CN107217232A - A kind of method for improving zinc oxide transparent conductive film chemical stability - Google Patents
A kind of method for improving zinc oxide transparent conductive film chemical stability Download PDFInfo
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- CN107217232A CN107217232A CN201710370997.3A CN201710370997A CN107217232A CN 107217232 A CN107217232 A CN 107217232A CN 201710370997 A CN201710370997 A CN 201710370997A CN 107217232 A CN107217232 A CN 107217232A
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- transparent conductive
- zinc oxide
- conductive film
- oxide transparent
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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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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Abstract
The invention discloses a kind of method for improving zinc oxide transparent conductive film chemical stability, by using be insoluble in acid, alkali high-valence state metal oxides doping zinc-oxide (ZnO) be target, using magnetron sputtering technique, with argon gas (Ar) and hydrogen (H2) it is sputter gas, realize the preparation of high-valence state metallic element and hydrogen (H) codope ZnO transparent conductive thin film.The invention has the advantages that：There is the ZnO film of preparation low-resistivity, wide spectrum to pass through and antiacid caustic corrosion ability；ZnO transparent conductive thin film acid-alkali-corrosive-resisting ability can effectively be improved, dye sensitization is not suitable as, organic etc. there is certain corrosive solar cel electrode material.It is thus possible to further expand the application field of ZnO transparent conductive thin film, the production cost of battery is reduced.
Description
Technical field
The present invention relates to thin film solar cell manufacturing technology field, and in particular to one kind improves zinc oxide transparent conductive film
The method of chemical stability.
Background technology
With the development of society, the mankind will be more and more to the demand of the energy.During traditional fossil energy use
The problem of reserves are reduced increasingly is not only faced with, huge pollution is also caused to environment in use.So, pursue and
Turn into the topic that mankind nowadays are paid close attention to jointly using cleaning, reproducible new energy.Solar energy is used as a kind of green cleaning
The energy has inexhaustible, nexhaustible advantage, is described as optimal green energy resource.Solar cell is one kind directly too
Sun can be converted into the device of electric energy, have broad application prospects.But, the greatest problem that current theCourse of PV Industry faces exists
In：Generate electricity into higher than traditional energy, the cost of wherein battery component has occupied more than the 50% of system price, therefore exploitation is high
Effect, inexpensive, long-life solar cell turn into the focus of whole world research.Occupy at present international photovoltaic market share 90% with
On product be crystal silicon cell.But, observable index is larger in process of production for silicon materials, and crystal silicon cell is to former material
The development that govern them of the big shortcoming of material consumption seriously.In recent years, thin film solar cell is so that cost is low, material consumption is few
Advantage is more and more paid attention to.Main thin film solar cell include silicon-based thin film solar cell, cadmium-Te solar battery,
CIGS solar cell, organic photovoltaic cell, dye-sensitized solar cells and the rapid perovskite sun electricity of latest developments
Pond etc..As the electrode material of above-mentioned thin film solar cell, transparent conductive oxide (TCO) film is indispensable part,
Its light, electricity and stability turn into an important factor of influence battery conversion efficiency.Conventional TCO thin film has Sn doping at present
In2O3Film (In2O3：Sn, ITO), F doping SnO2Film (SnO2：F, FTO) and the doping such as Al, Ga ZnO film.Although,
ITO and FTO photoelectric properties are more excellent, but rare and toxicity is restricted by raw material such as its main components In, Sn, they big
Sizable application is restricted.ZnO film is with abundant raw materials, and visible region transmitance height, electric conductivity are excellent after nontoxic, doping
Characteristic obtained extensive research, it is considered to be ITO alternative materials.
In Si base thin film solar batteries, in order to increase utilization rate of the battery obsorbing layer to incident light, it will usually in film
Surface introduces certain suede structure, utilizes its light path of the scattering increase light in absorbed layer to incident light.Due to ZnO film
With the characteristic for being easy to prepare certain suede structure by acid, alkali soluble corrosion and performance is stablized in H plasma environments,
It is widely applied to as electrode material in Si base thin film solar batteries.But, for organic, dye sensitization and calcium titanium
For the solar cell using solwution method preparation such as ore deposit, because the solution of preparation has certain corrosivity, which limits ZnO
It is used as application of the electrode material in above-mentioned battery.Therefore, on the basis of high conductance and high transmission is maintained, how ZnO is improved
The chemical stability of film is for extending application of the ZnO transparent conductive thin film in area of solar cell, for reduction electricity
The production cost in pond has important Research Significance.
The content of the invention
To solve the above problems, the invention provides a kind of side for improving zinc oxide transparent conductive film chemical stability
Method, can effectively improve the acid and alkali resistance corrosive power of zinc-oxide film, realize that ZnO transparent conductive thin film exists as electrode material
Organic, dye sensitization and perovskite etc. are using the application in the solar cell of solwution method preparation, to reach reduction battery production
The effect of cost.
To achieve the above object, the technical scheme taken of the present invention is：
A kind of method for improving zinc oxide transparent conductive film chemical stability, comprises the following steps：
S1, substrate is cleaned by ultrasonic in electronics cleaning fluid, deionized water successively, then dried up with nitrogen；
S2, clean substrate is put into sputtering chamber, then sputtering chamber is vacuumized, treats that vacuum reaches 5 × 105Pa
When, argon gas and hydrogen are passed through as sputter gas to sputtering chamber respectively, and by slide valve and mixed gas flow to intracavitary
Air pressure is regulated and controled；
S3, after the argon gas in chamber is stable, using high-valence state element doping zinc oxide as sputtering target material, using magnetron sputtering
Technology carries out zinc oxide transparent conductive film deposition at room temperature, prepares and is passed through with low-resistivity, wide spectrum and acid and alkali-resistance corruption
The zinc oxide transparent conductive film of erosion.
Wherein, described high-valence state element doping zinc oxide is to be insoluble in acid, the high-valence state metal oxide of aqueous slkali.
Wherein, described substrate is the flexible materials such as glass or polyimides.
Wherein, described underlayer temperature is 25 DEG C to 350 DEG C.
Wherein, the flow of the argon gas is 20-100sccm, and the flow of hydrogen is 0.2-30sccm, and hydrogen flowing quantity accounts for sputtering
The 0.6%-20% of total gas flow rate, sputtering pressure 0.2-1.0Pa.
Wherein, the high-valence state element doping zinc oxide ceramic target is ZnO：Nb2O5Or ZnO：V2O5Deng.
Wherein, the magnetron sputtering technology of preparing is that pulsed dc magnetron is sputtered or rf magnetron sputtering.
Wherein, the thickness of the zinc oxide transparent conductive film be 1-2 μm, 400-1400nm mean transmissivities 85% with
On, square resistance 10-15 Ω/, resistivity 10-4-10-3Ωcm。
The invention has the advantages that：
By using the high-valence state element doping zinc oxide of sour, alkali is insoluble in for target, while being introduced in sputtering atmosphere
Hydrogen, using the mode of hydrogen and high-valence state element codope, realizes low-resistivity, high transmittance and chemical stability stronger
The preparation of zinc oxide transparent conductive film；The zinc oxide transparent conductive film of preparation is higher than in 400-1400nm mean transmissivities
85%, square resistance is 10-15 Ω/, and resistivity is 10-4-10-3Ωcm；The film can be applied to organic photovoltaic cell, dye
The solar cell such as material sensitization and perovskite, is conducive to improving the conversion efficiency of battery, reduces the production cost of battery.
Brief description of the drawings
Fig. 1 is the zinc oxide transparent conductive film of the gained of the embodiment of the present invention 1 through spectrum.
Fig. 2 is the X-ray diffraction spectrum of the zinc oxide transparent conductive film of the gained of the embodiment of the present invention 1.
Fig. 3 square electricity in HCl and NaOH etchant solutions for the zinc oxide transparent conductive film obtained by the embodiment of the present invention 1
Resistance is with etching time variation relation.
Embodiment
In order that objects and advantages of the present invention are more clearly understood, the present invention is carried out with reference to embodiments further
Describe in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit this hair
It is bright.
As described in Fig. 1-3 it is of the invention
Embodiment 1
A kind of method for improving zinc oxide transparent conductive film chemical stability, is prepared using radiofrequency magnetron sputtering technology,
Step is as follows：
1) glass substrate after cleaning is placed in sputtering chamber；
2) sputtering chamber is vacuumized, base vacuum is 4.9 × 10-5Pa, is sputtered, argon using argon gas and hydrogen mixed gas atmosphere
Throughput is 28.8sccm, and hydrogen flowing quantity is 1.2sccm, and hydrogen flowing quantity accounts for the 4% of sputter gas flow, sputtering pressure
0.13Pa；
3) ZnO is used：Nb2O5Ceramic target carries out magnetron sputtering plating, wherein Nb2O5The mass ratio of doping is 2%, magnetic
Control sputter coating technological parameter be：Electrode spacing 50mm, sputtering power 180W, sedimentation time 28 minutes, on a glass substrate
The film thickness of preparation is 955.7nm zinc oxide transparent conductive film.
Test result is shown：The square resistance of the zinc oxide transparent conductive film is 13.42 Ω/, and mobility is
25.32cm2/ Vs, resistivity is 1.282 × 10-3Ωcm。
To sum up, originally it is embodied in while do not sacrifice zinc oxide transparent conductive film electrology characteristic, it is not only effective to expand
Transmitance of the film in Long wavelength region has been opened up, the chemical stability of zinc oxide transparent conductive film is also improved.Due to the oxidation
There is zinc transparent conductive film good chemical stability, low-resistivity and wide spectrum to pass through characteristic simultaneously, allow it as electrode
Materials application is to solar cells such as organic photovoltaic cell, dye sensitization, perovskites, so as to be conducive to improving the conversion efficiency of battery
With reduction production cost.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of method for improving zinc oxide transparent conductive film chemical stability, it is characterised in that comprise the following steps：
S1, substrate is cleaned by ultrasonic in electronics cleaning fluid, deionized water successively, then dried up with nitrogen；
S2, clean substrate is put into sputtering chamber, then sputtering chamber is vacuumized, treats that vacuum reaches 5 × 105During Pa, point
Argon gas and hydrogen are not passed through as sputter gas to sputtering chamber, and intracavitary air pressure is entered by slide valve and mixed gas flow
Row regulation and control；
S3, after after the stable gas pressure in chamber, the high-valence state element doping zinc oxide to be insoluble in acid, alkali is adopted as sputtering target material
Carry out zinc oxide transparent conductive film deposition at room temperature with magnetron sputtering technique, prepare and passed through with low-resistivity, wide spectrum
And the zinc oxide transparent conductive film of acid-alkali-corrosive-resisting.
2. according to claim 1 it is a kind of improve zinc oxide transparent conductive film chemical stability method, it is characterised in that：
Described high-valence state element doping zinc oxide is to be insoluble in acid, the high-valence state metal oxide of aqueous slkali.
3. according to claim 1 it is a kind of improve zinc oxide transparent conductive film chemical stability method, it is characterised in that：
Described substrate is glass or polyimides.
4. according to claim 1 it is a kind of improve zinc oxide transparent conductive film chemical stability method, it is characterised in that：
Described underlayer temperature is 25 DEG C to 350 DEG C.
5. according to claim 1 it is a kind of improve zinc oxide transparent conductive film chemical stability method, it is characterised in that：
The flow of the argon gas is 20-100sccm, and the flow of hydrogen is 0.2-30sccm, and hydrogen flowing quantity accounts for sputter gas total flow
0.6%-20%, sputtering pressure 0.2-1.0Pa.
6. according to claim 1 it is a kind of improve zinc oxide transparent conductive film chemical stability method, it is characterised in that：
The high-valence state element doping zinc oxide ceramic target is ZnO：Nb2O5Or ZnO：V2O5。
7. according to claim 1 it is a kind of improve zinc oxide transparent conductive film chemical stability method, it is characterised in that：
The magnetron sputtering technology of preparing is that pulsed dc magnetron is sputtered or rf magnetron sputtering.
8. according to claim 1 it is a kind of improve zinc oxide transparent conductive film chemical stability method, it is characterised in that：
The thickness of the zinc oxide transparent conductive film is 1-2 μm, 400-1400nm mean transmissivities more than 85%, square resistance 10-
15 Ω/, resistivity 10-4-10-3Ωcm。
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| CN201710370997.3A CN107217232A (en) | 2017-05-18 | 2017-05-18 | A kind of method for improving zinc oxide transparent conductive film chemical stability |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108588656A (en) * | 2018-04-11 | 2018-09-28 | 浙江师范大学 | Al-Doped ZnO film preparation method with quant's sign scale |
| CN108878058A (en) * | 2018-06-25 | 2018-11-23 | 湖北雄华科技有限公司 | Three-decker transparent conductive film and preparation method thereof for dimming glass |
| CN110735114A (en) * | 2019-09-30 | 2020-01-31 | 安徽省含山县锦华氧化锌厂 | composition for semiconductor sensor based on zinc oxide doping |
| CN111593310A (en) * | 2020-05-09 | 2020-08-28 | 哈尔滨工业大学 | Method for preparing transparent conductive film with high photoelectric stability by magnetron sputtering |
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| CN102034901A (en) * | 2010-10-27 | 2011-04-27 | 新奥光伏能源有限公司 | Transparent conductive thin film and preparation method thereof |
| CN102242345A (en) * | 2011-06-29 | 2011-11-16 | 南开大学 | Direct preparation method of textured zinc oxide transparent electroconductive film |
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2017
- 2017-05-18 CN CN201710370997.3A patent/CN107217232A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102034901A (en) * | 2010-10-27 | 2011-04-27 | 新奥光伏能源有限公司 | Transparent conductive thin film and preparation method thereof |
| CN102242345A (en) * | 2011-06-29 | 2011-11-16 | 南开大学 | Direct preparation method of textured zinc oxide transparent electroconductive film |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108588656A (en) * | 2018-04-11 | 2018-09-28 | 浙江师范大学 | Al-Doped ZnO film preparation method with quant's sign scale |
| CN108878058A (en) * | 2018-06-25 | 2018-11-23 | 湖北雄华科技有限公司 | Three-decker transparent conductive film and preparation method thereof for dimming glass |
| CN108878058B (en) * | 2018-06-25 | 2019-11-22 | 湖北雄华科技有限公司 | Three-decker transparent conductive film and preparation method thereof for dimming glass |
| CN110735114A (en) * | 2019-09-30 | 2020-01-31 | 安徽省含山县锦华氧化锌厂 | composition for semiconductor sensor based on zinc oxide doping |
| CN111593310A (en) * | 2020-05-09 | 2020-08-28 | 哈尔滨工业大学 | Method for preparing transparent conductive film with high photoelectric stability by magnetron sputtering |
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