CN108203807A - A kind of ZnO transparent conductive material with excellent environment stability and preparation method thereof - Google Patents
A kind of ZnO transparent conductive material with excellent environment stability and preparation method thereof Download PDFInfo
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- CN108203807A CN108203807A CN201611175322.5A CN201611175322A CN108203807A CN 108203807 A CN108203807 A CN 108203807A CN 201611175322 A CN201611175322 A CN 201611175322A CN 108203807 A CN108203807 A CN 108203807A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Abstract
The present invention relates to a kind of ZnO transparent conductive materials with excellent environment stability and preparation method thereof.Specifically, the invention discloses a kind of preparation method of zinc-oxide film, described method includes following steps：1) doped Zinc oxide-base target is provided；2) the doped Zinc oxide-base target is placed in magnetron sputtering apparatus, vacuumizes and reach first pressure；3) mixed gas of first gas and second gas is passed through, until inside cavity reaches second pressure；4) magnetron sputtering film is carried out using the doped Zinc oxide-base target on substrate, obtains the zinc-oxide film.The invention also discloses with zinc-oxide film and its application made from the preparation method.The zinc-oxide film has both excellent photoelectric characteristic and environmental stability, therefore can be widely applied to various occasions.The preparation method have the characteristics that it is simple for process, at low cost, can directly implement on existing.
Description
Technical field
The present invention relates to field of photovoltaic materials, are led more particularly to a kind of ZnO transparent with excellent environment stability
Electric material and preparation method thereof.
Background technology
Zinc oxide is passing through a fixed number as a kind of environmental-friendly, rich reserves multifunctional wide forbidden band oxide material
After the degeneracy doping (such as aluminium, gallium, indium, tin) of amount, the transparent conductive oxide material of high light electrical property can be become
(transparent conductive oxide, TCO) has UV Absorption, visible transparent, infrared light reflection and electricity
The advantages that characteristic is adjustable is learned, in photoelectricity such as FPD, thin-film solar cells, building energy conservation Low-E glass, intelligent glass
Message area is more and more applied, can as in thin-film solar cells transparent electrode layer, middle dielectric layer and
Back electrode high reflection layer, the function medium layer in energy saving Low-E glass, the transparent electrode layer of intelligent glass and household appliance glass
Infrared reflecting layer etc..
The technology of deposited oxide Zinc-based film is varied at present, wherein the most ripe with magnetron sputtering film forming, it has
Film consistency is high, uniformity with it is reproducible and adopt by industrial quarters receiving and extensively the advantages that be easy to large area high speed deposition
With.However the zinc oxide transparent conductive film of existing magnetron sputtering is also faced with some environmental stabilities in actual application
The problem of：(1) zinc oxide is amphoteric oxide in itself, it is easy to be corroded by acid, alkali；(2) high-temperature stability of zinc oxide
It is poor, such as in air atmosphere, the zinc oxide transparent conductive film of aluminium doping is difficult to bear 300 DEG C or more of high temperature；(3) oxygen
The hydrothermal stability of change zinc is poor, and the device of many photoelectricity classes needs 85 DEG C by such as 1000h and 85% humidity at present
Test or the test of equivalent accelerated ageing (HAST) high for 24 hours, Zinc-oxide-based transparent conductive film is easily subject to aqueous vapor
Erosion, lead to the failure of device.
Therefore, this field is badly in need of developing a kind of zinc-oxide film for having both excellent photoelectric characteristic and environmental stability, with into
One step promotes the popularization and application of zinc-oxide film.
Invention content
The purpose of the present invention is to provide a kind of zinc-oxide film for having both excellent photoelectric characteristic and environmental stability, with into
One step promotes the popularization and application of zinc-oxide film.
The first aspect of the present invention provides a kind of preparation method of zinc-oxide film, and described method includes following steps：
1) doped Zinc oxide-base target is provided；
2) the doped Zinc oxide-base target is placed in magnetron sputtering apparatus, vacuumizes and reach first pressure；
3) mixed gas of first gas and second gas is passed through, until inside cavity reaches second pressure；
4) magnetron sputtering film is carried out using the doped Zinc oxide-base target on substrate, obtains the zinc oxide
Film.
In another preferred example, the doped Zinc oxide-base target is prepared as follows：
I) the first mixture containing Zinc oxide powder, the first oxide powder and the second oxide powder is provided；
Ii first mixture, dispersant and solvent) are mixed to get the second mixture；
Iii) the second mixture described in ball-milling treatment, obtains third mixture；
Iv the third mixture) is dried, obtains the 4th mixture；
V) the 4th mixture optionally described in milled processed, obtains the 5th mixture；
Vi) mixture obtained by compression moulding abovementioned steps, obtains initial ceramic green body；
Vii) initial ceramic green body described in sintering processes obtains the doped Zinc oxide-base target.
In another preferred example, the grain size of the Zinc oxide powder is 100-500nm, preferably 200-400nm.
In another preferred example, first oxide powder is the oxide powder of doped chemical selected from the group below：Aluminium,
Gallium, indium, boron, or combination.
In another preferred example, first oxide is selected from the group：Aluminium oxide, gallium oxide, indium oxide, boron oxide or
A combination thereof.
In another preferred example, the grain size of first oxide powder is 100-500nm, preferably 200-400nm.
In another preferred example, second oxide powder is the oxide powder of doped chemical selected from the group below：Tin,
Magnesium, titanium, zirconium, silicon, yttrium, or combination.
In another preferred example, second oxide is selected from the group：Tin oxide, magnesia, titanium oxide, zirconium oxide, oxygen
SiClx, yttrium oxide, or combination.
In another preferred example, the grain size of second oxide powder is 100-500nm, preferably 200-400nm.
In another preferred example, the dispersant is selected from the group：Polyvinylpyrrolidone, polyvinyl alcohol, carboxymethyl cellulose
Element, polyacrylamide, polyethylene glycol, or combination.
In another preferred example, the solvent is water.
In another preferred example, the method has one or more features selected from the group below：
A) processing time of the ball-milling treatment is 2-30h, preferably 5-25h；
B) treatment temperature of the drying process is 50-120 DEG C, preferably 60-100 DEG C；
C) processing time of the drying process is 0.1-24h, preferably 0.5-12h；
D) processing time of the milled processed is 0.1-5h, preferably 0.3-2h；
E) compression moulding includes following two benches：
Stage one：The compression molding under 20-200MPa obtains the first ceramic body；With
Stage two：The cold isostatic compaction under 100-500MPa obtains initial ceramic green body；
F) treatment temperature of the sintering processes is 1000-1800 DEG C, preferably 1200-1600 DEG C；
G) processing time of the sintering processes is 0.5-15h, preferably 1-10h.
In another preferred example, Zinc oxide powder described in step i), first oxide powder and second oxygen
The mixing quality ratio of compound powder is 80-99：1-10：0.01-5；And/or
Step ii) described in the first mixture, the dispersant and the solvent mixing quality ratio be 80-120：0.1-
10：20-60.
In another preferred example, Zinc oxide powder described in step i), first oxide powder and second oxygen
The mixing quality ratio of compound powder is 85-98：2-8：0.05-3.
In another preferred example, step ii) described in the first mixture, the dispersant and the solvent mixing quality
Than for 90-110：0.5-6：30-50.
In another preferred example, the consistency ＞ 90% of the doped Zinc oxide-base target, preferably ＞ 95%, more
Good ground ＞ 98%.
In another preferred example, the first pressure is 1 × 10-5-1×10-3Pa。
In another preferred example, the first gas is selected from the group：Argon gas, helium, or combination；And/or
The second gas is selected from the group：Aqueous vapor, hydrogen, ammonia, or combination.
In another preferred example, the molar ratio of the first gas and the second gas is 1-3：0.01-0.5, preferably
Ground 1-2：0.05-0.3.
In another preferred example, the second pressure is 0.01-100Pa, preferably 0.1-10Pa.
In another preferred example, the substrate is selected from the group：Glass, quartz, silicon chip.
In another preferred example, the method has one or more features selected from the group below：
1-1) preset temperature of the substrate is 20-500 DEG C；
1-2) distance of the doped Zinc oxide-base target and the substrate is 3-30cm；
1-3) sputtering time of the magnetron sputtering is 5-300min；
1-4) Sputtering power density of the magnetron sputtering is 1-20w/cm2。
In another preferred example, the means of the magnetron sputtering are selected from the group：Direct current, radio frequency, or combination.
The second aspect of the present invention, provides a kind of zinc-oxide film, and the zinc-oxide film is using the present invention first
Prepared by aspect the method.
In another preferred example, the zinc-oxide film has one or more features selected from the group below：
1) thickness of the zinc-oxide film is 100-2000nm, preferably 200-1500nm, more preferably 300-
1000nm, more preferably 400-700nm, most preferably 450-500nm；
2) square resistance of the zinc-oxide film is 3-50 Ω/, preferably 6-20 Ω/, more preferably 7-15 Ω/
□；
3) resistivity of the zinc-oxide film is 2 × 10-4- 15 × 10-4Ω cm, preferably 3 × 10-4- 10 ×
10-4Ω·cm；
4) carrier concentration of the zinc-oxide film is 2 × 1020- 15 × 1020cm-3, preferably 4 × 1020- 9 ×
1020cm-3；
5) mobility of the zinc-oxide film is 10-40cm2/ vs, preferably 15-30cm2/v·s；
6) zinc-oxide film is 70%-90% in the optical transmittance of 400-800nm, preferably 75%-85%.
In another preferred example, the zinc-oxide film has one or more features selected from the group below：
I) zinc-oxide film impregnates 10 minutes in acid solution, resistance change rate≤50%, preferably≤40%,
More preferably≤30%；
Ii) zinc-oxide film temperature be 121 DEG C and humidity be 97% time processing for 24 hours after, sheet resistance change rate≤
80%, preferably 60%, preferably 40%, preferably 20%, most preferably 10%；
Iii after) zinc-oxide film handles 30min under the conditions of 500 DEG C of air atmosphere, sheet resistance change rate≤
80%, preferably 60%, preferably 40%, preferably 20%, preferably 10%, most preferably 5%.
In another preferred example, the pH value of the acid solution is 2-4, preferably 2.5-3.5.
In another preferred example, the acid solution is selected from the group：Nitric acid, hydrochloric acid, sulfuric acid, acetic acid, or combination.
In another preferred example, the resistance change rate is Δ R/R0, wherein R0Zinc-oxide film during not impregnate
Resistance, Δ R are resistance variations of the zinc-oxide film after acid solution immersion.
The third aspect of the present invention, provides a kind of product, and the product includes zinc oxide described in second aspect of the present invention
Film or zinc-oxide film is made as described in second aspect of the present invention.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, so as to form new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Description of the drawings
Fig. 1 is the surface SEM photograph of 4 gained zinc-oxide film 1 of embodiment.
Fig. 2 is the surface SEM photograph of 2 gained zinc-oxide film C1 of comparative example.
After Fig. 3 is impregnates 10min, 1 gained zinc-oxide film C1 (a) of comparative example and 4 gained zinc-oxide film 1 of embodiment
(b) the AFM shape appearance figures on surface.
Fig. 4 is 4 gained zinc-oxide film 1 of embodiment and 1 gained zinc-oxide film of comparative example under the different HAST testing times
The sheet resistivity situation of change of C1.
Specific embodiment
The present inventor's in-depth study by long-term is gone forward side by side a successive step magnetic control by adjusting the formula of zinc oxide target
A kind of zinc-oxide film for having both excellent photoelectric characteristic and environmental stability, institute is unexpectedly prepared in the preparation process of sputtering
It states zinc-oxide film and can be widely applied to various occasions.On this basis, inventor completes the present invention.
Term
In the present invention, term " zinc-oxide film ", " zinc-oxide-base transparent conducting film ", " ZnO transparent conductive material
Material " or " zinc oxide material " are used interchangeably.
Preparation method
The present invention also provides a kind of preparation methods of zinc-oxide film, and described method includes following steps：
1) doped Zinc oxide-base target is provided；
2) the doped Zinc oxide-base target is placed in magnetron sputtering apparatus, vacuumizes and reach first pressure；
3) mixed gas of first gas and second gas is passed through, until inside cavity reaches second pressure；
4) magnetron sputtering film is carried out using the doped Zinc oxide-base target on substrate, obtains the zinc oxide
Film.
In the present invention, the doped Zinc oxide-base target is prepared as follows：
I) the first mixture containing Zinc oxide powder, the first oxide powder and the second oxide powder is provided；
Ii first mixture, dispersant and solvent) are mixed to get the second mixture；
Iii) the second mixture described in ball-milling treatment, obtains third mixture；
Iv the third mixture) is dried, obtains the 4th mixture；
V) the 4th mixture optionally described in milled processed, obtains the 5th mixture；
Vi) mixture obtained by compression moulding abovementioned steps, obtains initial ceramic green body；
Vii) initial ceramic green body described in sintering processes obtains the doped Zinc oxide-base target.
In another preferred example, the grain size of the Zinc oxide powder is 100-500nm, preferably 200-400nm.
In another preferred example, first oxide powder is the oxygen for the doped chemical for including (but being not limited to) the following group
Compound powder：Aluminium, gallium, indium, boron, or combination.
In another preferred example, first oxide includes (but being not limited to)：Aluminium oxide, gallium oxide, indium oxide, oxygen
Change boron, or combination.
In another preferred example, the grain size of first oxide powder is 100-500nm, preferably 200-400nm.
In another preferred example, second oxide powder is the oxygen for the doped chemical for including (but being not limited to) the following group
Compound powder：Tin, magnesium, titanium, zirconium, silicon, yttrium, or combination.
In another preferred example, second oxide includes (but being not limited to)：Tin oxide, magnesia, titanium oxide, oxygen
Change zirconium, silica, yttrium oxide, or combination.
In another preferred example, the grain size of second oxide powder is 100-500nm, preferably 200-400nm.
In another preferred example, the dispersant includes (but being not limited to)：Polyvinylpyrrolidone, polyvinyl alcohol, carboxylic
Methylcellulose, polyacrylamide, polyethylene glycol, or combination.
In another preferred example, the solvent is water.
In another preferred example, the method has one or more features selected from the group below：
A) processing time of the ball-milling treatment is 2-30h, preferably 5-25h；
B) treatment temperature of the drying process is 50-120 DEG C, preferably 60-100 DEG C；
C) processing time of the drying process is 0.1-24h, preferably 0.5-12h；
D) processing time of the milled processed is 0.1-5h, preferably 0.3-2h；
E) compression moulding includes following two benches：
Stage one：The compression molding under 20-200MPa obtains the first ceramic body；With
Stage two：The cold isostatic compaction under 100-500MPa obtains initial ceramic green body；
F) treatment temperature of the sintering processes is 1000-1800 DEG C, preferably 1200-1600 DEG C；
G) processing time of the sintering processes is 0.5-15h, preferably 1-10h.
In the present invention, Zinc oxide powder described in step i), first oxide powder and second oxide
The mixing quality ratio of powder is 80-99：1-10：0.01-5；And/or
Step ii) described in the first mixture, the dispersant and the solvent mixing quality ratio be 80-120：0.1-
10：20-60.
In another preferred example, Zinc oxide powder described in step i), first oxide powder and second oxygen
The mixing quality ratio of compound powder is 85-98：2-8：0.05-3.
In another preferred example, step ii) described in the first mixture, the dispersant and the solvent mixing quality
Than for 90-110：0.5-6：30-50.
In another preferred example, the consistency ＞ 90% of the doped Zinc oxide-base target, preferably ＞ 95%, more
Good ground ＞ 98%.
In another preferred example, the first pressure is 1 × 10-5-1×10-3Pa。
In the present invention, the first gas includes (but being not limited to)：Argon gas, helium, or combination；And/or
The second gas includes (but being not limited to)：Aqueous vapor, hydrogen, ammonia, or combination.
In the present invention, the molar ratio of the first gas and the second gas is 1-3：0.01-0.5, preferably 1-
2：0.05-0.3.
In another preferred example, the second pressure is 0.01-100Pa, preferably 0.1-10Pa.
In another preferred example, the substrate includes (but being not limited to)：Glass, quartz, silicon chip.
In another preferred example, the method has one or more features selected from the group below：
1-5) preset temperature of the substrate is 20-500 DEG C；
1-6) distance of the doped Zinc oxide-base target and the substrate is 3-30cm；
1-7) sputtering time of the magnetron sputtering is 5-300min；
1-8) Sputtering power density of the magnetron sputtering is 1-20w/cm2。
In the present invention, the means of the magnetron sputtering include (but being not limited to)：Direct current, radio frequency, or combination.
In the present invention, a kind of typical preparation method is as follows：
Step 1: the preparation of Zinc oxide-base magnetic control spattering target
(1) by 86~98.99wt% Zinc oxide powders, 1~10wt% the first doped chemical oxide powder, 0.01~
Second of doped chemical oxide powder of 4wt% is mixed by weighing；
(2) using mass ratio, by above-mentioned powder mixture：Dispersant：Deionized water=100：0.5~4：20~60 press than
After example mixing by 8~ball milling for 24 hours, form slurry；
(3) slurry taking-up is placed in drying in 60~100 DEG C of baking oven, powder is formed using grinding, burnt as ceramics
Tie starting material；
(4) by step (3) formed isostatic cool pressing of the raw material through 30~150MPa compression moldings and 120~300MPa into
Type forms the ceramic body that relative density is 60~75%；
(5) green body in step (4) is put into chamber type electric resistance furnace, under the conditions of 1300~1400 DEG C be sintered 120~
480min obtains the required target sputtered, the consistency of target through supercooling and machining>98%.
The first described doped chemical is aluminium, one kind in gallium, indium, boron；
Second of doped chemical be：One kind in tin, magnesium, titanium, zirconium, silicon, yttrium；
The dispersant is：Polyvinylpyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, poly- second two
Alcohol, or combination；
Step 2: prepared by the magnetron sputtering of zinc-oxide-base transparent conducting film
(1) target is placed in magnetron sputtering apparatus, vacuumized, reach base vacuum 2~8 × 10-4Pa；
(2) being then passed through argon gas and second gas, (molar ratio of argon gas and second of gas is 1：0.01~0.2)
Mixed gas makes the pressure value stabilization of inside cavity in 0.1-1.2Pa.
(3) temperature of glass substrate is set as 25~450 DEG C, and the distance of target and glass substrate is 5~15cm, and magnetic control splashes
The time penetrated is 20~200min, and the power density of sputtering is 2~8w/cm2。
Second of the gas is aqueous vapor, one or two kinds of in hydrogen, ammonia.
Combination of the means of the magnetron sputtering for direct current, radio frequency or direct current and radio frequency.
Using
The present invention also provides a kind of zinc-oxide film, the zinc-oxide film is prepared using the method.
In the present invention, the zinc-oxide film has one or more features selected from the group below：
1) thickness of the zinc-oxide film is 100-2000nm, preferably 200-1500nm, more preferably 300-
1000nm, more preferably 400-700nm, most preferably 450-500nm；
2) square resistance of the zinc-oxide film is 3-50 Ω/, preferably 6-20 Ω/, more preferably 7-15 Ω/
□；
3) resistivity of the zinc-oxide film is 2 × 10-4- 15 × 10-4Ω cm, preferably 3 × 10-4- 10 ×
10-4Ω·cm；
4) carrier concentration of the zinc-oxide film is 2 × 1020- 15 × 1020cm-3, preferably 4 × 1020- 9 ×
1020cm-3；
5) mobility of the zinc-oxide film is 10-40cm2/ vs, preferably 15-30cm2/v·s；
6) zinc-oxide film is 70%-90% in the optical transmittance of 400-800nm, preferably 75%-85%.
In the present invention, the zinc-oxide film has one or more features selected from the group below：
I) zinc-oxide film impregnates 10 minutes in acid solution, resistance change rate≤50%, preferably≤40%,
More preferably≤30%；
Ii) zinc-oxide film temperature be 121 DEG C and humidity be 97% time processing for 24 hours after, sheet resistance change rate≤
80%, preferably 60%, preferably 40%, preferably 20%, most preferably 10%；
Iii after) zinc-oxide film handles 30min under the conditions of 500 DEG C of air atmosphere, sheet resistance change rate≤
80%, preferably 60%, preferably 40%, preferably 20%, preferably 10%, most preferably 5%.
In another preferred example, the pH value of the acid solution is 2-4, preferably 2.5-3.5.
In another preferred example, the acid solution includes (but being not limited to)：Nitric acid, hydrochloric acid, sulfuric acid, acetic acid or its
Combination.
In another preferred example, the resistance change rate is Δ R/R0, wherein R0Zinc-oxide film during not impregnate
Resistance, Δ R are resistance variations of the zinc-oxide film after acid solution immersion.
The present invention also provides a kind of product, the product includes the zinc-oxide film or by the zinc-oxide film system
Into.
Compared with prior art, the present invention has following major advantage：
(1) zinc-oxide film not only has excellent basic photoelectric characteristic, while also has excellent ambient stable
Property；
(2) zinc-oxide film has excellent hydrothermal stability, high-temperature stability and corrosion resistance characteristic；
(3) zinc-oxide film has the wider scope of application；
(4) preparation method have the characteristics that it is simple for process, at low cost, can directly implement on existing.
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Test method without specific conditions in the following example, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Unless otherwise defined, it anticipates known to all professional and scientific terms used in text and one skilled in the art
Justice is identical.In addition, any method similar or impartial to described content and material all can be applied in the method for the present invention.Wen Zhong
The preferred implement methods and materials are for illustrative purposes only.
Universal testing method
Basic photoelectric characteristic
Using the optical transmittance of measurement of ultraviolet-visible spectrophotometer film, the load of film is measured using hall measurement instrument
Sub- concentration, mobility and resistivity are flowed, using the hydrothermal stability of high accelerated aging test case testing film, test condition is
After being 97% time processing for 24 hours for 121 DEG C and humidity.
The preparation of 1 Zinc oxide-base magnetic control spattering target 1 of embodiment
(1) by Zinc oxide powder (grain size is about 300nm), aluminium oxide and tin oxide according to mass ratio 95：3：2 mixing, obtain
To solid mixture 1；
(2) by solid mixture 1, polyvinylpyrrolidone and deionized water according to mass ratio 100：2：30 mixing, by institute
It obtains product and carries out 10h ball millings, form mixed slurry 1；
(3) mixed slurry 1 is taken out and is placed in dry 60min in 80 DEG C of baking oven, powder is formed using grinding, as pottery
Porcelain is sintered starting material 1；
(4) raw material 1 that step (3) is formed, then with 250MPa cold isostatic compactions, is obtained through 100MPa compression moldings
To ceramic body 1；
(5) ceramic body 1 obtained by step (4) is put into chamber type electric resistance furnace, heating rate is 10 DEG C/min, at 1300 DEG C
Under the conditions of be sintered 200min, through supercooling and machining obtain target 1.
Through measuring and calculating, the consistency of 1 gained Zinc oxide-base target 1 of embodiment>98%.
The preparation of 2 Zinc oxide-base magnetic control spattering target 2 of embodiment
With embodiment 1, difference lies in：Zinc oxide powder, aluminium oxide and tin oxide are according to mass ratio 98：1.5：0.5 mixing.
The preparation of 3 Zinc oxide-base magnetic control spattering target 3 of embodiment
With embodiment 1, difference lies in：Aluminium oxide is replaced using indium oxide, tin oxide is replaced using titanium oxide.
Through measuring and calculating, the performance of Zinc oxide-base target 2 and Zinc oxide-base target 3 is substantially the same as Zinc oxide-base target 1.
It is prepared by the magnetron sputtering of 4 zinc-oxide-base transparent conducting film 1 of embodiment
(1) 1 gained Zinc oxide-base target 1 of embodiment is placed in magnetron sputtering apparatus, vacuumizes, reach base vacuum 2
~8 × 10-4Pa；
(2) being then passed through argon gas, (molar ratio of argon gas and hydrogen is 1 with hydrogen：0.1) mixed gas, makes inside cavity
Pressure value stabilization in 1Pa.
(3) temperature of glass substrate is set as 50 DEG C, and the distance of target and glass substrate is 10cm, the time of magnetron sputtering
For 100min, the power density of sputtering is 5w/cm2, obtain zinc-oxide film 1.
As a result
SEM, basic photoelectric characteristic, corrosion resistance, high-temperature stability and wet are carried out to 4 gained zinc-oxide film 1 of embodiment
The tests such as thermal stability.
Fig. 1 is the surface SEM photograph of 4 gained zinc-oxide film 1 of embodiment.
As can be seen from Figure 1：Zinc-oxide film 1 has comparatively dense institutional framework, this will be helpful to promote film sample
The environmental stability of product.
It is prepared by the magnetron sputtering of 5 zinc-oxide-base transparent conducting film 2 of embodiment
With embodiment 4, difference lies in：The molar ratio of argon gas and hydrogen is 1：0.05.
It is prepared by the magnetron sputtering of 6 zinc-oxide-base transparent conducting film 3 of embodiment
With embodiment 4, difference lies in：Hydrogen is replaced using aqueous vapor.
The performance of zinc-oxide film 2 and zinc-oxide film 3 is substantially the same as zinc-oxide film 1.
The preparation of 1 Zinc oxide-base magnetic control spattering target C1 of comparative example
With embodiment 1, difference lies in：Without using aluminium oxide and tin oxide.
It is prepared by the magnetron sputtering of 2 zinc-oxide-base transparent conducting film C1 of comparative example
With embodiment 4, difference lies in：Zinc oxide-base target 1 is replaced, and prepare using Zinc oxide-base magnetic control spattering target C1
Process is only passed through argon gas, is not passed through hydrogen.
As a result
With embodiment 4, SEM, basic photoelectric characteristic, corrosion resistance, high-temperature stability and wet are carried out to zinc-oxide film C1
The tests such as thermal stability.
Fig. 2 is the surface SEM photograph of 2 gained zinc-oxide film C1 of comparative example.
As can be seen from Figure 2：Film is of a relatively loose.
Basic photoelectric characteristic
Basic photoelectric characteristic ratio of the table 1 for 4 gained zinc-oxide film 1 and 2 gained zinc-oxide film C1 of comparative example of embodiment
Compared with.
Table 1
As can be seen from Table 1：Compared to zinc-oxide film C1, the resistivity of zinc-oxide film 1 is slightly promoted, from 3.8 ×
10-4Ω cm are promoted to 5.1 × 10-4Ω cm, but 400-800nm optical transmittances are kept approximately constant.The above results table
Bright zinc-oxide film of the present invention 1 still keeps quite excellent basic photoelectric characteristic.
Corrosion resistance
It is 2.7 that 4 gained zinc-oxide film 1 and 1 gained zinc-oxide film C1 of comparative example of embodiment is respectively placed in pH value
To investigate the corrosion resistance characteristic of sample in acid solution (such as nitric acid).
Table 2 is the electric property comparison of sample after different soaking times.
Table 2
As can be seen from Table 2：After 10 minutes impregnate, the resistance change rate of zinc-oxide film 1 is 27.4%, is far below
The resistance change rate 94.7% of zinc-oxide film C1.
After Fig. 3 is impregnates 10min, 1 gained zinc-oxide film C1 (a) of comparative example and 4 gained zinc-oxide film 1 of embodiment
(b) the AFM shape appearance figures on surface.
As can be seen from Figure 3：The size of the etch pit of zinc-oxide film 1 is significantly less than the etch pit of zinc-oxide film C1
Size, this illustrates that zinc-oxide film 1 has stronger resistance to acidic materials.
Hydrothermal stability
4 gained zinc-oxide film 1 and 1 gained zinc-oxide film C1 of comparative example of embodiment is respectively placed in accelerated ageing test
Influence of the wet heat condition to film sample sheet resistivity is investigated in case (HAST), the conditional parameter of test is：121 DEG C of temperature, it is wet
It is 97% to spend, and the time is 6h, 12h, 18h and for 24 hours respectively.
Fig. 4 is 4 gained zinc-oxide film 1 of embodiment and 1 gained zinc-oxide film of comparative example under the different HAST testing times
The sheet resistivity situation of change of C1.
As can be seen from Figure 4：Compared to zinc-oxide film C1, zinc-oxide film 1 has excellent hydrothermal stability, side
Resistive rate is only 9.8%, and zinc-oxide film C1 is then up to 3600%.
High-temperature stability
4 gained zinc-oxide film 1 and 1 gained zinc-oxide film C1 of comparative example of embodiment is respectively placed in 500 DEG C of air
30min under atmospheric condition investigates the high-temperature stability of sample.
Table 3 shows 4 gained zinc-oxide film 1 of embodiment and 1 gained zinc-oxide film C1 of comparative example at high temperature steady
Qualitative comparison.
Table 3
| Zinc-oxide film C1 | Zinc-oxide film 1 | |
| R before heat treatment0(Ω/□) | 7.6 | 11.3 |
| R (Ω/) after heat treatment | 36.2 | 11.6 |
| ΔR/R0 | 3.76 | 2.6% |
As can be seen from Table 3：Under the conditions of 500 DEG C of air atmosphere, zinc-oxide film 1 has high thermal stability, side
Resistive rate is only 2.6%, and the variation of zinc-oxide film C1 is then up to 3.76 times.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To be made various changes or modifications to the present invention, such equivalent forms equally fall within the model that the application the appended claims are limited
It encloses.
Claims (10)
1. a kind of preparation method of zinc-oxide film, which is characterized in that described method includes following steps：
1) doped Zinc oxide-base target is provided；
2) the doped Zinc oxide-base target is placed in magnetron sputtering apparatus, vacuumizes and reach first pressure；
3) mixed gas of first gas and second gas is passed through, until inside cavity reaches second pressure；
4) magnetron sputtering film is carried out using the doped Zinc oxide-base target on substrate, obtains the zinc oxide films
Film.
2. the method as described in claim 1, which is characterized in that the doped Zinc oxide-base target is prepared as follows：
I) the first mixture containing Zinc oxide powder, the first oxide powder and the second oxide powder is provided；
Ii first mixture, dispersant and solvent) are mixed to get the second mixture；
Iii) the second mixture described in ball-milling treatment, obtains third mixture；
Iv the third mixture) is dried, obtains the 4th mixture；
V) the 4th mixture optionally described in milled processed, obtains the 5th mixture；
Vi) mixture obtained by compression moulding abovementioned steps, obtains initial ceramic green body；
Vii) initial ceramic green body described in sintering processes obtains the doped Zinc oxide-base target.
3. method as claimed in claim 2, which is characterized in that Zinc oxide powder described in step i), first oxide
The mixing quality ratio of powder and second oxide powder is 80-99：1-10：0.01-5；And/or
Step ii) described in the first mixture, the dispersant and the solvent mixing quality ratio be 80-120：0.1-10：
20-60。
4. the method as described in claim 1, which is characterized in that the first gas is selected from the group：Argon gas, helium or its group
It closes；And/or
The second gas is selected from the group：Aqueous vapor, hydrogen, ammonia, or combination.
5. the method as described in claim 1, which is characterized in that the molar ratio of the first gas and the second gas is 1-
3：0.01-0.5.
6. the method as described in claim 1, which is characterized in that the means of the magnetron sputtering are selected from the group：Direct current, radio frequency,
Or combination.
7. a kind of zinc-oxide film, which is characterized in that the zinc-oxide film is prepared using claim 1 the method.
8. zinc-oxide film as claimed in claim 7, which is characterized in that the zinc-oxide film has one selected from the group below
Or multiple features：
1) thickness of the zinc-oxide film is 100-2000nm；
2) square resistance of the zinc-oxide film is 3-50 Ω/；
3) resistivity of the zinc-oxide film is 2 × 10-4- 15 × 10-4Ω·cm；
4) carrier concentration of the zinc-oxide film is 2 × 1020- 15 × 1020cm-3；
5) mobility of the zinc-oxide film is 10-40cm2/v·s；
6) zinc-oxide film is 70%-90% in the optical transmittance of 400-800nm.
9. zinc-oxide film as claimed in claim 7, which is characterized in that the zinc-oxide film has one selected from the group below
Or multiple features：
I) zinc-oxide film impregnates 10 minutes in acid solution, resistance change rate≤50%；
Ii) zinc-oxide film is 121 DEG C in temperature and humidity is sheet resistance change rate≤80% after 97% time processing for 24 hours；
Iii) zinc-oxide film is after processing 30min under the conditions of 500 DEG C of air atmosphere, sheet resistance change rate≤80%.
10. a kind of product, which is characterized in that the product includes zinc-oxide film described in claim 7 or by claim 7 institute
Zinc-oxide film is stated to be made.
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