CN102604334A - Self-supporting transparent highly-conductive poly-3,4-ethylenedioxythiophene (PEDOT) film and preparation method of the film - Google Patents
Self-supporting transparent highly-conductive poly-3,4-ethylenedioxythiophene (PEDOT) film and preparation method of the film Download PDFInfo
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Abstract
The invention discloses a self-supporting transparent highly-conductive poly-3,4-ethylenedioxythiophene (PEDOT) film and a preparation method of the film. The film is constituted by PEDOT and small molecule dopants. The preparation method of the film comprises coating a solution containing an oxidizing agent and an alkali inhibitor on the surface of a substrate after hydrophilic treatment to form a mixture layer containing the oxidizing agent and the alkali inhibitor, exposing the surface of the substrate to an atmosphere containing ethylenedioxythiophene monomers to allow the monomers to form a polymer film by polymerization on the surface of the substrate at a temperature of 7-120 DEG C, peeling the film off the surface of the substrate, and washing to obtain the target product. The PEDOT film disclosed by the invention obviates addition of a polymer film-forming agent, has excellent mechanical properties and electrical properties, and has an electrical conductivity controllable in the range of 10<-1>-10<3>S/cm and a light transmittance controllable in the range of 20% to 88%. The preparation process is simple, and easy to control.
Description
Technical field
The present invention relates to a kind of conductive film based on macromolecular material and preparation method thereof, relate in particular to a kind of self-supporting transparent high conductive PEDOT film and preparation method thereof, belong to field of photoelectric technology.
Background technology
Conducting polymer composite is novel functional high molecule material, has particular structural and excellent physical chemistry, and it is had a wide range of applications in fields such as the energy, opto-electronic device, transmitter, anti-corrosion of metal and information storage transmission process.Special; Be widely used as the transparent electrode material tin indium oxide (ITO) in the optoelectronic device at present; Have higher specific conductivity and transmittance preferably, but break easily on being applied to flexible substrate the time and lose specific conductivity, and cost receives the price limit of starting material indium.Conducting polymer thin film is regarded as the surrogate of very attractive.Along with the flexibility of devices such as organic photoelectric, ultra-thin light-weight development trend, particularly self-supporting (not relying on substrate) and the controlled method for manufacturing thin film of performance seem very important to the exploitation conductive polymer film.
Gather 3,4-enedioxy thiophene (PEDOT) is one of best conducting polymer of the present electroconductibility of being found, this material has high light transmittance and excellent environmental stability simultaneously.But the film strength that present compound method obtains is relatively poor, generally need depend on substrate base and exist, and can not form self-supporting film, need between each substrate, shift in use, complicated operation, to a great extent limit its use properties.Someone attempts adding macromolecule film former such as Z 150PH improving mechanical properties in films, but the electric property of film has been sacrificed in the introducing of nonconducting macromolecule film former to a certain extent.
How to bring into play the electric property of conducting polymer PEDOT and the mechanical property of self to greatest extent, the transparent high conductive film that obtains self-supporting easily is a technical barrier that needs to be resolved hurrily with the demand that adapts to the organic electro-optic device development.
Summary of the invention
The objective of the invention is to propose a kind of self-supporting transparent high conductive PEDOT film that has excellent mechanical property and electric property concurrently and preparation method thereof, thereby overcome deficiency of the prior art to deficiency of the prior art.
For realizing the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of self-supporting transparent high conductive polymeric film is characterized in that said film is by gathering 3; 4-enedioxy thiophene (that is, 3,4-enedioxy thiophene monomer) and small molecules doping agent formation; Gather 3, the repeating unit of 4-enedioxy thiophene and micromolecular mol ratio are between 1 ~ 10;
Said small molecules doping agent is small molecules acid and/or small molecules alkali;
Said small molecules acid is selected from tosic acid at least, by more than in the substituted tosic acid of part, hydrochloric acid, hydrogen bromide, hydrogen iodide, tetradecyl sulfonic acid, 4-vinyl benzenesulfonic acid and the camphorsulfonic acid any one;
Said small molecules alkali is selected from pyridine, pyrroles, imidazoles and four at least and replaces more than in (dimethylin) ethene any one.
The preparation method of self-supporting transparent high conductive polymeric film as stated; This method is: the solution that contains oxygenant and alkali suppressor factor in coating on the substrate surface after the hydrophilic treatment is formed with oxygenant and alkali inhibitor mixed thing layer; Then substrate surface is exposed in the atmosphere that contains the enedioxy thiophene monomer; Make the enedioxy thiophene monomer under 7 ℃ ~ 120 ℃ temperature, form polymeric film in the substrate surface polymerization; Polymeric film from substrate surface peeled off, wash, obtain target product thereafter;
Wherein, said oxygenant comprises trivalent iron salt, and said alkali suppressor factor comprises small molecules alkali; Solvent in the said solution comprises the small molecule alcohol solvent; And the mol ratio of said alkali suppressor factor and oxygenant is 0 ~ 1.25, and the content of oxygenant is 5wt% ~ 40wt% in the solution;
Said oxygenant is selected from any one in tosic acid iron and the iron(ic)chloride at least;
Said small molecules alkali is selected from any one in pyridine, pyrroles, imidazoles and four replacement (dimethylin) ethene at least.
Said small molecular alcohol kind solvent is selected from methyl alcohol at least, ethanol, any one in Virahol and the butanols.
Content＞the 20wt% of oxygenant in the said solution, and≤40wt%.
The said atmosphere that contains the enedioxy thiophene monomer is meant the volatility enedioxy thiophene monomer that air, nitrogen or argon gas flow and bring into down.
In this method, make the enedioxy thiophene monomer be preferably 50 ℃ in the temperature condition that the substrate surface polymerization forms polymeric film.
Preferably; In this method; Just the polymeric film detailed process of peeling off, washing from substrate surface is: the substrate that the surface is formed with polymeric film impregnated in the small molecular alcohol kind solvent; Break away from from substrate to polymeric film,, obtain target product again with aqueous solvent (like small molecule alcohol, water, THF, N or methyl-sulphoxide etc.) washing copolymer film.
A kind of self-supporting transparent high conductive polymeric film, it is prepared by following method:
To contain mol ratio be 0 ~ 1.25 the oxygenant and the solution of alkali suppressor factor on the substrate surface after the hydrophilic treatment, applying, thereby at substrate surface formation oxygenant and alkali inhibitor mixed thing layer, the content of oxygenant is 5wt% ~ 40wt% in the said solution;
This substrate surface is exposed in the atmosphere that contains the enedioxy thiophene monomer, makes the enedioxy thiophene monomer under 0 ℃～120 ℃ temperature, form polymeric film in the substrate surface polymerization;
Polymeric film is peeled off, washed from substrate surface, obtain target product;
Said oxygenant comprises trivalent iron salt, and said alkali suppressor factor comprises small molecules alkali, and the solvent in the said solution comprises alcoholic solvent.
Further, said film preferably adopts following method preparation:
On the glass substrate surface after the hydrophilic treatment, applying the solution that contains oxygenant and alkali suppressor factor, thereby forming oxygenant and alkali inhibitor mixed thing layer at substrate surface, the content＞20wt% of oxygenant in the said solution, but≤40wt%;
This substrate surface is exposed in the atmosphere that contains the enedioxy thiophene monomer, makes the enedioxy thiophene monomer under 7 ℃～120 ℃ temperature, form polymeric film in the substrate surface polymerization;
Substrate impregnated in the small molecular alcohol kind solvent, peel off from substrate surface,, obtain target product again with aqueous solvent (like small molecule alcohol, water, THF, N or methyl-sulphoxide etc.) washing copolymer film to polymeric film.
Said oxygenant is selected from any one in tosic acid iron and the iron(ic)chloride at least; Said alkali suppressor factor is selected from any one in pyridine, pyrroles, imidazoles and four replacement (dimethylin) ethene at least; Said small molecular alcohol kind solvent is selected from methyl alcohol at least; Ethanol, any one in Virahol and the butanols.
In this method, make the enedioxy thiophene monomer be preferably 50 ℃ in the temperature condition that the substrate surface polymerization forms polymeric film.
Be on the substrate to apply in the process of the mixture layer that forms oxygenant and alkali suppressor factor and in the process of enedioxy thiophene monomer polymerization formation polymeric film, preferably ambient moisture be controlled at 15% ~ 60%.
Compare in prior art; Beneficial effect of the present invention is: the conjugation long-chain and the high PEDOT film of compound with regular structure degree that obtain containing order orientation through the control to the polymerization environment; Thereby utilize the structure of PEDOT itself to greatest extent; Obtain good mechanical property and electric property, and make the complete disengaging substrate of film ability, thereby obtain the high conductive film of self-supporting through choice of Solvent.
Description of drawings
Fig. 1 is the photo of prepared PEDOT film in one embodiment of the present invention;
Fig. 2 is the specific conductivity and the light transmittance curve figure of prepared PEDOT film in one embodiment of the present invention;
Fig. 3 a and Fig. 3 b adopt the pyridine of different ratios and the AFM photo of molysite gained PEDOT film surface appearance among the present invention, wherein the mol ratio of pyridine and molysite is respectively 0.25 and 0.75 among Fig. 3 a and Fig. 3 b;
Fig. 4 is the XRD and the specific conductivity graphic representation of the PEDOT film that under different vapour phase polymerization temperature, obtains among the present invention.
Embodiment
As previously mentioned, though multiple PEDOT film occurred at present, all there are many deficiencies in it on performance and method of manufacture, and for this reason, this case contriver has proposed technical scheme of the present invention through studying for a long period of time and putting into practice.
Say that further the conductive polymers PEDOT single component self-supporting film that the present invention proposes is that the PEDOT macromolecular chain by compound with regular structure constitutes, and does not add macromolecule film former, has excellent mechanical property and electric property, specific conductivity is 10
-1~ 10
3Controlled in the S/cm scope, transmittance is controlled in 20% ~ 88% scope.
In order to regulate the conductivity of film; (pyridine, pyrroles, imidazoles or four replace (dimethylin) ethene small molecules doping agents such as (tetrakis (dimethylamino) ethylene, TDAE)) in aforementioned self-supporting film, also to add small molecules acid (for example tosic acid, the substituted tosic acid of part, hydrochloric acid, hydrogen bromide, hydrogen iodide, tetradecyl sulfonic acid, 4-vinyl benzenesulfonic acid or camphorsulfonic acid) or small molecules alkali.
This self-supporting transparent high conductive PEDOT film preferably adopts gas-phase synthesizing method to process, and it comprises the steps:
(1) substrate base is carried out hydrophilic treatment;
(2) prepare oxidizing agent solution A (comprising oxygenant, alkali suppressor factor and solvent), and A solution is applied to the mixture layer that substrate surface forms oxygenant and alkali suppressor factor;
The layer that (3) will contain above-mentioned oxygenant and alkali suppressor factor is exposed to and contains in the monomeric polymerization atmosphere of enedioxy thiophene (EDOT) polymerization film formation at a certain temperature;
(4) said polymeric film is immersed in the solvent to peel off from substrate obtain self-supporting film, and residual oxidizer, alkali suppressor factor and byproduct of reaction are removed in washing in solvent.
Among the aforementioned oxidizing agent solution A, oxygenant preferably adopts trivalent iron salt (like tosic acid iron, iron(ic)chloride etc., but be not limited thereto); The alkali suppressor factor is preferably small molecules alkali such as pyridine, solvent be preferably alcoholic solvent (like methyl alcohol, ethanol; Virahol, butanols etc., but be not limited thereto).Wherein the mol ratio of alkali suppressor factor and molysite is between 0 ~ 1.25, is preferably between 0.75 ~ 1; Iron salt solutions concentration is 5% ~ 40% (massfraction), is preferably more than 20%, but is less than or equal to 40%.
Aforementioned polymerization atmosphere is to bring evaporable EDOT monomer under air or the flow of nitrogen gas into, and polymerization temperature is preferably 7～120 ℃, especially is preferably 50～120 ℃.
In addition, in abovementioned steps (2), on substrate, apply to form in the process of mixture layer of oxygenant and alkali suppressor factor and preferably ambient moisture is controlled at 15% ~ 60% in the polymerization process.
The aforementioned solvent of peeling off use is preferably the small molecular alcohol kind solvent, and cleaning solvent is preferably aqueous solvent (like small molecule alcohol, water, THF, N or methyl-sulphoxide etc.).
The present invention utilizes good mechanical property and the electric property of PEDOT itself to greatest extent; And through control to polymerizing condition; Can regulate and control the structure and the electricity optical property of film accurately, thereby acquisition has the high conductive film of the self-supporting of good comprehensive electricity, light, mechanical property.
Below in conjunction with an accompanying drawing and a preferred embodiment technical scheme of the present invention is further introduced the present invention, but this embodiment should not be regarded as limitation of the present invention.
The compound method of the PEDOT film of the self-supporting that present embodiment is related comprises the steps:
(1) with after the careful washing of glass substrate, ydrogen peroxide 50 is handled, drying;
(2) preparation oxidizing agent solution: it is 40% solution that the tosic acid dissolved ferric iron is obtained massfraction in propyl carbinol; Add pyridine then with tosic acid iron equimolar amount; Mixing, be spun on the glass substrate in (1), is to carry out drying under 50% the environment in humidity;
(3) glass substrate that has oxygenant that (2) is obtained shifts in the polymerization reaction chamber, polymerization film formation in evaporable EDOT monomer, and humidity 20%, nitrogen flow rate 150 mL/min, temperature is controlled at 50
oC, two hours time;
The glass substrate that has polymeric film that (3) are obtained immerses in the ethanol, slowly moves glass substrate, can from substrate, complete the peeling off of polymeric film be obtained self-supporting film; And in ethanol, further wash to remove byproduct of reaction, consult Fig. 1, this film is a blue membrane; It can leave in all kinds of SOLVENTS; Only need cover during use on the target surface, after the drying, can rely on Van der Waals force tightly to adhere on the target surface.Its specific conductivity and light transmission are as shown in Figure 2.
Further, this case contriver is also through changing the processing condition in the preceding method, and studying different technology conditions may be to the influence of title product (that is self-supporting PEDOT film) performance generation.
The first; This case contriver is through the molar ratio of pyridine and tosic acid iron in the adjustment oxidizing agent solution; Study the influence that the amount ratio of pyridine and tosic acid iron may be caused the title product performance; Consult Fig. 3 a and Fig. 3 b, can find out pyridine to the molysite ratio when higher (such as, be preferably 0.75) film surface that obtains is particularly smooth.Therefore, through the molar ratio of pyridine and tosic acid iron in the adjusting oxygenant, can regulate and control preferably for the performance of film.
It two is, this case contriver has adjusted the temperature of polymerization reaction chamber, and polymerization temperature is respectively 30 ℃; 40 ℃, 50 ℃, 60 ℃; The molar ratio of pyridine and tosic acid iron is 0.75; Consult Fig. 4, can find out that the compound with regular structure degree of this self-supporting film is high, temperature has remarkable influence to the crystalline network of film.Preferred temperature is 50 ℃, and the regularity and the specific conductivity of gained film are the highest.Can regulate and control preferably the performance of film through attemperation.
Compared to prior art; Polymeric film of the present invention is easier to peel off; The product planeness is better, and this mainly is because the compound with regular structure Du Genggao (this point also can be found out from the crystalline network of product shown in Figure 4) of the film that the control of polymerizing condition technology is obtained.
Though illustrated and described specific embodiments of the present invention; But should not understand in limitation of the present invention; To those skilled in the art, other changes under the situation that does not deviate from essence of the present invention and scope, made and distortion are also within protection scope of the present invention.
Claims (11)
1. a self-supporting transparent high conductive polymeric film is characterized in that, said film is by gathering 3, and 4-enedioxy thiophene and small molecules doping agent constitute, and gather 3, and the repeating unit of 4-enedioxy thiophene and the mol ratio of small molecules doping agent are between 1 ~ 10;
Said small molecules doping agent is small molecules acid and/or small molecules alkali;
Said small molecules acid is selected from tosic acid at least, by more than in the substituted tosic acid of part, hydrochloric acid, hydrogen bromide, hydrogen iodide, tetradecyl sulfonic acid, 4-vinyl benzenesulfonic acid and the camphorsulfonic acid any one;
Said small molecules alkali is selected from pyridine, pyrroles, imidazoles and four at least and replaces more than in (dimethylin) ethene any one.
2. the preparation method of self-supporting transparent high conductive polymeric film according to claim 1; It is characterized in that; This method is: the solution that contains oxygenant and alkali suppressor factor in coating on the substrate surface after the hydrophilic treatment is formed with oxygenant and alkali inhibitor mixed thing layer; Then substrate surface is exposed in the atmosphere that contains the enedioxy thiophene monomer; Make the enedioxy thiophene monomer under 7 ℃ ~ 120 ℃ temperature, form polymeric film, thereafter polymeric film is peeled off, washed from substrate surface, obtain target product in the substrate surface polymerization;
Wherein, said oxygenant comprises trivalent iron salt, and said alkali suppressor factor comprises small molecules alkali, and the solvent in the said solution comprises small molecular alcohol, and the mol ratio of said alkali suppressor factor and oxygenant is 0 ~ 1.25, and the content of oxygenant is 5wt% ~ 40wt% in the solution;
Said oxygenant is selected from any one in tosic acid iron and the iron(ic)chloride at least;
Said small molecules alkali is selected from any one in pyridine, pyrroles, imidazoles and four replacement (dimethylin) ethene at least;
Said small molecular alcohol is selected from methyl alcohol at least, ethanol, any one in Virahol and the butanols.
3. the preparation method of self-supporting transparent high conductive polymeric film according to claim 2 is characterized in that, the content＞20wt% of oxygenant in the said solution, and≤40wt%.
4. the preparation method of self-supporting transparent high conductive polymeric film according to claim 2 is characterized in that: the said atmosphere that contains the enedioxy thiophene monomer is meant the volatility enedioxy thiophene monomer that air, nitrogen or argon gas flow and bring into down.
5. the preparation method of self-supporting transparent high conductive polymeric film according to claim 2 is characterized in that, in this method, makes the enedioxy thiophene monomer be preferably 50 ℃ in the temperature condition that the substrate surface polymerization forms polymeric film.
6. the preparation method of self-supporting transparent high conductive polymeric film according to claim 2; It is characterized in that; In this method, just the polymeric film detailed process of peeling off, washing from substrate surface is: the substrate that the surface is formed with polymeric film impregnated in the small molecular alcohol, breaks away from from substrate to polymeric film; With aqueous solvent washing copolymer film, obtain target product again;
Said aqueous solvent is selected from any one in small molecular alcohol, water, THF, N and the methyl-sulphoxide at least.
7. self-supporting transparent high conductive polymeric film is characterized in that said film is prepared by following method:
To contain mol ratio be 0 ~ 1.25 the oxygenant and the solution of alkali suppressor factor on the substrate surface after the hydrophilic treatment, applying, thereby at substrate surface formation oxygenant and alkali inhibitor mixed thing layer, the content of oxygenant is 5wt% ~ 40wt% in the said solution;
This substrate surface is exposed in the atmosphere that contains the enedioxy thiophene monomer, makes the enedioxy thiophene monomer under 0 ℃～120 ℃ temperature, form polymeric film in the substrate surface polymerization;
Polymeric film is peeled off, washed from substrate surface, obtain target product;
Said oxygenant comprises trivalent iron salt, and said alkali suppressor factor comprises small molecules alkali, and the solvent in the said solution comprises small molecular alcohol.
8. self-supporting transparent high conductive polymeric film according to claim 7 is characterized in that, said film preferably adopts following method preparation:
On the glass substrate surface after the hydrophilic treatment, applying the solution that contains oxygenant and alkali suppressor factor, thereby forming oxygenant and alkali inhibitor mixed thing layer at substrate surface, the content＞20wt% of oxygenant in the said solution, but≤40wt%;
This substrate surface is exposed in the atmosphere that contains the enedioxy thiophene monomer, makes the enedioxy thiophene monomer under 7 ℃～120 ℃ temperature, form polymeric film in the substrate surface polymerization;
Substrate impregnated in the small molecular alcohol kind solvent, peel off from substrate surface,, obtain target product again with aqueous solvent washing copolymer film to polymeric film;
Said aqueous solvent is selected from any one in small molecular alcohol, water, THF, N and the methyl-sulphoxide at least.
9. according to claim 7 or 8 described self-supporting transparent high conductive polymeric films; It is characterized in that; Said oxygenant is selected from any one in tosic acid iron and the iron(ic)chloride at least, and said alkali suppressor factor is selected from any one in pyridine, pyrroles, imidazoles and four replacement (dimethylin) ethene at least, and said small molecular alcohol is selected from methyl alcohol at least; Ethanol, any one in Virahol and the butanols.
10. according to claim 7 or 8 described self-supporting transparent high conductive polymkeric substance, it is characterized in that, in this method, make the enedioxy thiophene monomer be preferably 50 ℃ in the temperature condition that the substrate surface polymerization forms polymeric film.
11. according to claim 7 or 8 described self-supporting transparent high conductive polymkeric substance; It is characterized in that, on substrate, preferably ambient moisture is controlled at 15% ~ 60% in the process of the mixture layer of coating formation oxygenant and alkali suppressor factor and in the process of enedioxy thiophene monomer polymerization formation polymeric film.
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