvents such as NMP, .gamma.-BL, cyclohexanone, cyclopentanone or
mixtures thereof.
EXAMPLE 5
Synthesis of polymer 2
[0106] 15.81 g (0.05 mol) of bisaminophenol 2 are dissolved in 200
ml of distilled NMP. A solution of 8.82 g (0.03 mol) of
dicarboxylic acid chloride 3 and 3.53 g (0.0175 mol) of
dicarboxylic acid chloride 4 in 150 ml of distilled .gamma.-BL is
added dropwise to this solution at 10.degree. C. while stirring.
Stirring is continued for a further hour at 10.degree. C. and then
for 1 hour at 20.degree. C. After further cooling to 10.degree. C.,
0.52 g (0.005 mol) of endcap 1, dissolved in 20 ml of distilled
.gamma.-BL, is added dropwise to the reaction mixture, and stirring
is carried out for 1 hour at 10.degree. C. and then for 1 hour at
20.degree. C. The reaction mixture is cooled to 10.degree. C.,
after which 9.48 g (0.12 mol) of pyridine, dissolved in 30 ml of
distilled .gamma.-BL, are added to said reaction mixture and the
latter is warmed up to room temperature and stirred for 2 hour.
[0107] Polymer 2 is isolated and worked-up analogously to example
4.
EXAMPLE 6
Synthesis of polymer 3
[0108] 25 g (0.05 mol) of bisaminophenol 1 are dissolved in 200 ml
of distilled NMP. A solution of 5.56 g (0.02 mol) of dicarboxylic
acid chloride 2 in 80 ml of distilled .gamma.-BL is added dropwise
to this solution at 10.degree. C. while stirring. Stirring is
carried out for a further hour at 10.degree. C. and then for 1 hour
at 20.degree. C. Cooling is effected at 10.degree. C. and 5.55 g
(0.0275 mol) of dicarboxylic acid chloride 4, dissolved in 80 ml of
distilled .gamma.-BL, are added dropwise. Stirring is carried out
for a further hour at 10.degree. C. and then for 1 hour at
20.degree. C. After cooling to 10.degree. C., 0.78 g (0.005 mol) of
endcap 2 dissolved in 20 ml of distilled .gamma.-BL is added
dropwise to the reaction mixture, and stirring is carried out for 1
hour at 10.degree. C. and then for 1 hour at 20.degree. C. The
reaction mixture is cooled to 10.degree. C., after which 11.85 g
(0.15 mol) of pyridine, dissolved in 50 ml of distilled .gamma.-BL,
are added and said reaction mixture is warmed up to room
temperature and stirred for 2 hours.
[0109] Polymer 3 is isolated and worked-up analogously to example
4.
EXAMPLE 7
Synthesis of polymer 4
[0110] 25 g (0.05 mol) of bisaminophenol 1 and 20 g (0.05 mol) of
bisaminophenol 5 are dissolved in 400 ml of distilled NMP. A
solution of 27.93 g (0.095 mol) of dicarboxylic acid chloride 3 in
150 ml of distilled .gamma.-BL is added dropwise to this solution
at 10.degree. C. while stirring. Stirring is continued for a
further hour at 10.degree. C. and then for 1 hour at 20.degree. C.
After further cooling to 10.degree. C., 1.64 g (0.01 mol) of endcap
3, dissolved in 20 ml of distilled .gamma.-BL, are added dropwise
to the reaction mixture and stirring is carried out for 1 hour at
10.degree. C. and then for 1 hour at 20.degree. C. The reaction
mixture is cooled to 10.degree. C., after which 19.76 g (0.25 mol)
of pyridine, dissolved in 50 ml of distilled .gamma.-BL, are added
and said reaction mixture is warmed up to room temperature and
stirred for 2 hours.
[0111] Polymer 4 is isolated and worked-up analogously to example
4.
EXAMPLE 8
Synthesis of polymer 5
[0112] 18.97 g (0.06 mol) of bisaminophenol 2 and 15.2 g (0.04 mol)
of bisaminophenol 3 are dissolved in 300 ml of distilled NMP. A
solution of 14.7 g (0.05 mol) of dicarboxylic acid chloride 3 and
13.59 g (0.045 mol) of dicarboxylic acid chloride 5, dissolved in
250 ml of distilled .gamma.-BL, are added dropwise to this solution
at 10.degree. C. while stirring. Stirring is continued for 1 hour
at 10.degree. C. and for 1 hour at 200C. After further cooling to
10.degree. C., 1.56 g (0.01 mol) of endcap 2, dissolved in 50 ml of
distilled .gamma.-BL, are added dropwise to the reaction mixture,
and stirring is carried out for 1 hour at 10.degree. C. and then
for 1 hour at 20.degree. C. The reaction mixture is cooled to
10.degree. C., after which 19.76 g (0.25 mol) of pyridine,
dissolved in 50 ml of distilled .gamma.-BL, are added and said
reaction mixture is warmed up to room temperature and stirred for 2
hours.
[0113] The isolation and working-up of polymer 5 are effected
analogously to example 4.
EXAMPLE 9
Synthesis of polymer 6
[0114] 30.01 g (0.06 mol) of bisaminophenol 1 are dissolved in 220
ml of distilled NMP. A solution of 11.11 g (0.055 mol) of
dicarboxylic acid chloride 1 in 80 ml of distilled .gamma.-BL are
added dropwise to this solution at 10.degree. C. while stirring.
Stirring is continued for 1 hour at 10.degree. C. and for 1 hour at
20.degree. C. Cooling is effected to 10.degree. C. and 15.2 g (0.04
mol) of bisaminophenol 3, dissolved in 80 ml of distilled
.gamma.-BL, are added dropwise. Stirring is continued for 1 hour at
10.degree. C. and then for 1 hour at 20.degree. C. Further cooling
is effected to 10.degree. C. and 12.08 g (0.04 mol) of dicarboxylic
acid chloride 5, dissolved in 80 ml of distilled 7-BL, are added
dropwise. Stirring is carried out for a further hour at 10.degree.
C. and then for 1 hour at 20.degree. C. After further cooling to
10.degree. C., 1.04 g (0.01 mol) of endcap 1, dissolved in 20 ml of
distilled .gamma.-BL, are added dropwise to the reaction mixture,
and stirring is carried out for 1 hour at 10.degree. C. and then
for 1 hour at 20.degree. C. The reaction mixture is cooled to
10.degree. C., after which 19.76 g (0.25 mol) of pyridine,
dissolved in 50 ml of distilled .gamma.-BL, were added and said
reaction mixture is warmed up to room temperature and stirred for 2
hours.
[0115] Polymer 6 is isolated and worked-up analogously to example
4.
EXAMPLE 10
Determination of Thermal Stabilities
[0116] All polymers described have thermal stabilities of
>480.degree. C. according to TGA investigations (apparatus: STA
1500 from Rheometric Scientific, heating rate: 5 K/min, inert gas:
argon). The isothermal mass loss per hour (at 425.degree. C.) is
<0.7%. The polymers described therefore meet the requirements
for use as insulation in microchips.
EXAMPLE 11
Preparation of Polymer Solutions
[0117] 25 g of the polymers described in examples 4 to 9 are
dissolved in 75 g of distilled NMP or distilled .gamma.-BL. The
dissolution process is expediently effected on a shaking apparatus
at room temperature. The solution is then filtered under pressure
through a 0.2 .mu.m filter into a cleaned, particle-free glass
sample tube. The viscosity of the polymer solution can be changed
by varying the dissolved mass of polymer.
EXAMPLE 12
Improvement of the Adhesion by Adhesion Promoter Solutions
[0118] 0.5 g of adhesion promoter (e.g.
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane) are dissolved
in 95 g of methanol, ethanol or isopropanol and 5 g of
demineralized water at room temperature in a cleaned, particle-free
sample tube. After standing for 24 h at room temperature, the
adhesion promoter solution is ready for use. This solution is
usable for 3 weeks at the most.
[0119] The adhesion promoter should give a monomolecular layer on
the surface of the parts to be adhesively bonded. The adhesion
promoter can expediently be applied by the spin coating technique.
For this purpose, the adhesion promoter solution is applied via a
0.2 .mu.m prefilter to the surface to be adhesively bonded and is
spun for 30 s at 5 000 rpm. A drying step is then effected for 60 s
at 100.degree. C.
EXAMPLE 13
Application of a Polymer by the Spin Coating Method and Cyclization
to Give the polybenzoxazole
[0120] A processed silicon wafer that has lands and trenches up to
a minimum dimension of, in each case, about 150 nm is coated, as
described in example 10, with an adhesion promoter. The filtered
solution of polymer 1, which was obtained according to example 11,
is then applied to the wafer by using a syringe and is uniformly
distributed using a spin coater. The spin coater speed is 2,000
rpm. The polymer is then heated on a hotplate for 1 min at
120.degree. C. and for 2 min at 200.degree. C. The coated wafer is
then heated under nitrogen or argon in an oven to 425.degree. C.
for 60 min. The polybenzoxazole thus obtained is inert to acids,
bases and organic solvents.
EXAMPLE 14
Determination of the Adhesion of the Polymers to a Titanium Nitride
Layer
[0121] A 4'' silicon wafer is sputtered with a 50 nm thick titanium
nitride layer. The solution prepared in example 11 is applied to
this wafer by spin coating, at 500 rpm for 5 s and at 2,000 rpm for
25 s. After a short softbake of 1 min at 120.degree. C. on a
hotplate, 10 silicon chips having an edge length of 4.times.4 mm2,
which had likewise been sputtered with a 50 nm thick titanium
nitride layer, are then pressed onto the polymer film with a force
of 2 N. This stack is then heated in a nitrogen atmosphere for 1 h
at 425.degree. C. in an oven. Following cooling to room
temperature, an adhesion test was carried out using a shear tester,
Dage series 400. The mean value for polymer 1 that was required for
shearing off the chips is 15.51 N/mm.sup.2.
EXAMPLE 15
Determination of the Adhesion of the Polymers to a Tantalum Nitride
Layer
[0122] The experiment carried out was the same as that described in
Example 14, but the surface of the wafer and of the chips was
formed not of titanium nitride but of tantalum nitride. The mean
value of the force for polymer 1 that was required for shearing off
the chips is 16.01 N/mm.sup.2.
EXAMPLE 16
Determination of the Adhesion of the Polymer to a Silicon
Surface
[0123] The experiment carried out is the same as that described in
Example 14, but the surface of the wafer and of the chips is formed
not of titanium nitride but of silicon. The mean value of the force
for polymer 1 that was required for shearing off the chips is 17.05
N/mm.sup.2.
EXAMPLE 17
Determination of the Adhesion of the Polymers to a Silicon Nitride
Layer
[0124] The experiment carried out is the same as that described in
Example 14, but the surface of the wafer and of the chips is not
formed of titanium nitride but of silicon nitride. The mean value
of the force for polymer 1 that was required for shearing off the
chips is 15.16 N/mm.sup.2.
EXAMPLE 18
Determination of the Adhesion of the Polymers to a Silica Layer
[0125] The experiment carried out is the same as that described in
example 14, but the surface of the wafer and of the chips is formed
not of titanium nitride but of silica. The mean value of the force
for polymer 1 that was required for shearing off the chips is 16.20
N/mm.sup.2.
EXAMPLE 19
Determination of the Adhesion of the Polymers to a Silicon Carbide
Layer
[0126] The experiment carried out is the same as that described in
Example 14, but the surface of the wafer and of the chips was not
formed of titanium nitride but of silicon carbide. The mean value
of the force for polymer 1 that was required for shearing off the
chips is 15.73 N/mm.sup.2.
EXAMPLE 20
Determination of the Adhesion of the Polymers to a Tantalum
Layer
[0127] The experiment carried out is the same as that described in
Example 14, but the surface of the wafer and of the chips was not
formed of titanium nitride but of tantalum. The mean value of the
force for polymer 1 that was required for shearing off the chips is
16.68 N/mm.sup.2.
EXAMPLE 21
Determination of the Adhesion of the Polymers to a Titanium
Layer
[0128] The experiment carried out is the same as that described in
example 14, but the surface of the wafer and of the chips were
formed not of titanium nitride but of titanium. The mean value of
the force for polymer 1 that was required for shearing off the
chips is 15.84 N/mm.sup.2.
EXAMPLE 22
Determination of the Adhesion of the Polymers to a Polyimide
Layer
[0129] The experiment carried out is the same as that described in
Example 14, but the surface of the wafer and of the chips was not
formed of titanium nitride but of polyimide. The mean value of the
force for polymer 1 that was required for shearing off the chips is
16.26 N/mm.sup.2.
EXAMPLE 23
Comparative Example for Adhesion
[0130] A polymer was prepared analogously to Example 1 of U.S. Pat.
No. 5,077,378 and a polymer solution in NMP was prepared as
described in Example 11. The adhesion of the polymer was then
determined as described in examples 14 to 22. The following mean
values were found: TABLE-US-00001 TABLE 1 Adhesion of the
comparative polymers Surface Force for shearing off (N/mm.sup.2)
Titanium nitride 14.71 Tantalum nitride 15.69 Silicon 15.21 Silicon
nitride 14.03 Silica 14.94 Silicon carbide 13.37 Tantalum 13.96
Titanium 14.07 Polyimide 13.02
EXAMPLE 24
Determination of the Chemical Stability
[0131] The polymer 1 was applied from a 20% strength solution
(solvent: NMP) to a 4'' silicon wafer by spin coating, at 500 rpm
for 5 s and at 2 000 rpm for 25 s. After a short softbake of 1 min
at 120.degree. C. and 2 min at 200.degree. C. on a hotplate, the
wafer is heated in a nitrogen atmosphere for 1 h at 400.degree. C.
in an oven. After cooling to room temperature, the coated wafer is
heated in NMP to 80.degree. C. for 5 h. Thereafter, the wafer is
dried in vacuo for 60 min at 200.degree. C. and the mass difference
is determined.
[0132] The decrease in mass is 0.8%.
EXAMPLE 25
Determination of the Dielectric Constant of Polymer 1
[0133] The dielectric constant was measured using the configuration
shown in FIG. 1. For this purpose, the polymer 1 was dissolved in
NMP (25% strength solution) and the solution was filtered under
pressure through a membrane having 0.2 .mu.M pores. This solution
was applied by spin coating to a substrate 1 on which a 600 nm
thick titanium layer 2 is already present. The layer 3 is dried at
120.degree. C. and 200.degree. C., in each case for 2 min, on a
hotplate and then heated at 430.degree. C. for one hour in a
nitrogen atmosphere. Titanium electrodes 4 are then sputtered onto
this layer 3 by using a shadow mask shown in FIG. 2. For this
purpose, the shadow mask shown in FIG. 2 includes orifices 5 which
correspond to the position of the titanium electrodes 4. The
dielectric constant is determined using the impedance spectrometer
6 and is 2.31 in the frequency range from 100 Hz to 1 MHz.
EXAMPLES 26 To 29
Determination of the Dielectric Constants of Polymers 2 to 5
[0134] The dielectric constant was determined analogously to
example 25 in polymers 2 to 5. The values found are shown in Table
2.
EXAMPLE 30
Comparative Example for Dielectric Constant
[0135] A polymer was prepared analogously to Example 1 of U.S. Pat.
No. 5,077,378 and the dielectric constant is determined as
described in example 25. The value found is likewise shown in Table
2. TABLE-US-00002 TABLE 2 Dielectric constant of various polymers
Example Polymer Dielectric constant 25 1 2.31 26 2 2.32 27 3 2.44
28 4 2.31 29 5 2.39 30 U.S. Pat. No. 5,077,378 Ex. 1 3.1
* * * * *