CN106129174B - A kind of fluorine doped cuprous oxide film and preparation method thereof - Google Patents
A kind of fluorine doped cuprous oxide film and preparation method thereof Download PDFInfo
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- CN106129174B CN106129174B CN201610531429.2A CN201610531429A CN106129174B CN 106129174 B CN106129174 B CN 106129174B CN 201610531429 A CN201610531429 A CN 201610531429A CN 106129174 B CN106129174 B CN 106129174B
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- oxide film
- cuprous oxide
- fluorine doped
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- cosputtering
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 93
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 58
- 239000011737 fluorine Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000009792 diffusion process Methods 0.000 claims abstract description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052786 argon Inorganic materials 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 93
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 230000009257 reactivity Effects 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000004544 sputter deposition Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- -1 Flange is opened Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention discloses a kind of fluorine doped cuprous oxide film and preparation method thereof, wherein, methods described includes step：A, copper target is arranged on the target position of magnetron sputtering apparatus, is passed through high purity oxygen gas and high-purity argon gas and carries out reactive cosputtering, generate cuprous oxide film；B, the cuprous oxide film is put into tube furnace, using thermal diffusion method by CuF2Powder is doped in the cuprous oxide film, so as to generate fluorine doped cuprous oxide film.The method that the present invention prepares fluorine doped cuprous oxide film, its controllability is strong, technique simple, low manufacture cost, and the film generated has good tack and repeatability, can meet large-scale production needs；And fluorine doped cuprous oxide film prepared by the present invention has carrier mobility height, the low feature of resistivity, can effectively improve the solar cell photoelectric conversion efficiency that fluorine doped cuprous oxide film is made.
Description
Technical field
The present invention relates to photoelectric functional material field, more particularly to a kind of fluorine doped cuprous oxide film and preparation method thereof.
Background technology
The energy and environmental protection are the two large problems of facing mankind, are used as the important component of new energy, nexhaustible, cleaning
The solar energy of environmental protection gets most of the attention.But current monocrystalline silicon, non-crystalline silicon, cadmium telluride and copper indium gallium selenium solar cell has respectively
From defect, so still needing to that development environment is friendly and solar cell material of low cost, cuprous oxide is good candidate's material
Material.Because, cuprous oxide has many merits：The p type semiconductors of direct band gap, energy gap is about 2.1 eV, visible
There are very high absorption coefficient, larger minority diffusion length in optical range, and theoretical calculation shows cuprous oxide solar cell
Conversion efficiency can reach 20%, it is its nontoxicity, rich reserves, more stable below 300 DEG C.The many merits of cuprous oxide
It is set to have important application on novel solar battery, for example, cuprous oxide can be with other n-type semiconductors formation hetero-junctions
Solar cell, can be used as the top layer knot of the polycrystalline lamination solar cell based on CIGS, during cuprous oxide can also be used for
Between band solar cell because the optimal energy gap required by Intermediate Gray solar cell（1.9eV）With the taboo of cuprous oxide
Bandwidth is closely.
However, solar cell its conversion efficiency that experiment shows to be made of cuprous oxide film is not high, because
Undoped with cuprous oxide film due to resistivity it is high, it is impossible to obtain high photoelectric transformation efficiency, and the carrier mobility of material
Rate is to influence one of key factor of cell photoelectric conversion efficiency；Further, the method that prior art prepares cuprous oxide film
There is poor controllability, the problem of cost is higher.Therefore, technology present in cuprous oxide film preparation technology how is solved to ask
Topic, realizes high carrier mobility, the preparation of low-resistance cuprous oxide film, is to realize cuprous oxide film large-scale use
Key point.
As can be seen here, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of fluorine doped cuprous oxide film and its system
Preparation Method, it is intended to solve the problem of existing cuprous oxide film carrier mobility is low, resistivity is high.
Technical scheme is as follows：
A kind of preparation method of fluorine doped cuprous oxide film, wherein, including step：
A, copper target is arranged on the target position of magnetron sputtering apparatus, is passed through high purity oxygen gas and high-purity argon gas and carries out reactivity altogether
Sputtering, generates cuprous oxide film；
B, the cuprous oxide film is put into tube furnace, using thermal diffusion method by CuF2Powder is doped to the oxygen
Change in cuprous film, so as to generate fluorine doped cuprous oxide film.
It is preferred that the preparation method of described fluorine doped cuprous oxide film, wherein, the step B is specifically included：
B1, first the cuprous oxide film is placed on stainless steel stent, the stainless steel stent is then put into pipe
In formula stove；
B2, by CuF2Powder is placed on before the stainless steel stent at 7 ~ 9mm, using thermal diffusion method by the CuF2
Powder is doped in the cuprous oxide film, so as to generate fluorine doped cuprous oxide film.
It is preferred that the preparation method of described fluorine doped cuprous oxide film, wherein, in step A, the reactive cosputtering
Process is that 1sccm, argon gas stream are progress under the conditions of 12sccm in oxygen stream.
It is preferred that the preparation method of described fluorine doped cuprous oxide film, wherein, in step A, the reactive cosputtering
Air pressure is 1.5 ~ 2.5Pa, and reactive cosputtering voltage is 300 ~ 400V, and the reactive cosputtering time is 50 ~ 70min.
It is preferred that the preparation method of described fluorine doped cuprous oxide film, wherein, in step A, the reactive cosputtering
Air pressure is 2Pa, and reactive cosputtering voltage is 350V, and the reactive cosputtering time is 60min.
It is preferred that the preparation method of described fluorine doped cuprous oxide film, wherein, in step B, the thermal diffusion process exists
Argon gas stream is progress under conditions of 100sccm.
It is preferred that the preparation method of described fluorine doped cuprous oxide film, wherein, in step B, the gas in the tube furnace
Press as 350 ~ 450Pa.
It is preferred that the preparation method of described fluorine doped cuprous oxide film, wherein, in step B, the thermal diffusion temperature is
900 ~ 1200 DEG C, thermal diffusion time is 25 ~ 35min.
A kind of fluorine doped cuprous oxide film, wherein, it is made of preparation method as described above.
Beneficial effect：The present invention first passes through reaction cosputtering deposition technique and prepares cuprous oxide film, then passes through letter again
Fluorine element is doped in the cuprous oxide film by single hose furnace apparatus using thermal diffusion method, so as to generate carrier mobility
The fluorine doped cuprous oxide film that rate is high, resistivity is low, can effectively improve the solar cell light that fluorine doped cuprous oxide film is made
Photoelectric transformation efficiency.The method that the present invention prepares fluorine doped cuprous oxide film, its controllability is strong, technique simple, low manufacture cost, and
And the film of generation has good tack and repeatability, can meet large-scale production needs.
Brief description of the drawings
Fig. 1 is fluorine doped cuprous oxide film preparation method preferred embodiment flow chart of the present invention.
Fig. 2 penetrates for what the present invention was measured undoped with the X with embodiment 1 and the fluorine doped cuprous oxide film of the preparation of embodiment 2
Ray diffraction diagram composes comparison diagram.
Embodiment
The present invention provides a kind of fluorine doped cuprous oxide film and preparation method thereof, to make the purpose of the present invention, technical scheme
And effect is clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is not intended to limit the present invention only to explain the present invention.
The preparation method of a kind of fluorine doped cuprous oxide film provided by the present invention, as shown in figure 1, it includes step：
S10, copper target is arranged on the target position of magnetron sputtering apparatus, is passed through high purity oxygen gas and high-purity argon gas and carries out reactivity
Cosputtering, generates cuprous oxide film；
S20, the cuprous oxide film is put into tube furnace, using thermal diffusion method by CuF2Powder is doped to described
In cuprous oxide film, so as to generate fluorine doped cuprous oxide film.
Further, the step S20 is specifically included：
S21, first the cuprous oxide film is placed on stainless steel stent, the stainless steel stent is then put into pipe
In formula stove；
S22, by CuF2Powder is placed on before the stainless steel stent at 7 ~ 9mm, using thermal diffusion method by the CuF2
Powder is doped in the cuprous oxide film, so as to generate fluorine doped cuprous oxide film.
The present invention first prepares cuprous oxide film using reaction cosputtering deposition technique, is then filled again by simple tube furnace
Put and fluorine element is doped in the cuprous oxide film using thermal diffusion method, so as to generate carrier mobility height, resistance
The low fluorine doped cuprous oxide film of rate.The film that this method controllability is strong, technique simple and generates has good tack
And repeatability, large-scale production needs can be met.
Specifically, the present invention does substrate using quartz, and first substrate is cleaned by ultrasonic with organic solution before sputtering,
It is 6 × 10 to set base vacuum-4Pa, underlayer temperature is 400 DEG C, then carries out reactive cosputtering, the reactive cosputtering
Process is that 1sccm, argon gas stream are to carry out under the conditions of 12sccm in oxygen stream, and the oxygen is more than for mass percent
99.99% high purity oxygen gas, the argon gas is the high-purity argon gas that mass percent is more than 99.999%.
Further, reactive cosputtering air pressure of the present invention be 1.5 ~ 2.5Pa, reactive cosputtering voltage be 300 ~
400V, the reactive cosputtering time is 50 ~ 70min；Preferably, the reactive cosputtering air pressure is 2Pa, reactive cosputtering
Voltage is 350V, and the reactive cosputtering time is 60min, cuprous oxide film homoepitaxial can be made on this condition, and have
There are preferably tack and repeatability.
In addition, after the completion of reactive cosputtering process, the cuprous oxide film prepared to be put into special stainless steel
On support, it is subsequently placed into tube furnace, the tube furnace is electron tubes type sintering furnace, then by a certain amount of offer fluorine element
CuF2Powder is placed on before the stainless steel stent at 8mm, finally carries out thermal diffusion process.CuF is avoided in thermal diffusion process2
Powder is exposed in air for a long time, prevents it from contacting vapor and becoming blue.
Specifically, the thermal diffusion process is carried out under conditions of argon flow amount is 100sccm, further, this hair
The bright thermal diffusion temperature is 900 ~ 1200 DEG C, and thermal diffusion time is 25 ~ 35min, the air pressure in the tube furnace for 350 ~
450Pa；Preferably, the thermal diffusion temperature is 950 DEG C, and thermal diffusion time is 30min, and the air pressure in the tube furnace is
400Pa, on this condition, the fluorine element can be equably doped on the cuprous oxide film, moved so as to generate carrier
The fluorine doped cuprous oxide film that shifting rate is high, resistivity is low.
Further, after generation fluorine doped cuprous oxide film, the present invention has also carried out XRD and Hall test to it.
A kind of fluorine doped cuprous oxide film, wherein, it is made of preparation method as described above.
Based on the above method, the present invention also provides a kind of fluorine doped cuprous oxide film, and it uses preparation side as described above
Method is made, and the fluorine doped cuprous oxide film can be used for preparing solar cell.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
First, purity is fixed on target frame for 99.999 % Cu targets；Substrate is done with quartz, when cleaning substrate
Ultrasonic wave cleaning is carried out to substrate using acetone, alcohol and deionized water successively；Sputtering system base vacuum is evacuated to 6.0 × 10- 4Pa, is passed through the high purity oxygen gas that flow is 1sccm and the high-purity argon gas that flow is 12 sccm, and holding operating pressure is 2 Pa.It is heavy
First to Cu target pre-sputtering 10min before product film, to remove the oxide and impurity on target surface.When carrying out thin film sputtering deposition, lining
Bottom temperature is 400 DEG C, and the sputtering voltage in copper target is 350V, and sputtering time is 1 hour.After plated film terminates, close sputtering source and
Intake valve, when wait underlayer temperature is down to room temperature, closes vavuum pump and power supply and other switches, takes out sample successively.So
The cuprous oxide film afterwards prepared by sputtering is put on homemade stainless steel stent, and electron tubes type sintering is put into together with support
In the quartz ampoule of stove, placement holds CuF at 8 mm in front of stainless steel stent2The quartz boat of powder.In experiment, thermal diffusion
Reaction temperature be 950 DEG C, pressure is 410Pa, CuF2Quality be 102.1mg, argon flow amount be 100 sccm, experimental period
For 30 min.After diffusion terminates, certain value is cooled under temperature program control, Temperature fall is then carried out.Treat by nature
It is cooled to after room temperature and closes each gas valve, mechanical pump and vacuum meter, being passed through gas is consistent pressure inside and outside quartz ampoule,
Flange is opened, sample is taken out.
Fig. 2 is to measure undoped with the X-ray diffraction with fluorine doped cuprous oxide film（XRD）Collection of illustrative plates.Can from Fig. 2
Go out, prepared film has single cuprous oxide structure, and High temperature diffusion fluorine doped does not change the structure of film, and thin
The crystal property of film improves.
Table 1 is to measure undoped with the Hall effect test result with fluorine doped cuprous oxide film.
As it can be seen from table 1 fluorine doped makes the carrier mobility of cuprous oxide film substantially increase, resistivity reduces, and carries
Flow sub- concentration increase.Further it was found that, diffusion fluorine doped temperature it is higher, carrier concentration is bigger, and resistivity is smaller, but current-carrying
Transport factor diminishes.Because during impurity concentration increase, impurity scattering centric quantity also increases, and mobility diminishes.
Embodiment 2
Difference from Example 1 is on the technological parameter of diffusion that the reaction temperature of thermal diffusion is 900 DEG C, and pressure is
400Pa, CuF2Quality be 100.2mg, argon flow amount still be 100 sccm, experimental period still be 30 min.Fig. 2 also gives
The X ray diffracting spectrum of the gained cuprous oxide film of embodiment 2.Figure it is seen that the crystallinity of the gained film of embodiment 1
Crystallinity than the gained film of embodiment 2 is more preferable.Table 1 also gives the Hall effect of the cuprous oxide film measured by embodiment 2
Answer test result.As it can be seen from table 1 low, resistivity of the carrier mobility than embodiment 2 of the gained film of embodiment 1
It is lower than embodiment 2.
Embodiment 3
Difference from Example 1 is, during reactive cosputtering, and sputtering pressure is that 1.5Pa, sputtering voltage are
300V, sputtering time are 50 minutes；In thermal diffusion process, the air pressure in tube furnace is that 350Pa, thermal diffusion temperature are 900 DEG C, heat
Diffusion time is 25min；By the film obtained by embodiment 3, its crystallinity than the gained film of embodiment 2 crystallinity more
Difference, its carrier mobility is also lower than embodiment 2.
Embodiment 4
Difference from Example 1 is, during reactive cosputtering, and it is that 2.5Pa, sputtering voltage are to sputter neat waist
400V, building time are 70min；In thermal diffusion process, the air pressure in tube furnace is that 450Pa, thermal diffusion temperature are 1200 DEG C, heat
Diffusion time is 35min.By the film obtained by embodiment 3, its crystallinity than the gained film of embodiment 3 crystallinity more
Difference, its carrier mobility is also lower than embodiment 3.
In summary, the present invention first passes through reaction cosputtering deposition technique and prepares cuprous oxide film, then passes through letter again
Fluorine element is doped in the cuprous oxide film by single hose furnace apparatus using thermal diffusion method, so as to generate carrier mobility
The fluorine doped cuprous oxide film that rate is high, resistivity is low, can effectively improve the solar cell light that fluorine doped cuprous oxide film is made
Photoelectric transformation efficiency.The method that the present invention prepares fluorine doped cuprous oxide film, its controllability is strong, technique simple, low manufacture cost, and
And the film of generation has good tack and repeatability, can meet large-scale production needs.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (8)
1. a kind of preparation method of fluorine doped cuprous oxide film, it is characterised in that including step：
A, copper target is arranged on the target position of magnetron sputtering apparatus, is passed through high purity oxygen gas and high-purity argon gas and carries out reactivity and splash altogether
Penetrate, generate cuprous oxide film；
B, the cuprous oxide film is put into tube furnace, using thermal diffusion method by CuF2It is sub- that powder is doped to the oxidation
In Copper thin film, so as to generate fluorine doped cuprous oxide film；
The step B is specifically included：
B1, first the cuprous oxide film is placed on stainless steel stent, the stainless steel stent is then put into tube furnace
In；
B2, by CuF2Powder is placed on before the stainless steel stent at 7 ~ 9mm, using thermal diffusion method by the CuF2Powder
It is doped in the cuprous oxide film, so as to generate fluorine doped cuprous oxide film.
2. the preparation method of fluorine doped cuprous oxide film according to claim 1, it is characterised in that in step A, described anti-
Answering property cosputtering process is that 1sccm, argon gas stream are progress under the conditions of 12sccm in oxygen stream.
3. the preparation method of fluorine doped cuprous oxide film according to claim 1, it is characterised in that in step A, described anti-
Answering property cosputtering air pressure be 1.5 ~ 2.5Pa, reactive cosputtering voltage be 300 ~ 400V, the reactive cosputtering time be 50 ~
70min。
4. the preparation method of fluorine doped cuprous oxide film according to claim 3, it is characterised in that in step A, described anti-
Answering property cosputtering air pressure is 2Pa, and reactive cosputtering voltage is 350V, and the reactive cosputtering time is 60min.
5. the preparation method of fluorine doped cuprous oxide film according to claim 1, it is characterised in that in step B, the heat
Diffusion process is carried out under conditions of argon gas stream is 100sccm.
6. the preparation method of fluorine doped cuprous oxide film according to claim 1, it is characterised in that in step B, the pipe
Air pressure in formula stove is 350 ~ 450Pa.
7. the preparation method of fluorine doped cuprous oxide film according to claim 1, it is characterised in that in step B, the heat
Diffusion temperature is 900 ~ 1200 DEG C, and thermal diffusion time is 25 ~ 35min.
8. a kind of fluorine doped cuprous oxide film, it is characterised in that using the preparation method system as described in claim 1 to 7 is any
Into.
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| CN201610531429.2A CN106129174B (en) | 2016-07-07 | 2016-07-07 | A kind of fluorine doped cuprous oxide film and preparation method thereof |
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| CN106129174B true CN106129174B (en) | 2017-08-29 |
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| CN104846335B (en) * | 2015-05-28 | 2017-06-23 | 深圳大学 | A kind of N-shaped cuprous oxide film and preparation method thereof |
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