U.S. patent application number 16/245098 was filed with the patent office on 2020-04-30 for composite conductive polymers, preparation method and application thereof.
The applicant listed for this patent is UNIVERSITY OF ELECTRONIC SCIENCE AND TECHNOLOGY OF CHINA. Invention is credited to Yuanming CHEN, Wei HE, Yan HONG, Jiujuan Li, Chong WANG, Shouxu WANG, Dainan ZHANG, Guoyun ZHOU.
Application Number | 20200131378 16/245098 |
Document ID | / |
Family ID | 70325073 |
Filed Date | 2020-04-30 |
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United States Patent
Application |
20200131378 |
Kind Code |
A1 |
ZHOU; Guoyun ; et
al. |
April 30, 2020 |
COMPOSITE CONDUCTIVE POLYMERS, PREPARATION METHOD AND APPLICATION
THEREOF
Abstract
A composite conductive polymer, a preparation method thereof and
application thereof are disclosed, wherein a mixed solution A is
used in the preparation process of the composite conductive
polymer, which comprises the following two components: (i) a strong
oxidant selected from at least one of permanganate, persulfate,
dichromate and perchlorate; (ii) an oxidizing agent containing a
metal ion capable of being reduced to elementary substance. The
preparation process is simple and easy to operate, with low cost
and favorable environmental protection and the obtained composite
conductive polymer containing metal in elementary form, has good
film-forming property and the film thereof can completely cover the
surface of the insulating substrate, with excellent electrical
conductivity, which therefore can be widely used in electroplating
materials and semiconductor materials and other fields.
Inventors: |
ZHOU; Guoyun; (Chengdu,
CN) ; HONG; Yan; (Chengdu, CN) ; Li;
Jiujuan; (Chengdu, CN) ; HE; Wei; (Chengdu,
CN) ; CHEN; Yuanming; (Chengdu, CN) ; WANG;
Shouxu; (Chengdu, CN) ; ZHANG; Dainan;
(Chengdu, CN) ; WANG; Chong; (Chengdu,
CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
UNIVERSITY OF ELECTRONIC SCIENCE AND TECHNOLOGY OF CHINA |
Chengdu |
|
CN |
|
|
Family ID: |
70325073 |
Appl. No.: |
16/245098 |
Filed: |
January 10, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25D 21/10 20130101;
C08G 2261/3221 20130101; C25D 3/38 20130101; C25D 5/56 20130101;
C08G 2261/512 20130101; C08K 2003/0806 20130101; C09D 7/61
20180101; C08K 2003/085 20130101; C08K 2201/001 20130101; C09D
165/00 20130101; C08G 2261/3223 20130101; C08G 73/0266 20130101;
C09D 5/24 20130101; C08G 2261/43 20130101 |
International
Class: |
C09D 5/24 20060101
C09D005/24; C09D 165/00 20060101 C09D165/00; C25D 3/38 20060101
C25D003/38; C25D 5/56 20060101 C25D005/56; C25D 21/10 20060101
C25D021/10 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 24, 2018 |
CN |
201811244146.5 |
Claims
1. A composite conductive polymer comprising an elementary metal
and a polymer, and materials for synthesizing the composite
conductive polymer comprise a mixed solution A and a
monomer-containing solution for polymerization, wherein, the mixed
solution A comprises the following two components: (i) a strong
oxidant selected from at least one of permanganate, persulfate,
dichromate and perchlorate; and (ii) an oxidizing agent containing
a metal ion capable of being reduced to elementary sub stance;
wherein, the elementary metal is at least one selected from the
group consisting of Cu, Pd, Ag, Pt and Au.
2. The composite conductive polymer according to claim 1, wherein,
the permanganate, the persulphate, the dichromate or the
perchlorate is, a potassium salt or a sodium salt; the oxidizing
agent containing the metal ion capable of being reduced to the
elementary substance is at least one selected from the group
consisting of Cu salt, Pd salt, Ag salt, Pt salt, and Au salt, and
the oxidizing agent is Cu.sup.2+ salt or Ag.sup.+ salt; the mixed
solution A further comprises an acid as component (iii) and the
acid is, at least one selected from the group consisting of boric
acid, phosphoric acid, carboxyl group-containing organic acid,
sulfonic acid group-containing (--SO.sub.3H) organic acid, sulfinic
acid group-containing organic acid, and organic acid containing
sulphur carboxylic acid group (RCOSH), the acid is boric acid; and
the monomer is at least one selected from the group consisting of
pyrrole, aniline, thiophene and derivatives thereof, the monomer is
thiophene or derivatives thereof; and the derivatives of thiophene
is thiophene substituted by a C.sub.1-C.sub.10 alkyl group and/or
C.sub.1-C.sub.10 alkoxy group.
3. The composite conductive polymer according to claim 1, wherein,
a concentration of the monomer in the monomer-containing solution
is from 10 mL/L to 30 mL/L; a pH of the monomer-containing solution
can be further adjusted to 1.8 to 2.2 by using a pH-adjusting acid;
the pH-adjusting acid may be selected from the group consisting of
phosphoric acid, boric acid; the pH-adjusting acid is phosphoric
acid; a concentration of the pH-adjusting acid is, from 1 mL/L to 5
mL/L; a concentration of the component (i) in the mixed solution A
is from 0.2 wt % to 1 wt %; a concentration of the component (ii)
in the mixed solution A is, from 0.05 mol/L to 2.00 mol/L; and a
concentration of the component (iii) in the mixed solution A is,
from 5 g/L to 15 g/L.
4. A film comprising the composite conductive polymer according to
claim 1, wherein the film comprises 1.00 wt %-5.00 wt % of
elementary metal.
5. A mixed solution A, wherein, the mixed solution A comprises the
following two components: (i) a strong oxidant selected from at
least one of permanganate, persulfate, dichromate and perchlorate;
(ii) an oxidizing agent containing a metal ion capable of being
reduced to elementary substance.
6. The mixed solution A according to claim 5, wherein, the
permanganate, the persulphate, the dichromate or the perchlorate
is, a potassium salt or a sodium salt; the oxidizing agent
containing the metal ion capable of being reduced to the elementary
substance is at least one selected from the group consisting of Cu
salt, Pd salt, Ag salt, Pt salt, and Au salt; the mixed solution A
further comprises an acid as component (iii) and the acid is at
least one selected from the group consisting of boric acid,
phosphoric acid, carboxyl group-containing organic acid, sulfonic
acid group-containing (--SO.sub.3H) organic acid, sulfinic acid
group-containing organic acid, and organic acid containing sulphur
carboxylic acid group (RCOSH); a concentration of the component (i)
in the mixed solution A is from 0.2 wt % to 1 wt %; a concentration
of the component (ii) in the mixed solution A is from 0.05 mol/L to
2.00 mol/L; and a concentration of the component (iii) in the mixed
solution A is from 5 g/L to 15 g/L.
7. (canceled)
8. A method for preparing a composite conductive polymer, wherein
the method comprises the following steps: (a) providing the mixed
solution A according to claim 5 and placing an insulating substrate
in the mixed solution A; (b) placing the obtained insulating
substrate in a monomer-containing solution, and performing
polymerization of the monomer; wherein the composite conductive
polymer comprises elementary metal, and the elementary metal is at
least one selected from the group consisting of Cu, Pd, Ag, Pt and
Au.
9. The method according to claim 8, wherein the monomer is at least
one selected from the group consisting of pyrrole, aniline,
thiophene and derivatives thereof; and the derivatives of thiophene
is thiophene substituted by a C.sub.1-C.sub.10 alkyl group and/or
C.sub.1-C.sub.10 alkoxy group; in the monomer-containing solution
for polymerization, a concentration of the monomer in the
monomer-containing solution is from 10 mL/L to 30 mL/L; a pH of the
monomer-containing solution can be further adjusted to 1.8 to 2.2
by using a pH-adjusting acid; the pH-adjusting acid may be selected
from the group consisting of phosphoric acid, boric acid.
10. The method according to claim 8, wherein, in the step (a),
temperature under which the insulating substrate is placed in the
mixed solution A is from 60.degree. C. to 130.degree. C.; and a
residence time for placing is, 5-20 min; in the step (a), the
insulating substrate is placed in the mixed solution A to form an
oxide layer; in the step (b), a concentration of the thiophene
monomer is from 10 mL/L to 30 mL/L, a temperature for
polymerization of the monomer is from 15.degree. C. to 45.degree.
C., and time for polymerization of the monomer is from 2 h to 8 h;
further, a small amount of pH-adjusting acid is added to adjust a
pH of the monomer-containing solution, wherein, the pH-adjusting
acid is selected from phosphoric acid, boric acid.
11. The method according to claim 8, wherein, the method further
comprises a pretreatment step: degreasing, washing the insulating
substrate followed by plasma processing; wherein, in the degreasing
step, the degreasing liquid used is at least one selected from the
group consisting of an alkaline agent, a surfactant, and phosphate,
a mixture of sodium hydroxide, sodium dodecylbenzenesulfonate,
sodium carbonate, and trisodium phosphate with a ratio of 15-25
g/L:0.5-2 g/L:1-5 g/L:3-7 g/L; the degreasing process is carried
out at 40.degree. C.-80.degree. C. for 3-10 min, followed by
washing and drying; and the plasma process is carried out under an
atmospheric pressure of 70 pa-120 pa and with a frequency of 80
w-100 w.
12. A composite conductive polymer obtained by the preparation
method according to claim 8, wherein, the composite conductive
polymer comprises an elementary metal.
13. A method for electroplating comprising: 1) covering a substrate
with the composite conductive polymer according to claim 1; and 2)
electroplating the substrate obtained from step (1).
14. The method for electroplating according to claim 13, wherein
step (2) comprises: placing the substrate obtained from step (1) in
a plating solution, applying an electric current, electroplating
with air agitation at room temperature, and then washing and
drying; wherein, the plating solution comprises copper sulfate
pentahydrate, concentrated sulfuric acid and chloride ion, and a
concentration of the copper sulfate pentahydrate in the plating
solution is from 80 g/L to 120 g/L; a concentration of the
concentrated sulfuric acid in the plating solution is from 80 mL/L
to 120 mL/L; a density of the applied current is from 2 A/dm.sup.2
to 3 A/dm.sup.2; and time for electroplating with air inflation is
from 20 min to 50 min.
15. The composite conductive polymer according to claim 2, wherein,
a concentration of the monomer in the monomer-containing solution
is from 10 mL/L to 30 mL/L; a pH of the monomer-containing solution
can be further adjusted to 1.8 to 2.2 by using a pH-adjusting acid;
the pH-adjusting acid be selected from the group consisting of
phosphoric acid, boric acid; a concentration of the pH-adjusting
acid is from 1 mL/L to 5 mL/L; a concentration of the component (i)
in the mixed solution A is from 0.2 wt % to 1 wt %; a concentration
of the component (ii) in the mixed solution A is from 0.05 mol/L to
2.00 mol/L; and a concentration of the component (iii) in the mixed
solution A is from 5 g/L to 15 g/L.
16. A film comprising the composite conductive polymer according to
claim 2, wherein the film comprises 1.00 wt %-5.00 wt % of
elementary metal.
17. A film comprising the composite conductive polymer according to
claim 3, wherein the film comprises 1.00 wt %-5.00 wt % of
elementary metal.
18. (canceled)
19. The method according to claim 9, wherein, in the step (a),
temperature under which the insulating substrate is placed in the
mixed solution A is from 60.degree. C. to 130.degree. C.; and a
residence time for placing is 5-20 min; in the step (a), the
insulating substrate is placed in the mixed solution A to form an
oxide layer; in the step (b), a concentration of the thiophene
monomer is from 10 mL/L to 30 mL/L, a temperature for
polymerization of the monomer is from 15.degree. C. to 45.degree.
C., and time for polymerization of the monomer is from 2 h to 8 h;
further, a small amount of pH-adjusting acid is added to adjust a
pH of the monomer-containing solution, wherein, the pH-adjusting
acid is, selected from phosphoric acid, boric acid.
20. The method according to claim 9, wherein, the method further
comprises a pretreatment step: degreasing, washing the insulating
substrate followed by plasma processing; wherein, in the degreasing
step, the degreasing liquid used is at least one selected from the
group consisting of an alkaline agent, a surfactant, and phosphate,
a mixture of sodium hydroxide, sodium dodecylbenzenesulfonate,
sodium carbonate, and trisodium phosphate with a ratio of 15-25
g/L:0.5-2 g/L:1-5 g/L:3-7 g/L; the degreasing process is carried
out at 40.degree. C.-80.degree. C. for 3-10 min, followed by
washing and drying; and the plasma process is carried out under an
atmospheric pressure of 70 pa-120 pa and with a frequency of 80
w-100 w.
Description
RELATED APPLICATION
[0001] The present application claims the priority of the Chinese
Patent Application No. 201811244146.5 filed on Oct. 24, 2018, which
is incorporated herein by reference as part of the disclosure of
the present application.
TECHNICAL FIELD
[0002] Embodiments of the present disclosure relate to a composite
conductive polymer containing metal, a preparation method and
applications thereof.
BACKGROUND
[0003] Conductive polymers can be classified into composite
conductive polymers and structural conductive polymers, according
to the structure, composition and preparation method. The composite
conductive polymers is a multi-phase polymer composite material
with conductive properties prepared by using a polymer structural
material as a matrix, which is incorporated with conductive fillers
such as carbon powder and metal powder, and employing techniques
such as dispersion, layering and surface recombination. The
composite conductive polymers, with advantages of simple process,
low price and good practicality, easy to be commercially produced,
is more developed than structural conductive polymers.
[0004] At present, common synthesis methods of the composite
conductive polymers membranes mainly include electrochemical
polymerization and chemical polymerization. The composite
conductive polymers can be formed on the conductive substrates by
electrochemical polymerization, and the thickness of the resulting
film can be controlled by adjusting the current and voltage. The
electrochemical polymerization processes are complicated, costly,
restricted by demand for conductive substrates and difficult to be
applicable in large scale production, while preparation of
composite conductive polymers by chemical polymerization has the
advantages of simple preparation process, low cost and mass
production. However, the following problems often emerge in the
process of preparing the composite conductive polymers by chemical
polymerization: 1. it is difficult to avoid the use of toxic
solvents such as chloroform, toluene, tetrahydrofuran during
synthesis process; 2. an oxidant with a single component is used in
the synthesis process, resulting in long polymerization time,
generally more than 20 h; 3. the doping processes of some composite
conductors in which the dopants exist in the form of ions are
complicated and cumbersome to manipulate; 4. most of the composite
conductive polymers which are prepared by chemical polymerization
methods are solid powder and difficult to form film, thus greatly
limiting the application field of the product.
SUMMARY
[0005] Embodiments of the present disclosure provide a composite
conductive polymer comprising an elementary metal and a polymer,
and materials for synthesizing the composite conductive polymer
comprise a mixed solution A and a monomer-containing solution for
polymerization.
[0006] According to an embodiment of the present disclosure, in the
composite conductive polymer, the elementary metal is, for example,
at least one selected from the group consisting of Cu, Pd, Ag, Pt
and Au, and for example, the elementary metal is selected from Cu,
Ag.
[0007] The monomer for synthesizing the polymer is at least one
selected from the group consisting of pyrrole, aniline, thiophene
and derivatives thereof, for example, the monomer is thiophene or
derivatives thereof; and the derivatives of thiophene is, for
example, a thiophene substituted by a C.sub.1-C.sub.10 alkyl group
and/or C.sub.1-C.sub.10 alkoxy group.
[0008] The mixed solution A comprises the following two
components:
[0009] (i) a strong oxidant selected from at least one of
permanganate, persulfate, dichromate and perchlorate; wherein, the
permanganate, persulphate, dichromate or perchlorate is, for
example, a potassium salt or a sodium salt.
[0010] (ii) an oxidizing agent containing a metal ion capable of
being reduced to elementary substance; the oxidizing agent
containing the metal ion capable of being reduced to elementary
substance is at least one selected from the group consisting of Cu
salt, Pd salt, Ag salt, Pt salt and Au salt, and for example, the
oxidizing agent is Cu.sup.2+ salt or Ag.sup.+ salt, such as
CuCl.sub.2 or AgNO.sub.3.
[0011] The mixed solution A may further comprise an acid as
component (iii). The acid is, for example, at least one selected
from the group consisting of boric acid, phosphoric acid, carboxyl
group-containing organic acid, sulfonic acid group-containing
(--SO.sub.3H) organic acid, sulfinic acid group-containing organic
acid, and organic acid containing sulphur carboxylic acid group
(RCOSH), such as boric acid.
[0012] A concentration of the component (i) in the mixed solution A
is from 0.2 wt % to 1 wt %, for example, from 0.4 wt % to 0.6 wt %,
and for another example, 0.5 wt %; a concentration of the component
(ii) in the mixed solution A is, for example, from 0.05 mol/L to
2.00 mol/L, for example, from 0.10 mol/L to 1.5 mol/L, and for
another example, from 0.15 mol/L to 1.0 mol/L; and a concentration
of the component (iii) in the mixed solution A is, for example,
from 5 g/L to 15 g/L, for example, from 8 g/L to 12 g/L, and for
another example, 10 g/L.
[0013] In the monomer-containing solution for polymerization, a
concentration of the monomer is, for example, from 10 mL/L to 30
mL/L, for example, 20 mL/L; for example, a pH of the
monomer-containing solution can be further adjusted to 1.8 to 2.2
by using a pH-adjusting acid. For example, the pH is adjusted to 2.
The pH-adjusting acid may be selected from the group consisting of
phosphoric acid and boric acid. For example, the pH-adjusting acid
is phosphoric acid. A concentration of the pH-adjusting acid is,
for example, from 1 mL/L to 5 mL/L.
[0014] Embodiments of the present disclosure further provide a film
comprising the above composite conductive polymer. The square
resistance of the film is from 500.OMEGA./.quadrature. to
3.times.10.sup.3.OMEGA./.quadrature.; A metal content of the film
is from 1.00 wt % to 5.00 wt %, for example, from 1.50 wt % to 4.50
wt %, and for example, 2.00.+-.0.50 wt %, 3.00.+-.0.50 wt %, or
4.00.+-.0.50 wt %.
[0015] An embodiment of the present disclosure further provides a
mixed solution A. The mixed solution A is as defined above.
[0016] An embodiment of the present disclosure further provides use
of the mixed solution A for preparing a metal-containing composite
conductive polymer and a film thereof. The metal-containing
composite conductive polymer is the composite conductive polymer as
defined above, and the metal-containing composite conductive
polymer film is the film of the composite conductive polymer as
defined above.
[0017] In another aspect, an embodiment of the present disclosure
provides a method for preparing a composite conductive polymer,
which comprises:
[0018] (a) providing the above mixed solution A and placing an
insulating substrate in the mixed solution A;
[0019] (b) placing the obtained insulating substrate in a
monomer-containing solution and performing polymerization of the
monomer.
[0020] According to an embodiment of the present disclosure, the
method comprises the steps of:
[0021] (a) placing the insulating substrate in the mixed solution A
to form an oxide layer on the insulating substrate, washing and
drying the insulating substrate;
[0022] (b) placing the obtained insulating substrate in the
monomer-containing solution and performing polymerization of the
monomer, to form metal-containing composite conductive polymer on
the insulating substrate, washing and drying the insulating
substrate.
[0023] According to an embodiment of the present disclosure, in the
composite conductive polymer, the metal exists in elementary form,
for example, the metal is at least one selected from the group
consisting of Cu, Pd, Ag, Pt and Au, for example, the elementary
metal is selected from Cu, Ag.
[0024] The insulating substrate is selected from an insulating
material such as resin, rubber, glass, polyimide (PI) or
polyethylene terephthalate (PET). The monomer is, for example, at
least one selected from the group consisting of pyrrole, aniline,
thiophene and derivatives thereof, for example, the monomer is
thiophene or derivatives thereof, and the derivatives of thiophene
are, for example, thiophene substituted by a C.sub.1-C.sub.10 alkyl
group and/or C.sub.1-C.sub.10 alkoxy group.
[0025] According to an embodiment of the present disclosure, the
mixed solution A comprises the following two components:
[0026] (i) a strong oxidant selected from at least one of
permanganate, persulfate, dichromate and perchlorate; (ii) an
oxidizing agent containing a metal ion capable of being reduced to
elementary substance; wherein, the permanganate, the persulphate,
the dichromate or the perchlorate is, for example, a potassium salt
or a sodium salt. The oxidizing agent containing a metal ion
capable of being reduced to elementary substance is at least one
selected from the group consisting of Cu salt, Pd salt, Ag salt, Pt
salt and Au salt, and for example, the oxidizing agent is Cu.sup.2+
salt or Ag.sup.+ salt, such as CuCl.sub.2, or AgNO.sub.3. The mixed
solution A may further comprise an acid as component (iii).
[0027] A concentration of the component (i) in the mixed solution A
is from 0.2 wt % to 1 wt %, for example, from 0.4 wt % to 0.6 wt %,
and for another example, 0.5 wt %; a concentration of the component
(ii) in the mixed solution A is, for example, from 0.05 mol/L to
2.00 mol/L, for example, from 0.10 mol/L to 1.5 mol/L, and for
another example, from 0.15 mol/L to 1.0 mol/L. For example, the
concerntration of the component (ii) can be 0.30 mol/L, 0.4 mol/L,
0.5 mol/L, 0.6 mol/L or 0.70 mol/L; and a concentration of the
component (iii) in the mixed solution A is, for example, from 5 g/L
to 15 g/L, for example, from 8 g/L to 12 g/L, and for another
example, 10 g/L.
[0028] According to an embodiment of the present disclosure, in the
step (a), a temperature under which the insulating substrate is
placed in the mixed solution A is from 60.degree. C. to 130.degree.
C. For example, the temperature is from 80.degree. C. to
110.degree. C., from 85.degree. C. to 95.degree. C., and 90.degree.
C.; and a time for placing is, for example, 5 min-20 min, for
example 6 min-15 min, and for example 10 min. In the step (a), the
insulating substrate is placed in the mixed solution A to form an
oxide layer.
[0029] According to an embodiment of the present disclosure, in the
step (b), a concentration of the thiophene monomer is from 10 mL/L
to 30 mL/L, for example, 20 mL/L, a temperature for polymerization
of the monomer is from 15.degree. C. to 45.degree. C., for example
at room temperature, and a time for polymerization of the monomer
is from 2 h to 8 h, for example from 3 h to 6 h, for example 4 h.
Further, a small amount of pH-adjusting acid is added to adjust a
pH of the solution for polymerization. The pH-adjusting acid is,
for example, selected from phosphoric acid and boric acid. For
example, the acid is phosphoric acid with a concentration from 1
mL/L to 5 mL/L.
[0030] According to an embodiment of the present disclosure, the
method further comprises a pretreatment step (step before the step
(a)): degreasing, washing the insulating substrate followed by
plasma processing. In the degreasing step, the degreasing liquid
used is at least one selected from the group consisting of an
alkaline agent, a surfactant, and a phosphate. For example, the
degreasing liquid is a mixture of sodium hydroxide, sodium
dodecylbenzenesulfonate, sodium carbonate, and trisodium phosphate.
A ratio of the above components in the mixture is, for example,
15-25 g/L: 0.5-2 g/L: 1-5 g/L: 3-7 g/L; for example 20 g/L: 1 g/L:
3 g/L: 5 g/L; for example, the degreasing process is carried out at
40.degree. C.-80.degree. C. (for example, 40.degree. C.-60.degree.
C.) for 3 min-30 min (for example, 3 min-10 min) followed by
washing and drying. The plasma process is carried out under
atmospheric pressure of 70 pa-120 pa and with a frequency of 80
w-100 w. For example, the pressure is 90 pa, and the frequency is
90 w.
[0031] An embodiment of the present disclosure further provides a
composite conductive polymer obtained by the above preparation
methods, comprising an elementary metal. An embodiment of the
present disclosure further provides use of the metal-containing
composite conductive polymer in electroplating.
[0032] In another aspect, an embodiment of the present disclosure
provides a method for electroplating, which comprises:
electroplating a substrate covered with the composite conductive
polymer.
[0033] According to an embodiment of the present disclosure, the
electroplating method comprises: placing a substrate covered with
the composite conductive polymer in a plating solution, applying
electric current, electroplating with air agitation at room
temperature, and then washing and drying.
[0034] The plating solution comprises copper sulfate pentahydrate,
concentrated sulfuric acid and chloride ion, and a concentration of
the copper sulfate pentahydrate in the plating solution is from 80
g/L to 120 g/L, for example, from 90 g/L to 110 g/L, and for
example, 100 g/L; a concentration of concentrated sulfuric acid in
the plating solution is from 80 mL/L to 120 mL/L, for example, from
90 mL/L to 110 mL/L, for example, 100 mL/L.
[0035] A density of the applied current is from 2 A/dm.sup.2 to 3
A/dm.sup.2, for example 2.5 A/dm.sup.2; and time for electroplating
with air inflation is, for example, 20 min-50 min, for example 25
min-35 min, for example 30 min.
[0036] The beneficial effects of the disclosure are as follows:
[0037] 1. The composite conductive polymer synthesized by
embodiments of the present disclosure, containing elementary metal,
has good film-forming property and the film obtained can completely
cover the surface of the insulating substrate, with a square
resistance from 500.OMEGA./.quadrature. to
3.times.10.sup.3.OMEGA./.quadrature. and excellent electrical
conductivity, which therefore can be widely used in electroplating
materials and semiconductor materials and other fields.
[0038] 2. The mixed solution A employed in embodiments of the
present disclosure contributes to synchronization of polymerization
and metal element formation, and enables short time to produce a
composite conductive polymer.
[0039] 3. The preparation process of embodiments of the present
disclosure enables a composite conductive polymer film to grow on
all kinds of insulating materials.
[0040] 4. The preparation process of the composite conductive
polymer according to embodiments of the present disclosure is
simple and easy to operate, with low cost, during which, the
solution employed in the polymerization reaction, without any toxic
organic solvent, can be reused, thus is environment-friendly
synthesis process for materials.
BRIEF DESCRIPTION OF THE DRAWINGS
[0041] FIG. 1 is a physical view of an original insulating
substrate;
[0042] FIG. 2 is a physical view of the sample of FIG. 1 covered by
a copper-containing conductive polythiophene, following the
proceedings of example 1;
[0043] FIG. 3 is an XRD pattern of the sample of FIG. 2;
[0044] FIG. 4 is a physical view of the sample of FIG. 2 plated
with copper.
DETAILED DESCRIPTION
[0045] The preparation method of the present invention will be
further described in detail below with reference to specific
examples. It is understood that the following examples are merely
illustrative of the invention and are not to be construed as
limiting the scope of the invention. The technology implemented
based on the above description of the present invention is intended
to be within the scope of the present invention. The experimental
methods used in the following examples are all conventional methods
unless otherwise specified; The reagents, materials and the like
used in the following examples are commercially available unless
otherwise specified.
Example 1: Preparation of Composite Conductive Polymer
[0046] An insulating substrate (epoxy resin substrate, as shown in
FIG. 1), after reacting with a degreasing solution (a mixture of 20
g/L sodium hydroxide, 1 g/L sodium dodecylbenzene sulfonate, 3 g/L
sodium carbonate and 5 g/L of trisodium phosphate) at 50.degree. C.
for 5 minutes, was washed and dried. Then, the degreased insulating
substrate was subjected to air plasma treatment at room temperature
for 5 minutes, under a pressure of 90 Pa, and a frequency of 90 W.
Subsequently, the treated insulating substrate was immersed in a
mixture of 0.5 wt % potassium permanganate, 0.1 mol/L
CuCl.sub.2.2H.sub.2O and 10 g/L boric acid at 90.degree. C. for 10
min to form an oxide layer on the insulating substrate, which was
then washed and dried. After that, the insulating substrate was
immersed in a solution containing 20 mL/L of thiophene monomer for
polymerization at room temperature (the solution for polymerization
was purchased from Guangdong Guanghua Technology Co., Ltd., code
2303), added with 3 mL/L of phosphoric acid to adjust the pH value
of the solution for polymerization, followed by reacting for 4
hours to obtain a copper-containing conductive polythiophene on the
insulating substrate, and then washed and naturally dried.
[0047] The copper-containing conductive polythiophene obtained by
the polymerization of example 1 is shown in FIG. 2. By comparing
FIG. 1 and FIG. 2, it can be seen that the copper-containing
polythiophene film prepared by the embodiment of the present
disclosure has good coverage property. Information about the
crystal face of the elementary copper contained in the product is
detected by XRD, which shows a face-centered cubic structure (see
FIG. 3).
[0048] The obtained copper-containing polythiophene film was
subjected to a four-probe detector to measure the square resistance
to characterize its electrical conductivity, and the measured
square resistance is 1.83.times.10.sup.3.OMEGA./.quadrature.. In
addition to this, a content of copper in the copper-containing
polythiophene film was measured by XPS to be 1.68 wt %.
Example 2: Preparation of the Substrate Plated with Copper
[0049] A substrate grown with a copper-containing conductive
polythiophene was immersed in a plating solution comprising 100 g/L
of copper sulfate pentahydrate, 100 mL/L of concentrated sulfuric
acid, and 60 mg/L of chloride ion, applied a current of 2.5
A/dm.sup.2, plated with air agitation for 30 minutes at room
temperature, and taken out for washing and drying. The copper
conductive layer was evenly covered on the substrate, which was as
shown in FIG. 4, and it can be seen that the copper-containing
conductive polythiophene film prepared by the present embodiment
has excellent properties suitable for electroplating
application.
Example 3: Preparation of Composite Conductive Polymer
[0050] The composite conductive polymer was prepared referring to
example 1, under the same conditions as example 1 except that the
concentration of CuCl.sub.2.2H.sub.2O was changed to 0.5 mol/L.
Finally, a copper-containing conductive polythiophene film on the
surface of the substrate was obtained.
[0051] The square resistance of the film is 590.OMEGA./.quadrature.
and the copper content of the film is 3.57 wt %.
Example 4 Preparation of Composite Conductive Polymer
[0052] The composite conductive polymer was prepared referring to
example 1, under the same conditions as example 1 except that 0.1
mol/L AgNO.sub.3 was used instead of CuCl.sub.2.2H.sub.2O. Finally,
a silver-containing conductive polythiophene film on the surface of
the substrate was obtained.
[0053] The square resistance of the film is
1.36.times.10.sup.3.OMEGA./and the copper content of the film is
2.02 wt %.
[0054] The embodiments of the present disclosure have been
described above. However, the present invention is not limited to
the above embodiments. Any modifications, equivalent substitutions,
improvements, etc., made within the spirit and scope of the
invention are intended to be included within the scope of the
present invention.
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