CN108123001A - The preparation method of copper indium gallium selenium solar cell absorbed layer - Google Patents
The preparation method of copper indium gallium selenium solar cell absorbed layer Download PDFInfo
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- CN108123001A CN108123001A CN201711421161.8A CN201711421161A CN108123001A CN 108123001 A CN108123001 A CN 108123001A CN 201711421161 A CN201711421161 A CN 201711421161A CN 108123001 A CN108123001 A CN 108123001A
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- copper
- substrate
- indium
- absorbed layer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000004544 sputter deposition Methods 0.000 claims abstract description 34
- 229910052738 indium Inorganic materials 0.000 claims abstract description 33
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 32
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 29
- 229910000058 selane Inorganic materials 0.000 claims abstract description 22
- 239000011261 inert gas Substances 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 229910052711 selenium Inorganic materials 0.000 claims 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000007493 shaping process Methods 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
- C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
-
- 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
- C23C14/0623—Sulfides, selenides or tellurides
-
- 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
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- 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
Abstract
The invention discloses a kind of preparation methods of copper indium gallium selenium solar cell absorbed layer, it includes into chamber while is passed through hydrogen selenide gas and inert gas, and copper gallium target and indium target are sputtered to substrate at room temperature by magnetron sputtering technique under the first power and in first time period；The temperature of substrate is improved to preset temperature, copper gallium target and indium target are sputtered to substrate by magnetron sputtering technique in second time period；By the first power ascension to the second power, copper gallium target and indium target are sputtered to substrate by magnetron sputtering technique under the conditions of preset temperature and within the 3rd period.The preparation method of copper indium gallium selenium solar cell absorbed layer provided by the invention, by sputtering CuGa targets and In targets simultaneously in H2Se atmosphere, CIGS absorbed layers is made only can to sputter shaping by a step, processing technology is effectively simplified, improves production efficiency and control accuracy.
Description
Technical field
The present invention relates to technical field of solar batteries more particularly to a kind of systems of copper indium gallium selenium solar cell absorbed layer
Preparation Method.
Background technology
Cu (In, Ga) Se2 (CIGS) is direct band-gap semicondictor, and with the incorporation of Ga elements, the band gap width of CIGS can
To be adjusted between 1.02eV and 1.68eV.CIGS is high to visible absorption coefficient, is most to hold promise for making efficiently
The material of inexpensive thin-film solar cells.It is more by sputtering that present magnetron sputtering technique, which prepares CIGS battery obsorbing layers,
First target (for example single target sputtering, copper-rich target and poor copper target sputter simultaneously or successively) prepares CIGS precursor thin films, right afterwards
CIGS precursor thin films are heat-treated:Simple substance Se sources are thermally formed the full of Se in vacuum or the inert atmosphere of certain air pressure
And vapour pressure, selenization is carried out to forerunner's preformed layer, it is final to prepare CIGS absorbed layers.
But the defects of prior art is that CIGS absorbed layers preparation process is complicated, it is necessary to selenizing again after being sputtered by multistep.
Requirement is prepared to reach CIGS since each layer of sputtering is required for accurately control to regulate and control optimal constituent content ratio, therefore, it is difficult to control
Each film layer processing quality.
The content of the invention
It is above-mentioned existing to solve the object of the present invention is to provide a kind of preparation method of copper indium gallium selenium solar cell absorbed layer
There is the problem of in technology, simplify technique, reduce production cost, improve CIGS thin film and prepare quality.
The present invention provides a kind of preparation method of copper indium gallium selenium solar cell absorbed layer, wherein, include the following steps：
Hydrogen selenide gas and inert gas are passed through simultaneously into chamber, under the first power and passes through magnetic in first time period
Sputtering technology is controlled to substrate sputtering copper gallium target at room temperature and indium target；
The temperature of the substrate is improved to preset temperature, by magnetron sputtering technique to the substrate in second time period
Sputter copper gallium target and indium target；
By first power ascension to the second power, lead under the conditions of the preset temperature and within the 3rd period
It crosses magnetron sputtering technique and sputters copper gallium target and indium target to the substrate, to form CuInGaSe absorbed layer.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, it is described by described in
First power ascension to the second power passes through magnetron sputtering technique under the conditions of the preset temperature and within the 3rd period
Copper gallium target and indium target are sputtered to the substrate, after forming CuInGaSe absorbed layer, the method further includes：
Insulation annealing processing is carried out to the CuInGaSe absorbed layer.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, it is described to chamber
In be passed through hydrogen selenide gas and inert gas simultaneously, by magnetron sputtering technique to room under the first power and in first time period
Before substrate sputtering copper gallium target and indium target under temperature, the method further includes：
Block whole positions of the substrate；
The inert gas is passed through into the chamber, is splashed in the 4th period under first power and by magnetic control
It penetrates the substrate of the technique after blocking and persistently sputters copper gallium target and indium target.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, it is described to chamber
In be passed through hydrogen selenide gas and inert gas simultaneously, by magnetron sputtering technique to room under the first power and in first time period
Substrate sputtering copper gallium target and indium target under temperature specifically include：
Hydrogen selenide gas and inert gas are passed through simultaneously into chamber, passes through magnetic control under conditions of sputtering power is 70W
Sputtering technology persistently sputters copper gallium target and indium target 5min to substrate at room temperature.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, the raising institute
The temperature of substrate is stated to preset temperature, in second time period by magnetron sputtering technique to the substrate sputter copper gallium target and
Indium target specifically includes：
The temperature of the substrate is improved to 500~550 degree, copper gallium is persistently sputtered to the substrate by magnetron sputtering technique
Target and indium target 15min.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, it is described by described in
First power ascension to the second power passes through magnetron sputtering technique under the conditions of the preset temperature and within the 3rd period
Copper gallium target is sputtered to the substrate and indium target specifically includes：
Sputtering power is promoted to 80W by 70W, temperature under conditions of 500~550 degree by magnetron sputtering technique to
The substrate sputtering copper gallium target and indium target 25min.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, the indifferent gas
Body is argon gas.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, the hydrogen selenide
The gas flow ratio scope of gas and the argon gas is 0.1~10.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, the copper gallium target
The sputtering angle formed between material and the indium target is 140 °~145 °.
The preparation method of copper indium gallium selenium solar cell absorbed layer as described above, these, it is preferred to, to the chamber
In simultaneously be passed through hydrogen sulfide gas.
The preparation method of copper indium gallium selenium solar cell absorbed layer provided by the invention, by being splashed simultaneously in H2Se atmosphere
CuGa targets and In targets are penetrated, CIGS absorbed layers is made only can to sputter shaping by a step, are effectively simplified processing technology,
Production efficiency is improved, while is also solved and is needed to control multiple steps in the prior art and cause control accuracy low
Problem.
Description of the drawings
The specific embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the flow of the preparation method for the copper indium gallium selenium solar cell absorbed layer that an embodiment of the present invention provides
Figure；
Fig. 2 is the flow of the preparation method for the copper indium gallium selenium solar cell absorbed layer that another embodiment of the present invention provides
Figure.
Specific embodiment
The embodiment of the present invention is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or similar label represents same or similar element or has the function of same or like element.Below with reference to attached
The embodiment of figure description is exemplary, and is only used for explaining the present invention, and is not construed as limiting the claims.
As shown in Figure 1, the preparation an embodiment of the present invention provides a kind of copper indium gallium selenide (CIGS) solar battery obsorbing layer
Method includes the following steps：
S100, hydrogen selenide (H2Se) gas and inert gas are passed through simultaneously into chamber, under the first power and when first
Between copper gallium (CuGa) target and indium (In) target are sputtered to substrate at room temperature by magnetron sputtering technique in section.
S200, the temperature for improving substrate are splashed in second time period to preset temperature by magnetron sputtering technique to substrate
Penetrate CuGa targets and In targets.
S300, by the first power ascension to the second power, pass through under the conditions of preset temperature and within the 3rd period
Magnetron sputtering technique sputters CuGa targets and In targets to substrate, to form CIGS absorbed layers.
The preparation method of copper indium gallium selenium solar cell absorbed layer provided in an embodiment of the present invention, by H2Se atmosphere
CuGa targets and In targets are sputtered simultaneously, CIGS absorbed layers is made only can to sputter shaping by a step, is effectively simplified and adds
Work technique improves production efficiency, while also solves and need to control multiple steps in the prior art and cause to control
The problem of precision is low.
Specifically, step S100 is specifically included：
Hydrogen selenide gas and inert gas are passed through simultaneously into chamber, passes through magnetic control under conditions of sputtering power is 70W
Sputtering technology persistently sputters CuGa targets and In targets 5min to substrate at room temperature.
Wherein, at room temperature substrate temperature is relatively low, and the sputtering for carrying out the short time to substrate at room temperature in advance is conducive to
Quick forming core in sputtering process.
Specifically, step S200 is specifically included：
The temperature of substrate is improved to 550~550 degree, CuGa targets and In are persistently sputtered to substrate by magnetron sputtering technique
Target 30min.Due to having completed forming core in preceding 5min, but low temperature environment can slow down the rate of crystallization；Therefore in order to accelerate to crystallize,
The temperature of substrate in 15min can be increase gradually to 500~550 degree, in the present embodiment, be preferably 520 degree, thus may be used
To accelerate crystal growth rate, simultaneously because the temperature of substrate is gradually increasing, so as to ensure that the stability of crystal growth and
Even property.
Specifically, step S300 is specifically included：
It is persistently splashed to substrate by magnetron sputtering technique under conditions of sputtering power is 80W, temperature is 500~550 degree
Penetrate copper gallium target and indium target 25min.Wherein, due to by gradually heating up that crystal growing process is made to tend towards stability to substrate,
It is possible thereby to accelerate to sputter by improving sputtering power, the sedimentation rate of CIGS thin film is improved, quickly to form CIGS absorptions
Layer.
Further, as shown in Fig. 2, being further included after step S300：
S400, insulation annealing processing is carried out to CIGS absorbed layers, to ensure the stability of CIGS absorbed layers.
Further, as shown in Fig. 2, being further included before step S100：
S10, the whole positions for blocking substrate.
S20, inert gas is passed through into chamber, under the first power and the 4th period in by magnetron sputtering technique to
Substrate after blocking persistently sputters copper gallium target and indium target.It is possible thereby to target is cleaned before being sputtered to substrate, with
It improves subsequently to the sputtering quality of substrate.Wherein it is possible to by substrate baffler being set to be blocked to realize to substrate,
After the completion of being cleaned to target, baffler can be removed, subsequently to be sputtered to substrate, in addition, the 4th period can be
5-10min。
It is understood that the inert gas used in sputtering process can be nitrogen (N2), argon gas (Ar) etc.,
It is preferably Ar in the present embodiment, by regarding Ar as work carrier gas, H2Se gases can be carried to substrate surface and deposited.
It should be noted that in order to ensure the concentration of Se in H2Se atmosphere, while crystallinity is improved, H2Se gases and Ar's
Gas flow ratio can be 0.1~10, i.e. 0.1≤H2Se/Ar≤10, it is preferred that the gas flow of H2Se gases and Ar
Proportion is 1.5~5.
In order to improve the uniformity that CuGa targets and In targets sputter on substrate, formed between CuGa targets and In targets
Sputtering angle for 140 °~145 °, in the present embodiment be preferably 142 °.
In order to reduce Interface composites, adjusting and optimizing band gap width increases open-circuit voltage, increases battery efficiency, CuGa targets
The quality accounting of middle Ga can be 5~30wt%.
It should be noted that when being sputtered using magnetron sputtering technique, radio-frequency sputtering and direct current can be specifically used
Sputter the mode that be combined with each other, can also only with the mode of d.c. sputtering, and in order to improve the Forming Quality of CIGS absorbed layers,
Simplify sputtering technology, the magnetron sputtering technique employed in the present embodiment is d.c. sputtering, Sputtering power density for 0.3~
5Wcm-2, range is 5~20cm, and operating air pressure is 0.2~20Pa, and the vacuum degree of chamber is 10-4Pa；Preferably, work(is sputtered
Rate density is 1.24Wcm-2, range is 8~15cm, and operating air pressure is 0.5~5Pa.
It is understood that when needing to prepare Cu-In-Ga-Se-S (CIGSS) absorbed layer, can be passed through in H2Se atmosphere
Hydrogen sulfide (H2S) gas makes CuGa targets and In targets simultaneously in H2Se, H2It is sputtered in the atmosphere that S and Ar is formed, thus
The preparation to CIGSS absorbed layers can only can be realized by a step.
The preparation method of copper indium gallium selenium solar cell absorbed layer provided in an embodiment of the present invention, by H2Se atmosphere
CuGa targets and In targets are sputtered simultaneously, CIGS absorbed layers is made only can to sputter shaping by a step, is effectively simplified and adds
Work technique improves production efficiency, while also solves and need to control multiple steps in the prior art and cause to control
The problem of precision is low.
The structure, feature and effect of the present invention, more than institute are described in detail based on the embodiments shown in the drawings
Only presently preferred embodiments of the present invention is stated, but the present invention is not to limit practical range shown in drawing, it is every according to structure of the invention
Want made change or be revised as the equivalent embodiment of equivalent variations, when not going beyond the spirit of the description and the drawings,
It should all be within the scope of the present invention.
Claims (10)
1. a kind of preparation method of copper indium gallium selenium solar cell absorbed layer, which is characterized in that include the following steps：
Hydrogen selenide gas and inert gas are passed through simultaneously into chamber, is splashed in first time period under the first power and by magnetic control
Technique is penetrated to substrate sputtering copper gallium target at room temperature and indium target；
The temperature of the substrate is improved to preset temperature, is sputtered in second time period by magnetron sputtering technique to the substrate
Copper gallium target and indium target；
By first power ascension to the second power, pass through magnetic under the conditions of the preset temperature and within the 3rd period
It controls sputtering technology and sputters copper gallium target and indium target to the substrate, to form CuInGaSe absorbed layer.
2. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 1, which is characterized in that described to incite somebody to action
First power ascension passes through magnetron sputtering to the second power under the conditions of the preset temperature and within the 3rd period
Technique sputters copper gallium target and indium target to the substrate, and after forming CuInGaSe absorbed layer, the method further includes：
Insulation annealing processing is carried out to the CuInGaSe absorbed layer.
3. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 1, which is characterized in that it is described to
Hydrogen selenide gas and inert gas are passed through simultaneously in chamber, under the first power and passes through magnetron sputtering technique in first time period
Before substrate sputtering copper gallium target at room temperature and indium target, the method further includes：
Block whole positions of the substrate；
The inert gas is passed through into the chamber, under first power and passes through magnetron sputtering work in the 4th period
The substrate of the skill after blocking persistently sputters copper gallium target and indium target.
4. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 1, which is characterized in that it is described to
Hydrogen selenide gas and inert gas are passed through simultaneously in chamber, under the first power and passes through magnetron sputtering technique in first time period
It is specifically included to substrate sputtering copper gallium target at room temperature and indium target：
Hydrogen selenide gas and inert gas are passed through simultaneously into chamber, passes through magnetron sputtering under conditions of sputtering power is 70W
Technique persistently sputters copper gallium target and indium target 5min to substrate at room temperature.
5. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 1, which is characterized in that described to carry
The temperature of the high substrate sputters copper gallium target by magnetron sputtering technique in second time period to preset temperature to the substrate
Material and indium target specifically include：
The temperature of the substrate is improved to 500~550 degree, copper gallium target is persistently sputtered to the substrate by magnetron sputtering technique
With indium target 15min.
6. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 1, which is characterized in that described to incite somebody to action
First power ascension passes through magnetron sputtering to the second power under the conditions of the preset temperature and within the 3rd period
Technique sputters copper gallium target to the substrate and indium target specifically includes：
Sputtering power is promoted to 80W by 70W, temperature under conditions of 500~550 degree by magnetron sputtering technique to described
Substrate sputters copper gallium target and indium target 25min.
7. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 1, which is characterized in that described lazy
Property gas be argon gas.
8. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 7, which is characterized in that the selenium
The gas flow ratio scope for changing hydrogen and the argon gas is 0.1~10.
9. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 1, which is characterized in that the copper
The sputtering angle formed between gallium target and the indium target is 140 °~145 °.
10. the preparation method of copper indium gallium selenium solar cell absorbed layer according to claim 1, which is characterized in that institute
It states in chamber while is passed through hydrogen sulfide gas.
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| CN109943816A (en) * | 2019-04-17 | 2019-06-28 | 扬州旭磁智能科技有限公司 | BaZrS3Film and preparation method thereof and its application |
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