CN113248767B - Bending-resistant thermoelectric thin film and preparation method thereof - Google Patents
Bending-resistant thermoelectric thin film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000005452 bending Methods 0.000 title claims abstract description 22
- 239000010409 thin film Substances 0.000 title description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000004544 sputter deposition Methods 0.000 claims abstract description 32
- 229920001721 polyimide Polymers 0.000 claims abstract description 29
- 239000004642 Polyimide Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002899 Bi2Te3 Inorganic materials 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- -1 hexafluoro dianhydride Chemical compound 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims abstract description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007781 pre-processing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000002791 soaking Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000013598 vector Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000005676 thermoelectric effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a bending-resistant thermoelectric film and a preparation method thereof, belonging to the technical field of thermoelectric materials. The method comprises the following steps: s11, 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine reacts with hexafluoro dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride and then reacts with acetic anhydride and triethylamine in a solvent; s12, precipitating, centrifuging and drying to obtain polyimide; s13, dissolving the polyimide in a solvent, defoaming in vacuum, casting a glass plate, heating to remove the solvent, and stripping to obtain a film; s14, preprocessing the film; s15, sputtering N-type Bi2Te 3. According to the preparation method of the bending-resistant thermoelectric film, the polyimide film is used as a substrate, and the N-type Bi2Te3 is sputtered by adopting a magnetron sputtering method, so that the obtained thermoelectric film has good thermoelectric performance and bending resistance.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a bending-resistant thermoelectric thin film and a preparation method thereof.
Background
The thermoelectric material is a functional material capable of converting thermal energy and electric energy into each other, and the seebeck effect discovered in 1823 and the peltier effect discovered in 1834 provide theoretical bases for applications of thermoelectric energy converters and thermoelectric refrigeration.
The thermoelectric material can directly convert temperature difference into electric energy, and has the potential of energy conservation and emission reduction in daily life and industrial production. Most of the current studies on the thermoelectric conversion efficiency of thermoelectric materials are one of the key factors limiting the applications of the thermoelectric materials. The thermoelectric thin film material has high thermoelectric conversion efficiency and wide applicability in various devices. The application of the thermoelectric thin film substrate such as quartz glass and magnesium oxide is limited due to the relatively poor bending property.
Disclosure of Invention
In order to solve the above problems, the present invention proposes a thermoelectric thin film material of a flexible substrate.
The first aspect of the present invention discloses a method for producing a bending-resistant thermoelectric thin film, comprising the steps of:
s11, 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine reacts with hexafluoro dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride and then reacts with acetic anhydride and triethylamine in a solvent;
s12, precipitating, centrifuging and drying to obtain polyimide;
s13, dissolving the polyimide in a solvent, defoaming in vacuum, casting a glass plate, heating to remove the solvent, and stripping to obtain a film;
s14, preprocessing the film;
s15, sputtering N-type Bi2Te 3.
In some embodiments of the invention, in S11, the solvent is N, N-dimethylformamide.
In some embodiments of the present invention, in S11, the weight ratio of the 2,2 '-bis-trifluoromethyl-4, 4' -biphenyldiamine to the hexafluorodianhydride, the 3,3',4,4' -biphenyltetracarboxylic dianhydride, the acetic anhydride, and the triethylamine is (8.6-9.0): (7.2-7.4): (3.1-3.3): (11.0-11.5): (5.5-5.8), preferably 8.8:7.3:3.2:11.2: 5.6.
In some embodiments of the invention, in S12, the precipitation is a precipitate after mixing with absolute ethanol.
In some embodiments of the present invention, in S13, the polyimide is dissolved in dimethylacetamide, and the weight volume percentage of the polyimide is 0.01% to 0.6%, preferably 0.1% to 0.3%, and more preferably 0.25%.
In some embodiments of the present invention, in S14, the pretreatment is hydrogen peroxide soaking and acetone-absolute ethyl alcohol mixed liquor soaking, and preferably, the volume ratio of the acetone-absolute ethyl alcohol mixed liquor is 1: 1.
In some embodiments of the invention, the sputtering of N-type Bi2Te3 in S15 is performed at room temperature and in a vacuum of less than 5 × 10-4Pa, argon flow of 150-250sccm, argon pressure of 0.6-1.0Pa, DC sputtering power of 10-20W, target-substrate distance of 15-30mm, and deposition time of 0.5-2 h.
In some embodiments of the present invention, in S14, the soaking time T1 of the acetone-absolute ethanol mixed solution is determined by the following method:
wherein, a is the time of soaking in hydrogen peroxide and is 10-60min, K is the volume ratio of acetone to absolute ethyl alcohol in the adopted acetone-absolute ethyl alcohol mixed solution, Ki is the volume ratio of acetone to absolute ethyl alcohol in the standard acetone-absolute ethyl alcohol mixed solution and is (0.8-1.2): (0.8-1.2) and b is an adjustment coefficient in
When the ratio is 0.8-0.9; in that
In this case, the ratio is 1.1-1.2.
In some embodiments of the present invention, S13 further comprises stirring the polyimide dissolved in dimethylacetamide:
s21, taking 20 samples of the dimethylacetamide mixed solution of polyimide with the same concentration, stirring the samples according to a preset stirring time agent with the minimum value within the stirring time range and a fixed interval larger than the minimum value, measuring the viscosity, and recording the viscosity as vectors X1 and X2;
s22, calculating the homogeneity of X1 and X2 by:
if both t1 and t2 are greater than-1.35, determining the minimum value in the preset stirring time range as the stirring time;
if one of t1 and t2 is less than-1.35, repeating S21 and S22, stirring the stirring time agent which is one fixed interval and two fixed intervals larger than the minimum value in the preset stirring time range, and measuring the viscosity until t1 and t2 are both more than-1.35.
A second aspect of the present invention is to disclose the bend resistant thermoelectric film produced by the method of the first aspect.
The beneficial technical effects of the invention are as follows:
(1) according to the preparation method of the bending-resistant thermoelectric film, the polyimide film is used as a substrate, and the N-type Bi2Te3 is sputtered by adopting a magnetron sputtering method, so that the obtained thermoelectric film has good thermoelectric performance and bending resistance.
(2) In the exploration of the preparation method of the bending-resistant thermoelectric film, the Seebeck coefficient of the obtained thermoelectric film can be remarkably improved by soaking the polyimide film in hydrogen peroxide and acetone-absolute ethyl alcohol mixed solution before sputtering.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. The examples and comparative examples were, unless otherwise specified, parallel tests in which the components, the component contents, the production steps, and the production parameters were the same.
Example 1
A preparation method of a bending-resistant thermoelectric film comprises the following steps:
(1) preparation of the substrate:
a, reaction: adding 8.8g of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine into 100ml of N, N-dimethylformamide, stirring for dissolving, adding 7.3g of hexafluoro dianhydride and 3.2g of 3,3',4,4' -biphenyltetracarboxylic dianhydride, reacting for 10 hours, adding 11.2g of acetic anhydride and 5.6g of triethylamine, and reacting for 10 hours;
b, separation: adding the reaction solution into 100ml of absolute ethyl alcohol, precipitating, centrifuging and drying;
c, film preparation: preparing a dimethylacetamide solution of polyimide according to the proportion of 0.1% (w/v), defoaming in vacuum, casting a glass plate, heating to remove a solvent, and stripping to obtain a film;
d, pretreatment: soaking the film in hydrogen peroxide for 10min, drying, soaking in acetone-absolute ethyl alcohol mixed solution with the volume ratio of 1:1 for 10min, drying, washing with deionized water for 3 times, and drying;
(2) sputtering N type Bi2Te3
Sputtering is carried out at room temperature and the vacuum degree is less than 5 multiplied by 10-4Pa, argon flow of 200sccm, argon pressure of 0.8Pa, direct-current sputtering power of 15W, target-substrate distance of 20mm, and deposition time of 1 h.
Example 2
A preparation method of a bending-resistant thermoelectric film comprises the following steps:
(1) preparation of the substrate:
a, reaction: adding 8.8g of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine into 100ml of N, N-dimethylformamide, stirring for dissolving, adding 7.3g of hexafluoro dianhydride and 3.2g of 3,3',4,4' -biphenyltetracarboxylic dianhydride, reacting for 10 hours, adding 11.2g of acetic anhydride and 5.6g of triethylamine, and reacting for 10 hours;
b, separation: adding the reaction solution into 100ml of absolute ethyl alcohol, precipitating, centrifuging and drying;
c, film preparation: preparing a dimethylacetamide solution of polyimide according to the proportion of 0.2% (w/v), defoaming in vacuum, casting a glass plate, heating to remove a solvent, and stripping to obtain a film;
d, pretreatment: soaking the film in hydrogen peroxide for 10min, drying, soaking in acetone-absolute ethyl alcohol mixed solution with the volume ratio of 1:1 for 10min, drying, washing with deionized water for 3 times, and drying;
(2) sputtering N type Bi2Te3
Sputtering is carried out at room temperature and the vacuum degree is less than 5 multiplied by 10-4Pa, argon flow of 200sccm, argon pressure of 0.8Pa, direct-current sputtering power of 15W, target-substrate distance of 20mm, and deposition time of 1 h.
Example 3
A preparation method of a bending-resistant thermoelectric film comprises the following steps:
(1) preparation of the substrate:
a, reaction: adding 8.8g of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine into 100ml of N, N-dimethylformamide, stirring for dissolving, adding 7.3g of hexafluoro dianhydride and 3.2g of 3,3',4,4' -biphenyltetracarboxylic dianhydride, reacting for 10 hours, adding 11.2g of acetic anhydride and 5.6g of triethylamine, and reacting for 10 hours;
b, separation: adding the reaction solution into 100ml of absolute ethyl alcohol, precipitating, centrifuging and drying;
c, film preparation: preparing a dimethylacetamide solution of polyimide according to the proportion of 0.25% (w/v), defoaming in vacuum, casting a glass plate, heating to remove a solvent, and stripping to obtain a film;
d, pretreatment: soaking the film in hydrogen peroxide for 10min, drying, soaking in acetone-absolute ethyl alcohol mixed solution with the volume ratio of 1:1 for 10min, drying, washing with deionized water for 3 times, and drying;
(2) sputtering N type Bi2Te3
Sputtering is carried out at room temperature and the vacuum degree is less than 5 multiplied by 10-4Stream of Pa, argonThe amount of the target material is 200sccm, the argon gas pressure is 0.8Pa, the direct current sputtering power is 15W, the distance between the target material and the substrate is 20mm, and the deposition time is 1 h.
Example 4
A preparation method of a bending-resistant thermoelectric film comprises the following steps:
(1) preparation of the substrate:
a, reaction: adding 8.8g of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine into 100ml of N, N-dimethylformamide, stirring for dissolving, adding 7.3g of hexafluoro dianhydride and 3.2g of 3,3',4,4' -biphenyltetracarboxylic dianhydride, reacting for 10 hours, adding 11.2g of acetic anhydride and 5.6g of triethylamine, and reacting for 10 hours;
b, separation: adding the reaction solution into 100ml of absolute ethyl alcohol, precipitating, centrifuging and drying;
c, film preparation: preparing a dimethylacetamide solution of polyimide according to the proportion of 0.3% (w/v), defoaming in vacuum, casting a glass plate, heating to remove a solvent, and stripping to obtain a film;
d, pretreatment: soaking the film in hydrogen peroxide for 10min, drying, soaking in acetone-absolute ethyl alcohol mixed solution with the volume ratio of 1:1 for 10min, drying, washing with deionized water for 3 times, and drying;
(2) sputtering N type Bi2Te3
Sputtering is carried out at room temperature and the vacuum degree is less than 5 multiplied by 10-4Pa, argon flow of 200sccm, argon pressure of 0.8Pa, direct-current sputtering power of 15W, target-substrate distance of 20mm, and deposition time of 1 h.
Example 5
A preparation method of a bending-resistant thermoelectric film comprises the following steps:
(1) preparation of the substrate:
a, reaction: adding 8.8g of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine into 100ml of N, N-dimethylformamide, stirring for dissolving, adding 7.3g of hexafluoro dianhydride and 3.2g of 3,3',4,4' -biphenyltetracarboxylic dianhydride, reacting for 10 hours, adding 11.2g of acetic anhydride and 5.6g of triethylamine, and reacting for 10 hours;
b, separation: adding the reaction solution into 100ml of absolute ethyl alcohol, precipitating, centrifuging and drying;
c, film preparation: preparing a dimethylacetamide solution of polyimide according to the proportion of 0.01% (w/v), defoaming in vacuum, casting a glass plate, heating to remove a solvent, and stripping to obtain a film;
d, pretreatment: soaking the film in hydrogen peroxide for 10min, drying, soaking in acetone-absolute ethyl alcohol mixed solution with the volume ratio of 1:1 for 10min, drying, washing with deionized water for 3 times, and drying;
(2) sputtering N type Bi2Te3
Sputtering is carried out at room temperature and the vacuum degree is less than 5 multiplied by 10-4Pa, argon flow of 200sccm, argon pressure of 0.8Pa, direct-current sputtering power of 15W, target-substrate distance of 20mm, and deposition time of 1 h.
Example 6
A preparation method of a bending-resistant thermoelectric film comprises the following steps:
(1) preparation of the substrate:
a, reaction: adding 8.8g of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine into 100ml of N, N-dimethylformamide, stirring for dissolving, adding 7.3g of hexafluoro dianhydride and 3.2g of 3,3',4,4' -biphenyltetracarboxylic dianhydride, reacting for 10 hours, adding 11.2g of acetic anhydride and 5.6g of triethylamine, and reacting for 10 hours;
b, separation: adding the reaction solution into 100ml of absolute ethyl alcohol, precipitating, centrifuging and drying;
c, film preparation: preparing a dimethylacetamide solution of polyimide according to the proportion of 0.6% (w/v), defoaming in vacuum, casting a glass plate, heating to remove a solvent, and stripping to obtain a film;
d, pretreatment: soaking the film in hydrogen peroxide for 10min, drying, soaking in acetone-absolute ethyl alcohol mixed solution with the volume ratio of 1:1 for 10min, drying, washing with deionized water for 3 times, and drying;
(2) sputtering N type Bi2Te3
Sputtering is carried out at room temperature and the vacuum degree is less than 5 multiplied by 10-4Pa, argon flow of 200sccm, argon pressure of 0.8Pa, direct-current sputtering power of 15W, target-substrate distance of 20mm, and deposition time of 1 h.
Example 7
A method for manufacturing a bending-resistant thermoelectric film, which is different from example 1 in that, in S14, the time T1 for soaking in the acetone-absolute ethyl alcohol mixed solution is determined by the following method:
wherein, a is the time of soaking in hydrogen peroxide and is 10-60min, K is the volume ratio of acetone to absolute ethyl alcohol in the adopted acetone-absolute ethyl alcohol mixed solution, Ki is the volume ratio of acetone to absolute ethyl alcohol in the standard acetone-absolute ethyl alcohol mixed solution and is (0.8-1.2): (0.8-1.2) and b is an adjustment coefficient in
When the ratio is 0.8-0.9; in that
In this case, the ratio is 1.1-1.2.
In research, the soaking time of the film substrate in the acetone-absolute ethyl alcohol mixed solution is related to the soaking time of hydrogen peroxide and the volume ratio of acetone to absolute ethyl alcohol in the acetone-absolute ethyl alcohol mixed solution. The soaking time of the acetone-absolute ethyl alcohol mixed solution determined by the method of the embodiment can not only effectively pretreat the film substrate, but also prevent the damage to the microstructure on the surface of the film substrate.
Example 8
A method for preparing a bending-resistant thermoelectric film, which is different from example 1 in that, in S13, the method further comprises the step of stirring the polyimide dissolved in dimethylacetamide:
s21, taking 20 samples of the dimethylacetamide mixed solution of polyimide with the same concentration, stirring the samples according to a preset stirring time agent with the minimum value within the stirring time range and a fixed interval larger than the minimum value, measuring the viscosity, and recording the viscosity as vectors X1 and X2;
s22, calculating the homogeneity of X1 and X2 by:
if both t1 and t2 are greater than-1.35, determining the minimum value in the preset stirring time range as the stirring time;
if one of t1 and t2 is less than-1.35, repeating S21 and S22, stirring the stirring time agent which is one fixed interval and two fixed intervals larger than the minimum value in the preset stirring time range, and measuring the viscosity until t1 and t2 are both more than-1.35.
The preset stirring time range can be 10-20min under mechanical stirring of 300-500rmp, and the fixed interval can be 30s or 1 min.
In the research, the concentration of the polyimide in the step of dissolving the polyimide in the dimethylacetamide has a significant influence on the thermoelectric effect (Seebeck coefficient) of the obtained thermoelectric thin film. The minimum stirring time at a fixed stirring speed determined by the method of this example ensures sufficient uniformity of the mixed liquid, eliminating inhomogeneities in the thickness of the resulting thin film due to insufficient stirring.
Comparative example 1
A preparation method of a bending-resistant thermoelectric film comprises the following steps:
(1) preparation of the substrate:
a, reaction: adding 8.8g of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine into 100ml of N, N-dimethylformamide, stirring for dissolving, adding 7.3g of hexafluoro dianhydride and 3.2g of 3,3',4,4' -biphenyltetracarboxylic dianhydride, reacting for 10 hours, adding 11.2g of acetic anhydride and 5.6g of triethylamine, and reacting for 10 hours;
b, separation: adding the reaction solution into 100ml of absolute ethyl alcohol, precipitating, centrifuging and drying;
c, film preparation: preparing a dimethylacetamide solution of polyimide according to the proportion of 1% (w/v), defoaming in vacuum, casting a glass plate, heating to remove a solvent, and stripping to obtain a film;
d, pretreatment: soaking the film in an acetone-absolute ethyl alcohol mixed solution with the volume ratio of 1:1 for 10min, drying, washing with deionized water for 3 times, and drying;
(2) sputtering N type Bi2Te3
Sputtering is carried out at room temperature and the vacuum degree is less than 5 multiplied by 10-4Pa, argon flow of 200sccm, argon pressure of 0.8Pa, direct-current sputtering power of 15W, target-substrate distance of 20mm, and deposition time of 1 h.
Comparative example 2
A preparation method of a bending-resistant thermoelectric film comprises the following steps:
(1) preparation of the substrate:
a, reaction: adding 8.8g of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine into 100ml of N, N-dimethylformamide, stirring for dissolving, adding 7.3g of hexafluoro dianhydride and 3.2g of 3,3',4,4' -biphenyltetracarboxylic dianhydride, reacting for 10 hours, adding 11.2g of acetic anhydride and 5.6g of triethylamine, and reacting for 10 hours;
b, separation: adding the reaction solution into 100ml of absolute ethyl alcohol, precipitating, centrifuging and drying;
c, film preparation: preparing a dimethylacetamide solution of polyimide according to the proportion of 1% (w/v), defoaming in vacuum, casting a glass plate, heating to remove a solvent, and stripping to obtain a film;
d, pretreatment: soaking the film in hydrogen peroxide for 10min, drying, washing with deionized water for 3 times, and drying;
(2) sputtering N type Bi2Te3
Sputtering is carried out at room temperature and the vacuum degree is less than 5 multiplied by 10-4Pa, argon flow of 200sccm, argon pressure of 0.8Pa, direct-current sputtering power of 15W, target-substrate distance of 20mm, and deposition time of 1 h.
Examples of the experiments
The Seebeck coefficient was measured at room temperature using a standard four-stage method for the thermoelectric thin films obtained in examples and comparative examples. The maximum 90 ° number of bends with a change in resistance of less than 15% was examined. The results are shown in Table 1.
TABLE 1 Seebeck coefficient of thermoelectric film
| Seebeck coefficient/uVK-1 | Maximum number of bends | |
| Example 1 | 1.21d | 96a |
| Example 2 | 1.48e | 102b |
| Example 3 | 1.53f | 106b |
| Example 4 | 1.19d | 107b |
| Example 5 | 1.09 c | 92a |
| Example 6 | 1.12c | 114c |
| Comparison ofExample 1 | 0.92 b | 98a |
| Comparative example 2 | 0.64 a | 95a |
In the same column of data, the marked different lower case letters indicate that the difference is significant, and P is less than 0.05
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (8)
1. A preparation method of a bending-resistant thermoelectric film is characterized by comprising the following steps:
s11, 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldiamine reacts with hexafluoro dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride and then reacts with acetic anhydride and triethylamine in a solvent;
s12, precipitating, centrifuging and drying to obtain polyimide;
s13, dissolving the polyimide in a solvent, defoaming in vacuum, casting a glass plate, heating to remove the solvent, and stripping to obtain a film;
s14, preprocessing the film;
s15, sputtering N-type Bi2Te 3;
wherein the pretreatment comprises hydrogen peroxide soaking and acetone-absolute ethyl alcohol mixed liquor soaking, and the volume ratio of the acetone-absolute ethyl alcohol mixed liquor is 1: 1.
2. The method according to claim 1, wherein the solvent in S11 is N, N-dimethylformamide.
3. The method of claim 1, wherein in S11, the weight ratio of 2,2 '-bistrifluoromethyl-4, 4' -biphenyldiamine to hexafluorodianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, acetic anhydride, and triethylamine is (8.6-9.0): (7.2-7.4): (3.1-3.3): (11.0-11.5): (5.5-5.8).
4. The method according to claim 1, wherein in S12, the precipitation is carried out by mixing with absolute ethanol.
5. The method according to claim 1, wherein in S13, the polyimide is dissolved in dimethylacetamide, and the weight volume percentage of the polyimide is 0.01-0.6%.
6. The method of claim 1, wherein the sputtering of N-type Bi2Te3 in S15 is performed at room temperature and vacuum degree of less than 5 x 10-4Pa, argon flow of 150-250sccm, argon pressure of 0.6-1.0Pa, DC sputtering power of 10-20W, target-substrate distance of 15-30mm, and deposition time of 0.5-2 h.
7. The method of claim 1, wherein in S14, the soaking time T1 of the acetone-absolute ethanol mixture is determined by the following method:
wherein, a is the time of soaking in the hydrogen peroxide and is 10-60min, K is the volume ratio of acetone to absolute ethyl alcohol in the adopted acetone-absolute ethyl alcohol mixed solution, Ki is the volume ratio of acetone to absolute ethyl alcohol in the standard acetone-absolute ethyl alcohol mixed solution and is (0.8-1.2) to (0.8-1.2), b is an adjusting coefficient, and
when it is 0.8-0.9; in that
In this case, the ratio is 1.1-1.2.
8. The method as claimed in claim 1, wherein the step of stirring the polyimide dissolved in dimethylacetamide is further included in S13:
s21, taking 20 samples of the dimethylacetamide mixed solution of polyimide with the same concentration, stirring the samples according to a preset stirring time agent with the minimum value within the stirring time range and a fixed interval larger than the minimum value, measuring the viscosity, and recording the viscosity as vectors X1 and X2;
s22, calculating the homogeneity of X1 and X2 by:
if both t1 and t2 are greater than-1.35, determining the minimum value in the preset stirring time range as the stirring time;
if one of t1 and t2 is less than-1.35, repeating S21 and S22, stirring the stirring time agent which is one fixed interval and two fixed intervals larger than the minimum value in the preset stirring time range, and measuring the viscosity until t1 and t2 are both more than-1.35.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617877A (en) * | 2012-04-10 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparation method for polyimide film |
| CN104209524A (en) * | 2014-09-11 | 2014-12-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method of flexible pyroelectric film |
| CN108565331A (en) * | 2018-04-22 | 2018-09-21 | 佛山市领卓科技有限公司 | A kind of thermoelectric material |
| CN109087989A (en) * | 2018-07-24 | 2018-12-25 | 北京航空航天大学 | A kind of preparation method of Multifunction thermoelectric film power generation and light intensity sensor part |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617877A (en) * | 2012-04-10 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparation method for polyimide film |
| CN104209524A (en) * | 2014-09-11 | 2014-12-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method of flexible pyroelectric film |
| CN108565331A (en) * | 2018-04-22 | 2018-09-21 | 佛山市领卓科技有限公司 | A kind of thermoelectric material |
| CN109087989A (en) * | 2018-07-24 | 2018-12-25 | 北京航空航天大学 | A kind of preparation method of Multifunction thermoelectric film power generation and light intensity sensor part |
Non-Patent Citations (2)
| Title |
|---|
| Optimization of thermoelectric properties on Bi2Te3 thin films deposited by thermal co-evaporation;L.M. Goncalves等;《Thin Solid Films》;20090904;第2816-2821页 * |
| 预处理浸泡对聚酰亚胺重离子微孔膜蚀刻的影响;梁海英等;《核技术》;20170131;第40卷(第1期);第1-4页 * |
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