CN111431498A - Conductive polymer solution for crystal resonator and application thereof - Google Patents
Conductive polymer solution for crystal resonator and application thereof Download PDFInfo
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- CN111431498A CN111431498A CN202010245410.8A CN202010245410A CN111431498A CN 111431498 A CN111431498 A CN 111431498A CN 202010245410 A CN202010245410 A CN 202010245410A CN 111431498 A CN111431498 A CN 111431498A
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- aqueous dispersion
- crystal resonator
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 57
- 239000013078 crystal Substances 0.000 title claims abstract description 46
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005507 spraying Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000123 polythiophene Polymers 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000000080 wetting agent Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
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- 239000000243 solution Substances 0.000 claims description 71
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- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 23
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- 238000000034 method Methods 0.000 description 15
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- 229920002873 Polyethylenimine Polymers 0.000 description 13
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ODYWKGZHVSUTKO-UHFFFAOYSA-N 2-ethylhexan-1-ol;oxirane Chemical compound C1CO1.CCCCC(CC)CO ODYWKGZHVSUTKO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LTGBAYNSCXFXSH-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCN.CCCN(C)C.CCCN(C)C.Cl Chemical compound CCCCCCCCCCCCCCCCCCN.CCCN(C)C.CCCN(C)C.Cl LTGBAYNSCXFXSH-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
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- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- KGOGNDXXUVELIQ-UHFFFAOYSA-N dioctadecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC KGOGNDXXUVELIQ-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
- H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
- H03H3/00—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators
- H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
- H03H3/02—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of piezoelectric or electrostrictive resonators or networks
-
- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
- H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
- H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
- H03H9/15—Constructional features of resonators consisting of piezoelectric or electrostrictive material
- H03H9/17—Constructional features of resonators consisting of piezoelectric or electrostrictive material having a single resonator
- H03H9/19—Constructional features of resonators consisting of piezoelectric or electrostrictive material having a single resonator consisting of quartz
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the technical field of electronic components and discloses a conductive polymer solution for a crystal resonator and application thereof, wherein the conductive polymer solution comprises the following raw material components in parts by mass: 80-98.5 parts of polar proton solution; 1-10 parts of modified polythiophene aqueous dispersion; 0.1-3 parts of nano graphite flake aqueous dispersion; 0.01-0.05 part of a dispersant; 0.01-0.05 part of a leveling agent; 0.01-0.05 part of wetting agent. The nano graphite flakes with good water dispersibility are added into the modified polythiophene aqueous dispersion, so that the defect that micron-sized fillers influence the flatness of the conductive coating is overcome, the wetting agent ensures that the conductive polymer solution has good wettability on a wafer, and the surface regularity and the spraying efficiency of the coating are improved. The conductive polymer solution is sprayed on the surface of the wafer by a spray gun to prepare the quartz wafer for the resonator, the surface of which is coated with the conductive polymer electrode. The wafer has an electrode with good conductivity, the surface resistance of the wafer can be as low as 232 omega, and the wafer is expected to replace metal silver to be applied to the field of crystal resonators.
Description
Technical Field
The invention relates to the technical field of electronic components, in particular to a conductive polymer solution for a crystal resonator and application thereof.
Background
The crystal resonator is a quartz crystal resonator made of quartz material, commonly called crystal oscillator, and is an electromechanical device made of quartz crystal with small electric loss through precision cutting, grinding, plating electrodes and welding lead wires, playing a role in generating frequency, and has the characteristics of stability and good anti-interference performance, and is widely applied to various electronic products. If the crystal resonator is electrified, the crystal resonator generates mechanical oscillation, the oscillation frequency of the mechanical oscillation is closely related to the shape, the material, the cutting direction and the like of the crystal resonator, and the size of electrodes adopted by the quartz crystal resonator at different frequency points is different.
In the prior art, the crystal resonator is electrified by plating silver on the surface of the quartz crystal resonator and then connecting the quartz crystal resonator with an electrode. The silver metal has good conductivity and oxidation stability, and is a common raw material for the electrode plated on the surface of the crystal resonator at present. The electrode material generally uses silver with a purity of 99.99% or more, and a small amount of chromium (Cr) or nickel (Ni) is plated before silver plating in order to improve the adhesion strength of the electrode.
CN103684318A discloses a method for manufacturing a quartz crystal resonator with silver plated on the surface, which sequentially comprises the following steps: (1) cutting quartz crystals; (2) grinding the wafer; (3) measuring an angle by X-ray; (4) sticking and grinding the mound; (5) cutting and width grinding; (6) melting and chamfering; (7) frequency sorting; step (8) etching, namely etching the surface of the wafer by using a chemical solvent; the method is characterized in that: cleaning in step (9), cleaning the wafer with cleaning agent to remove plaster, oil stain and chemical residual liquid, and further cleaning with clean water; (10) silver plating, namely plating a silver layer on the surface of the wafer according to the size of the electrode; (11) dispensing on a shelf and curing with silver adhesive, placing the silver-plated wafer on a fixed support, fixing with the silver adhesive, and curing at 100-120 ℃. The silver layer of the invention is uniform, easy to fall off, convenient for fixing the silver colloid and connecting with the electrode, not easy to damage and long in service life.
CN 102832902A discloses a quartz crystal resonator and a processing method thereof, comprising a shell, a base, pins, a spring piece, conductive adhesive, a coated electrode and a wafer; the coated electrode comprises a basic electrode and a fine tuning electrode connected with the basic electrode; the wafer with the plated electrode attached to the surface of the wafer sequentially comprises a lower chromium plated layer, a silver plated layer and an upper chromium plated layer from inside to outside. The invention can improve the parasitic response characteristic of the quartz crystal resonator, and greatly improves the performance and quality of the produced quartz crystal resonator.
However, the processes of silver plating, chromium plating and the like in the prior art have high requirements on the process and the purity of metal raw materials, and the processes of silver plating and chromium plating on the crystal surface have complex processes and high cost. The development of novel electrode materials which are easy to spray and have high conductivity is a key problem for improving the current wafer preparation process.
Disclosure of Invention
The invention aims to solve the problems of high process requirement, complex process and high cost of silver plating on the crystal surface in the prior art, provides a high-molecular solution which is easy to spray and high in conductivity, and forms a conductive film on the crystal surface by using the conductive high-molecular solution to replace metal to be applied to the field of crystal resonators.
In order to achieve the purpose, the invention adopts the technical scheme that:
a conductive polymer solution for a crystal resonator comprises the following raw material components in 100 parts by mass:
80-98.5 parts of polar proton solution;
1-10 parts of modified polythiophene aqueous dispersion;
0.1-3 parts of nano graphite flake aqueous dispersion;
0.01-0.05 part of a dispersant;
0.01-0.05 part of a leveling agent;
0.01-0.05 part of wetting agent;
the mass ratio of the modified polythiophene aqueous dispersion to the nano graphite flake aqueous dispersion is 100: 50-100: 1.
Preferably, the mass ratio of the modified polythiophene aqueous dispersion to the graphite nanoplatelets aqueous dispersion is 100: 30-100: 5, and under the ratio, the obtained conductive polymer solution has better conductivity and the wafer resistance prepared by using the conductive polymer solution is lower.
The polar proton solution is a mixed solution of a polar organic solvent and water, and the polar organic solvent comprises polar proton solvents commonly used in the field, such as an alcohol solvent, a ketone solvent, N-methylpyrrolidone (NMP) and the like. The mass part of the water in the polar proton solution in the conductive polymer solution is 40-70 parts.
The alcohol solvent comprises methanol, ethanol, butanol, isopropanol, glycerol, ethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, etc.; the ketone solvent includes acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
By adjusting the components of the solvent, the dispersion stability of the modified polythiophene and the nano graphite sheet in the solvent, the wettability of the solvent to a wafer and the volatilization speed of the solvent can be improved. Preferably, the polar organic solvent is ethanol. The solvent has high volatilization speed, and the conductive polymer solution is sprayed on the surface of the wafer and is less prone to condensation, so that the wafer has better wettability.
The modified polythiophene water dispersion is an aqueous dispersion of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), wherein the average particle size of the poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) is 50-100 nm, and the solid content in water is 0.5-2.0%. Preferably, the modified polythiophene aqueous dispersion is a CleviospH 1000 product of Herley Germany.
The average particle size of the graphite nanoplatelets in the graphite nanoplatelet aqueous dispersion is 10-500 nm, and the solid content in water is 0.1-10%. The nano graphite sheet has good water dispersibility and good dispersion stability in polar proton solution, the obtained conductive polymer solution is sprayed on a wafer to form a film, the nano graphite sheet in the film is uniformly distributed, and the conductivity is good.
The dispersant is one or more of surfactants commonly used in the art, such as one or more of cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants.
The cationic surfactant comprises an amine salt type cationic surfactant, a quaternary ammonium salt type cationic surfactant, a cationic polymer surfactant and the like.
Further, the amine salt type cationic surfactant includes octadecyl amine hydrochloride, dioctadecyl amine hydrochloride, N-dimethyloctadecyl amine hydrochloride, polyacrylamide hydrochloride, etc.
Further, the quaternary ammonium salt cationic surfactant includes dioctadecyldimethylammonium chloride, octadecyldimethylbenzylammonium chloride, octadecylamide dimethylpropylammonium chloride, octadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, oleamidomethylpropylammonium chloride, erucamidopropyltrimethylammonium chloride, and the like.
Further, the cationic polymer surfactant comprises polyethyleneimine, polyvinylpyrrolidone, quaternized polyacrylamide and the like.
The anionic surfactant comprises sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl ether sulfate, triethanolamine alkyl ether sulfate, ammonium alkyl ether sulfate, sodium alkyl ether phosphate, sodium fluoroalkylcarboxylate and the like.
The nonionic surfactant includes polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, polyoxyethylene alkyl ester, propylene glycol-propylene oxide copolymer, perfluoroalkyl ethylene oxide adduct, 2-ethylhexanol ethylene oxide adduct, and the like.
The amphoteric surfactant comprises alkyl amino acetic acid betaine, alkyl amide acetic acid betaine, imidazole betaine and the like.
Because the surface of the nano graphite sheet contains certain hydroxyl or carboxyl and presents weak electronegativity, the dispersant of the invention is preferably a cationic surfactant which can neutralize the electronegativity of the nano graphite sheet and ensure that the nano graphite sheet is dispersed in solution more stably.
More preferably, the dispersant is polyethyleneimine, the polyethyleneimine exists as a polymeric cation in water, and can neutralize or adsorb all anionic substances, and amino groups contained in a molecular chain of the polyethyleneimine can react with carboxyl groups to generate hydrogen bonds, react with the carboxyl groups to generate ionic bonds, and react with carbonyl groups to generate covalent bonds. The polyethyleneimine can have stronger interaction with the graphite nanoplatelets, and is beneficial to the dispersion of the graphite nanoplatelets in aqueous solution.
The leveling agent is an acrylic copolymer leveling agent, an organic silicon leveling agent or a fluorocarbon surfactant.
Preferably, the leveling agent is an acrylic copolymer leveling agent, which is commonly used in solvent type and water-based paint systems, and accumulates on the surface of a coating by means of a similar compatibility principle, so that the surface tension of a high-molecular conductive solution system is greatly reduced, particularly the wettability of a substrate can be improved, and shrinkage cavities can be prevented.
Further preferably, the leveling agent is an ionic acrylate copolymer solution BYK381 from Bick, Germany.
The wetting agent is organosilicon gemini surfactant or acetylene glycol gemini surfactant, and the surface tension of the conductive polymer solution is 7 × 10-4～8×10-4N·cm-1Slightly higher than the surface tension of the quartz wafer (about 7 × 10)-4N·cm-1) Therefore, the wetting effect of the conductive polymer solution on the quartz wafer is not good. The wetting agent is added to cooperate with the flatting agent, so that the surface tension of the conductive polymer solution is reduced, the good infiltration of the conductive polymer solution to quartz crystals is promoted, surface defects such as shrinkage cavities or shrinkage edges are prevented, and the fluidity, the leveling property and the adhesive force of the solution are increased.
Preferably, the wetting agent is an acetylene glycol gemini surfactant, which not only can reduce balance and dynamic surface tension, but also can remarkably improve fluidity and leveling property, can easily enter a substrate surface difficult to wet, and improves the wetting performance of the conductive polymer solution on a quartz wafer.
Further preferably, the wetting agent is Dynol 607, United states gas company.
Preferably, the dispersant is a cationic surfactant, the leveling agent is an acrylic copolymer leveling agent, and the wetting agent is an acetylene glycol gemini surfactant. Under the combination, the wettability, the fluidity and the fluidity of the conductive polymer solution are better.
Further preferably, the dispersant is polyethyleneimine, the leveling agent is an ionic acrylate copolymer solution BYK381 from Bick, Germany, and the wetting agent is Dynol 607 from American gas company. Under the combination, various performances of the conductive polymer solution are optimal.
When the conductive polymer solution for the crystal resonator is applied to the crystal resonator, the conductive polymer solution is coated on the surface of a wafer in a spray gun spraying mode.
The main component of the conductive polymer solution is water, so that the wetting effect of water on the quartz wafer is poor, and water drops are condensed on the surface of the quartz wafer in the spraying process, so that the surface of a coating is uneven. Except that a leveling agent and a wetting agent are added into the solution to improve the wetting effect, the temperature of the quartz wafer is also increased to accelerate the rapid volatilization of the spraying liquid, and the proper temperature range of the quartz wafer is 100-150 ℃, and is preferably 120 ℃.
Meanwhile, the solution is prevented from condensing into water drops on the surface of the quartz wafer to cause uneven coating surface during the spraying process of the spray gun. If liquid drops appear on the surface of the wafer, immediately stopping spraying, and putting the wafer into an oven with the temperature of 100-150 ℃ for heat treatment to volatilize the spraying liquid on the surface of the wafer into a film; and then continuing spraying, and after the spraying is finished, putting the wafer into an oven to be treated at the temperature of 100-150 ℃ for 2-15 min to remove the solvent. And (4) removing the template to obtain the quartz wafer for the resonator, the surface of which is coated with the conductive polymer electrode.
The wafer has an electrode with good conductivity, the surface resistance of the wafer can be as low as 232 omega, the crystal resonator prepared by taking the conductive polymer solution as the electrode can successfully vibrate, the resonance frequency of the resonator can be adjusted between 3.99-4.02 MHz, and the wafer is expected to replace metal silver to be applied to the field of crystal resonators.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nano-graphite with good water dispersibility is added into the modified polythiophene aqueous dispersion, so that the defect that the flatness of the conductive coating is influenced by the micron filler is overcome;
(2) the adopted nano-graphite has good dispersibility in water, and the dispersing agent is added to ensure the dispersion stability of the nano-graphite in the water solution;
(3) by adding the wetting agent and adjusting the solvent ratio, the conductive polymer solution is ensured to have good wettability and proper volatility to the wafer, and the surface regularity and the spraying efficiency of the coating are improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The starting materials used in the following examples are all commercially available products. The modified polythiophene aqueous dispersion is Herrich Clevios Germany PH 1000, and the solid content is 1.0 percent; the nano graphite sheet is produced by a certain domestic manufacturer, the average particle size is 10-100 nm, and the solid content is 10%; the dispersant is polyethyleneimine which is a general commercial product; the leveling agent is ionic acrylate copolymer solution BYK381 of Germany Bike company; the wetting agent is acetylene glycol gemini surfactant Dynol 607 from gas company of America.
Example 1
Preparing a conductive polymer solution from an ethanol water solution, a modified polythiophene aqueous dispersion, a nano graphite flake aqueous dispersion, polyethyleneimine, BYK381 and Dynol 607, wherein the mass ratios of the components are respectively as follows: 40% of water, 49.36% of ethanol, 10% of modified polythiophene aqueous dispersion, 0.6% of graphite nanoplatelet aqueous dispersion, 0.02% of polyethyleneimine, 0.01% of BYK381 and 0.01% of Dynol 607.
Before spraying, firstly, placing a wafer on a specific template, heating the wafer in an oven to 120 ℃, then taking out the wafer, spraying the prepared conductive polymer solution by using a spray gun, keeping track of the wetting condition of the conductive polymer solution on the surface of the wafer at any time in the spraying process, immediately stopping spraying if liquid drops appear on the surface of the wafer, placing the wafer in the oven at 120 ℃ for heat treatment for 1min, then taking out the wafer and continuing spraying until the single side of the wafer is sprayed with 1.5g of the conductive polymer solution. Then, 1.55g of the conductive polymer solution was sprayed on the other surface of the wafer in the same manner. After the spraying was completed, the wafer was placed in an oven for treatment at 120 ℃ for 10min to remove the solvent. And finally, removing the template to obtain the quartz wafer for the resonator, the surface of which is coated with the conductive polymer electrode.
Examples 2 to 3
The conductive polymer solution prepared in example 1 was sprayed on the surface of a wafer according to the spraying process of example 1, and the spraying amounts of the single-sided wafer were 2.5g (example 2) and 5g (example 3), respectively.
Example 4
Preparing a conductive polymer solution from an ethanol water solution, a modified polythiophene aqueous dispersion, a nano graphite flake aqueous dispersion, polyethyleneimine, BYK381 and Dynol 607, wherein the mass ratios of the components are respectively as follows: 50% of water, 39.36% of ethanol, 9% of modified polythiophene aqueous dispersion, 1.6% of graphite nanoplatelet aqueous dispersion, 0.02% of polyethyleneimine, 0.01% of BYK381 and 0.01% of Dynol 607.
The conductive polymer solution prepared in this example was sprayed on the surface of a wafer according to the spraying process of example 1, and the spraying amount of the single-sided wafer was 2.5 g.
Example 5
Preparing a conductive polymer solution from an ethanol water solution, a modified polythiophene aqueous dispersion, a nano graphite flake aqueous dispersion, polyethyleneimine, BYK381 and Dynol 607, wherein the mass ratios of the components are respectively as follows: 70 percent of water, 19.36 percent of ethanol, 8.5 percent of modified polythiophene aqueous dispersion, 2.1 percent of nano graphite flake aqueous dispersion, 0.02 percent of polyethyleneimine, 0.01 percent of BYK381 and 0.01 percent of Dynol 607.
The conductive polymer solution prepared in this example was sprayed on the surface of a wafer according to the spraying process of example 1, and the spraying amount of the single-sided wafer was 2.5 g.
Comparative example 1
Preparing a conductive polymer solution from a modified polythiophene aqueous dispersion, wherein the modified polythiophene aqueous dispersion accounts for 10% by mass, and the water accounts for 90%. The conductive polymer solution prepared in this comparative example was sprayed on the surface of a wafer according to the spray coating process of example 1, and the amount of the sprayed one-sided wafer was 2.5 g.
The contents of the components in the conductive polymer solutions of examples 1 to 5 and comparative example 1 are summarized in Table 1, and the amount of one-sided wafer spraying.
TABLE 1 conductive Polymer solution Components content and Single-sided wafer spray coating amount
The surface resistance and the resonant frequency of the wafers prepared in examples 1 to 5 and comparative example 1 were measured, the impedance of the electrode was measured using an Agilent 34401A multimeter, the resonant frequency of the crystal was measured using an E5100 analyzer and a 250B network analyzer, and the test results are shown in Table 2. From the data in Table 2, it can be found that the surface resistance of the wafer prepared by using the conductive polymer solutions of examples 1 to 5 decreases with the increase of the spraying amount; the content of the nano graphite flakes in the conductive polymer solution system is increased, the content of the modified polythiophene aqueous dispersion is reduced, the surface resistance of the wafer is further reduced to 232 omega at the lowest, and the conductivity is excellent;
meanwhile, under the condition that the spraying amount of one side is 2.5g, the resistance of the wafer sprayed by the conductive polymer solution only containing the modified polythiophene in the comparative example 1 is 2349 omega, while the surface resistance of the wafer prepared in the example 2 is 1592 omega, which shows that the conductivity of the solution can be greatly improved by adding the nano graphite sheet, the crystal resonator prepared by taking the conductive liquid as an electrode can be smoothly vibrated, the resonance frequency of the resonator can be adjusted between 3.99 and 4.02MHz, and the conductive polymer solution is expected to replace metal silver to be applied to the field of the crystal resonator.
TABLE 2 resonance frequency and surface resistance of wafers prepared in examples
| Numbering | Resonance frequency (Hz) | Surface resistance (Ohms) |
| Example 1 | 4,023,493.00 | 3576.21 |
| Example 2 | 4,016,154.10 | 1592.55 |
| Example 3 | 3,999,527.78 | 1098.80 |
| Example 4 | 4,016,232.10 | 920.53 |
| Example 5 | 4,016,737.91 | 232.16 |
| Comparative example 1 | 4,017,017.52 | 2349.22 |
Claims (10)
1. A conductive polymer solution for a crystal resonator is characterized by comprising the following raw material components in 100 parts by mass:
80-98.5 parts of polar proton solution;
1-10 parts of modified polythiophene aqueous dispersion;
0.1-3 parts of nano graphite flake aqueous dispersion;
0.01-0.05 part of a dispersant;
0.01-0.05 part of a leveling agent;
0.01-0.05 part of wetting agent.
2. The conductive polymer solution for the crystal resonator according to claim 1, wherein the mass ratio of the modified polythiophene aqueous dispersion to the graphite nanoplatelets aqueous dispersion is 100:50 to 100: 1.
3. The conductive polymer solution for a crystal resonator according to claim 1, wherein the polar protic solution is a mixed solution of a polar organic solvent and water, and the polar organic solvent includes one or more of methanol, ethanol, and acetone.
4. The conductive polymer solution for a crystal resonator according to claim 1 or 2, wherein the aqueous dispersion of modified polythiophene is an aqueous dispersion of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), wherein the poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) has an average particle diameter of 50 to 100nm and a mass content in water of 0.5 to 2.0%.
5. The conductive polymer solution for a crystal resonator according to claim 1 or 2, wherein the aqueous dispersion of graphite nanoplatelets is an aqueous dispersion of graphite nanoplatelets, the graphite nanoplatelets having an average particle size of 10 to 500nm and a mass content in water of 0.1 to 10%.
6. The conductive polymer solution for a crystal resonator according to claim 1, wherein the dispersant is one or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
7. The conductive polymer solution for the crystal resonator according to claim 1, wherein the leveling agent is an acrylic copolymer leveling agent, an organic silicon leveling agent, or a fluorocarbon surfactant.
8. The conductive polymer solution for a crystal resonator according to claim 1, wherein the wetting agent is a silicone gemini surfactant or an acetylene glycol gemini surfactant.
9. The conductive polymer solution for a crystal resonator according to claim 1, wherein the dispersant is a cationic surfactant, the leveling agent is an acrylic copolymer-based leveling agent, and the wetting agent is an acetylene glycol-based gemini surfactant.
10. The use of the conductive polymer solution for crystal resonators according to any of claims 1 to 9 in crystal resonators, wherein the conductive polymer solution according to any of claims 1 to 9 is applied to the surface of a wafer by spray coating with a spray gun.
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