CN106297968B - A kind of PEDOT films of high thickness high conductivity and preparation method thereof - Google Patents
A kind of PEDOT films of high thickness high conductivity and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of PEDOT films of high thickness high conductivity and preparation method thereof, using EDOT monomers as raw material, with the high alcohol-soluble molysite FeX containing weakly-basic anion3For oxidant, use vapor phase method or solwution method that composition is prepared as PEDOT:X PEDOT films, wherein X are the weakly-basic anion of high alcohol-soluble, preferably at least one of camphorsulfonic acid radical ion, chain alkyl benzenesulfonate ion, alkyl naphthalene sulfonic acid radical ion, dialkyl napthalene sulfonic acids radical ion and dinonylnaphthalene disulfonic acid radical ion.The present invention utilizes the high alcohol-soluble of presoma iron salt oxidization agent solution, improves the concentration and viscosity of spin coating liquid, suppresses the crystallization of oxidant in course of reaction, without adding the anti-crystallization inhibitor of copolymer（Pyridine, PEPG etc.）, so as to obtain the PEDOT films of high thickness.
Description
Technical field
The invention belongs to field of energy source materials, and in particular to a kind of PEDOT films of high thickness high conductivity and its preparation
Method, product have high thickness and high conductivity, optimize traditional handicraft, preferably meet the needs of application.
Background technology
Conducting polymer materials have more preferable ductility, machinability and lower compared to the inorganic block materials of tradition
Cost, poly- 3,4-rthylene dioxythiophene (PEDOT) are conducting polymer thermoelectric materials most outstanding at present, PSS doping
Because electrical conductivity is high, has commercially produced etc., reason is most often used PEDOT, the highest ZT of the PEDOT films of the preparation such as Kim
Value has reached 0.42 (Nat Mater, 2013,12,719).In addition, prepared by solwution method, vapor phase method and electrochemical polymerization
Small molecule doping PEDOT, such as PEDOT:Tos, because man-to-man doping make it that the structure of main chain is compacter, advises
Whole, Seebeck coefficient is high, equally with excellent thermoelectricity capability, its it is complete it is doped under the initial power factor up to 40 μ W/mK2
More than, and can further optimize its thermoelectricity capability by adjusting doping level, such as：Park etc. is synthesized using solwution method
Afterwards using the PEDOT of electrochemical process reduction:Tos power factors are up to 1260 μ W/mK2(Energy&Environmental
Science, 2013,6,788), Wang etc. utilizes the PEDOT reduced after vapor phase method or electrochemical polymerization with hydrazine power factor
In 165.3 μ W/mK2More than (Organic Electronics, 2015,17,151).
However, current preparation technology has two deficiencies, PEDOT application is constrained, is too low thickness first.Pass
The thickness of PEDOT films prepared by system method is less than 200nm mostly, and low thickness adds the internal resistance of thin-film device, reduces device
The power output of part, greatly it is degrading its performance；Moreover, low thickness reduces the test signal of analytical instrument, letter is increased
Make an uproar than and error so that structure to film and performance test, which characterize, becomes difficult；In addition, it is PEDOT thin as electrode material
The main application fields of film, low thickness can increase the sheet resistance of electrode material, not meet electrode material to low sheet resistance
It is required that.These factors all constrain the application of PEDOT films in practice significantly.If it is possible to improve PEDOT films
Thickness, its application in practice will be expanded significantly.
Because film uniformity, flatness and the performance that drop coating obtains are poor, mainly prepared at present by spin coating method
High performance PE DOT films, the main reason for thickness is low, are that the concentration of spin coating liquid is low.For example, macromolecular PEDOT:PSS passes through rotation
The aqueous solution for applying PEDOT obtains, in order to avoid the reunion of polymer, PEDOT:The concentration of the PSS aqueous solution is less than 1.3% mass point
Number；Small molecule PEDOT films are mainly synthesized by solwution method and vapor phase method, and the former is to dissolve iron salt oxidization agent and monomer together
Spin coating liquid is made into alcohol, after spin coating, is made after heating response；The latter is directly by iron salt oxidization agent wiring solution-forming, after spin coating,
React and be made in the vapor atmosphere of monomer.Common iron salt oxidization agent FeTos3、FeOtf3Solubility it is relatively low, to avoid separating out,
Rotation coating liquid concentration is generally less than 40% mass fraction.Low concentration causes conventional method to be used for the viscosity for preparing PEDOT spin coating liquid
Decline, film thickness made from reaction is difficult to more than 200nm after spin coating.Multiple spin coating can make it that upper strata spin coating liquid dissolving lower floor is thin
Film, be can not spin coating obtain thickness film, and repeat spin coating reactions steps not only bother, can also produce the boundary of layer and layer
Face, film performance is reduced, and PEDOT also has the risk of pyrolysis during Repeat-heating.Therefore, single spin reacts to obtain
Thick PEDOT films are a urgent problems.
Second deficiency, is FeTos3And FeOtf3Etc. conventional oxidation agent also have following two it is big unstable the characteristics of, limit
Its application is made：Firstly, since FeTos3And FeOtf3Middle anion is strong acid radical ion, and the pH value of solution is higher, accelerates
Reaction speed, too fast reaction speed cause the formation of fault of construction, reduce thermoelectricity capability, it is therefore desirable to add pyridine etc
Alkaline inhibitor improves the pH of solution, and slowed down reaction speed, pyridine is larger to the toxicity of people, and it, which volatilizees, causes the dirt of environment
Dye.Secondly as solubility is relatively low, precipitation is easily crystallized when reacting and heating, defect is formed in the film, is unfavorable for carrier
Transmission, therefore also need to additionally to add copolymer and crystallization suppressed, as polyethylene glycol-propylene-ethylene glycol ternary is total to
Polymers (PEPG), being incorporated in PEDOT for PEPG introduce non-conductive second phase, reduce the homogeneity and conductive capability of film.
Moreover, the addition of copolymer reduce further the concentration of oxidant, thickness is set to reduce by more than 50%.
The content of the invention
In view of the above-mentioned problems, present invention aims at provide a kind of PEDOT films with the high thickness of high conductivity.
Therefore, the invention provides a kind of PEDOT films with high thickness and high conductivity, using EDOT monomers as original
Material, using the high alcohol-soluble molysite FeX containing weakly-basic anion3For oxidant, and then directly use vapor phase method or solution legal system
The standby composition that obtains is PEDOT:X PEDOT films, wherein X are the weakly-basic anion of high alcohol-soluble, preferably camphorsulfonic acid root
Ion, chain alkyl benzenesulfonate ion, alkyl naphthalene sulfonic acid radical ion, dialkyl napthalene sulfonic acids radical ion and dinonylnaphthalene disulfonic acid
At least one of radical ion.
The present invention utilizes the high alcohol-soluble of presoma iron salt oxidization agent solution, improves the concentration and viscosity of spin coating liquid, suppresses
The crystallization of oxidant in course of reaction, without adding the anti-crystallization inhibitor of copolymer (pyridine, PEPG etc.), so as to obtain high thickness
PEDOT films.Secondly the weakly-basic anion in iron salt oxidization agent is utilized to combine caused hydrogen ion during the course of the reaction,
Regulate and control the actual concentrations of hydrogen ion and ferric ion, so as to control reaction speed, obtain the PEDOT films of high conductivity.
It is preferred that the thickness of the PEDOT films is 0.3~3 μm.
It is preferred that the electrical conductivity of the PEDOT films is more than 200S/cm, preferably more than 750S/cm, more preferably
More than 1100S/cm.
The present invention provides a kind of method that vapor phase method prepares the above-mentioned PEDOT films with high thickness and high conductivity, bag
Include：
By high alcohol-soluble molysite FeX3Solution carries out spin coating on substrate, obtains molysite FeX3Film；
By gained molysite FeX3Film be placed in reaction vessel, be passed through inert gas and EDOT monomer vapors, and will be anti-
Container is answered to react 5~40 minutes at 60~100 DEG C to the molysite FeX3Film color changed completely by yellow or brown
Au bleu is black-and-blue, after being washed with ethanol, spontaneously dries at room temperature, obtains the PEDOT films.
Also, it is preferred that the inert gas is at least one of nitrogen, argon gas.
The present invention provides a kind of method that solwution method prepares the above-mentioned PEDOT films with high thickness and high conductivity, bag
Include：
By EDOT monomers and high alcohol-soluble molysite FeX3Solution uniformly mixing after spin coating is carried out on substrate, obtain EDOT and
Molysite FeX3The film of mixture；
By gained EDOT and molysite FeX3The film of mixture reacts 15 seconds~1 minute to the EDOT at 70~80 DEG C
With molysite FeX3The color of the film of mixture changes au bleu by yellow completely, naturally dry at room temperature after being washed with ethanol
It is dry, obtain the PEDOT films.
Also, it is preferred that the EDOT monomers and high alcohol-soluble molysite FeX3Mol ratio be 1:4~1:1.
It is preferred that the high alcohol-soluble molysite FeX3High alcohol-soluble molysite FeX in solution3Mass fraction for 46%~
84%, solvent is methanol, ethanol, propyl alcohol, at least one of butanol.
Also, the it is preferred that high alcohol-soluble molysite FeX3Also include the free doping that mass fraction is 1-20% in solution
Acid, the free dopant acid are preferably camphorsulfonic acid, chain alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, dialkyl napthalene sulfonic acids and two nonyls
At least one of base naphthalenedisulfonic acid.
It is preferred that the substrate is one kind in sheet glass, quartz plate, silicon chip and plastic sheet.
It is preferred that the rotating speed of the spin coating is 5000~8500rpm.
PEDOT films prepared by the present invention have high thickness and high conductivity, and thickness may be up to 1.79 μm, and electrical conductivity is reachable
More than 1100S/cm, sheet resistance can as little as 5 below Ω, and realize zero addition of inhibitor, simplify technique, reduce into
This, environmental pollution is small, preferably meets the needs of practical application.
Brief description of the drawings
Fig. 1 is PEDOT prepared by the embodiment of the present invention 1:DBSA Raman spectrogram；
Fig. 2 is PEDOT prepared by the present invention:DBSA sheet resistances (a) and electrical conductivity (b) with thickness variation relation；
Fig. 3 is PEDOT prepared by the embodiment of the present invention 2:BNSA Raman spectrogram；
Fig. 4 is PEDOT prepared by the embodiment of the present invention 3:CSA Raman spectrogram.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention uses the high alcohol-soluble molysite containing weakly-basic anion as oxidant, and then directly uses vapor phase method or molten
The PEDOT films of high thickness high conductivity are prepared in liquid method.Consisting of PEDOT:(wherein X is the alkalescent of high alcohol-soluble to X
Anion：Camphorsulfonic acid radical ion, chain alkyl benzenesulfonate ion, alkyl naphthalene sulfonic acid radical ion, dialkyl napthalene sulfonic acids root from
At least one of son, dinonylnaphthalene disulfonic acid radical ion).
The preparation of the present invention is by synthesizing oxidant molysite FeX3, prepare precursor solution, spin coating, polymerization, washing work
Skill is realized.The present invention can also ensure that thermoelectricity capability does not drop while effectively lifting thickness, avoiding the addition of pyridine and PEPG
It is low.
The present invention is reacted using Doped ions sodium salt, barium salt or acid as raw material with ferric trichloride or ferric sulfate,
Method or solution deposition method are steamed to prepare oxidant molysite by barium sulfate precipitate method, hydrogen chloride, it is molten to be then dissolved in alcohol
In agent.Solvent can be the one or more in methanol, ethanol, propyl alcohol, butanol or alcohol-water blending agent, and concentration is in 46%-
Between 84% mass fraction.Based on the PEDOT of method provided by the present invention synthesis, due to the acid weak and alcohol-soluble of presoma
Good, synthesis can be carried out in methanol, ethanol, propyl alcohol, butanol or alcohol-water blending agent, have very big solvent range of choice,
Improve traditional synthesis and largely rely on present situation of the butanol as solvent.
According to an aspect of the present invention, PEDOT films are synthesized by gaseous polymerization.Iron salt solutions are revolved on substrate
Apply film forming.Spin coating process is carried out in spin coating instrument, and spin coating speed is 5000-8500rpm (such as 7500rpm), spin-coating time 10-
30s (such as 15s).By the good molysite FeX of spin coating3Film be placed in quartz or glass material the flat reaction vessel of bilateral in,
It is passed through inert gas and saturation EDOT monomer vapors, gas mole ratio 1:2~4:1, and reaction vessel is placed in plane heating
On platform react 5-40min (such as 25min), heating and temperature control 60-100 DEG C (such as 90 DEG C) to film color completely by Huang
Color (or brown) transformation au bleu (or black-and-blue) takes out film afterwards, after being washed with ethanol, spontaneously dries at room temperature.
According to an aspect of the present invention, PEDOT films are synthesized by solution spin-coating method.By EDOT monomers and iron salt solutions
By mol than 1:4-1:1 mixing, after being uniformly dissolved on substrate spin-coating film.Spin coating process is carried out in spin coating instrument, spin coating speed
For 5000-8500rpm (such as 7500rpm), spin-coating time 10-30s (such as 15s).The good precursor thin-film of spin coating is placed in
15s-1min (such as 20s) is reacted on plane heating platform, heating and temperature control is complete to film color at 65-80 DEG C (such as 70 DEG C)
Film is taken out after changing au bleu by yellow entirely, after being washed with ethanol, is spontaneously dried at room temperature.
According to an aspect of the present invention, it is corresponding that 1%-20% mass fractions (such as 5% mass fraction) can be added
Free dopant acid, such as camphorsulfonic acid, chain alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, dialkyl napthalene sulfonic acids, dinonylnaphthalene disulfonic acid
Hydrogen ion concentration can be improved, so as to accelerate polymerization speed.Based on the PEDOT of method provided by the present invention synthesis, can pass through
Extra dopant acid is added to accelerate, improves preparation efficiency.Typically added in right amount according to the acidity of dopant acid, addition
Generally no greater than 20% mass fraction, split-phase otherwise easily occurs.
Based on the PEDOT of method provided by the present invention synthesis, micron-sized thick film can be obtained.What traditional handicraft used
Spin coating liquid is due to solubility limit, it is difficult to more than 40% mass fraction.And has high alcohol-soluble iron salt oxidization agent FeX3Can be direct
The spin coating liquid of 70% mass fraction concentrations above is configured, and can be by changing precursor solution concentration, type of solvent, spin coating speed
Spend to adjust thickness, the film thickness for reacting to obtain after single spin is up to 0.3-3 μm, and electrical conductivity does not decline, and sheet resistance can
5 below Ω are down to, it is convenient that the application and sign for thermoelectric material provide.
Based on the PEDOT of method provided by the present invention synthesis, without adding alkaline inhibitor, course of reaction is gentle and steady
It is fixed.Traditional oxidant acid radical anion containing strong acid, p-methyl benzenesulfonic acid iron (FeTos3) this highly acid oxidant closes
Into PEDOT, if not adding pyridine, PEDOT:Tos polymerisation almost complete by moment, oligomerization caused by being reacted due to high speed
The defects of degree and structure, thin film thermoelectric degraded performance, electrical conductivity is only 19S/cm, and Seebeck coefficient is only 13.2 μ V/K.And adopt
With the iron salt oxidization agent containing weakly-basic anion of high alcohol-soluble, such as camphorsulfonic acid iron (FeCSA3), in identical condition
Lower synthesis PEDOT:CSA, reaction time extend to 22s, illustrate effectively suppress hydrionic concentration containing weakly-basic anion,
Control reaction is gentle to be carried out, and calculates the iron salt solutions for finding 1mol/L under simulation aqueous systems, and the latter is hydrionic during reaction end
Concentration is only the former 3% less than gentle reaction improves the degree of polymerization, the defects of avoiding structure, PEDOT:CSA electrical conductivity
Up to 752S/cm, Seebeck coefficient reacts obtained PEDOT up to 26.4 μ V/K, and traditional addition pyridine:Tos has reached equal
Level.
Based on the PEDOT of method provided by the present invention synthesis, without adding anti-crystallization inhibitor, the homogeneity of film
Good, thickness loss is small.Traditional handicraft such as FeTos3Vapor phase method prepares PEDOT:Tos, if not adding PEPG, due to low solubility
FeTos3Precipitation cause substantial amounts of film internal flaw, but 1wt% PEPG addition allow for thickness reduce by 50% with
On, and introduce nonconducting second phase.And high alcohol-soluble oxidant is used, such as DBSA iron (FeDBSA3),
, can the directly smooth PEDOT of vapor phase method synthesis of densified due to the high alcohol-soluble of Doped ions:DBSA films, without any crystallization
Phenomenon, surface roughness (Rq) are only 4-6nm, and AFM is shown as unformed homogeneous phase, and electrical conductivity reaches 1140S/cm, Sai Bei
Gram coefficient reaches 24.7 μ V/K, and power factor reaches 69.6 μ W/mK2, more than the full doping PEDOT of overwhelming majority report thermoelectricity
Performance.
Based on the PEDOT of method provided by the present invention synthesis, synthesized according to gas phase synthesis method, first by molysite FeX3
It is dissolved in solvent, then the spin-coating film on substrate, is put into be connected with the reaction vessel of inert gas and monomer vapor and reacts
5-40min, 60-100 DEG C of heating-up temperature, is washed after taking-up with ethanol, and naturally dry, and it is excellent that this method can be applied to processability
Different thin film thermoelectric materials.
Based on the PEDOT of method provided by the present invention synthesis, synthesized according to solution spin-coating method, first by molysite FeX3
It is dissolved in solvent, then the spin-coating film on substrate, is placed on plane heating platform and reacts 15s-1min, heating-up temperature 70-80
DEG C, washed after taking-up with ethanol, and naturally dry, this method can be used for it is quick, be prepared on a large scale thin film thermoelectric materials.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1PEDOT:DBSA (PEDOT:DBSA) material
9.00mmol Iron(III) chloride hexahydrates and 18.00mmol neopelexes are dissolved in deionized water respectively
In, liquor ferri trichloridi is added dropwise in neopelex solution with vigorous stirring, by detergent alkylate sulphur
Sour iron precipitation is washed with deionized 10 times until without Cl-Detection.Then the dissolving of 250mL ethanol is added, and in Rotary Evaporators
In be evaporated.Then solid is redissolved in ethanol, the ethanol solution for being made into 74.3%-83.1% mass fractions is standby.Will be above-mentioned
Solution spin-coating film, rotating speed 5000-10000rpm, spin-coating time 15s on 18*18mm calcium soda-lime glass substrates.Spin coating is good
DBSA molysite film is placed in the flat reaction vessel of bilateral of quartz or glass material, is passed through nitrogen and saturation
EDOT monomer vapors, gas mole ratio 1:1, and reaction vessel is placed on plane heating platform after 90 DEG C of reaction 25min and taken out, use
Ethanol washes twice, and spontaneously dries at room temperature.The Raman spectrogram of film is as shown in Figure 1, it is seen that 438cm-1、573cm-1、
990cm-1Dioxane peak and 1364cm-1、1429cm-1The major absorbance peak such as thiphene ring benzene formula vibration peak belong to
PEDOT and its Doped ions, no miscellaneous peak, it is doped PEDOT to show film.The film for reacting gained is distinguished using step instrument
Thickness is measured, film thickness is obtained and is 0.31 μm -1.79 μm (wherein 1.79 μm of film samples are the ethanol of 83.1% mass fraction
Solution is taken to react after 5000rpm spin coatings 15s and obtained), and the sample conductance that vanderburg method measures different thickness is respectively adopted
Shown in rate such as accompanying drawing 2 (b), as seen from the figure, by configuring the iron salt solutions of various concentrations, or change the rotating speed of spin coating, can be with
The film of different-thickness is obtained, and with the change of thickness, electrical conductivity can maintain essentially in 1100S/cm or so, and this method has
Repeatability and thickness adjustability well.And it was found from Fig. 2 (a), due to electrical conductivity as thickness change keeps stable, therefore with
Thickness rise, sheet resistance persistently reduces, and the minimum PEDOT film surfaces resistance for measuring 1.79 μ m thicks is 4.983 Ω.Entirely
PEDOT Seebeck coefficient is substantially invariable under doping condition, therefore randomly selects wherein 1085nm thick specimens, using R types
Thermocouple measurement Seebeck coefficient is 24.7 μ V/K, PEDOT:The power factor of DBSA films reaches 69.4 μ W/mK2。
Embodiment 2PEDOT:Butyl naphthalene sulfonic acids (PEDOT:BNSA) material
9.00mmol Iron(III) chloride hexahydrates and 18.00mmol sodium butylnaphthalenesulfonates are dissolved in deionized water respectively,
Be stirred vigorously it is lower liquor ferri trichloridi is added dropwise in sodium butylnaphthalenesulfonate solution, by butyl naphthalene sulfonic acids iron precipitation spend from
Sub- water washing 10 times without Cl ions until detect.Then the dissolving of 250mL ethanol is added, and is evaporated in Rotary Evaporators.Then
Solid is redissolved in ethanol, is made into that the ethanol solution of 80.1% mass fraction is standby, then adds the dibutyl naphthalene of 5% mass fraction
Sulfonic acid.By above-mentioned solution on 18*18mm calcium soda-lime glass substrates spin-coating film, rotating speed 6000rpm, spin-coating time 15s.By spin coating
Good precursor thin-film is placed in the flat reaction vessel of bilateral of quartz or glass material, is passed through argon gas and saturation EDOT is mono-
Body steam, gas mole ratio 2:1, and reaction vessel is washed as being taken out on plane heating platform after 90 DEG C of reaction 35min with ethanol
Wash twice, spontaneously dry at room temperature.The Raman spectrogram of film is as shown in Figure 3, it is seen that 438cm-1、573cm-1、990cm-1
Dioxane peak and 1364cm-1、1429cm-1The major absorbance peak such as thiphene ring benzene formula vibration peak be doping PEDOT
Characteristic peak, it is doped PEDOT to show film.Step instrument measures sample thickness 700nm, and vanderburg method measures electrical conductivity 200S/
Cm, R type thermocouple measurement Seebeck coefficients is used as 26.7 μ V/K, the μ W/mK of power factor 14.32。
Embodiment 3PEDOT:Camphorsulfonic acid (PEDOT:CSA) material
6.06mmol barium hydroxide octahydrates and 13.20mmol D-10- camphorsulfonic acids are dissolved in suitable quantity of water wiring solution-forming A,
Then 2.00mmol ferric sulphate hydrates are dissolved in deionized water wiring solution-forming B, B solution is added dropwise to the solution A of stirring
In, centrifuge washing removes precipitation, and obtained camphorsulfonic acid ferrous solution is formed into 46% mass fraction with being dissolved in ethanol after being evaporated
Solution for standby.Above-mentioned solution is pressed into mol ratios 1 by EDOT monomers and iron salt solutions:2.25 addition EDOT monomers, after stirring and dissolving
Spin-coating film on 18*18mm calcium soda-lime glass substrates, rotating speed 8000rpm, spin-coating time 30s.Spin coating there are into oxidant and EDOT
Substrate is placed on heating platform and removed after 70 DEG C of heating response 1min, is washed twice with ethanol, spontaneously dried at room temperature.Film
Raman spectrogram as shown in Figure 4, it is seen that 438cm-1、573cm-1、990cm-1Dioxane peak and 1364cm-1、
1429cm-1The major absorbance peak such as thiphene ring benzene formula vibration peak be the characteristic peak for adulterating PEDOT, show film to be doped
PEDOT.Step instrument measures sample thickness 575nm, and vanderburg method measures electrical conductivity 752S/cm, using R type thermocouple measurement plug shellfishes
Gram coefficient is 26.4 μ V/K, the μ W/mK of power factor 52.42。
Claims (9)
1. a kind of preparation method of the PEDOT films with high thickness and high conductivity, it is characterised in that using EDOT monomers as original
Material, with the high alcohol-soluble molysite FeX containing weakly-basic anion3Solution is oxidant, use vapor phase method be prepared composition for
PEDOT:X PEDOT films, wherein X are the weakly-basic anion of high alcohol-soluble, and X is camphorsulfonic acid radical ion, long-chain alkyl benzene
In sulfonate ion, alkyl naphthalene sulfonic acid radical ion, dialkyl napthalene sulfonic acids radical ion and dinonylnaphthalene disulfonic acid radical ion at least
It is a kind of；The high alcohol-soluble molysite FeX3High alcohol-soluble molysite FeX in solution3Mass fraction be 46%~84%, solvent is first
Alcohol, ethanol, propyl alcohol, at least one of butanol；The high alcohol-soluble molysite FeX3It is 1~20% also to include mass fraction in solution
Free dopant acid, the free dopant acid be camphorsulfonic acid, chain alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, dialkyl napthalene sulfonic acids
At least one of with dinonylnaphthalene disulfonic acid；
The vapor phase method includes：
By high alcohol-soluble molysite FeX3Solution carries out spin coating on substrate, obtains molysite FeX3Film；
By gained molysite FeX3Film be placed in reaction vessel, be passed through inert gas and EDOT monomer vapors, and by reaction vessel
5~40 minutes are reacted at 60~100 DEG C to the molysite FeX3Film color au bleu is changed by yellow or brown completely
Or it is black-and-blue, after being washed with ethanol, spontaneously dry at room temperature, obtain the PEDOT films.
2. a kind of preparation method of the PEDOT films with high thickness and high conductivity, it is characterised in that using EDOT monomers as original
Material, with the high alcohol-soluble molysite FeX containing weakly-basic anion3For oxidant, use solwution method be prepared composition for
PEDOT:X PEDOT films, wherein X are the weakly-basic anion of high alcohol-soluble, and X is camphorsulfonic acid radical ion, long-chain alkyl benzene
In sulfonate ion, alkyl naphthalene sulfonic acid radical ion, dialkyl napthalene sulfonic acids radical ion and dinonylnaphthalene disulfonic acid radical ion at least
It is a kind of；
The solwution method includes：
By EDOT monomers and high alcohol-soluble molysite FeX3Solution carries out spin coating after uniformly mixing on substrate, obtains EDOT and molysite
FeX3The film of mixture, the high alcohol-soluble molysite FeX3High alcohol-soluble molysite FeX in solution3Mass fraction for 46%~
84%, solvent is methanol, ethanol, propyl alcohol, at least one of butanol, the high alcohol-soluble molysite FeX3Also include quality in solution
Fraction be 1~20% free dopant acid, the free dopant acid be camphorsulfonic acid, chain alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid,
At least one of dialkyl napthalene sulfonic acids and dinonylnaphthalene disulfonic acid；
By gained EDOT and molysite FeX3The film of mixture reacts 15 seconds~1 minute to the EDOT and iron at 70~80 DEG C
Salt FeX3The color of the film of mixture changes au bleu by yellow completely, after being washed with ethanol, spontaneously dries, obtains at room temperature
To the PEDOT films.
3. according to the method for claim 2, it is characterised in that the EDOT monomers and high alcohol-soluble molysite FeX3Mole
Than for 1:4~1:1.
4. method according to claim 1 or 2, it is characterised in that the substrate is sheet glass, quartz plate, silicon chip and modeling
One kind in tablet.
5. method according to claim 1 or 2, it is characterised in that the rotating speed of the spin coating is 5000~8500 rpm.
6. PEDOT films prepared by the method according to any one of claim 1-5, it is characterised in that the PEDOT is thin
The thickness of film is 0.3~3 μm.
7. PEDOT films according to claim 6, it is characterised in that the electrical conductivity of the PEDOT films is 200 S/cm
More than.
8. PEDOT films according to claim 7, it is characterised in that the electrical conductivity of the PEDOT films is 750 S/cm
More than.
9. PEDOT films according to claim 8, it is characterised in that the electrical conductivity of the PEDOT films is 1100 S/
More than cm.
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| CN109912936B (en) * | 2017-12-12 | 2021-04-16 | 中国科学院上海硅酸盐研究所 | High-performance PEDOT-tellurium nanoparticle composite film and preparation method thereof |
| CN108400230B (en) * | 2018-05-04 | 2021-02-26 | 河南工程学院 | Method for improving ZT value of PPy-Cl-PVA film by gas-phase post-treatment |
| CN110041544B (en) * | 2019-05-10 | 2022-07-29 | 广东聚华印刷显示技术有限公司 | Method for processing PEDOT-PSS, quantum dot light-emitting diode and display device |
| CN112062992A (en) * | 2020-09-17 | 2020-12-11 | 重庆大学 | Sodium benzenesulfonate-modified PEDOT/PSS film, preparation method thereof and application thereof in solar cell |
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