CN103043654A - Film containing graphene and/or graphene oxide, and preparation method thereof - Google Patents
Film containing graphene and/or graphene oxide, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a film containing graphene and/or graphene oxide, and a preparation method thereof. The method comprises the following steps of (1) dispersing a graphene and/or graphene oxide gel in a solvent to prepare a dispersing solution containing the graphene and/or graphene oxide with a concentration of 0.01-20 mg/mL; (2) making the dispersing solution form a uniform wet film on a substrate by a wire rod coating method, wherein the diameter of the wire used in the wire rod coating method is 0.01-2 mm; and (3) evaporating solvent from the wet film obtained from the step (2). The invention also provides a film containing the graphene and/or graphene oxide with a thickness of 0.6-2,300 nm, and the thickness deviation of the film is smaller than or equal to 37%. The preparation method provided by the invention has the advantages of fast preparation speed and solution economization.
Description
Technical field
The present invention relates to a kind of film that contains Graphene and/or graphene oxide and preparation method thereof.
Background technology
Graphene is the material that a kind of carbon atom of two dimensional surface monoatomic layer thickness Hexagonal array consists of, and it has high charge mobility, high mechanical strength, the performance that high surface area etc. are excellent.It is in thin-film solar cells, the flat pannel display electrode, and electrical condenser, the aspects such as lithium electricity and coating machine intensity enhancing have a wide range of applications.
At present the preparation method of Graphene or graphene oxide film mainly contained drop-coating, spin-coating method, micro-filtration, self-assembly, LB embrane method, spraying method.Drop-coating and micro-filtration method can only prepare the graphene film than small area.Spin coating method is a kind of method of laboratory preparation film commonly used, prepare fairly simple, but the weak point of the method is to cause tank solution to waste, simultaneously because the cause of spin coating centrifugal force, the film thickness of preparation becomes certain distribution, and is in addition, also relatively harsh to the requirement of solution.LB film and self-assembling method be the thickness of controlling diaphragm effectively, but the mechanical stability of LB film is poor, and the LB film is a kind of metastable structure, to the stability of heat, chemical environment, time and external pressure a little less than; And the LB film is special to the structural requirement of membrane-forming molecule, must be amphiphilic, and film-forming apparatus is also expensive; The film of self-assembling method preparation is subjected to the impact of several factors, and is all influential to the film of self-assembling method preparation such as the chemical constitution of substrate surface, the chemical property of substrate surface and the character of tunic molecule self etc.Spraying method can the big area serialization prepare graphene film, but because the restriction of technology is difficult to the thickness of controlling diaphragm, and thickness deviation (thickness-mean thickness at the minimum place of the thickness of thickness maximum or thickness)/mean thickness calculates) be generally 40-50%.It is a kind of method for preparing ink film that is proposed the earliest by Mayer Rod that the line rod is filmed.The preparation of the people such as Dan by the method success carbon nano-tube film (ACS Nano 2009,3:835-843).The people such as Hu have successfully prepared the nano silver wire film by Mayer rod method, and (ACS Nano 2010,4 (5), 2955-2963).But up to the present the report that adopts the method to prepare graphene film and graphene composite film is not arranged also.
Summary of the invention
The object of the invention is to overcome the shortcoming of the method for preparing Graphene and/or graphene oxide film of prior art, providing a kind of utilizes the preparation of line rod coating method to contain film of Graphene and/or graphene oxide and preparation method thereof, the method has the film that contains Graphene and/or graphene oxide that can make even thickness and has the advantage that preparation speed is fast, save solution, utilize the prepared film thickness of the method even, and thickness deviation is much smaller than the thickness deviation of the film of prior art preparation.
The invention provides a kind of thin film technology method that contains Graphene and/or graphene oxide, the method may further comprise the steps: (1) is dispersed in Graphene and/or graphene oxide colloidal sol and is mixed with Graphene in the solvent and/or graphene oxide concentration is the dispersion liquid that contains Graphene and/or graphene oxide of 0.01-20mg/ml; (2) adopt line rod coating method to make dispersion liquid form wet film in substrate, the diameter of the line of the used line rod of wherein said line rod coating method is 0.01-2mm; (3) solvent in the wet film that obtains in the volatilization step (2).
The present invention also provides a kind of film that contains Graphene and/or graphene oxide, and the thickness of described film is the 0.6-2300 nanometer, and the thickness deviation of film is less than or equal to 37%.
The thin film technology method that contains Graphene and/or graphene oxide provided by the invention, concentration by Graphene and graphene oxide in the control dispersion liquid, and be used with the line of special diameter, so that the method can make the film that contains Graphene and/or graphene oxide of even thickness and have the advantage that preparation speed is fast, save solution.Adopt the thickness deviation of the film that contains Graphene and/or graphene oxide that method of the present invention makes to be less than or equal to 37%, and the film that contains Graphene and/or graphene oxide that utilizes method of the present invention preparation is 50-～90000 Ω/sq by the scope of the centre plane resistance that the four point probe tester records, the transmittance that records at the 550nm place by ultraviolet-visible-near infrared spectrometer is 57.8%～97.1%, utilize the film that contains Graphene and/or graphene oxide of method preparation of the present invention can be applied to prepare the transparent electrode material that contains Graphene, electrode for capacitors, lithium electricity electrode, solar cell and can be used as functional coating etc.
Description of drawings
Fig. 1 is that the present invention utilizes the preparation of Mayer Rod line rod coating method to contain the principle schematic of the film of Graphene and/or graphene oxide;
Fig. 2 is the photo of the laminated film that contains Graphene for preparing of the present invention;
Fig. 3 is the atomic force microscopy of the laminated film that contains Graphene for preparing of the present invention, wherein a be the embodiment of the invention 1 to adopt graphene oxide concentration be the atomic force microscope electromicroscopic photograph of the film that contains Graphene of the dispersion liquid preparation that contains graphene oxide of 0.1mg/ml, b is that to adopt graphene oxide concentration be the atomic force microscope electromicroscopic photograph of the film that contains Graphene of the dispersion liquid preparation that contains graphene oxide of 1mg/ml to the embodiment of the invention 1;
The statistical Butut of the surface resistance of Fig. 4 film that contains Graphene that to be the embodiment of the invention 10 form in polyethylene terephthalate (PET) substrate.
Embodiment
The invention provides a kind of thin film technology method that contains Graphene and/or graphene oxide, the method may further comprise the steps: (1) is dispersed in Graphene and/or graphene oxide colloidal sol and is mixed with Graphene in the solvent and/or graphene oxide concentration is the dispersion liquid that contains Graphene and/or graphene oxide of 0.01-20mg/ml; (2) adopt line rod coating method to make dispersion liquid form uniform wet film in substrate, the diameter of the line of the used line rod of wherein said line rod coating method is 0.01-2mm; (3) solvent in the wet film that obtains in the volatilization step (2).
According to the present invention, described solvent can be deionized water and/or organic solvent, described organic solvent can be the various organic solvents that can dissolve Graphene and/or graphene oxide colloidal sol and volatile character, for example can be in deionized water, ethanol, methyl alcohol, acetone, ether, dme, ethylene glycol, methylene dichloride, tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone (NMP), the DMF (DMF) one or more; Preferred described solvent is one or more in N-Methyl pyrrolidone, dme, acetone and the ethanol.
According to the present invention, the dispersion liquid that will contain Graphene and/or graphene oxide is mixed with Graphene and/or graphene oxide concentration is the dispersion liquid of 0.01-20mg/mL, be preferably 0.1-20mg/mL, more preferably 0.5-20mg/mL further is preferably 1-20mg/mL.Among the present invention, Graphene and/or graphene oxide concentration refer to the total concn of Graphene and graphene oxide, and when the concentration that does not contain graphene oxide when containing Graphene in the dispersion liquid and be graphene oxide was 0, this concentration was the concentration of Graphene; When the concentration that does not contain Graphene when containing graphene oxide in the dispersion liquid and be Graphene was 0, this concentration was the concentration of graphene oxide.
Line rod in the line rod coating method also can be called Mayer Rod line rod; According to the present invention, the diameter that forms the line of line rod is 0.01-2mm, is preferably 0.1-2mm, more preferably 0.6-2mm; The speed that described line rod is pulled through dispersion liquid is 10mm/s-300mm/s, is preferably 150mm/s.
According to the present invention, described substrate can be rigidity or flexible substrates, is preferably in glass, quartz, silicon chip, polyethylene terephthalate (PET), polyimide, Copper Foil and the aluminium foil one or more.
The size of described substrate can be determined according to the size of the Graphene that will obtain and/or graphene oxide film.Because the present invention adopts line rod coating method to prepare film, therefore can obtain relatively large-area film, can be larger thereby the area of described substrate is corresponding, for example width can be up to 3 meters.
According to the present invention, under the preferable case, described dispersion liquid can also contain one or more in small organic molecule, superpolymer, metal oxide, the salt.The preparation of this dispersion liquid can comprise: will contain first a kind of mixing the in Graphene and/or graphene oxide colloidal sol and small organic molecule, superpolymer, metal oxide, the salt, redispersion is mixed with dispersion liquid in solvent.Wherein, described small organic molecule, superpolymer, metal oxide, salt can be for to not containing uniform and stable one or more that are dispersed in the various small organic molecules that cause disadvantageous effect in the solvent, superpolymer, metal oxide, the salt of Graphene and/or graphene oxide colloidal sol.Described small organic molecule can for contain in the uniform and stable various organic molecules that are dispersed in the solvent of Graphene and/or graphene oxide colloidal sol one or more, for example can be in sucrose, glucose, the chitosan one or more, be preferably sucrose; Described superpolymer can for contain in the uniform and stable various superpolymer that are dispersed in the solvent of Graphene and/or graphene oxide colloidal sol one or more, for example can be in polymethylmethacrylate, 2-glycidyl ethers dihydroxyphenyl propane, Polythiophene, polypyrrole and the polydimethylsiloxane one or more, be preferably in polymethylmethacrylate, 2-glycidyl ethers dihydroxyphenyl propane and the Polythiophene one or more, the adding of superpolymer can obtain the film of different purposes in the dispersion liquid, optical waveguide film for example, high dielectric coat etc.; Described metal oxide can for contain in the uniform and stable various metal oxides that are dispersed in the solvent of Graphene and/or graphene oxide colloidal sol one or more, for example can be stannic oxide, Indium sesquioxide, cobalt sesquioxide, in Manganse Dioxide and the titanium dioxide one or more, be preferably stannic oxide, one or more in Manganse Dioxide and the titanium dioxide; Described salt can for contain in the uniform and stable various inorganic or organic salt that is dispersed in the solvent of Graphene and/or graphene oxide colloidal sol one or more, for example can be Palladous chloride, platinum chloride, ruthenium trichloride, in gold perchloride and the Silver Nitrate one or more, be preferably Palladous chloride, one or more in platinum chloride and the ruthenium trichloride.
According to the present invention, the total amount of the small organic molecule in the graphene oxide in the described dispersion liquid and/or Graphene and the dispersion liquid, superpolymer, metal oxide, salt is counted in mass ratio and can be 1: the 0.1-30 mass ratio is preferably 1: 1-10.
According to the present invention, the method that graphene oxide film is reduced to graphene film be will contain and various physics and chemical reduction method comprised, be preferably a kind of in high temperature thermal reduction, hydrazine steam reduction, hydrogen iodide steam or the catalytic hydrogenation.
According to the present invention, the thickness of described wet film is the 1-200 micron, the thickness of the film that the solvent in the described volatilization wet film obtains is more preferably 30-2300 nanometer of 0.6-2300 nanometer, wherein is less than or equal to 37% according to the thickness deviation that (thickness-mean thickness at the minimum place of the thickness of thickness maximum or thickness)/mean thickness calculates.Particularly, the present inventor also finds, when the concentration of control dispersion liquid at 1-2mg/ml, the diameter of line rod center line during in the 30-2222.3 nanometer, can make the thickness deviation of graphene oxide film less than 10% at 0.6-2mm and the mean thickness of film that contains graphene oxide.Adopt length and the width of graphene oxide that method of the present invention can obtain or graphene film unqualified, those skilled in the art can be as required or the large freedom in minor affairs of area of base limit.
According to the present invention, under the preferable case, the method is removed substrate after also being included in the solvent of removing in the wet film.The method of removing substrate is well known to those skilled in the art, does not repeat them here.
According to a kind of embodiment of the present invention, this preparation method specifically may further comprise the steps:
(1) Graphene and/or graphene oxide colloidal sol are dispersed in the solvent, use vibrator or agitator or ultrasonic apparatus to mix 1-2 hour, preferred 1 hour, be mixed with the dispersion liquid of stable and uniform;
(2) the used line rod of line rod coating method is pulled through dispersion liquid with the speed of 10mm/s-300mm/s, and preferred 150mm/s is pulled through dispersion liquid in substrate, forms uniform wet film;
(3) solvent in the wet film that obtains in the volatilization step (2), and remove substrate, obtaining thickness is the more preferably film that contains Graphene and/or graphene oxide of 30-2300 nanometer of 0.6-2300 nanometer.
Preparation in accordance with the present invention, wherein, under the preferable case, the method also is included in step (2) before, form first the film of a kind of superpolymer and/or metal oxide in substrate, the method of the film of formed superpolymer and/or metal oxide prepares according to the thin film technology method that contains Graphene and/or graphene oxide of the present invention, difference is Graphene and/or graphene oxide to be dispersed in to replace with in the solvent superpolymer and/or metal oxide are dispersed in the solvent, and namely this preparation method specifically may further comprise the steps:
(1) superpolymer and/or metal oxide are dispersed in the solvent, use vibrator or agitator or ultrasonic apparatus to mix 1-2 hour, preferred 1 hour, be mixed with the dispersion liquid of stable and uniform;
(2) the used line rod of line rod coating method is pulled through dispersion liquid with the speed of 10mm/s-300mm/s, and preferred 150mm/s is pulled through dispersion liquid in substrate, forms uniform wet film;
(3) solvent in the wet film that obtains in the volatilization step (2), obtain containing the film of superpolymer and/or metal oxide, and then form the film that contains Graphene and/or graphene oxide at the film of the superpolymer that forms and/or metal oxide, the method that formation contains the film of Graphene and/or graphene oxide prepares according to the thin film technology method that contains Graphene and/or graphene oxide of the present invention, and remove substrate, obtain containing the mixed film of Graphene and/or graphene oxide and superpolymer and/or metal oxide.
The present invention also provides a kind of film that contains Graphene and/or graphene oxide by the aforesaid method preparation, and the thickness of described film is preferably the 0.6-2300 nanometer, further is preferably the 30-2300 nanometer, and the thickness deviation of film is less than or equal to 37%.
Below in conjunction with accompanying drawing the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
Below will describe the present invention by embodiment.In following examples, the described thickness that contains Graphene and/or graphene oxide film records by atomic force microscope (Nanoman IIdimention3100); The surface resistance parameter records according to GB/T1551-2009 by four point probe resistance meter (the two electrical measurement four point probe testers of RTS-9 type, Guangzhou four point probe scientific ﹠ technical corporation); The transmittance parameter records by ultraviolet-visible-near infrared spectrometer (Lambda950UV/VIS/NIR, perkin elmer Instr Ltd.).
Containing Graphene and/or graphene oxide colloidal sol prepares by the method in preparation example 1 and the preparation example 2.
Preparation example 1
Natural graphite powder (1 part of quality) was processed 3 hours under condition of ice bath with the vitriol oil (30 parts of quality) and potassium permanganate (3 parts of quality), be warmed up to about 35 ℃, kept 30 minutes, the water that adds 45 parts of quality 95 ℃ of temperature, react after 15 minutes, add 30 % by weight hydrogen peroxide of 3.5 parts of quality and the water of 26.5 parts of quality, obtain jonquilleous suspension.With suspension filtered, use the hydrochloric acid washing leaching cake 3 times of 3 % by weight, with the filter cake that obtains 60 ℃ of oven dry, the gained filter cake is scattered in the water, namely get graphene oxide colloidal sol, with this colloidal sol centrifugation, again disperse, (generally processing more than 3 times) obtains purer graphene oxide colloidal sol (wherein the content of graphene oxide is the 20mg/ml % by weight) after repeatedly processing, for the preparation of the film that contains graphene oxide.
Preparation example 2
Thermal expansion Graphite Powder 99 or micro crystal graphite or natural graphite (1 part of quality) are joined in the N-Methyl pyrrolidone solvent (1000 parts) ultrasonic 30min in the ultrasonic apparatus of 300w power.Use whizzer with the dispersion liquid centrifugal 60min under 500 rev/mins rotating speed that obtains.Discard the thick graphite flake layer in bottom, obtain the colloidal sol of upper strata grey.The colloidal sol of this upper strata grey is centrifugal under 5000 rev/mins speed conditions, and the bottom obtains the Graphene colloidal sol (wherein the content of Graphene is the 1mg/ml % by weight) of black, for the preparation of the film that contains Graphene.
The graphene oxide colloidal sol of preparation example 1 preparation is dispersed in the alcohol dispersion liquid that is mixed with graphene oxide concentration graphene oxide as shown in table 1 below in the ethanol, uses the vibrator concussion to mix 1h, obtain homodisperse stable dispersion liquid.Get the end at the bottom of 0.5ml drops in the silicon wafer-based of 5cm * 5cm, then use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is as shown in table 1 below, forms the uniform wet film of one deck at the silicon wafer-based basal surface.Wet film vapors away solvent in flowing air, and removes substrate, obtains graphene oxide film, uses atomic force microscope that the graphene oxide film of preparation method's preparation of the present invention is characterized, and the mean thickness of this graphene oxide film provides at table 1.
Table 1
The thickness deviation that contains graphene oxide film of preparation in accordance with the present invention preparation is in the 2.0%-37% scope, much smaller than the thickness deviation of prior art 40%-50% from table 1.It can also be seen that from the result of table 1, when control dispersion liquid concentration at 1-2mg/ml, the diameter of line rod center line during in the 30-2222.3 nanometer, can make the thickness deviation of graphene oxide film less than 10% at 0.6-2mm and the mean thickness of film that contains graphene oxide.
Fig. 3 is the atomic force microscope electromicroscopic photograph, a is that embodiment 1 graphene oxide dispersion liquid concentration is 0.1mg/ml, be coated in the film that contains graphene oxide on the silicon chip under the line rod linear diameter 0.2mm condition, b is that embodiment 1 graphene oxide dispersion liquid concentration is 1mg/ml, be coated in the film that contains graphene oxide on the silicon chip under the line rod linear diameter 0.2mm condition, a can find out that the thickness of film is 0.9-1.5nm from figure, and the mean thickness of film is 1.1nm, and thickness deviation is 37%; B can find out that the thickness of film is 10.2-15.3nm from figure, and the mean thickness of film is 12.3nm, and thickness deviation is 17.1%.Figure a and figure b show that the film that contains graphene oxide of preparation method's preparation of the present invention is more even.
The Graphene colloidal sol that obtains in the preparation example 2 is dispersed in the N-Methyl pyrrolidone dispersion liquid that is mixed with Graphene concentration Graphene as shown in table 2 below in the N-Methyl pyrrolidone, uses the ultrasonic 1h of ultrasonic apparatus, obtain homodisperse stable dispersion liquid.Get the end at the bottom of 1ml drops in the silicon wafer-based of 10cm * 10cm, then use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is as shown in table 2 below, forms the uniform wet film of one deck at the silicon wafer-based basal surface.Wet film vapors away solvent in flowing air, and removes substrate, obtains containing the film of Graphene, uses atomic force microscope that the film that contains Graphene of preparation method's preparation of the present invention is characterized, and the mean thickness of graphene film provides at table 2.
Table 2
The thickness deviation that contains graphene film of preparation in accordance with the present invention preparation is in the 5.5%-36.0% scope, much smaller than the thickness deviation of prior art 40%-50% from table 2.
Use the four point probe resistance meter that the thickness of the preparation method of the present invention preparation film that contains Graphene as 0.6nm is characterized, the centre plane resistance that records film is 1000 Ω/sq, and recording the transmittance of this graphene film at the 550nm place by ultraviolet-visible-near infrared spectrometer is 97.1%.
Embodiment 3
Graphene oxide colloidal sol and the sucrose of preparation in the preparation example 1 are mixed with graphene oxide concentration as the alcohol dispersion liquid of graphene oxide and the sucrose of 1mg/mL take mass ratio as 1: 1 ratio blending dispersion in ethanol, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get 1ml and drop in a section of quartz plate, use the line rod to be pulled through solution with the speed of 150mm/s, form the uniform wet film of one deck on the quartz plate surface.Wet film removes solvent in the flowing air volatilization, obtains the laminated film of graphene oxide-sucrose.Then graphene oxide-sucrose laminated film is placed high temperature reaction stove, at H
2Under the mixed atmosphere of Ar, 1100 ℃ of reaction annealing vapor away solvent, and remove substrate, obtain Graphene-sucrose laminated film, use atomic force microscope that the Graphene of preparation method's preparation of the present invention-sucrose laminated film is characterized, obtain mean thickness and be 6.8nm, thickness deviation and be 9% Graphene-sucrose laminated film.Use the four point probe resistance meter that the Graphene-sucrose laminated film that contains of preparation method's preparation of the present invention is characterized, the centre plane resistance that records this film is 1173 Ω/sq, and recording the transmittance of this Graphene-sucrose laminated film at the 550nm place by ultraviolet-visible-near infrared spectrometer is 83%.
Polymethylmethacrylate (PMMA) is dispersed in is mixed with the solution that concentration is 10 % by weight in the dme, get the end that 1ml drops in PET, use the line rod to be pulled through solution with the speed of 150mm/s, form the uniform wet film of one deck at the pet sheet face, remove solvent by oven dry, obtain the film of polymethylmethacrylate.The graphene oxide colloidal sol of preparation in the preparation example 1 is dispersed in and is mixed with the alcohol dispersion liquid that graphene oxide concentration is the graphene oxide of 0.1mg/ml in the ethanol, use the vibrator concussion to mix 1h, obtain homodisperse stable dispersion liquid, get the end that 2ml drops in the PET that scribbles PMMA, use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.2mm, oven dry, and remove substrate, obtain containing graphene oxide/PMMA laminated film, the graphene oxide that the use atomic force microscope prepares preparation method of the present invention/PMMA laminated film characterizes, the mean thickness of graphene oxide/PMMA laminated film is 198.6nm, and thickness deviation is 7.3%.Recording the transmittance of this graphene oxide/PMMA laminated film at the 550nm place by ultraviolet-visible-near infrared spectrometer is 60%.
Embodiment 5
Graphene oxide and the Resins, epoxy of preparation in the preparation example 1 are mixed with graphene oxide concentration as the graphene oxide of 1mg/ml and the acetone dispersion liquor of Resins, epoxy take mass ratio as 1: 10 ratio blending dispersion in acetone, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get the 1ml dispersant liquid drop at one section of quartz plate, use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 2mm, form the uniform wet film of one deck on the quartz plate surface, wet film is removed solvent in the flowing air volatilization, and remove substrate, use atomic force microscope that the laminated film of the graphene oxide-Resins, epoxy of preparation method's preparation of the present invention is characterized, the laminated film mean thickness of the graphene oxide-Resins, epoxy that obtains is 2 microns, and thickness deviation is 3.5%.The transmittance of laminated film at the 550nm place that records this graphene oxide-Resins, epoxy by ultraviolet-visible-near infrared spectrometer is 60%.
Graphene and the Polythiophene of preparation in the preparation example 1 are mixed with Graphene concentration as the Graphene of 0.2mg/ml and the N-Methyl pyrrolidone dispersion liquid of Polythiophene take mass ratio as 1: 1 ratio blending dispersion in N-Methyl pyrrolidone, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get the 1ml dispersant liquid drop at one section of quartz plate, use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.1mm, form the uniform wet film of one deck on the quartz plate surface, wet film is removed solvent by oven dry or in the flowing air volatilization, and remove substrate, use atomic force microscope that the laminated film of the Graphene-Polythiophene of preparation method's preparation of the present invention is characterized, the mean thickness of the laminated film of the Graphene-Polythiophene that obtains is 2nm, and thickness deviation is 13.0%.Use the four point probe resistance meter that the Graphene-polythiophene film of preparation method's preparation of the present invention is characterized, the centre plane resistance that draws film is 2000 Ω/sq.Recording the transmittance of this Graphene-polythiophene film at the 550nm place by ultraviolet-visible-near infrared spectrometer is 95.2%.
Embodiment 7
The Graphene of preparation in the preparation example 2 and ITO colloidal sol are mixed with Graphene concentration are the dispersion liquid of the water of the Graphene of 0.1mg/ml and ITO take mass ratio as 1: 30 ratio blending dispersion in water, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get the 1ml dispersant liquid drop at an end of the PET of 10cm * 10cm substrate, then use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 1mm, forms the uniform wet film of one deck at the pet sheet face.Wet film vapors away solvent in flowing air, the Graphene that the use atomic force microscope prepares preparation method of the present invention-ITO laminated film characterizes, and the mean thickness of the Graphene that obtains-ITO laminated film is 300nm, and thickness deviation is 27.5%.The centre plane resistance that records Graphene-ITO laminated film by the four point probe tester is 100/sq, and recording the transmittance of this Graphene-ITO laminated film at the 550nm place by ultraviolet-visible-near infrared spectrometer is 85%.
Graphene oxide colloidal sol and the stannic oxide of preparation in the preparation example 1 are mixed with graphene oxide concentration as the graphene oxide of 1mg/ml and the aqueous dispersions of stannic oxide take mass ratio as 1: 2 ratio blending dispersion in water, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get the 1ml dispersant liquid drop at an end of the Copper Foil substrate of 10cm * 10cm, then use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 2mm, form the uniform wet film of one deck at copper foil surface, the oven dry wet film, and remove substrate, obtain graphene oxide-stannic oxide laminated film.With this graphene oxide-stannic oxide laminated film as for high temperature reduction in the atmosphere of hydrogen, obtain Graphene-stannic oxide laminated film, the Graphene that the use atomic force microscope prepares preparation method of the present invention-stannic oxide laminated film characterizes, the mean thickness of the Graphene that obtains-stannic oxide laminated film is 600nm, and thickness deviation is 6.8%.The Graphene that use four point probe resistance meter prepares preparation method of the present invention-stannic oxide laminated film characterizes, the centre plane resistance that draws film is 50 Ω/sq, and recording the transmittance of this Graphene-stannic oxide laminated film at the 550nm place by ultraviolet-visible-near infrared spectrometer is 57.8%.
Embodiment 9
Graphene oxide colloidal sol and the Manganse Dioxide of preparation in the preparation example 1 are mixed with graphene oxide concentration as the alcohol dispersion liquid of graphene oxide and the Manganse Dioxide of 1mg/ml take mass ratio as 1: 3 ratio blending dispersion in ethanol, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get the 1ml dispersant liquid drop at an end of the nickel foil substrate of 10cm * 10cm, then use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 1mm, form the uniform wet film of one deck on the nickel foil surface, the oven dry wet film, and remove substrate, obtain graphene oxide-Manganse Dioxide laminated film.With this graphene oxide-Manganse Dioxide laminated film as for high temperature reduction in the atmosphere of hydrogen, obtain Graphene-Manganse Dioxide laminated film, the Graphene that the use atomic force microscope prepares preparation method of the present invention-Manganse Dioxide laminated film characterizes, the mean thickness of the Graphene that obtains-Manganse Dioxide laminated film is 400nm, and thickness deviation is 8%.The Graphene that use four point probe resistance meter prepares preparation method of the present invention-Manganse Dioxide laminated film characterizes, the centre plane resistance that records film is 100 Ω/sq, and recording the transmittance of this Graphene-Manganse Dioxide laminated film at the 550nm place by ultraviolet-visible-near infrared spectrometer is 58.0%.
With graphene oxide colloidal sol and the PdCl in the preparation example 1
2In ethanol, be mixed with graphene oxide concentration as graphene oxide and the PdCl of 1mg/ml take mass ratio as 1: 0.1 ratio blending dispersion
2Alcohol dispersion liquid, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get the 1ml dispersant liquid drop at an end of the PET of 10cm * 10cm substrate, then use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.2mm, forms the uniform wet film of one deck at the pet sheet face.Wet film vapors away solvent in flowing air, and removes substrate, obtains graphene oxide-PdCl
2Laminated film.With this graphene oxide-PdCl
2Laminated film is as in the atmosphere of hydrogen, and reduction 6h obtains Graphene-PdCl
2Laminated film uses atomic force microscope to the Graphene-PdCl of preparation method's preparation of the present invention
2Laminated film characterizes, Graphene-PdCl that oven dry obtains
2The mean thickness of laminated film is 10.8nm, and thickness deviation is 35.8%.Record the Graphene-PdCl of preparation method's preparation of the present invention by the four point probe tester
2The centre plane resistance of laminated film is 1670 Ω/sq, records this Graphene-PdCl by ultraviolet-visible-near infrared spectrometer
2The transmittance of laminated film at the 550nm place is 65%.
Fig. 4 is Graphene-PdCl that embodiment 10 obtains
2The statistical Butut of the centre plane resistance of equally distributed 100 points of laminated film, as can be seen from the figure Graphene-PdCl
2The standard deviation of laminated film centre plane resistance is 3.7%, shows the Graphene-PdCl of preparation method's preparation of the present invention
2The laminated film resistance ratio is more even.
Embodiment 11
With graphene oxide colloidal sol and the PtCl in the preparation example 1
2In ethanol, be mixed with graphene oxide concentration as graphene oxide and the PtCl of 0.5mg/ml take mass ratio as 1: 0.5 ratio blending dispersion
2Alcohol dispersion liquid, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get the 1ml dispersant liquid drop at an end of the PET of 10cm * 10cm substrate, then use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.2mm, forms the uniform wet film of one deck at the pet sheet face.Wet film vapors away solvent in flowing air, and removes substrate, obtains graphene oxide-PtCl
2Laminated film.With this graphene oxide-PtCl
2Laminated film is as in the atmosphere of hydrogen, and 80 ℃ of reduction 6h obtain Graphene-PtCl
2Laminated film uses atomic force microscope to the Graphene-PtCl of preparation method's preparation of the present invention
2Laminated film characterizes, Graphene-PtCl that oven dry obtains
2The mean thickness of laminated film is 2.8nm, and thickness deviation is 35%.Record the Graphene-PtCl of preparation method's preparation of the present invention by the four point probe tester
2The centre plane resistance of composite membrane is 90000 Ω/sq, records this Graphene-PtCl by ultraviolet-visible-near infrared spectrometer
2The transmittance of laminated film at the 550nm place is 90%.
With graphene oxide colloidal sol and the RuCl in the preparation example 1
3In ethanol, be mixed with graphene oxide concentration as graphene oxide and the RuCl of 3mg/ml take mass ratio as 1: 1 ratio blending dispersion
3Alcohol dispersion liquid, the even 1h of mechanically mixing obtains homodisperse stable dispersion liquid.Get the 1ml dispersant liquid drop at an end of the polyimide substrate of 10cm * 10cm, then use the line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.1mm, forms the uniform wet film of one deck at polyimide surface.Wet film vapors away solvent in flowing air, and removes substrate, obtains graphene oxide-RuCl
3Laminated film.With graphene oxide-RuCl
3Laminated film is as in the atmosphere of hydrogen, and 160 ℃ of reduction 6h are dried, and obtain Graphene-RuCl
3Laminated film uses atomic force microscope to the Graphene-RuCl of preparation method's preparation of the present invention
3Laminated film characterizes, the Graphene-RuCl that obtains
3The mean thickness of laminated film is 12.2nm, and thickness deviation is 15%.The centre plane resistance of testing this film by the four point probe tester is 400 Ω/sq, records this Graphene-RuCl by ultraviolet-visible-near infrared spectrometer
3The transmittance of laminated film at the 550nm place is 60.0%.
Claims (12)
1. thin film technology method that contains Graphene and/or graphene oxide, the method may further comprise the steps: (1) is dispersed in the dispersion liquid that contains Graphene and/or graphene oxide that the concentration that is mixed with Graphene and/or graphene oxide in the solvent is 0.01-20mg/ml with Graphene and/or graphene oxide colloidal sol; (2) adopt line rod coating method to make dispersion liquid form uniform wet film in substrate, the diameter of the line of the used line rod of wherein said line rod coating method is 0.01-2mm; (3) solvent in the wet film that obtains in the volatilization step (2).
2. preparation method according to claim 1, wherein, described solvent is deionized water and/or organic solvent, preferred described solvent is one or more in N-Methyl pyrrolidone, dme, acetone and the ethanol.
3. preparation method according to claim 1, wherein, the content of Graphene and/or graphene oxide is 0.1-20mg/ml in the described dispersion liquid.
4. preparation method according to claim 1, wherein, the pulling rate of described line rod coating method center line rod is 10mm/s-300mm/s.
5. preparation method according to claim 1, wherein, described substrate is rigidity or flexible substrates, is preferably in glass, quartz, silicon chip, polyethylene terephthalate, polyimide, Copper Foil and the aluminium foil one or more.
6. preparation method according to claim 1, wherein, described dispersion liquid also contains one or more in small organic molecule, superpolymer, metal oxide and the salt.
7. according to claim 1 or 6 described preparation methods, wherein, the total amount of the small organic molecule in the Graphene in the described dispersion liquid and/or graphene oxide and the dispersion liquid, superpolymer, metal oxide and salt counts 1 in mass ratio: 0.1-30.
8. preparation method according to claim 7, wherein, described small organic molecule is one or more in sucrose, glucose and the chitosan, described superpolymer is one or more in polymethylmethacrylate, 2-glycidyl ethers dihydroxyphenyl propane, Polythiophene, polypyrrole and the polydimethylsiloxane, described metal oxide is one or more in stannic oxide, Indium sesquioxide, cobalt sesquioxide, Manganse Dioxide and the titanium dioxide, and described salt is one or more in Palladous chloride, platinum chloride, ruthenium trichloride, gold perchloride and the Silver Nitrate.
9. the described preparation method of any one according to claim 1-8, wherein, the method also is included in step (2) before, form first the film of a kind of superpolymer and/or metal oxide in substrate, and then form the film that contains Graphene and/or graphene oxide at the film of the superpolymer that forms and/or metal oxide.
10. the described preparation method of any one according to claim 1-9, wherein, the described dispersion liquid that contains Graphene and/or graphene oxide is the dispersion liquid that contains graphene oxide, and the method also comprises reduces the thermal reduction of step (3) products therefrom employing high temperature, hydrazine steam reduction, hydrogen iodide steam or catalytic hydrogenation.
11. the film by the described preparation method's preparation of any one among the claim 1-10.
12. film according to claim 11, wherein, the thickness of described film is the 0.6-2300 nanometer, and the thickness deviation of film is less than or equal to 37%.
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