CN102943253A - Aluminum-doped zinc oxide (AZO) transparent conducting film and preparation method thereof - Google Patents
Aluminum-doped zinc oxide (AZO) transparent conducting film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a method for preparing an aluminum-doped zinc oxide (AZO) transparent conducting film, which comprises the following steps: preparing a spin coating solution from a low-boiling solvent, a stabilizer and a hydrolyzable raw material, carrying out spin coating on a hydrophilic substrate, aging, and carrying out heat treatment and atmosphere annealing to obtain the AZO transparent conducting film. The method provided by the invention has the advantages of accessible raw materials, low cost and environment friendliness, and is simple to operate and suitable for flexible substrates. The invention also relates to an AZO transparent conducting film prepared by the method. The AZO transparent conducting film has the advantages of excellent compactness, low resistivity, adjustable doping rate and film thickness and excellent properties, and has wide application prospects in the field of photoelectricity.
Description
[technical field]
The present invention relates to technical field of semiconductor, be specifically related to a kind of aluminum-doped zinc oxide transparent conductive film, and preparation method thereof.
[background technology]
Transparent conductive film is owing to have high conductivity, energy absorbing ultraviolet light, very high light transmission is arranged in visible-range, and many having a few such as very high reflectivity are arranged in the infrared light scope, and it is widely used in fields such as mancarried electronic aid, flexible electronic devices, solar cell, liquid-crystal display, multi-functional window and Organic Light Emitting Diodes.
At present transparent conductive material is a lot, but production technique the most ripe, most widely used mainly be two kinds of tin indium oxide (ITO) and fluorine-doped tin oxides (FTO), they have higher electric conductivity and at the good light transmission rate of visible region.But both also have some larger shortcomings for they, such as ITO its application of de-stabilising effect in hydrogen plasma atmosphere, to produce and adopt magnetron sputtering technique, the film preparation cost is high, and need to use the limited heavy metal indium of reserves, be unfavorable for environmental protection and do not meet the requirement of Sustainable development; FTO generally adopts the on-line coating method of aumospheric pressure cvd (APCVD), need to mix with fluorine gas, can produce toxic gas.Therefore, seeking the alternative currently available products of new transparent conductive material is the major issue that needs at present solution.
The ZnO of desirable stoichiometric ratio is insulating material, because the existence of native defect, so that ZnO becomes a kind of direct band-gap semicondictor of N-shaped broad-band gap.Behind the F element doping by the B of III family, Al, Ga, In or VII family, form the ZnO-based transparent conductive film with excellent photoelectric properties.
Wherein, Al-Doped ZnO (AZO) transparent conductive film is because its raw material sources are extensive, nontoxic, cost is low, has the high conductivity that is only second to ITO, surpass the advantage such as stable under 90% transmitance and the hydrogen plasma atmosphere in the visible-range, be with a wide range of applications at photoelectric field, be described as the conductive film of new generation of the most possible ITO of substituting.
The method of the current AZO of preparation transparent conductive film has a lot, mainly is divided into physical method and wet method and prepares two kinds.Wherein, the magnetron sputtering in the Physical is the AZO method for manufacturing thin film of commonly using, and has the advantages such as fast, the suitable big area preparation of deposition; But the shortcoming such as early investment is high, complex process, target are expensive makes it not reach commercial degree.
Wet method is prepared with spray method, sol-gel method and electrochemical process etc.Wet method preparation has that cost is low, growth temperature is low and can in advantages such as molecular level controlled doping content, be the desired solution of preparation AZO.But come with some shortcomings equally, need to use poisonous organic solvent such as sol-gel method, need 150 ℃～350 ℃ pre-treatment, be unfavorable at the upper plated film of flexible substrate (general tolerable temperature is below 200 ℃); Electrochemical process need to consume electric energy, and cost is high, also is not suitable for big area production simultaneously.
[summary of the invention]
It is a kind of simple, low-cost and can be applied to the aluminum-doped zinc oxide transparent conductive film preparation method of flexible substrate that the technical problem to be solved in the present invention is to provide.
One aspect of the present invention provides a kind of method for preparing aluminum-doped zinc oxide transparent conductive film, may further comprise the steps:
S101 preparation spin coating liquid: Zinc diacetate dihydrate and aluminium salt are dissolved in the low boiling point solvent, add lower boiling stablizer and ultrapure water, obtain spin coating liquid, wherein Zinc diacetate dihydrate concentration is 0.05-0.3mol/L, the amount of aluminium salt is the 1-5% of Zinc diacetate dihydrate molar weight, the volume ratio of low boiling point solvent and water is 1-5: 1, and the volume ratio of lower boiling stablizer and water is 0.05-0.2: 1;
S102 spin coating plated film: spin coating liquid is spun on the substrate of hydrophilic treatment, obtains the film precursor;
S103 is aging: the film precursor was left standstill in the room temperature environment of relative humidity 60-80% aging 10-48 hour, obtain through aging film precursor;
S104 thermal treatment: will through aging film precursor at 120-200 ℃ of thermal treatment 10-60 minute, obtain sull;
S105 atmosphere annealing: sull in inert atmosphere, 150-600 ℃ of annealing 10-60 minute, is made the sull in-situ crystallization, obtain aluminum-doped zinc oxide transparent conductive film.
Described aluminium salt can be selected from ANN aluminium nitrate nonahydrate, aluminium acetylacetonate, aluminum ethylate, aluminum isopropylate, aluminium butoxide, or their arbitrary combination.
Described low boiling point solvent can be selected from methyl alcohol, ethanol, propyl alcohol, Virahol, or their arbitrary combination.
Described lower boiling stablizer can be selected from formic acid, acetic acid, butyric acid, or their arbitrary combination.
Described substrate can be by the hard transparent material that comprises soda-lime glass, borate glass, silica glass, or comprises that the flexible clear materials that polyethylene terephthalate, polyimide, rice draw consists of.
In some embodiments, described method can also be included in after the step S104, repeating step S 102, S103, S104 operation at least one times.
Described substrate through hydrophilic treatment can be prepared as follows: use successively dish detergent, ammoniacal liquor-hydrogen peroxide mixed solution, water, hydrochloric acid-hydrogen peroxide mixed solution, water ultrasonic cleaning substrate, air-flow dries up afterwards, obtains the substrate through hydrophilic treatment.
Step S102 can adopt one section or two sections rotating speeds to carry out, and when adopting two sections rotating speeds, low rotation speed is 500-2000rpm, and the high speed rotating speed is 1500-2500rpm.
The aluminum-doped zinc oxide transparent conductive film that the present invention also provides the method according to this invention to prepare on the other hand, the particle diameter of Al-Doped ZnO particle can be 5-15nm in the described film; Film thickness can be 50-500nm; The doping of aluminium can be 1-5% in the Al-Doped ZnO.
The present invention has following beneficial effect: adopt low boiling point solvent, lower boiling stablizer and facile hydrolysis raw material, can just decompose fully at low temperatures, avoid pyroprocessing, can be applicable to flexible substrate; By atmosphere annealing, make film experience amorphous in-situ crystallization, the film that obtains has very strong sticking power, is conducive to increase the antistripping ability of flexible substrate upper film; Use nontoxic or low toxicity reagent, avoid environmental pollution; Compared with prior art, preparation method's raw material sources of the present invention are extensive, cost is low, preparation technology is simple, and the aluminum-doped zinc oxide transparent conductive film oxide grain particle diameter that makes is little, transmittance is high, resistivity is less, aluminium doping and film thickness are adjustable.
[description of drawings]
Fig. 1 is the schema that the method according to this invention prepares the AZO transparent conductive film.
Fig. 2 a and 2b are respectively according to the AZO transparent conductive film of embodiment of the invention preparation and positive and cross section scanning electron microscope (SEM) photograph.
Fig. 3 a and 3b are respectively uv-absorbing and the transmitted light spectrogram according to the AZO transparent conductive film of embodiment of the invention preparation.
[embodiment]
The present invention adopts wet method to prepare the AZO transparent conductive film, use lower boiling solvent, stablizer, and utilize the raw material of facile hydrolysis, so that the spin coating liquid of preparation can be when the substrate surface that is spun to through hydrophilic treatment, be able to fast hydrolyzing, form basic oxide or basic zinc salt; Experience subsequently the weathering process under certain humidity condition, so that hydrolysis fully; Being hydrolyzed completely, film has formed sull after Overheating Treatment; Afterwards, by the atmosphere annealing steps, so that sull experience amorphous in-situ crystallization finally forms aluminum-doped zinc oxide transparent conductive film.
The present invention prepares the particular flow sheet of aluminum-doped zinc oxide transparent conductive film can be referring to Fig. 1.As can be seen from Fig. 1, preparation AZO transparent conductive film mainly comprises following step:
At first be S101, preparation spin coating liquid.Spin coating liquid adopts low boiling point solvent, lower boiling stablizer and facile hydrolysis raw material to prepare.The facile hydrolysis raw material is dissolved in the low boiling point solvent, and adds lower boiling stablizer and ultrapure water, form spin coating liquid after mixing.
The facile hydrolysis raw material is Zinc diacetate dihydrate and aluminium salt, and aluminium salt can be ANN aluminium nitrate nonahydrate, aluminium acetylacetonate, aluminum ethylate, aluminum isopropylate, aluminium butoxide, etc., or their mixture.
The contriver finds that in the spin coating liquid, the concentration of Zinc diacetate dihydrate has considerable influence for hydrolysis rate, and the too small hydrolysis rate of concentration is slower, thereby causes might not having in the substrate or seldom being hydrolyzed precursor; The excessive zinc acetate that then can cause of concentration is separated out in the process of spin coating, affects film quality.Therefore, among the preparation method of the present invention, the concentration of Zinc diacetate dihydrate can be 0.05-0.3mol/L.
Regulate the mol ratio of Zinc diacetate dihydrate and aluminium salt, the doping that can realize regulating aluminium in the Al-Doped ZnO film.For example, the amount of aluminium salt is the 1-5% of Zinc diacetate dihydrate molar weight, and so, in the Al-Doped ZnO film that obtains, the doping of aluminium then is 1-5%, i.e. [Al/Zn]=1-5%.
Low boiling point solvent can be the boiling points such as methyl alcohol, ethanol, propyl alcohol, Virahol at the lower boiling alcohols below 100 ℃, or their mixture.The lower boiling stablizer can be the boiling points such as formic acid, acetic acid, butyric acid at the higher boil organic acid below 100 ℃, or their mixture.Use the effect of organic acid stablizer to be to keep the slightly acidic of spin coating liquid, thereby avoid facile hydrolysis raw material Zinc diacetate dihydrate and aluminium salt before being spin-coated to substrate, to be hydrolyzed.
In the spin coating liquid, the volume ratio of low boiling point solvent and water can be 1-5: 1, and the volume ratio of lower boiling stablizer and water can be 0.05-0.2: 1.
Step S102 afterwards, spin coating plated film: the spin coating liquid of above-mentioned preparation is spin-coated on the substrate of hydrophilic treatment, obtains the film precursor.When chip area is larger, can adopt two sections rotating speed spin coatings, the uniform film to obtain smooth, wherein low rotation speed can be 500-2000rpm, the high speed rotating speed can be 1500-2500rpm.The spin coating of first paragraph rotating speed is so that spin coating liquid uniform spreading on matrix, and second segment makes at a high speed unnecessary spin coating liquid throw away, and increases solvent evaporates, forms at last uniform film.When chip area hour, can directly use one section spin coating.Concrete which kind of spin coating mode that adopts can be selected according to actual needs by those skilled in the art.
The used substrate of the present invention can be hard transparent material, and such as soda-lime glass, borate glass, silica glass etc. also can be adopted flexible clear materials, such as polyethylene terephthalate, polyimide, Mi La etc.
It is in order to increase the reactive force of spin coating liquid and substrate that substrate is carried out hydrophilic treatment, so that spin coating liquid can infiltrate substrate surface, simultaneously so that the enhancing of the bonding force of the film of follow-up formation and substrate.The hydrophilic treatment of substrate can adopt this area substrate hydrophilic treatment method commonly used to carry out.Perhaps, also can adopt method of the present invention to carry out, namely use successively dish detergent, ammoniacal liquor-hydrogen peroxide mixed solution, water, hydrochloric acid-hydrogen peroxide mixed solution, water ultrasonic cleaning substrate, air-flow dries up afterwards.
Particularly, use first dish detergent clean surface visible spot, and rinse well with tap water; Then soak with ultrapure water, ammoniacal liquor-hydrogen peroxide mixed solution, and ultrasonic cleaning, wash with ultrapure water again; Then soak ultrasonic cleaning with ultrapure water, hydrochloric acid-hydrogen peroxide mixed solution, rinse well with ultrapure water equally.After in the end using the ultrapure water ultrasonic cleaning, substrate is kept in the ethanol for subsequent use, dries up with air-flow during use.
When spin coating liquid is applied to substrate surface through hydrophilic treatment, lower boiling solvent and lower boiling stablizer will be easy to volatilization, after weak acid and alcoholic solvent vapor away, facile hydrolysis raw material in the spin coating liquid is also with fast hydrolyzing, thereby forms the basic oxide of aluminum and zinc or the AZO film precursor of basic zinc salt at substrate surface.Yet, because the spin coating operation is very fast, in the spin coating process, be not that all matter of substrate surface all is transformed into the AZO precursor.Because the hydrophilic nmature of substrate also exists some residual zinc source and aluminium sources on the substrate surface.
The spin coating coating process can adopt a spin coating, also can adopt multiple spin coating.To obtain the precursor film of different thickness.
At step S103, carry out burin-in process afterwards: namely, in room temperature (being generally 18-25 ℃), make the film precursor in the environment of certain humidity condition, leave standstill aging for some time.Normally in the relative humidity environment of 60-80%, digestion time can be 10-48 hour.In aging film precursor, the hydrolysis of facile hydrolysis raw material is more complete, and aging operation can make zinc source remaining on the substrate surface and aluminium source complete hydrolysis be transformed into AZO film precursor.
Subsequently, carry out the heat treatment step of S104: namely, thermal treatment is through aging film precursor, and the film precursor of the basic oxide of aluminum and zinc or basic zinc salt changes into the sull of zinc and aluminium.Heat treatment step normally carried out 10-60 minute 120-200 ℃ temperature.
In order to obtain different film thicknesses, can be after heat treatment step S104, repeat once or more times S102 spin coating plated film, aging, the heat treated step of S104 of S103, until obtain the film thickness that needs.
For example the thickness of prepared according to the methods of the invention AZO transparent conductive film can be in the scope of 50-500nm.
After the thermal treatment, be step S105, atmosphere annealing: in inert atmosphere, make sull in annealing temperature 10-60 minute of 150-600 ℃.The purpose of annealing steps is, makes the sull in-situ crystallization, obtains aluminum-doped zinc oxide transparent conductive film.
Because the used organism of the present invention all is the volatile material of easily removing, therefore in the process of spin coating, the organism overwhelming majority such as solvent, stablizer have been volatilized, so that present method can be finished the transformation of precursor in annealing process.And because present method is to make the sull in-situ crystallization become the AZO transparent conductive film, so the film that forms has been densification.Densification helps to improve the transmitance of light, and simultaneously, owing to closely is connected between particle and the particle, the contact resistance minimizing is conducive to electronics at particle and intergranular hop transmission.
Annealing temperature is chosen between 150～600 ℃, can consider substrates of different, and the bonding force of film and substrate, and adopts different annealing temperatures.
After atmosphere annealing, the particle diameter of Al-Doped ZnO crystal grain can be in the scope of 5-15nm in the AZO transparent conductive film of acquisition.Such particle size range can guarantee that the Al-Doped ZnO film that obtains has enough compactness, thereby possesses good transparency and specific conductivity.
The characteristics of electrically conducting transparent compound are that its visible region has electroconductibility in the time of transparent, in conventional conductor, because there are not band gap in conduction band and valence band, its conduction is to produce by unbound electron, because unbound electron absorbs the energy of visible light easily, therefore the material of general conduction is opaque.And the electrically conducting transparent compound is owing to be to pass through semiconductor doping, so that fermi level enters conduction band, increase the carrier concentration of conduction band, thereby conduction, but there are a fixed gap in their conduction bands and valence band, general visible light energy deficiency is so that electronics transits to conduction band from valence band, and therefore, they are transparent at visible region.
Just because of this, the band gap of general electrically conducting transparent compound must be more than 3.0eV, and it is transparent at visible region for guarantee; On the other hand, because in the middle of the practical application, the electrically conducting transparent compound generally conducts electricity as the bottom of photoelectric device, in order not affect the transmission of visible light, for example on photovoltaic cell, photoactive layer need to absorb all light as much as possible, and the as far as possible extinction not of other coatings is so the transmitance of this layer of electrically conducting transparent compound is more high better.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Raw material and instrument
Zinc diacetate dihydrate, ANN aluminium nitrate nonahydrate, aluminium acetylacetonate and aluminum ethylate are all available from Chemical Reagent Co., Ltd., Sinopharm Group.
Soda-lime glass, borate glass, ultra-clear glasses, rice draw (Mylar), polyimide (PI) available from Shenzhen examination Science and Technology Ltd..
The spin coating instrument is the Kai Meite scientific instrument
Sol evenning machine.
Transmitance is by Shimadzu UV-3600 ultraviolet-visible light-near infrared spectrometer test.Concrete operations be with substrate as reference, the transmitance of film in the test 300-800nm visible-range.
Carrier concentration obtains the band gap of film by the absorption of Shimadzu UV-3600 ultraviolet-visible light-near infrared spectrometer testing film at ultraviolet region, then is converted into carrier concentration by Bandgap extension.
Embodiment 1
Take by weighing Zinc diacetate dihydrate 0.8g, ANN aluminium nitrate nonahydrate 0.0137g adds 18ml ethanol, stirs, and then adds 6ml water and 0.6ml glacial acetic acid, forms clear solution.[Al/Zn] is 1%,
Use common soda-lime glass as the spin coating substrate.Substrate is through dish detergent clean surface visible spot; Tap water is rinsed well.Then the mixing solutions with ultrapure water, ammoniacal liquor-hydrogen peroxide soaks rear ultrasonic cleaning; The ultrapure water flushing.Then soak ultrasonic cleaning with ultrapure water, hydrochloric acid-hydrogen peroxide mixed solution; Rinse well with ultrapure water.Be kept in the middle of the ethanol, air-flow dries up before using.
Use spin coating instrument plated film.Static lower even dropping liquid is at first spared glue 10 seconds under the 500rpm rotating speed, then spare glue 40 seconds under the 1800rpm rotating speed, repeats 4 spin coatings.
Substrate behind the plated film is put into 60%RH environment aged at room temperature 18h.
Substrate through overaging after 10 minutes, repeats spin coating plated film, aging, heat treated operation, until thickness is about 100nm 160 ℃ of hot platform thermal treatments.
450 ℃ of nitrogen atmosphere annealing 20min make aluminum-doped zinc oxide transparent conductive film, particle diameter 5nm, film thickness 110nm.
Transmitance is more than 80% in visible light window 300nm-800nm scope for this film, and carrier concentration reaches 3.7 * 10
18/ cm
-3Carrier concentration be can with document in prepare on the carrier concentration order of magnitude that the AZO film obtains by same characterization method consistent with other wet methods.
Embodiment 2
Similar to Example 1, difference only is: the addition of ANN aluminium nitrate nonahydrate is 0.0683g, 200 ℃ of thermal treatment temps.[Al/Zn] is 5%.
Embodiment 3
Similar to Example 1, difference only is: the addition of ANN aluminium nitrate nonahydrate is 0.0683g, and stablizer is 0.4ml formic acid.[Al/Zn] is 5%.
Embodiment 4
Take by weighing Zinc diacetate dihydrate 0.75g, aluminium acetylacetonate 0.0222g, add 14ml methyl alcohol, stir, then add 4ml water and 0.2ml acetic acid, form clear solution.[Al/Zn] is 2%.
Use borate glass as the spin coating substrate, the hydrophilic treatment method of substrate is with embodiment 1.
Use spin coating instrument plated film.Static lower even dropping liquid is at first spared glue 18 seconds under the 600rpm rotating speed, then spare glue 50 seconds under the 1600rpm rotating speed, repeats 4 spin coatings.
Substrate behind the plated film is put into the aging 16h of 70%RH environment.
Substrate through overaging after 20 minutes, repeats spin coating plated film, aging, heat treated operation, until thickness is about 100nm 150 ℃ of hot platform thermal treatments.
500 ℃ of nitrogen atmosphere annealings 30 minutes make Al-Doped ZnO film.
Transmitance is more than 80% in visible light 300nm-800nm scope for this film, and carrier concentration reaches 3.7 * 10
18/ cm
-3
Similar to Example 4, difference only is: solvent is the 16ml Virahol.
Embodiment 6
Take by weighing Zinc diacetate dihydrate 1.58g, aluminum ethylate 0.0350g, add 18ml ethanol, stir, then add 6ml water and 0.6ml glacial acetic acid, form clear solution.[Al/Zn] is 3%.
Use ultra-clear glasses as the spin coating substrate, processing method for substrate is with embodiment 1.
Use spin coating instrument plated film, static lower even dropping liquid is at first spared glue 18 seconds under the 600rpm rotating speed, then spare glue 50 seconds under the 1600rpm rotating speed, repeats 4 spin coatings.
Substrate behind the plated film is put into the aging 48h of 70%RH environment.
Substrate through overaging after 20 minutes, repeats spin coating plated film, aging, heat treated operation, until the about 100nm of thickness 150 ℃ of hot platform thermal treatments.
At 500 ℃ of nitrogen atmosphere annealing 30min, make Al-Doped ZnO film.
Transmitance is more than 80% in visible light 300nm-800nm scope for this film, and carrier concentration reaches 3.7 * 10
18/ cm
-3
Embodiment 7
Take by weighing Zinc diacetate dihydrate 0.75g, ANN aluminium nitrate nonahydrate 0.0256g adds 18ml ethanol, stirs, and then adds 5ml water and 0.5ml formic acid, forms clear solution.[Al/Zn] is 2%.
Use rice to draw (Mylar) as the spin coating substrate, processing method for substrate is with embodiment 1.
Use spin coating instrument plated film, static lower even dropping liquid is at first spared glue 15 seconds under the 700rpm rotating speed, then spare glue 50 seconds under the 1600rpm rotating speed, repeats 4 spin coatings.
Substrate behind the plated film is put into the aging 20h of 70%RH environment.Substrate through overaging after 20 minutes, repeats spin coating plated film, aging, heat treated operation, until thickness is about 100nm 150 ℃ of hot platform thermal treatments.
180 ℃ of nitrogen atmosphere annealings 30 minutes, make Al-Doped ZnO film.
Transmitance is more than 80% in visible light 300nm-800nm scope for this film, and carrier concentration reaches 3.7 * 10
18/ cm
-3
Embodiment 8
Take by weighing Zinc diacetate dihydrate 0.13g, ANN aluminium nitrate nonahydrate 0.0113g adds 10ml ethanol, stirs, and then adds 2ml water and 0.1ml acetic acid, forms transparent settled solution.[Al/Zn] is 5%.
Use polyimide (PI) to make the spin coating substrate, all the other are with example 7.
Embodiment 9
Take by weighing Zinc diacetate dihydrate 0.66g, aluminium butoxide 0.0148g adds the 5ml Virahol, stirs, and then adds 5ml water and 1ml acetic acid, forms transparent settled solution.[Al/Zn] is 2%.
All the other are with example 7.
Fig. 2 a is depicted as the front scan Electronic Speculum figure of the AZO transparent conductive film of embodiment 6 preparations.Fig. 2 b is its cross section scanning electron microscope (SEM) photograph.As seen from the figure: film thickness is 110nm, the about 5nm of particle diameter.Little and the homogeneous of thin film layer particle diameter, particle and particle Contact are tight, and compactness is good.
Fig. 3 a is depicted as the abosrption spectrogram of AZO transparent conductive film in the 300-800nm wavelength region for preparing according to embodiments of the invention 1-7.Fig. 3 b is AZO transparent conductive film the transmittance figure 300nm-800nm wavelength region in corresponding with Fig. 3 A.
Can see that from Fig. 3 a there is an obvious acromion in the AZO film at the 380nm place, can know that by converting band gap is about 3.4eV, consistent with the ZnO band gap.This proves that on the one hand film is AZO, rather than aluminum oxide or other materials, and the optical band gap of transparent conductor will be more than 3.0eV on the other hand, and its optical absorption of guarantee is in the ultraviolet region like this, and (400-700nm) is transparent at visible-range.
Fig. 3 b can see obviously in visible-range that the film transmitance illustrates that all more than 80% Al-Doped ZnO film of the present invention has good visible light transmissivity.
The electrically conducting transparent Al-Doped ZnO film of the present invention's preparation has the visible light transmissivity more than 80%, in use, can greatly reduce the loss of light in light path in the device.And all methods of the present invention are simple, and cost is lower than existing magnetron sputtering method, and energy consumption is low.
The above the specific embodiment of the present invention does not consist of the restriction to protection domain of the present invention.Various other corresponding changes and distortion that any technical conceive according to the present invention has been done all should be included in the protection domain of claim of the present invention.
Claims (11)
1. method for preparing aluminum-doped zinc oxide transparent conductive film may further comprise the steps:
S101 preparation spin coating liquid: Zinc diacetate dihydrate and aluminium salt are dissolved in the low boiling point solvent, add lower boiling stablizer and ultrapure water, obtain spin coating liquid, wherein Zinc diacetate dihydrate concentration is 0.05-0.3mol/L, the amount of aluminium salt is the 1-5% of Zinc diacetate dihydrate molar weight, the volume ratio of low boiling point solvent and water is 1-5: 1, and the volume ratio of lower boiling stablizer and water is 0.05-0.2: 1;
S102 spin coating plated film: spin coating liquid is spun on the substrate of hydrophilic treatment, obtains the film precursor;
S103 is aging: the film precursor was left standstill in the room temperature environment of relative humidity 60-80% aging 10-48 hour, obtain through aging film precursor;
S104 thermal treatment: will through aging film precursor at 120-200 ℃ of thermal treatment 10-60 minute, obtain sull;
S105 atmosphere annealing: sull in inert atmosphere, 150-600 ℃ of annealing 10-60 minute, is made the sull in-situ crystallization, obtain aluminum-doped zinc oxide transparent conductive film.
2. method according to claim 1 is characterized in that, described aluminium salt is selected from ANN aluminium nitrate nonahydrate, aluminium acetylacetonate, aluminum ethylate, aluminum isopropylate, aluminium butoxide, or their arbitrary combination.
3. method according to claim 1 is characterized in that, described low boiling point solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, or their arbitrary combination.
4. method according to claim 1 is characterized in that, described lower boiling stablizer is selected from formic acid, acetic acid, butyric acid, or their arbitrary combination.
5. method according to claim 1 is characterized in that, described substrate is by the hard transparent material that comprises soda-lime glass, borate glass, silica glass, or comprises that the flexible clear materials that polyethylene terephthalate, polyimide, rice draw consists of.
6. method according to claim 1 is characterized in that, step S102 comprises a spin coating plated film, twice above spin coating plated film.
7. method according to claim 1 is characterized in that, described method also is included in step S104 afterwards repeating step S102, S103, S104 operation at least one times.
8. method according to claim 1 is characterized in that, the substrate through hydrophilic treatment described in the step S102 is prepared as follows:
Use successively dish detergent, ammoniacal liquor-hydrogen peroxide mixed solution, water, hydrochloric acid-hydrogen peroxide mixed solution, water ultrasonic cleaning substrate, air-flow dries up afterwards, obtains the substrate through hydrophilic treatment.
9. method according to claim 1 is characterized in that, one section of step S102 employing or two sections rotating speeds carry out, and when adopting two sections rotating speeds, low rotation speed is 500-2000rpm, and the high speed rotating speed is 1500-2500rpm.
10. method according to claim 1 is characterized in that, the particle diameter of described Al-Doped ZnO particle is 5-15nm, and the thickness of described film is 50-500nm.
11. the aluminum-doped zinc oxide transparent conductive film that each described method prepares according to claim 1-10.
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