CN113241211B - Preparation method of organic film - Google Patents
Preparation method of organic film Download PDFInfo
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- CN113241211B CN113241211B CN202110491116.XA CN202110491116A CN113241211B CN 113241211 B CN113241211 B CN 113241211B CN 202110491116 A CN202110491116 A CN 202110491116A CN 113241211 B CN113241211 B CN 113241211B
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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Abstract
The invention provides a preparation method of an organic film, which relates to the technical field of conductive material preparation and comprises the following steps: providing at least one modified conductive nanoparticle; providing mother liquor A formed by carboxylated carbon nanotubes, 3, 4-ethylenedioxythiophene and polyvinylpyrrolidone; providing mother liquor B containing poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid, a photosensitizer, ethanol and modified conductive nanoparticles; providing a substrate, and spin-coating a coating solution formed by mother liquor A and mother liquor B on the substrate to form a film; and providing ultraviolet curing, heat treatment and annealing treatment to prepare an organic film; the haze of the organic film is not higher than 1%, and the thickness of the organic film is not higher than 0.2 mm. The preparation method provided by the invention can improve the light transmittance of the film, reduce the resistance, improve the conductivity and specific capacity and improve the cycle stability; the prepared film is a flexible transparent conductive film, and has stable specific capacity and charge-discharge efficiency, high conductivity and charge storage capacity.
Description
Technical Field
The invention belongs to the technical field of conductive material preparation, and particularly relates to a preparation method of an organic film.
Background
With the development of electronic products, the conductive material tends to be more flexible, and therefore, the development of new flexible transparent conductive materials is urgent. The organic transparent conductive film has excellent conductivity, light transmittance, and flexibility and solution processability, which facilitates the wide application of the organic transparent conductive film as a substitute for conventional transparent electrodes in many important applications, such as solar cells, supercapacitors, Light Emitting Diodes (LEDs), electrochemical cells, and the like. The most commonly known material used as a transparent conductive layer is Indium Tin Oxide (ITO). However, the raw materials used for ITO materials are expensive and limited in supply, and the ITO layer is fragile and lacks flexibility. The manufacturing method mainly includes electron beam evaporation (E-gun) or sputtering (Sputter), which requires harsh vacuum conditions during the manufacturing process, wherein the high temperature process will have a destructive effect on the epitaxial layer. The development of alternatives to ITO has become imperative.
At present, a variety of novel materials have been found to be useful for preparing organic transparent conductive films, including carbon nanotubes, graphene, metal nanowires, conductive polymers, and the like. Conductive polymers such as Polyaniline (PANI), polypyrrole (PPY), poly 3, 4-ethylenedioxythiophene (PEDOT), and the like have the characteristics of good conductivity, high charge storage capacity, environment-friendly stability, excellent reversibility, and the like in a doped state, and are widely used in the fields of energy storage and the like, such as supercapacitors, solar cells, and the like. The conductive polymer poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT/PSS) has great potential in manufacturing transparent conductive films. PEDOT/PSS is a mixture of poly (3, 4-ethylenedioxythiophene) and polystyrene sulfonic acid, with different formulations allowing the overall solution to exhibit different viscosities and conductivities. The PEDOT/PSS film has high transparency, good flexibility and excellent thermal stability in the visible light range, also shows good film forming performance, environmental stability and adjustable electronic structure, and becomes the best and applicable conductive polymer nowadays. However, before PEDOT/PSS films are widely used as electrodes for commercial products, there are still many problems to be solved, such as relatively poor conductivity, low adhesion on hydrophobic substrates, and low conductivity when exposed to high humidity air.
Therefore, one problem that needs to be urgently solved by those skilled in the art is: how to provide an organic flexible conductive film which can be produced in a large scale, has high conductivity and good performance stability, and expand the application range of the organic flexible conductive film.
Disclosure of Invention
The invention aims to provide a preparation method of an organic film, which can improve the light transmittance of the film, reduce the resistance, improve the cycle stability and improve the conductivity and the specific capacity.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method of making an organic thin film, comprising:
providing at least one modified conductive nanoparticle, wherein the size of the conductive nanoparticle is less than or equal to 100 nm;
providing mother liquor A formed by carboxylated carbon nanotubes, 3, 4-ethylenedioxythiophene and polyvinylpyrrolidone;
providing mother liquor B containing poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid, a photosensitizer, ethanol and the modified conductive nanoparticles;
providing a substrate, and spin-coating a film on the substrate by using a coating solution formed by the mother solution A and the mother solution B; and the number of the first and second groups,
providing ultraviolet curing, heat treatment and annealing treatment to prepare the organic film;
the haze of the organic film is not higher than 1%, and the thickness of the organic film is not higher than 0.2 mm.
According to the invention, the conductive nano particles and the carbon nano tubes are combined in the PEDOT/PSS film material, so that the migration rate of charges in the film can be improved, the conductivity and the specific capacity of the film can be improved, the charge storage capacity and the cycling stability of the film material can be enhanced, the temperature required in the preparation process is low, the thermal damage to a substrate or an epitaxial layer can be reduced, and the organic film product has better mechanical stability and electrochemical performance.
According to the present invention, the material of the conductive nanoparticles includes metal, metal oxide, semiconductor, or any combination thereof. Preferably, the metal is silver or gold, the metal oxide is zinc oxide or manganese dioxide or tungsten trioxide, and the semiconductor is titanium dioxide. Preferably, the size is 5-30 nm.
According to the invention, the modified conductive nanoparticles are prepared by the following steps: mixing the conductive nanoparticles, a silane coupling agent, a dispersing agent and a modifying agent, and then carrying out surface modification for 30-60min under the conditions that the ultrasonic condition is 35-40kHz/20-25kHz, the single-frequency working time is 20-30s and the temperature is 30-60 ℃ to obtain the modified conductive nanoparticles. In the modification process, the silane coupling agent is used for linking the conductive nano particles, the modifying agent and the dispersing agent into a whole, and then the coupling agent and the modifying agent are combined with other components in the mother solution through chemical bonds, so that the modified conductive nano particles are uniformly dispersed in the coating mother solution, higher loading capacity is provided, the conductivity and the electric conductivity of the film product are enhanced, and meanwhile, the conductive nano particles also have the effect of adjusting the chromaticity of the organic film of the product.
According to the invention, the weight ratio of the conductive nano-particles, the silane coupling agent, the dispersing agent and the modifying agent is 2:0.1-0.5:0.01-0.05: 0.05-0.3; the modifier is at least one selected from organic acid and organic acid anhydride. Preferably, the organic acid is methacrylic acid or acrylic acid; the organic acid anhydride is at least one selected from the group consisting of maleic anhydride, pyromellitic anhydride and trimellitic anhydride. Preferably, the silane coupling agent is gamma-methacryloxypropyltriethoxysilane or gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane.
According to the invention, the dispersant is 1-aminophosphonic acid and p-nitroacetophenone in a weight ratio of 3: 5-7. The existence of the dispersing agent enables the conductive nano particles to form a basically stable homogeneous system in the modification system and the coating mother liquor, so that the nano particles are uniformly dispersed in the product film, the light transmittance of the film is not reduced due to the accumulation effect of the nano particles, the effect of improving the light transmittance of the film is shown, and the resistance of the film is reduced to enhance the conductivity of the film; the dispersing agent and the modifying agent in the homogeneous system fix the nano particles in the film, so that the problem that nano metal ions are easy to migrate is solved, the conductive nano particles can provide stable ion and electron transmission rate for a long time, and rapid current response can be provided in charge-discharge circulation, so that stable specific capacity and charge-discharge efficiency can be maintained, and the specific capacity and the charge-discharge efficiency are controlled at 20mA/cm 2 After the constant current charge-discharge is carried out for 3000 times under the current density, the specific capacity retention rate of the organic film can reach more than 90%, and the charge-discharge efficiency is kept more than 98%, so that the cycle stability of the film is improved.
According to the invention, the contents of the polyvinylpyrrolidone and the carboxylated carbon nanotube in the mother liquor A are respectively 15-30 wt% and 5-8 wt%; the weight ratio of the 3, 4-ethylenedioxythiophene to the carboxylated carbon nanotube is 4-8: 1. The carbon nano tube is formed into stable dispersion liquid, and then the dispersion liquid and other components are prepared into the conductive film, so that the property of the film can be ensured to be more stable. The carbon nano tube has excellent conductivity and mechanical properties, and can effectively improve the specific capacity, the rapid charge and discharge performance and the cycling stability of the conductive polymer by compounding with the conductive polymer.
According to the invention, the contents of the modified conductive nano-particles, the photosensitizer and the ethanol in the mother liquor B are respectively 0.05-0.2 wt%, 0.05-0.1 wt% and 0.5-2.5 wt%; the solid content of the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid is 1.3-1.7%, and the solvent is water.
Specifically, the photosensitizer is a benzoin ether photosensitizer. The carboxylated carbon nanotube has the purity of more than or equal to 90 wt%, the inner diameter of 0.8-1.6nm, the outer diameter of 1-2nm and the length of 5-30 μm. The solid content of the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid is 1.3-1.7%, and the solvent is water.
Preferably, the mother liquor is prepared by the following specific implementation method: adding the carboxylated carbon nanotube, 3, 4-ethylenedioxythiophene and polyvinylpyrrolidone into pure water, and performing ultrasonic dispersion for 60-80min under the condition that the power is 100-; adding modified conductive nanoparticles, a photosensitizer and ethanol into the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid, and uniformly mixing to obtain a mother solution B.
According to the invention, the weight ratio of the mother solution A to the mother solution B in the coating solution is 1: 34-45. Preferably, when spin coating is performed to form the film, the coating solution is uniformly spin coated on the substrate by using a spin coating method, and the rotation speed of the spin coater is set to 2000-4000 rpm.
According to the present invention, the above ultraviolet curing conditions are as follows: the power is 50-90W, and the irradiation intensity is 90-150 muW/cm 2 The lamp distance is 1.5-2m, the ambient temperature is 10-20 ℃, and the time is 2-3 h.
According to the invention, the above heat treatment conditions are as follows: the temperature is 130-160 ℃, and the time is 1-2 h; the annealing conditions were as follows: the annealing temperature is 90-110 deg.C, and the annealing time is 10-20 min.
Preferably, the heat treatment and the annealing treatment are carried out as follows: and placing the semi-finished film and the substrate obtained by ultraviolet curing on a heating plate for heat treatment, then annealing the film after heat treatment, then washing the film by methanol in a rotating way, and drying at 50-70 ℃ to obtain the organic film. The internal crystal grain structure and the surface roughness of the film can be improved by annealing and then carrying out spin washing by using methanol, so that the flexible transparent conductive organic film with high light transmittance, low surface roughness, low resistance and stable structure and performance is prepared.
According to the invention, the conductive nanoparticles and the carbon nanotubes are combined in the PEDOT/PSS film material to prepare the organic film with the conductive property, so that the organic film has the following beneficial effects: 1) the preparation method is beneficial to improving the migration rate of charges in the film, can improve the conductivity and specific capacity of the film,the charge storage capacity and the cycling stability of the film material are enhanced, the temperature required in the preparation process is low, the thermal damage to the substrate or the epitaxial layer can be reduced, and the organic film product has better mechanical stability and electrochemical performance; 2) the prepared organic film is a high-flexibility transparent conductive film, and has the characteristics of high light transmittance, high conductivity, low square resistance, high specific capacity, excellent energy storage performance, rapid charge and discharge performance and good cycle stability, the light transmittance of the organic film at the wavelength of 550nm reaches more than 90%, and the square resistance is not higher than 70 omega/sq; 3) when the organic film is used as a capacitor material, the thickness is 20mA/cm 2 After the constant current charge-discharge cycle is carried out for 3000 times under the current density, the specific capacity retention rate of the organic film can reach more than 90 percent, the charge-discharge efficiency is kept more than 98 percent, and the stable electrochemical capacity performance is shown; 4) the prepared organic film can be used in the fields of flexible displays, flexible touch screens, solar cells, conductive film glass and electromagnetic shielding; the organic thin film can also be used as an energy storage material and/or an electrode material in the field of flexible solid-state capacitors.
Therefore, the preparation method of the organic thin film has the advantages of high light transmittance, high conductivity, low square resistance, high specific capacity, excellent energy storage performance, excellent rapid charge and discharge performance and good cycle stability.
Drawings
FIG. 1 shows the results of testing the cycling stability of various organic films;
FIG. 2 is a graph of the square resistance change of different organic films in a bending test.
Detailed Description
The technical scheme of the invention is further described in detail by combining the detailed description and the attached drawings:
in a specific implementation scenario, the substrate in the present invention includes a rigid or/and flexible substrate; examples of rigid substrates include, but are not limited to, glass, plexiglass, PC polycarbonate, and the like; examples of flexible substrates include, but are not limited to, polyester, polyethylene, cyclic olefin polymer, polyimide, polypropylene, polyethylene, and the like. The resulting organic film is peelable, and those skilled in the art can select a peeling process according to actual production requirements, or a rigid or flexible substrate according to production needs.
As an improvement of the scheme, 0.5 to 1.0 weight percent of 3-aminothiophenol and 0.3 to 1.5 weight percent of m-carboxyphenylboronic acid are also added into the mother liquor A. The carbon nano tube and the conductive nano particle can improve the crosslinking compactness among the components in the film during curing, relieve the phenomena of shape collapse and shrinkage mismatch of the carbon nano tube and the conductive nano particle when the film is bent by external force, play a role in buffering, improve the bending resistance of the film, ensure that the resistance change rate is lower than 8 percent after 10000 times of bending, and improve the resistance stability of the film; the compactness of membrane structure promotes, can also promote the weatherability of conducting film for the film demonstrates the promotion that is showing resistant high humidity and cold and hot shock resistance, and the luminousness change rate is less than 3%, and the square resistance change rate is less than 5%, has promoted the electrically conductive stability of film.
The present invention and the conventional techniques in the embodiments are known to those skilled in the art and will not be described in detail herein.
It is to be understood that the foregoing description is to be considered illustrative or exemplary and not restrictive, and that changes and modifications may be made by those skilled in the art within the scope and spirit of the appended claims. In particular, the present invention covers other embodiments having any combination of features from the different embodiments described above and below, without the scope of the invention being limited to the specific examples below. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
Example 1:
a method for preparing an organic thin film, comprising the steps of:
1) mixing conductive nanoparticles, a silane coupling agent, a dispersing agent and a modifying agent, and then carrying out surface modification for 45min under the conditions that the ultrasonic condition is 35kHz/25kHz and works alternately, the single-frequency working time is 30s and the temperature is 50 ℃ to obtain modified conductive nanoparticles; wherein the silane coupling agent is gamma-aminopropyl triethoxysilane; the modifier is methacrylic acid and trimellitic anhydride with the weight ratio of 1: 1; the weight ratio of the conductive nano particles to the silane coupling agent to the dispersing agent to the modifying agent is 2:0.15:0.05: 0.2; the size of the conductive nano-particles is 5-30nm, and the material is titanium dioxide; the dispersant is 1-amino phosphonic acid and p-nitroacetophenone, and the weight ratio of the dispersant to the p-nitroacetophenone is 3: 6.5;
2) adding a carboxylated carbon nanotube, 3, 4-ethylenedioxythiophene and polyvinylpyrrolidone into pure water, and performing ultrasonic dispersion for 70min under the condition that the power is 120W to prepare mother liquor A; the content of polyvinylpyrrolidone and the content of carboxylated carbon nanotubes in the mother solution A are respectively 20 wt% and 7.5 wt%, and the weight ratio of 3, 4-ethylenedioxythiophene to the carboxylated carbon nanotubes is 7: 1;
3) adding modified conductive nanoparticles, benzoin ethyl ether photosensitizer and ethanol into poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid, and uniformly mixing to obtain mother liquor B; the contents of the modified conductive nanoparticles, the photosensitizer and the ethanol in the mother liquor B are respectively 0.15 wt%, 0.1 wt% and 2.5 wt%; the solid content of the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid is 1.7 percent, and the solvent is water;
4) uniformly mixing the mother solution A and the mother solution B according to the weight ratio of 1:40 to obtain a coating solution; uniformly spin-coating the coating solution on a substrate by adopting a spin coating method to form a film, setting the rotating speed of the spin coating machine to 3000rpm, and then carrying out spin coating at the power of 80W and the irradiation intensity of 120 muW/cm 2 Ultraviolet curing for 2.5 hours under the conditions that the lamp distance is 1.5m and the ambient temperature is 15 ℃ to obtain a semi-finished film; the substrate is glass;
5) and (3) placing the semi-finished film and the substrate on a heating plate at the temperature of 150 ℃ for heat treatment for 1.5h, then annealing the heat-treated film for 15min at the annealing temperature of 100 ℃, then washing the film with methanol in a rotating manner, drying at the temperature of 60 ℃, and stripping to obtain the organic film with the thickness of 354 nm.
Example 2:
a method of preparing an organic thin film, which in operation differs from example 1 only in that:
in the step 1), the silane coupling agent is gamma-methacryloxypropyltriethoxysilane, and the modifier is methacrylic acid and maleic anhydride in a weight ratio of 1: 1; the conductive nano particles are made of manganese dioxide;
in the step 4), the substrate is a polyethylene plate with the thickness of 2 mm.
Example 3:
a method of preparing an organic thin film, which in operation differs from example 1 only in that:
in the step 1), the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane, and the modifier is acrylic acid and pyromellitic dianhydride in a weight ratio of 1: 1; the conductive nano particles are made of silver;
in the step 4), the substrate is a PC polycarbonate plate with the thickness of 2 mm.
Example 4:
a method of preparing an organic thin film, which in operation differs from example 1 only in that:
in step 2), 0.75 wt% of 3-aminothiophenol and 1.25 wt% of m-carboxyphenylboronic acid were also added to the mother liquor A when it was prepared.
Comparative example 1:
a method of preparing an organic thin film which, in operation, differs from example 1 only in that:
in the step 1), the dispersant is only 1-aminophosphonic acid, and p-nitroacetophenone is not added.
Comparative example 2:
a method of preparing an organic thin film, which in operation differs from example 1 only in that:
in the step 1), the dispersant is only p-nitroacetophenone, and 1-aminophosphonic acid is not added.
Comparative example 3:
a method of preparing an organic thin film, which in operation differs from example 1 only in that:
in the step 1), when the modified conductive nanoparticles are prepared, the dispersing agent 1-aminophosphonic acid and p-nitroacetophenone are not added into the modified system.
Comparative example 4:
a method of preparing an organic thin film which, in operation, differs from example 4 only in that:
in step 2), when mother liquor A is prepared, 0.75 wt% of 3-aminothiophenol is also added, and m-carboxyphenylboronic acid is not added.
Comparative example 5:
a method of preparing an organic thin film, which in operation differs from example 4 only in that:
in step 2), when mother liquor A is prepared, 1.25 wt% of m-carboxyphenylboronic acid is also added, and 3-aminothiophenol is not added.
Experimental example 1:
performance testing of organic films
The experimental method comprises the following steps: the organic thin films prepared in examples 1 to 3 and comparative examples 1 to 3 were used as experimental samples, an ITO conductive film was coated on a glass substrate as a control 1, and a pure PEDOT/PSS thin film material prepared on a glass substrate as a control 2 (the preparation conditions and parameters were the same as those of example 1, and the amount of PEDOT/PSS was the same as that of example 1). The thickness of the film is controlled at 350-380 nm. The light transmittance is detected by a WGT-S type light transmittance haze detector and is measured by a strip substrate, and the wavelength is 550 nm. The square resistance is tested by an SX-1934 type digital four-probe tester. Each group was made in triplicate. The results are shown in Table 1.
TABLE 1 results of Performance testing of different organic films
| Examples1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Control group 1 | Control group 2 | |
| Light transmittance% | 93.4 | 90.7 | 91.3 | 85.1 | 87.3 | 85.7 | 91.5 | 92.3 |
| Haze%) | 0.3 | 0.5 | 0.6 | 0.4 | 0.4 | 0.3 | 0.2 | 0.2 |
| Square resistance omega/sq | 63.8 | 68.2 | 66.3 | 83.1 | 79.2 | 82.6 | 53.1 | 72.4 |
The result shows that the substrate has certain influence on the square resistance and the light transmittance of the film, a proper substrate is selected in the practical production, and the comparison with the comparison group 1 shows that the electric conductivity of the organic film prepared by the invention is not much different from that of the comparison group 1 and the comparison group 2, and the organic film can replace an ITO conductive film and a pure PEDOT/PSS film. The results of comparative example 1 and comparative examples 1-3 show that the presence of the dispersant in example 1 synergistically and effectively increases the light transmittance of the film, and exhibits the beneficial effects of reducing the sheet resistance and enhancing the electrical conductivity.
Experimental example 2:
testing of cycling stability of organic films
The experimental method comprises the following steps: the organic films prepared in example 1 and comparative examples 1 to 3 were used as experimental samples, and pure PEDOT/PSS film materials prepared in example 1 were used as a control. Taking an organic film as a working electrode, a Saturated Calomel Electrode (SCE) as a reference electrode, a platinum sheet as an auxiliary electrode, and 0.5mol/L H 2 SO 4 And 0.5mol/L of KNO 3 The mixed solution is used as an electrolyte solution to perform a constant current charge and discharge experiment on the electrode material, wherein the voltage window of the constant current charge and discharge experiment is-0.4-1.2V, and the current density is 2-20mA/cm 2 . The specific capacity is calculated by the following formula: cp ═ I Δ t/(m Δ E), where Δ E is the voltage drop of discharge, V; Δ t is the discharge time, s; i is a discharge current, A; m is the electrode material mass, g. Then at a current density of 20mA/cm 2 3000 times of constant current charge-discharge circulation is carried out, and the circulation stability of the film is measured. Each group was made in triplicate. The results are shown in FIG. 1.
FIG. 1 shows the results of the cycling stability tests for various organic films. When the film prepared in example 1 was used as an electrode material, the discharge current was 2mA/cm 2 When the specific capacity is up to 335.47F/g, the discharge current is increased to 20mA/cm 2 The specific capacity can reach 268.34F/g. The results show that each set of films had a dramatic capacity fade during the first 1000 cycles, after whichThe circulation capacity is basically kept stable; under 3000-cycle constant-current charge and discharge of the control group, the specific capacity is attenuated most, the specific capacity retention rate is only 77.9%, and the charge-discharge efficiency (namely coulombic efficiency) is kept at 93.8%; the cycling stability of the embodiment 1 is optimal, the specific capacity retention rate can reach 93.3%, and the charge and discharge efficiency is kept at 98.5%; the specific capacity retention rate of the comparative example 3 can reach 87.3%, and the charge-discharge efficiency is kept at 95.4%; the retention of comparative examples 1-3 was significantly lower than that of example 1; the organic thin film of the present invention shows more stable electrochemical capacity performance than pure PEDOT/PSS thin film. The existence of the dispersing agent in the embodiment 1 can synergistically improve the cycle stability of the film, is beneficial to maintaining stable specific capacity and charge-discharge efficiency of the film, and improves the application range and service life of the film as a capacitor material.
Experimental example 3:
bending resistance test of organic thin film
The experimental method comprises the following steps: the organic films prepared in examples 1 and 4 and comparative examples 4 and 5 were used as experimental samples, and pure PEDOT/PSS film material prepared in Experimental example 1 was used as a control. The sample was placed in a bending tester and bent 90 °/10000 times, and then the sheet resistance was measured and the average Rs1 was calculated, compared with the sheet resistance Rs0 when not bent, and the rate of change of the sheet resistance was calculated according to the following formula: the square resistance change rate is (Rs1-Rs0)/Rs0 × 100%. Each group was made in triplicate. The results are shown in FIG. 2.
FIG. 2 is a graph of the square resistance change of different organic films in a bending test. After each group of films are bent for 10000 times, the film layer has no cracks and no fracture. The results show that the bending resistance and the resistance stability of the material in example 4 are optimal, the resistance change rate after 10000 times of bending is only 6.7%, and the final resistance is 1.07 times of the initial resistance; the resistance change rate of example 1 was 9.8%; the resistance change rate of the control group was 15.4%, and the organic thin film of the present invention showed more excellent bending resistance and resistance stability than the pure PEDOT/PSS film. The preparation method of the embodiment 4 can synergistically improve and relieve the phenomena of morphology collapse and shrinkage mismatch of the carbon nanotubes and the conductive nanoparticles, and play a role in buffering, so that the bending resistance and the resistance stability of the film are improved, the service life is prolonged, and the application range is expanded.
Experimental example 4:
weatherability testing of organic films
The experimental method comprises the following steps: the organic films prepared in examples 1 and 4 and comparative examples 4 and 5 were used as experimental samples, and pure PEDOT/PSS film material prepared in Experimental example 1 was used as a control. Respectively placing the sample in a high-temperature high-humidity environment and a cold and hot impact environment for weather resistance test, wherein the high-temperature high-humidity condition is as follows: the temperature is 85 ℃, the humidity is 80 percent, and the time is 240 h; the cold and hot impact environmental conditions are as follows: the temperature is low at minus 30 ℃ and high at 80 ℃, the time interval of temperature conversion is 10 h/time, and the total time is 240 h. Each group was made in triplicate. The results are shown in Table 2.
TABLE 2 weather resistance test results for different organic films
The results show that example 4 exhibits optimal weatherability in both high temperature and high humidity environments and cold thermal shock environments, with a rate of change in light transmittance of less than 3% and a rate of change in sheet resistance of less than 5%; and the organic film of the present invention shows more excellent weather resistance than pure PEDOT/PSS film. The preparation method of the embodiment 4 can synergistically improve the weather resistance of the conductive film, further improve the conductive stability of the film, prolong the service life and enlarge the application range.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (8)
1. A method of making an organic thin film, comprising:
providing at least one modified conductive nano particle, mixing the conductive nano particle, a silane coupling agent, a dispersing agent and a modifying agent, and then carrying out surface modification for 30-60min under the conditions that the ultrasonic condition is 35-40kHz/20-25kHz and works alternately, the single-frequency working time is 20-30s and the temperature is 30-60 ℃ to obtain the modified conductive nano particle, wherein the size of the conductive nano particle is less than or equal to 100 nm;
providing a mother solution A formed by carboxylated carbon nanotubes, 3, 4-ethylenedioxythiophene and polyvinylpyrrolidone;
providing a mother solution B containing poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid, a photosensitizer, ethanol and the modified conductive nanoparticles;
providing a substrate, and spin-coating a film on the substrate by using a coating solution formed by the mother solution A and the mother solution B to form a film; and (c) a second step of,
providing ultraviolet curing, heat treatment and annealing treatment to prepare the organic film;
the weight ratio of the conductive nano particles to the silane coupling agent to the dispersing agent to the modifying agent is 2:0.1-0.5:0.01-0.05:0.05-0.3, the modifying agent is at least one of organic acid and organic acid anhydride, the dispersing agent is 1-aminophosphonic acid and p-nitroacetophenone, and the weight ratio is 3: 5-7;
the haze of the organic film is not higher than 1%, and the thickness of the organic film is not higher than 0.2 mm.
2. The method for preparing an organic thin film according to claim 1, wherein: the material of the conductive nanoparticles comprises metal, metal oxide, semiconductor or any combination thereof.
3. The method for preparing an organic thin film according to claim 1, wherein: the content of the polyvinylpyrrolidone and the carboxylated carbon nanotube in the mother solution A is 15-30 wt% and 5-8 wt% respectively; the weight ratio of the 3, 4-ethylenedioxythiophene to the carboxylated carbon nanotube is 4-8: 1.
4. The method for preparing an organic thin film according to claim 1, wherein: 0.5-1.0 wt% of 3-aminothiophenol and 0.3-1.5 wt% of m-carboxyphenylboronic acid are also added into the mother liquor A.
5. The method for preparing an organic thin film according to claim 1, wherein: the content of the modified conductive nano particles, the content of the photosensitizer and the content of the ethanol in the mother solution B are respectively 0.05-0.2 wt%, 0.05-0.1 wt% and 0.5-2.5 wt%; the solid content of the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid liquid is 1.3-1.7%, and the solvent is water.
6. The method for preparing an organic thin film according to claim 1, wherein: the weight ratio of the mother solution A to the mother solution B in the film coating liquid is 1: 34-45.
7. The method for preparing an organic thin film according to claim 1, wherein: the ultraviolet curing conditions were as follows: the power is 50-90W, and the irradiation intensity is 90-150 muW/cm 2 The lamp distance is 1.5-2m, the ambient temperature is 10-20 ℃, and the time is 2-3 h.
8. The method for preparing an organic thin film according to claim 1, wherein: the heat treatment conditions were as follows: the temperature is 130-160 ℃, and the time is 1-2 h; the annealing treatment conditions were as follows: the annealing temperature is 90-110 deg.C, and the annealing time is 10-20 min.
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