CN115678347B - Preparation method of low-temperature plasma induction functional film and key material thereof - Google Patents
Preparation method of low-temperature plasma induction functional film and key material thereof Download PDFInfo
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- CN115678347B CN115678347B CN202211094189.6A CN202211094189A CN115678347B CN 115678347 B CN115678347 B CN 115678347B CN 202211094189 A CN202211094189 A CN 202211094189A CN 115678347 B CN115678347 B CN 115678347B
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- 230000006698 induction Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 23
- 238000004528 spin coating Methods 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000009832 plasma treatment Methods 0.000 claims abstract description 5
- 230000001939 inductive effect Effects 0.000 claims abstract description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 66
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 66
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 66
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 60
- 229910052751 metal Inorganic materials 0.000 claims description 60
- 239000002184 metal Substances 0.000 claims description 60
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 58
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 claims description 54
- 150000003839 salts Chemical class 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 32
- LSIWWRSSSOYIMS-UHFFFAOYSA-L copper;diformate;tetrahydrate Chemical group O.O.O.O.[Cu+2].[O-]C=O.[O-]C=O LSIWWRSSSOYIMS-UHFFFAOYSA-L 0.000 claims description 29
- 150000001412 amines Chemical class 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 claims description 12
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000007639 printing Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000000976 ink Substances 0.000 description 214
- 239000010408 film Substances 0.000 description 142
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 41
- 229910052802 copper Inorganic materials 0.000 description 41
- 239000010949 copper Substances 0.000 description 41
- 239000011521 glass Substances 0.000 description 30
- 239000011112 polyethylene naphthalate Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 23
- 239000000523 sample Substances 0.000 description 21
- 238000004321 preservation Methods 0.000 description 20
- 238000011419 induction treatment Methods 0.000 description 18
- 239000010409 thin film Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000005452 bending Methods 0.000 description 14
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 14
- 238000007865 diluting Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- XUWSLVKFZWLINO-UHFFFAOYSA-N copper;tetrahydrate Chemical compound O.O.O.O.[Cu] XUWSLVKFZWLINO-UHFFFAOYSA-N 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- -1 polyethylene naphthalate Polymers 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 150000004699 copper complex Chemical class 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 230000002776 aggregation Effects 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- 230000009477 glass transition Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a preparation method of a low-temperature plasma induction functional film and a key material thereof. The invention is described inThe preparation method comprises the following steps: s1: cleaning the flexible substrate; s2: spin-coating ink on a flexible substrate; s3: placing the flexible substrate with the spin-coated ink on a heating plate for preheating treatment, placing the flexible substrate on a plasma device, setting the power, time and gas flow of plasma treatment, and then introducing N 2 /H 2 And (5) inducing the mixed gas to obtain the functional film. The functional film prepared by the invention has the advantages of excellent stability, oxidation resistance, compact curing structure, excellent conductivity and larger adhesive force with the flexible substrate.
Description
Technical Field
The invention relates to the technical field of flexible films and circuit preparation, in particular to a preparation method of a low-temperature plasma induction functional film and key materials thereof.
Background
Compared with the traditional functional thin film and circuit preparation processes such as vacuum evaporation, chemical deposition and photoetching, the flexible electronic printing technology has certain advantages in the aspects of flexibility, operation convenience, processability, low cost, large-area manufacture and the like, so that the flexible electronic printing technology gradually enters the field of view of people in recent years. Flexible electronic printing technology has been used in the fields of light emitting diodes, RFID radio frequency antennas, thin film transistors, solar cells, biomaterials, etc. Printing ink is a very important part in the flexible electronic printing technology, and the market at present mainly uses metal particle ink, wherein silver particle ink is widely applied due to the advantages of high conductivity, relatively low melting point, oxidation resistance and the like. However, silver ink is expensive as a noble metal and has problems such as electromigration. So the learner proposed to replace the silver ink with copper ink.
Copper inks can be classified into copper particle-free inks and copper particle-free inks, depending on the presence or absence of copper particles in the ink. In order to prevent copper oxidation, the copper particle ink needs to wrap a layer of organic matters or inactive metals on the surfaces of the copper particles, which not only increases the manufacturing difficulty and the manufacturing cost, but also causes particle agglomeration phenomenon in the ink. Thus, particle-free copper inks, particularly copper complex inks, are more suitable for practical applications. A great deal of researches show that copper complex ink is spin-coated or printed on a substrate such as glass, and a copper film can be obtained after sintering for a period of time at a high temperature of 150 ℃ or more under the protection atmosphere of inert gas or reducing gas. This is because the copper complex ink is decomposed into copper atoms at high temperature, and the copper atoms undergo nucleation, growth, and the like to obtain a copper film.
However, a large number of experiments show that although the copper film obtained by thermally sintering the copper complex ink shows lower resistivity, flexible substrates with low glass transition temperatures such as PEN, PET and the like are difficult to withstand high-temperature calcination at a temperature of more than 150 ℃, and the copper film with the copper complex ink aggregation incapable of being prepared by the traditional thermal sintering process is easy to be prepared by the traditional thermal sintering process, so that the high-performance copper film is difficult to prepare in the flexible electronic printing field. In addition, copper films obtained by conventional thermal sintering processes have unsatisfactory properties in terms of adhesion strength to a substrate, bending stability, oxidation resistance, densification of a cured structure, and the like.
The ink formulation plays a critical role in ink stability and electrical performance of the prepared copper film, but related researches fail to obtain a high-conductivity copper film while guaranteeing the ink stability, which also greatly limits the application of the high-conductivity copper film in real-life production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a low-temperature plasma induction functional film and key materials thereof. According to the invention, the traditional thermal sintering process is replaced by a mode of plasma-induced copper complex ink decomposition, and the copper mold is successfully prepared by plasma induction through optimizing process parameters and improving the ink formula, and the prepared copper mold has the advantages of excellent stability, oxidation resistance, compact cured structure, excellent conductivity and larger adhesive force with a flexible substrate.
The technical scheme of the invention is as follows:
an ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 24.9 to 47.1 percent of metal salt, 9.8 to 13.4 percent of 2-ethylhexyl amine, 14.3 to 27.9 percent of 2-amino-2-methyl-propanol, 1 to 5 percent of binder and 10 to 50 percent of organic solvent.
Further, the metal salt is copper formate tetrahydrate or a mixture of copper formate tetrahydrate and other metal salts, and the other metal salts are one or two of nickel formate dihydrate and silver oxalate; the mass ratio of the copper formate tetrahydrate to other metal salts is 2-20:1.
Further, the organic solvent is one or two of n-butanol and ethylene glycol.
Further, the binder is polyvinylpyrrolidone, the purity of the polyvinylpyrrolidone is 99%, and the molecular weight is 44000-54000.
Further, the molar ratio of the 2-amino-2-methyl-propanol to the 2-ethylhexyl amine is 1-3.2:1. The molar amount of the metal salt to the total molar amount of 2-ethylhexyl amine and 2-amino-2-methyl-propanol was 1:2.
The preparation method of the ink comprises the following steps of:
(1) Grinding metal salt to obtain metal salt powder;
(2) Mixing 2-amino-2 methyl-propanol with 2-ethylhexyl amine to obtain a mixed amine;
(3) Adding the mixed amine prepared in the step (2) into the metal salt powder obtained in the step (1), stirring for reaction, adding a solvent, stirring uniformly, adding a binder, and stirring for 10-12 h to obtain the printing ink for preparing the functional film by plasma induction.
Further, in the step (1), the particle diameter of the metal salt powder is 1-10 μm; the stirring speed in the step (3) is 1000-2000 r/min, and the stirring reaction time is 5-10 min.
A functional film prepared by using the ink.
The preparation method of the functional film comprises the following steps:
s1: cleaning the flexible substrate;
s2: spin-coating the ink on a flexible substrate;
s3: placing the flexible substrate with the spin-coated ink on a heating plate for preheating treatment, placing the flexible substrate on a plasma device, and setting the power, time and the plasma treatmentThe gas flow is then introduced into N 2 /H 2 And (5) inducing the mixed gas to obtain the functional film.
Further, in the step (1), the cleaning is performed by using UV light for 10-30 min; in the step (1), the flexible substrate is PEN (polyethylene naphthalate), PET (poly-p-benzoate), PI (polyimide), glass or photo paper.
Further, in the step (2), the spin coating speed is 3000r/min, and the time is 40-60 s.
Further, in the step (3), the preheating treatment is to heat to 100-120 ℃ at a speed of 10-20 ℃/min, and keep the temperature for 5-15 min; the power of the plasma treatment is 150-200W, the time is 2-10 min, and the gas flow is 5-40 ml/min.
The beneficial technical effects of the invention are as follows:
(1) The invention improves the ink formula and prepares the copper ink which can be used for flexible substrates and can be well combined with a low-temperature plasma induction method. The copper ink is formed by complexing metal salt with two specific amines in a specific proportion, the decomposition temperatures of the complexes corresponding to the two amines are different, and metal particles with different sizes are respectively obtained after decomposition, so that staggered filling of the large and small particles is realized, small particle metals fill gaps before the large particle metals, the compactness and the conductivity of the film are improved, and the phenomenon that the film solidification structure is not compact enough due to the fact that the film is full of the large particles or the film is full of the small particles, the connecting force of the particles is not strong enough and the film is cracked is avoided.
(2) The molar ratio of the 2-amino-2 methyl-propanol to the 2-ethylhexyl amine in the ink raw materials prepared by the invention is 1-3: 1, the 2-amino-2-methyl-propanol complex has poor air water absorbability and high stability, and when the amount of 2-amino-2-methyl-propanol is too small, the ink has poor stability, and when the amount of 2-amino-2-methyl-propanol is too large, the resulting film has poor conductivity. Therefore, the proportion greatly improves the stability of the ink while ensuring the excellent conductivity of the obtained film. A small amount of nickel/silver salt is added into the printing ink, and finally the formed antioxidation nickel/silver is doped in copper, so that the stability and antioxidation of the copper film in the air are greatly improved; the polyvinylpyrrolidone (PVP) long-chain polymer added into the ink plays a role of a binder in the metal film forming process, and copper/nickel/silver atoms cannot excessively aggregate in the nucleation process under the effect of the binder, so that copper/nickel/silver nucleation and growth are more uniform, and the micro-curing structure of the film is improved. According to the invention, the ink with good stability is prepared through the synergy of the components, and the functional film with uniform microstructure, excellent conductivity and stability can be obtained by combining the ink with a plasma treatment process.
(3) The invention adopts a mode of decomposing the plasma-induced complex ink to lead the ink treated by the plasma to be decomposed immediately to form metal, thereby avoiding the flow aggregation of the ink before decomposition, and being capable of preparing a functional film with the thickness of 10-150 nm; meanwhile, the plasma can activate the substrate while inducing the ink to form metal, so that the adhesion between the metal and the substrate is improved. The copper thin film prepared by combining the copper ink and the plasma induction has high bending stability, strong oxidation resistance, compact solidification structure, excellent conductivity and large adhesive force with the flexible substrate.
(4) According to the invention, the solvent, the redundant amine and the crystal water in the metal salt in the ink are removed by preheating treatment, so that the damage of volatilization of the substances to the microstructure of the film in the plasma induction stage is avoided, and the efficiency of plasma induction is improved.
Drawings
FIG. 1 is a schematic diagram of the plasma induction of the present invention.
FIG. 2 is a photograph of a copper film prepared in example 1 of the present invention.
FIG. 3 is a graph showing the relationship between the resistivity and the preheating treatment time of the thin film prepared in example 2 of the present invention.
FIG. 4 is a schematic representation of the effect of PVP on long chain polymers in examples 1-5 of the present invention.
FIG. 5 is a mirror image of the copper film prepared in comparative example 6 of the present invention.
FIG. 6 shows copper prepared after the inks prepared in example 1 and comparative examples 2 to 5 were left for 10 days and 20 days, respectivelyResistance of film R/R relative to resistance of copper film prepared in example 1 and comparative examples 2 to 5 0 。
FIG. 7 shows the relative resistance R/R in the bending test of the film according to example 1 of the present invention at a bending radius of 5mm 0 Is a variation of (c).
FIG. 8 is a graph showing the mixing of particles when two amines are used in accordance with the present invention.
FIG. 9 is an electron microscope image of the micro-cured structure of the thin film prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
The invention adopts a mode of plasma-induced complex ink decomposition to lead the plasma-treated ink to be immediately decomposed into metal, and the principle is shown in figure 1: when N is 2 /H 2 When the mixed plasma bombards the surface of the complex ink from different directions, the kinetic energy or chemical energy of the mixed plasma can break chemical bonds between bivalent copper/nickel/silver ions and ligands in the complex, and electrons of the bivalent copper/nickel/silver ions are changed into monovalent ions and then into copper/nickel/silver atoms, and then the nucleation and growth processes are carried out, so that a continuous film is finally formed on the flexible substrate.
Example 1
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 45.2% of metal salt (all copper tetrahydrate), 13.0% of 2-ethylhexyl amine, 26.8% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Taking 45.2% of copper formate tetrahydrate and grinding into powder, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 26.8% of 2-amino-2-methyl-propanol and 13.0% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground copper powder tetrahydrate into a glass bottle obtained by mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light washer for 30min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 60s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 20 ℃/min, the heat preservation temperature is 120 ℃, the heat preservation time is 15min, and the obtained sample is shown in figure 2;
(4) By N 2 /H 2 And (3) carrying out induction treatment on the heat-treated sample by using mixed plasma, wherein the gas flow is 40ml/min, the power of the induction treatment is 200W, and the time is 2min, so that the functional film with compact cured structure and excellent conductivity is obtained.
Example 2
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 35.1% of metal salt (all copper tetrahydrate), 13.4% of 2-ethylhexyl amine, 18.5% of 2-amino-2-methyl-propanol, 3% of polyvinylpyrrolidone (PVP) and 30% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Taking 35.1% of copper formate tetrahydrate and grinding into powder, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 18.5% of 2-amino-2-methyl-propanol and 13.4% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground copper powder tetrahydrate into a glass bottle obtained by mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 7.5min at 1500r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 30% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) 3% polyvinylpyrrolidone (PVP) was slowly added to the stirring ink and the ink was stirred for 11h to give a complex ink that was stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light cleaner for 20min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 50s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 15 ℃/min, the heat preservation temperature is 110 ℃, and the heat preservation time is 10min;
(4) By N 2 /H 2 And (3) carrying out induction treatment on the heat-treated sample by using mixed plasma, wherein the gas flow is 10ml/min, the power of the induction treatment is 165W, and the time is 5.5min, so that the functional film with compact cured structure and excellent conductivity is obtained.
Example 3
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 24.9% of metal salt (all copper tetrahydrate), 9.8% of 2-ethylhexyl amine, 14.3% of 2-amino-2-methyl-propanol, 1% of polyvinylpyrrolidone (PVP) and 50% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Taking 24.9% of copper formate tetrahydrate and grinding into powder, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 14.3% of 2-amino-2-methyl-propanol and 9.8% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground copper powder tetrahydrate into a glass bottle obtained by mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 10min at 1000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 50% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) 1% polyvinylpyrrolidone (PVP) was slowly added to the ink being stirred and the ink was stirred for 10 hours to give a complex ink that was stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating a flexible polyethylene naphthalate (PEN) substrate with a UV light cleaner for 10min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 40s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 10 ℃/min, the heat preservation temperature is 100 ℃, and the heat preservation time is 5min;
(4) By N 2 /H 2 And (3) carrying out induction treatment on the heat-treated sample by using mixed plasma, wherein the gas flow is 5ml/min, the power of the induction treatment is 150W, and the time is 10min, so that the functional film with compact cured structure and excellent conductivity is obtained.
Example 4
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 43.7% of metal salt (the mass ratio of the copper formate tetrahydrate to the nickel formate dihydrate is 2:1), 13.4% of 2-ethylhexyl amine, 27.9% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Grinding copper formate tetrahydrate and nickel formate dihydrate with the mass ratio of 2:1, mixing according to the mass ratio of 2:1, and taking mixed powder of 43.7% of copper formate tetrahydrate and nickel formate dihydrate as metal salt, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 27.9% of 2-amino-2-methyl-propanol and 13.4% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground metal salt powder into a glass bottle after mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light washer for 30min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 60s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 20 ℃/min, the heat preservation temperature is 120 ℃, and the heat preservation time is 15min;
(4) By N 2 /H 2 The mixed plasma is used for carrying out induction treatment on the sample after heat treatment, the gas flow is 40ml/min, the power of the induction treatment is 2000W, and the time isAnd 2min, obtaining the functional film with compact cured structure and excellent conductivity.
Example 5
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 44.8% of metal salt (the mass ratio of the copper formate tetrahydrate to the nickel formate dihydrate is 10:1), 13.1% of 2-ethylhexyl amine, 27.1% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Grinding copper formate tetrahydrate and nickel formate dihydrate with the mass ratio of 10:1, mixing according to the mass ratio of 10:1, and taking 44.8% of mixed powder of the copper formate tetrahydrate and the nickel formate dihydrate as metal salt, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 27.1% of 2-amino-2-methyl-propanol and 13.1% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground metal salt powder into a glass bottle after mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light washer for 30min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 60s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 20 ℃/min, the heat preservation temperature is 120 ℃, and the heat preservation time is 15min;
(4) By N 2 /H 2 And (3) carrying out induction treatment on the heat-treated sample by using mixed plasma, wherein the gas flow is 40ml/min, the power of the induction treatment is 200W, and the time is 2min, so that the functional film with compact cured structure and excellent conductivity is obtained.
Example 6
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 45.0% of metal salt (the mass ratio of the copper formate tetrahydrate to the nickel formate dihydrate is 20:1), 13.0% of 2-ethylhexyl amine, 27.0% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Grinding copper formate tetrahydrate and nickel formate dihydrate with the mass ratio of 20:1, mixing according to the mass ratio of 20:1, and taking 45.0% of mixed powder of the copper formate tetrahydrate and the nickel formate dihydrate as metal salt, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 27.0% of 2-amino-2-methyl-propanol and 13.0% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground metal salt powder into a glass bottle after mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light washer for 30min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 60s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 20 ℃/min, the heat preservation temperature is 120 ℃, and the heat preservation time is 15min;
(4) By N 2 /H 2 And (3) carrying out induction treatment on the heat-treated sample by using mixed plasma, wherein the gas flow is 40ml/min, the power of the induction treatment is 200W, and the time is 2min, so that the functional film with compact cured structure and excellent conductivity is obtained.
Example 7
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 47.1% of metal salt (the mass ratio of the copper tetrahydrate to the silver oxalate is 2:1), 12.3% of 2-ethylhexyl amine, 25.6% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Grinding copper formate tetrahydrate and silver oxalate with a mass ratio of 2:1, mixing according to a mass ratio of 2:1, and taking mixed powder of 47.1% of copper formate tetrahydrate and silver oxalate as metal salt, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 25.6% of 2-amino-2-methyl-propanol and 12.3% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground metal salt powder into a glass bottle after mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light washer for 30min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 60s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 20 ℃/min, the heat preservation temperature is 120 ℃, and the heat preservation time is 15min;
(4) By N 2 /H 2 And (3) carrying out induction treatment on the heat-treated sample by using mixed plasma, wherein the gas flow is 40ml/min, the power of the induction treatment is 200W, and the time is 2min, so that the functional film with compact cured structure and excellent conductivity is obtained.
Example 8
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 45.7% of metal salt (the mass ratio of the copper tetrahydrate to the silver oxalate is 10:1), 12.8% of 2-ethylhexyl amine, 26.5% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Grinding copper formate tetrahydrate and silver oxalate with the mass ratio of 10:1, mixing according to the mass ratio of 10:1, and taking 45.7% of mixed powder of the copper formate tetrahydrate and the silver oxalate as metal salt, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 26.5% of 2-amino-2-methyl-propanol and 12.8% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground metal salt powder into a glass bottle after mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light washer for 30min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 60s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 20 ℃/min, the heat preservation temperature is 120 ℃, and the heat preservation time is 15min;
(4) By N 2 /H 2 And (3) carrying out induction treatment on the heat-treated sample by using mixed plasma, wherein the gas flow is 40ml/min, the power of the induction treatment is 200W, and the time is 2min, so that the functional film with compact cured structure and excellent conductivity is obtained.
Example 9
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 45.5% of metal salt (the mass ratio of the copper tetrahydrate to the silver oxalate is 20:1), 12.9% of 2-ethylhexyl amine, 26.6% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol).
The preparation method of the ink comprises the following steps of:
(1) Grinding copper formate tetrahydrate and silver oxalate with a mass ratio of 20:1, mixing according to a mass ratio of 20:1, and taking 45.5% of mixed powder of the copper formate tetrahydrate and the silver oxalate as metal salt, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 26.6% of 2-amino-2-methyl-propanol and 12.9% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground metal salt powder into a glass bottle after mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional film is prepared by the ink through a low-temperature plasma induction method, and the preparation of the functional film comprises the following steps:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light washer for 30min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 60s;
(3) Placing the spin-coated sample on a heating table for preheating treatment, wherein the heating speed is 20 ℃/min, the heat preservation temperature is 120 ℃, and the heat preservation time is 15min;
(4) By N 2 /H 2 And (3) carrying out induction treatment on the heat-treated sample by using mixed plasma, wherein the gas flow is 40ml/min, the power of the induction treatment is 200W, and the time is 2min, so that the functional film with compact cured structure and excellent conductivity is obtained.
Comparative example 1
The formulation and preparation method of the ink were the same as in example 1, except that the thermal sintering process was used in comparative example 1 when the obtained ink was used to prepare a film, specifically:
(1) Treating the flexible polyethylene naphthalate (PEN) substrate with a UV light washer for 30min;
(2) Spin-coating ink on a flexible PEN substrate at a speed of 3000r/min for 60s;
(3) Placing the spin-coated sample on a closed heating table for heat sintering treatment, wherein the heating speed is 10 ℃/min, the heat preservation temperature is 150 ℃, the heat preservation time is 10min, and the atmosphere is N 2 The flow rate was 3L/min. Obtaining the functional film corresponding to the traditional sintering process.
Comparative example 2
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 42.2 percent of metal salt (all copper tetrahydrate), 30.3 percent of 2-ethylhexyl amine, 12.5 percent of 2-amino-2-methyl-propanol, 5 percent of polyvinylpyrrolidone (PVP) and 10 percent of organic solvent (n-butanol). Wherein the molar ratio of the 2-amino-2-methyl-propanol to the 2-ethylhexyl amine is changed from original 3:1 to 3:5.
The preparation method of the ink comprises the following steps of:
(1) Taking 42.2% of copper formate tetrahydrate and grinding into powder, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 12.5% of 2-amino-2-methyl-propanol and 30.3% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground copper powder tetrahydrate into a glass bottle obtained by mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional thin film was prepared by a low temperature plasma induction method using the above ink, and the preparation of the functional thin film was the same as that of example 1.
Comparative example 3
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 43.2% of metal salt (all copper tetrahydrate), 24.7% of 2-ethylhexyl amine, 17.1% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol). Wherein the molar ratio of the 2-amino-2-methyl-propanol to the 2-ethylhexyl amine is changed from original 3:1 to 1:1.
The preparation method of the ink comprises the following steps of:
(1) Taking 43.2% of copper formate tetrahydrate and grinding into powder, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 17.1% of 2-amino-2-methyl-propanol and 24.7% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground copper powder tetrahydrate into a glass bottle obtained by mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) 3% polyvinylpyrrolidone (PVP) was slowly added to the stirring ink and the ink was stirred for 12h to give a complex ink that was stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional thin film was prepared by a low temperature plasma induction method using the above ink, and the preparation of the functional thin film was the same as that of example 1.
Comparative example 4
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 44.2% of metal salt (all copper tetrahydrate), 19.0% of 2-ethylhexyl amine, 21.8% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol). Wherein the molar ratio of the 2-amino-2-methyl-propanol to the 2-ethylhexyl amine is changed from original 3:1 to 5:3.
The preparation method of the ink comprises the following steps of:
(1) Taking 44.2% of copper formate tetrahydrate and grinding into powder, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 21.8% of 2-amino-2-methyl-propanol and 19.0% of 2-ethylhexyl amine in a cleaned, dried and cooled glass bottle, and uniformly mixing;
(3) Adding the ground copper powder tetrahydrate into a glass bottle obtained by mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional thin film was prepared by a low temperature plasma induction method using the above ink, and the preparation of the functional thin film was the same as that of example 1.
Comparative example 5
An ink for preparing a functional film by plasma induction comprises the following raw materials in percentage by mass: 47.5% of metal salt (all copper tetrahydrate), 37.5% of 2-amino-2-methyl-propanol, 5% of polyvinylpyrrolidone (PVP) and 10% of organic solvent (n-butanol). Wherein the molar ratio of the 2-amino-2-methyl-propanol to the 2-ethylhexyl amine is changed from original 3:1 to 1:0.
The preparation method of the ink comprises the following steps of:
(1) Taking 47.5% of copper formate tetrahydrate and grinding into powder, wherein the particle size of the powder is 1-10 mu m;
(2) Weighing 37.5% 2-amino-2 methyl-propanol in a cleaned, dried and cooled glass bottle;
(3) Adding the ground copper powder tetrahydrate into a glass bottle obtained by mixing 2-amino-2 methyl-propanol and 2-ethylhexyl amine, and stirring and reacting for 5min at 2000r/min by using a planetary stirrer to obtain an ink primary product;
(4) Adding 10% n-butanol into the ink initial product, and uniformly diluting the ink by stirring with a magnetic stirrer;
(5) Slowly add 5% polyvinylpyrrolidone (PVP) to the stirring ink and stir the ink for 12h to give a complex ink that is stable in air at room temperature and pressure for plasma induction.
A functional film prepared by the ink.
The functional thin film was prepared by a low temperature plasma induction method using the above ink, and the preparation of the functional thin film was the same as that of example 1.
Comparative example 6
Comparative example 6 was identical to example 1, except that PVP was not included in the ink formulation: 47.9% of metal salt (all copper tetrahydrate), 13.7% of 2-ethylhexyl amine, 28.4% of 2-amino-2-methyl-propanol and 10% of organic solvent (n-butanol).
The rest is the same as in example 1.
Comparative examples 7 to 14
Comparative examples 7 to 14 are the same as example 1, except that the amine used in comparative example 7 was 2-amino-2-methyl-propanol and n-octylamine (molar ratio 3:1), and the amine used in comparative example 8 was 2-amino-2-methyl-propanol and dibutylamine (molar ratio 3:1). The amine used in comparative example 9 was 2-ethylhexyl amine and n-octyl amine (molar ratio 3:1); the amine used in comparative example 10 was 2-ethylhexyl amine, dibutylamine (molar ratio 3:1), and the amine used in comparative example 11 was n-octyl amine and 2-amino-2 methyl-propanol (molar ratio 3:1); the amine used in comparative example 12 was n-octylamine, 2-ethylhexyl amine (molar ratio 3:1); the amine used in comparative example 13 was n-octylamine and dibutylamine (molar ratio 3:1); the amines used in comparative example 14 were dibutylamine and 2-amino-2 methyl-propanol (molar ratio 3:1).
Comparative example 15
The ink formulation and preparation method of comparative example 15 were the same as in example 1, except that after the ink was prepared, the process of preparing a thin film in example 1 was subjected to a preheating treatment, whereas comparative example 15 was not subjected to a preheating treatment. Other preparation steps of the film were the same as in example 1.
Test example:
(1) Resistivity test
The resistivity of the functional films prepared in examples 1 to 9 and comparative examples 1 to 15 was measured with a four-point probe, and the results are shown in tables 1 to 2.
Table 1 resistivity of functional films prepared in examples 1 to 9
TABLE 2 resistivity of functional films prepared in comparative examples 1 to 15
Continuous table 2
As can be seen from Table 1, the films prepared in examples 1 to 5 all have lower resistance under the respective optimal process parameters, and can completely replace the conventional thermal sintering process. The optimal preheating treatment duration is different in different embodiments, and the resistivity of the film in each embodiment is firstly reduced and then increased along with the increase of the preheating treatment duration, which is mainly caused by the different contents of the solvents in different embodiments. The relationship between the resistivity of the film obtained in example 2 and the preheating treatment time is shown in FIG. 3. As can be seen from FIG. 3, the resistivity of the film obtained in example 2 was minimized when the preheating treatment time was 6 minutes. Furthermore, it can be seen from tables 1-2 that whether PVP is contained has a great influence on the optimal resistivity of the obtained film because PVP long-chain polymer plays a role of a binder in the metal film forming process, copper/nickel/silver atoms are not excessively aggregated in the nucleation process under the effect of the PVP long-chain polymer, so that copper/nickel/silver nucleation and growth are more uniformly improved in the micro-solidification structure of the film, the schematic diagram of which is shown in FIG. 4, and thus the solidification structure of the film obtained in comparative example 6 without PVP is liable to crack (FIG. 5) to thereby increase the resistivity thereof. The process can be used for PEN, PET, PI, photo paper and glass substrates, and compared with the conventional sintering process, the process can only be applied to heat-resistant PI, rigid glass and other substrates, and the application of the method is wider. As can be seen from tables 1-2, the 2-amino-2-methyl-propanol used in example 1 was mixed with 2-ethylhexyl amine 3: the molar ratio of 1 is the optimal ratio of the four amines. When the ratio of the two amines is changed, the stability or conductivity of the ink is reduced because the water absorption of the ink and the compactness of the microstructure of the prepared copper film are changed; when the two amines 2-amino-2 methyl-propanol and 2-ethylhexyl amine used in the present application are changed into other amines, the prepared ink has a higher resistivity because the particles of the obtained copper film are less mutually filled.
(2) Ink stability test
Resistance R of thin film prepared after 10 days and 20 days of standing with the ink prepared in comparative example 1 and comparative examples 2 to 5 and resistance R of thin film prepared directly without the ink (directly prepared ink) 0 Is the relative resistance R/R 0 The storage stability of the ink was examined by the change in the relative resistance of the resulting film. The method comprises the following steps: the films prepared in example 1 and comparative examples 2 to 5 were tested for resistance, bit R 0 The inks prepared in examples 1 and comparative examples 2 to 5 were left for 10 days and 20 days, respectively, and then films were prepared in the method of example 1, and the resistance of the films prepared with the inks after 10 days and 20 days was measured and denoted as R, and the relative resistance of the films prepared with the inks for 10 days and 20 days and the films prepared without the inks was R/R 0 The relative resistances of the films obtained after the inks prepared in example 1 and comparative examples 2 to 5 were left for 10 days and 20 days are shown in Table 3。
TABLE 3 stability test of inks prepared in example 1 and comparative examples 2-5
As can be seen from Table 3 and FIG. 6, the resistances of the copper films prepared by leaving the inks prepared in example 1 and comparative examples 2 to 5 for 10 days and 20 days, respectively, were R/R relative to the resistances of the copper films prepared in example 1 and comparative example 5 0 Smaller, but from table 2 the resistivity of the film prepared in comparative example 5 is greater; the resistance of the copper film prepared by leaving the inks prepared in comparative examples 2 to 4 for 10 days and 20 days, respectively, was R/R relative to the resistance of the copper film prepared in comparative examples 2 to 4 0 Larger. Therefore, the ink provided by the invention has good stability in air at normal temperature and normal pressure.
(2) Film stability test
The films prepared in examples 1 to 9 have a resistance after 16 hours of standing at 100℃relative to the initial resistance R/R 0 The results of (2) are shown in Table 4.
TABLE 4 stability of films prepared in examples 1-5
| Relative resistance R/R 0 | |
| Example 1 | 1.5 |
| Example 2 | 3.1 |
| Example 3 | 6.5 |
| Example 4 | 1.0 |
| Example 5 | 1.1 |
| Example 6 | 1.3 |
| Example 7 | 1.0 |
| Example 8 | 1.1 |
| Example 9 | 1.2 |
As is clear from Table 4, the films prepared in examples 1 to 9 have resistances after being left for 16 hours at 100℃relative to the initial resistance R/R 0 The films prepared in examples 4 to 9, in which nickel and silver were added, were smaller. Therefore, the film prepared by the invention has good stability.
(3) Bending and adhesion test
The films prepared in example 1 and comparative example 1 of the present invention were subjected to bending test (1000 times) and adhesion test (3M (Scotch Cat.600 tape, 3M) tape, and the results are shown in tables 5 and 6, respectively, in Table 5, the relative resistances are the resistance R of different bending radii and the resistance R of an unbent film 0 Is a ratio of (2); in Table 6, the relative resistances are the resistance R of films with different numbers of adhesion and the resistance R of films without adhesion 0 Is a ratio of (2).
TABLE 5 bending properties versus relative resistance of films prepared in example 1 and comparative example 1
TABLE 6 relationship between the number of film pastes and relative resistance for the preparation of example 1 and comparative example 1
As can be seen from tables 5 to 6, the films prepared by the process of the present invention have better bending stability and adhesion than those prepared by the conventional thermal sintering process. FIG. 7 shows the relative resistance R/R in the bending test of the film according to example 1 of the present invention at a bending radius of 5mm 0 From the graph, it can be seen that the relative resistance R/R after 1000 times of bending 0 There is no significant change. Therefore, the functional film prepared by the invention has better bending stability and adhesive force. The ink and the process can be applied to preparing the high-performance functional film with high bending stability, strong oxidation resistance, compact curing structure, excellent conductivity and large adhesion with the flexible substrate on the flexible substrate with low glass transition temperature.
The complex in the printing ink is formed by complexing metal salt (copper formate tetrahydrate, nickel formate dihydrate and silver oxalate) with two amines, the decomposition temperatures of the complexes corresponding to the two amines are different, and metal particles with different sizes can be obtained after the decomposition, as shown in figure 8, small-particle metal can be filled in gaps among large-particle metal by adopting the mixing of the two amines, so that the compactness and conductivity of the prepared film are improved, and the defect that the film solidification structure is not compact enough due to all large particles in the film or the connecting force between the particles is not strong enough due to all small particles in the film is avoided, so that the film has cracks.
Fig. 9 is a micro-cured structure of the film prepared in example 1 of the present application. The polyvinylpyrrolidone (PVP) long-chain polymer added into the ink plays a role of a binder in the metal film forming process, and copper/nickel/silver atoms cannot excessively aggregate in the nucleation process under the effect of the binder, so that copper/nickel/silver nucleation and growth are more uniform, and the micro-curing structure of the film is improved.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that those skilled in the art, based on the technical solutions provided by the present invention, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (6)
1. The preparation method of the functional film is characterized by comprising the following steps:
s1: cleaning the flexible substrate;
s2: spin-coating ink on a flexible substrate;
s3: placing the flexible substrate with the spin-coated ink on a heating plate for preheating treatment, placing the flexible substrate on a plasma device, setting the power, time and gas flow of plasma treatment, and then introducing N 2 /H 2 Inducing the mixed gas to obtain a functional film;
in the step S2, the ink comprises the following raw materials in percentage by mass: 24.9-47.1% of metal salt, 9.8-13.4% of 2-ethylhexyl amine, 14.3-27.9% of 2-amino-2-methyl-propanol, 1-5% of binder and 10-50% of organic solvent;
the metal salt is copper formate tetrahydrate or a mixture of copper formate tetrahydrate and other metal salts, and the other metal salts are one or two of nickel formate dihydrate and silver oxalate; the mass ratio of the copper formate tetrahydrate to other metal salts is 2-20:1;
in the step S3, the preheating treatment is to heat to 100-120 ℃ at a speed of 10-20 ℃/min, and the temperature is kept for 5-15 min; the power of the plasma treatment is 150-200W, the time is 2-10 min, and the gas flow is 5-40 ml/min;
The adhesive is polyvinylpyrrolidone, the purity of the polyvinylpyrrolidone is 99%, and the molecular weight is 44000-54000.
2. The method according to claim 1, wherein the organic solvent is one or both of n-butanol and ethylene glycol.
3. The preparation method of the ink according to claim 1, wherein the preparation method of the ink comprises the following steps in percentage by mass:
(1) Grinding metal salt to obtain metal salt powder;
(2) Mixing 2-amino-2 methyl-propanol with 2-ethylhexyl amine to obtain a mixed amine;
(3) Adding the mixed amine prepared in the step (2) into the metal salt powder obtained in the step (1), stirring for reaction, adding a solvent, stirring uniformly, adding a binder, and stirring for 10-12 hours to obtain the printing ink for preparing the functional film by plasma induction.
4. The method according to claim 3, wherein in the step (1), the metal salt powder has a particle diameter of 1 to 10 μm; the stirring speed in the step (3) is 1000-2000 r/min, and the stirring reaction time is 5-10 min.
5. The method according to claim 1, wherein in step S1, the cleaning is performed with UV light for 10 to 30 minutes; in the step S2, the spin coating speed is 3000 r/min, and the spin coating time is 40-60S.
6. A functional film prepared by the method of any one of claims 1 to 5.
Priority Applications (1)
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| JP2017022125A (en) * | 2016-08-23 | 2017-01-26 | 大日本印刷株式会社 | Copper nanoparticle dispersion and method of manufacturing conductive substrate |
| CN106833130A (en) * | 2017-03-24 | 2017-06-13 | 清华大学 | A kind of method for improving copper ion stability of ink and copper film electric conductivity |
| WO2019068770A1 (en) * | 2017-10-03 | 2019-04-11 | Luxembourg Institute Of Science And Technology (List) | Room-temperature plasma-assisted inkjet-printing of a liquid mod ink on a porous substrate |
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| US7629017B2 (en) * | 2001-10-05 | 2009-12-08 | Cabot Corporation | Methods for the deposition of conductive electronic features |
| WO2016017836A1 (en) * | 2014-07-30 | 2016-02-04 | (주)피이솔브 | Conductive ink |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017022125A (en) * | 2016-08-23 | 2017-01-26 | 大日本印刷株式会社 | Copper nanoparticle dispersion and method of manufacturing conductive substrate |
| CN106833130A (en) * | 2017-03-24 | 2017-06-13 | 清华大学 | A kind of method for improving copper ion stability of ink and copper film electric conductivity |
| WO2019068770A1 (en) * | 2017-10-03 | 2019-04-11 | Luxembourg Institute Of Science And Technology (List) | Room-temperature plasma-assisted inkjet-printing of a liquid mod ink on a porous substrate |
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