CN105390373A - Method for preparing copper antimony sulfide solar cell light-absorbing layer film - Google Patents
Method for preparing copper antimony sulfide solar cell light-absorbing layer film Download PDFInfo
- Publication number
- CN105390373A CN105390373A CN201510707654.2A CN201510707654A CN105390373A CN 105390373 A CN105390373 A CN 105390373A CN 201510707654 A CN201510707654 A CN 201510707654A CN 105390373 A CN105390373 A CN 105390373A
- Authority
- CN
- China
- Prior art keywords
- antimony
- sulphur
- copper
- evaporation
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CHRUUJJXTYHZCK-UHFFFAOYSA-N antimony;sulfanylidenecopper Chemical compound [Sb].[Cu]=S CHRUUJJXTYHZCK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title abstract description 23
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 40
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001704 evaporation Methods 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims description 39
- 230000008020 evaporation Effects 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 239000005864 Sulphur Substances 0.000 claims description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 238000007747 plating Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 230000031700 light absorption Effects 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 238000010549 co-Evaporation Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 2
- 239000002344 surface layer Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000005137 deposition process Methods 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 31
- 239000010409 thin film Substances 0.000 description 8
- 229940007424 antimony trisulfide Drugs 0.000 description 6
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KGHMFMDJVUVBRY-UHFFFAOYSA-N antimony copper Chemical compound [Cu].[Sb] KGHMFMDJVUVBRY-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 210000001142 back Anatomy 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- -1 salt compounds Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention discloses a method for preparing a copper antimony sulfide solar cell light-absorbing layer film. Light-absorbing layer copper antimony sulfide is prepared by stree-step multi-source co-evaporation deposition process, the anti-evaporation of antimony sulfide is effectively compensated, a film composition is precisely controlled, the crystallinity of the film is improved, film bottom is in antimony, the film adhesion is enhanced, a surface layer is rich in antimony, the generation of a surface layer rich copper phase is inhibited, and the leakage current of a solar cell is reduced. Compared with a chemical method, the method of the invention has the advantages that the crystallinity and component controllability of the copper antimony sulfide is improved, the miscellaneous phase formation is suppressed, the carrier recombination of a space charge region is reduced, and the improvement of cell efficiency is facilitated.
Description
One, technical field
The present invention relates to a kind of preparation method of solar cell light absorption layer film, specifically a kind of preparation method of copper antimony sulphur solar cell light absorption layer film.
Two, background technology
Copper antimony sulphur (CuSbS
2) be similar to traditional efficient thin-film solar cell absorbed layer Copper Indium Gallium Selenide, also there is the advantage that the absorption coefficient of light is high, band gap is mated with solar spectrum, and relative to Copper Indium Gallium Selenide, its element antimony than indium and gallium price low, in addition, its crystallization temperature, far below Copper Indium Gallium Selenide, therefore greatly reduces raw material and production cost, is considered to the most promising solar cell of new generation.
Copper antimony sulphur light absorbing zone is the most crucial one deck of battery.Current bibliographical information many employings chemical method prepares copper antimony sulphur light absorbing zone, although the method comparatively vacuum method reduces manufacturing cost, but there is several subject matter: first, chemical method needs to use organic solvent or aqueous solvent, solute mostly is the salt compounds of each component, therefore easily introduce impurity, and semi-conducting material is to the content quite sensitive of impurity, the impurity of minute quantity all may reduce its electric property greatly.Secondly, comparatively vacuum method is poor for its crystallinity of semiconductive thin film of preparing of chemical method, can introduce more defect, cause the compound of photo-generated carrier, reduction battery performance.3rd, in Composition Control, vacuum method especially adopts the multi-source coevaporation method of electron gun stove, more accurate to the control of each component, and in coating process, each element ratio can be adjusted in real time, realize thin film composition and distribute, with the band structure of optimised devices along the gradient of film thickness direction.
The particularity of copper antimony sulfur materials coevaporation technique.Metallic element copper in Copper Indium Gallium Selenide, indium, gallium, its evaporating temperature is all at about 1000 DEG C, all higher, and in coating process, the selenides of each element is counter to be evaporated more weak, not easily causes loss of elements, therefore thin film composition more easy to control.And in copper antimony sulphur, the evaporating temperature of copper and antimony differs greatly, especially the evaporating temperature of antimony only has 500-600 DEG C, and the saturated vapor pressure of its simple substance and sulfide is higher, very easily instead evaporates, cause the loss of antimony element, according to one-step method preparation, underlayer temperature once higher, then can cause a large amount of losses of antimony element, the rich copper of film, the copper antimony sulphur of rich copper is the Cu that resistance is very low
12sb
4s
13phase, this thing is met and is caused battery drain, can not as light absorbing zone.If underlayer temperature is lower, although can reduce the anti-evaporation of antimony trisulfide, its crystallinity of copper antimony sulphur generated at a lower temperature is poor, and defect is more.Therefore, suppress the anti-evaporation of antimony trisulfide, generating the copper antimony sulphur of single-phase, and improve its crystallinity, is the key of coevaporation technique.In addition, rich antimony bottom film, is conducive to improving the adhesive force between copper antimony sulphur and substrate molybdenum, the rich antimony in film top layer, be conducive to the copper-rich phase reducing heterojunction region, reduce short circuit current, this is also 2 points that coevaporation technique needs to realize in the gradient control of thin film composition.
Three, summary of the invention
The present invention aims to provide a kind of preparation method of copper antimony sulphur solar cell light absorption layer film, technical problem to be solved suppresses the anti-evaporation of antimony trisulfide, suppress copper-rich phase to generate, improve crystallinity and the adhesive force of film, thus improve the photoelectric conversion efficiency of battery.
The preparation method of copper antimony sulphur solar cell light absorption layer film of the present invention, adopts three steps to steam legal system altogether standby, comprises the steps:
Substrate plating molybdenum glass substrate being placed in conventional multi-source thermal evaporation coating system is evacuated to 5 × 10
-4pa, rises to 1100-1200 DEG C, 500-600 DEG C and 100-200 DEG C keep constant respectively respectively by the electron gun furnace temperature of copper, antimony and sulphur; The first step, is warming up to 200-300 DEG C and keeps constant by underlayer temperature, to plating molybdenum glass substrate surface evaporation antimony and sulphur 10-15 minute, make the rich antimony of film substrate, improve the adhesive force with substrate molybdenum; Second step, after antimony and sulphur evaporation terminate, keeps underlayer temperature constant and simultaneously copper steam-plating, antimony and sulphur 30-40 minute, makes the rich antimony of film; 3rd step, after copper, antimony and sulphur evaporation terminate, underlayer temperature is warming up to 350-450 DEG C, continue evaporation antimony and sulphur 20-30 minute again, object makes copper antimony sulphur improve crystallinity at relatively high temperatures, and the atmosphere of the rich antimony of film and antimony and sulphur can the anti-evaporation of antimony trisulfide in compensation film; After antimony and sulphur evaporation terminate, underlayer temperature is down to the copper antimony sulphur film that room temperature obtains meeting stoichiometric proportion.The evaporation amount of copper, antimony and sulphur was regulated and controled by temperature and evaporation time.
The present invention prepares copper antimony sulphur (CuSbS by coevaporation method
2) film adopt equipment be multi-source thermal evaporation coating system, be made up of parts such as mechanical pump, molecular pump, vacuum cavity, electron gun stove, temperature controller, substrate heater, substrate rotation mechanism, slide valve, vacuum gauges.This system can realize multiple evaporation source independence accurate temperature controlling, simultaneously can to silicon temperature control, for the preparation of multi-element compounds semiconductor film.
The mode of heating of substrate heater is noncontact heating, keeps 1-5 millimeter spacing between heater and substrate, and heater passes through the mode of infrared emanation to silicon, guarantees that substrate is heated evenly everywhere.
The concrete steps that coevaporation method of the present invention prepares copper antimony sulphur film are as follows:
1, plating molybdenum glass substrate is fixed on the substrate of multi-source thermal evaporation coating system, closes cavity, with mechanical pump and molecular pump, the background vacuum of inside cavity is evacuated to 5 × 10
-4pa, starts electron gun stove heater, and guarantees electron gun stove flapper closure.
2, the electron gun furnace temperature of copper, antimony and sulphur is risen to respectively 1100-1200 DEG C, 500-600 DEG C and 100-200 DEG C, and keep constant.
3, first stage evaporation: substrate heater heats up by room temperature, within 3-8 minute, rise to 200-300 DEG C and keep constant, now open antimony, sulphur electron gun fender plate starts first stage evaporation, to the evaporation of plating molybdenum glass substrate antimony, sulphur, after 10-15 minute, evaporation terminates the first stage;
4, second stage evaporation: this step silicon actuator temperature is still 200-300 DEG C and keeps constant, open copper electron gun stove plate washer simultaneously, evaporate copper, antimony, sulphur to plating molybdenum glass substrate, after 30-40 minute, second stage evaporation terminates simultaneously, closes copper electron gun stove plate washer;
5, phase III evaporation: substrate heater heats up by 200-300 DEG C, close copper electron gun stove plate washer simultaneously, to the evaporation of plating molybdenum glass substrate antimony, sulphur, within 5-10 minute, back substrate heter temperature rises to 350-450 DEG C and keeps constant, starts timing this moment, after 20-30 minute, evaporation terminates the phase III, substrate heater slow cooling, is down to 200-300 DEG C after 15-30 minute, then closes substrate heater, Temperature fall, to room temperature, obtains copper antimony sulphur film.
Copper antimony sulphur crystalline property prepared by the inventive method is good, and its X-ray diffraction spectrum (Fig. 1) shows that this copper antimony sulphur film is chalcostibite structure, and it is larger that ESEM (SEM) image (Fig. 2) shows copper antimony sulphur crystallite dimension.
The Composition Control of copper antimony sulphur film, phase control and crystallinity have vital impact for battery efficiency.The three-step approach Co-evaporated Deposition technique of the inventive method, the first step and second step be deposited copper antimony sulphur under lower underlayer temperature, effectively can reduce the anti-evaporation of antimony trisulfide, thin film composition is made to reach rich antimony, 3rd step-up height underlayer temperature afterwards, steams antimony and sulphur altogether simultaneously, had both improve the crystallinity of film, compensate for again the anti-evaporation of antimony trisulfide, make thin film composition finally reach stoichiometric proportion.In addition, the 3rd step makes the rich antimony in copper antimony sulphur film top layer that copper-rich phase can be suppressed to generate, and reduce battery drain, improve battery efficiency, and the first step makes the rich antimony of film substrate effectively can improve adhesive force, improve the mechanical performance of battery.
Four, accompanying drawing explanation
Fig. 1 is the XRD spectra of copper antimony sulphur film of the present invention.As can be seen from Figure 1, XRD peak meets copper antimony sulphur (CuSbS
2) diffraction peak of standard powder diffraction card, diffraction maximum is sharp-pointed, illustrates that crystallinity is very well, does not detect the peak of other thing phases, copper antimony sulphur (CuSbS in film is described
2) phase purity higher.
Fig. 2 be the SEM image of copper antimony sulphur film of the present invention as can be seen from Figure 2, crystallinity is better, and crystallite dimension is at micron order.
Fig. 3 is the structural representation of copper antimony sulphur hull cell.Substrate is soda-lime glass, and back electrode is molybdenum layer, copper antimony sulphur (CuSbS
2) be p-type light absorbing zone, cadmium sulfide is N-shaped resilient coating, and native oxide zinc and tin indium oxide are electrically conducting transparent Window layer.
Fig. 4 is the section SEM image of copper antimony sulphur hull cell.As can be seen from Figure 4, each layer of battery is distinguished obviously, copper antimony sulphur (CuSbS
2) section crystal grain is comparatively large, density is high, is conducive to photo-generated carrier transmission and collects.
Five, embodiment
Embodiment 1: copper antimony sulphur (CuSbS
2) preparation of film
1, plating molybdenum glass substrate is fixed on the substrate of multi-source thermal evaporation coating system, closes cavity, with mechanical pump and molecular pump, the background vacuum of inside cavity is evacuated to 5 × 10
-4pa, starts electron gun stove heater, and guarantees electron gun stove flapper closure.
2, the electron gun furnace temperature of copper, antimony, sulphur is risen to respectively 1100-1200 DEG C, 500-600 DEG C and 100-200 DEG C, and keep constant.
3, substrate heater heats up by room temperature, within 3-8 minute, rises to 200-300 DEG C and keeps constant, now opens antimony, sulphur electron gun fender plate starts first stage evaporation, and to the evaporation of plating molybdenum glass substrate antimony, sulphur, after 10-15 minute, evaporation terminates the first stage; Second stage evaporation, this step silicon actuator temperature is still 200-300 DEG C and keeps constant, opens copper electron gun stove plate washer simultaneously, and evaporate copper, antimony, sulphur to plating molybdenum glass substrate, after 30-40 minute, second stage evaporation terminates simultaneously, closes copper electron gun stove plate washer; Phase III evaporation, substrate heater heats up by 200-300 DEG C, closes copper electron gun stove plate washer simultaneously, to the evaporation of plating molybdenum glass substrate antimony, sulphur, within 5-10 minute, back substrate heter temperature rises to 350-450 DEG C and keeps constant, start timing, after 20-30 minute, evaporation terminates the phase III, substrate heater slow cooling this moment, 200-300 DEG C is down to after 15-30 minute, then close substrate heater, Temperature fall, to room temperature, obtains copper antimony sulphur film.
Embodiment 2:
With copper antimony sulphur (CuSbS of the present invention
2) film preparation solar cell, as shown in Figure 3, preparation method's idiographic flow is as follows for its structure:
1, on soda-lime glass, the molybdenum dorsum electrode layer of 600 nanometer thickness is plated with direct current magnetron sputtering process;
2, on plating molybdenum glass, use three stage Co-evaporation legal system for the copper antimony sulphur (CuSbS of 1.2 micron thickness
2) thin-film light-absorbing layer;
3, the cadmium sulfide resilient coating of 50 nanometer thickness is prepared with chemical baths;
4, the native oxide zinc layers of 100 nanometer thickness is prepared with magnetron sputtering method;
5, the indium tin oxide transparent conducting window layer of 500 nanometer thickness is prepared with magnetron sputtering method;
6, silver electrode is prepared with thermal evaporation.
Its section of copper antimony S film solar battery SEM photo prepared by the present embodiment as shown in Figure 4.
Claims (2)
1. a preparation method for copper antimony sulphur solar cell light absorption layer film, is characterized in that comprising the steps:
Substrate plating molybdenum glass substrate being placed in multi-source thermal evaporation coating system is evacuated to 5 × 10
-4pa, rises to 1100-1200 DEG C, 500-600 DEG C and 100-200 DEG C keep constant respectively respectively by the electron gun furnace temperature of copper, antimony and sulphur; The first step, is warming up to 200-300 DEG C and keeps constant by underlayer temperature, to plating molybdenum glass substrate surface evaporation antimony and sulphur 10-15 minute; Second step, after antimony and sulphur evaporation terminate, keeps underlayer temperature constant and simultaneously copper steam-plating, antimony and sulphur 30-40 minute; 3rd step, is warming up to 350-450 DEG C by underlayer temperature after copper, antimony and sulphur evaporation terminate, then continues evaporation antimony and sulphur 20-30 minute; After antimony and sulphur evaporation terminate, underlayer temperature is down to the copper antimony sulphur film that room temperature obtains meeting stoichiometric proportion.
2. preparation method according to claim 1, is characterized in that:
The mode of heating of substrate heater is noncontact heating, keeps 1-5 millimeter spacing between heater and substrate, and heater passes through the mode of infrared emanation to silicon, guarantees that substrate is heated evenly everywhere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510707654.2A CN105390373B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of copper antimony sulphur solar cell light absorption layer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510707654.2A CN105390373B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of copper antimony sulphur solar cell light absorption layer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105390373A true CN105390373A (en) | 2016-03-09 |
| CN105390373B CN105390373B (en) | 2018-02-06 |
Family
ID=55422533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510707654.2A Expired - Fee Related CN105390373B (en) | 2015-10-27 | 2015-10-27 | A kind of preparation method of copper antimony sulphur solar cell light absorption layer film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105390373B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107248534A (en) * | 2017-05-27 | 2017-10-13 | 华中科技大学 | A kind of semiconducting alloy film of composition continuous gradation and its preparation method and application |
| CN114899281A (en) * | 2022-05-11 | 2022-08-12 | 江西理工大学 | Preparation device and preparation method of copper antimony sulfide solar cell absorption layer film |
| CN115161610A (en) * | 2022-09-07 | 2022-10-11 | 合肥工业大学 | Preparation method of copper antimony selenium solar cell light absorption layer film |
| CN112481593B (en) * | 2020-11-24 | 2024-01-26 | 福建师范大学 | Method for preparing antimony tetrasulfide tri-copper film of solar cell absorption layer through gas-solid reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02103747A (en) * | 1988-10-11 | 1990-04-16 | Ricoh Co Ltd | Phase transfer type optical information recording medium |
| CN101983254A (en) * | 2008-03-14 | 2011-03-02 | 朗姆研究公司 | Method for depositing a film onto a substrate |
-
2015
- 2015-10-27 CN CN201510707654.2A patent/CN105390373B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02103747A (en) * | 1988-10-11 | 1990-04-16 | Ricoh Co Ltd | Phase transfer type optical information recording medium |
| CN101983254A (en) * | 2008-03-14 | 2011-03-02 | 朗姆研究公司 | Method for depositing a film onto a substrate |
Non-Patent Citations (1)
| Title |
|---|
| A.RABHI, ET AL.: "Investigation on dispersive optical constant and microstructural parameters of the absorber CuSbS2 thin films", 《VACUUM》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107248534A (en) * | 2017-05-27 | 2017-10-13 | 华中科技大学 | A kind of semiconducting alloy film of composition continuous gradation and its preparation method and application |
| CN112481593B (en) * | 2020-11-24 | 2024-01-26 | 福建师范大学 | Method for preparing antimony tetrasulfide tri-copper film of solar cell absorption layer through gas-solid reaction |
| CN114899281A (en) * | 2022-05-11 | 2022-08-12 | 江西理工大学 | Preparation device and preparation method of copper antimony sulfide solar cell absorption layer film |
| CN114899281B (en) * | 2022-05-11 | 2024-04-26 | 江西理工大学 | Preparation device and preparation method of copper-antimony chalcogenide solar cell absorption layer film |
| CN115161610A (en) * | 2022-09-07 | 2022-10-11 | 合肥工业大学 | Preparation method of copper antimony selenium solar cell light absorption layer film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105390373B (en) | 2018-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5748787B2 (en) | Solar cell and manufacturing method thereof | |
| JP5956397B2 (en) | Copper / indium / gallium / selenium (CIGS) or copper / zinc / tin / sulfur (CZTS) thin film solar cell and method of manufacturing the same | |
| CN100541824C (en) | A kind of mechanical laminated AlSb/CIS thin film solar cell | |
| WO2011040645A1 (en) | Photoelectric conversion device, method for producing the same, and solar battery | |
| CN105390373A (en) | Method for preparing copper antimony sulfide solar cell light-absorbing layer film | |
| CN105244416A (en) | Low-temperature deposition process of copper-antimony-selenium solar cell light absorption layer film | |
| CN209963073U (en) | Novel high-efficiency double-sided incident light CdTe perovskite laminated photovoltaic cell | |
| WO2014001817A1 (en) | Photovoltaic device and method of fabricating thereof | |
| US20140246089A1 (en) | Solar cell module and preparing method of the same | |
| US20140256082A1 (en) | Method and apparatus for the formation of copper-indiumgallium selenide thin films using three dimensional selective rf and microwave rapid thermal processing | |
| CN103014624A (en) | Preparation method of light-absorbing film of solar cell | |
| KR20140047760A (en) | Manufacturing method of solar cell light absortion layer | |
| KR101275156B1 (en) | Apparatus for making the photovoltaic absorber layer, photovoltaic absorber layer and solar cell | |
| CN104051577A (en) | Manufacturing method capable of improving crystallization property of copper zinc tin sulfur film of solar cell absorption layer | |
| CN103346213A (en) | Preparation method for solar cell absorbing layer | |
| KR101908472B1 (en) | Method of manufacturing of CZTS-based absorber layer using metal and compound thin film | |
| CN103098233A (en) | Solar cell and method for manufacturing same | |
| CN106684210B (en) | Film and include the solar cell of the film prepared by a kind of copper zinc tin sulfur selenium method for manufacturing thin film for solar cell, this method | |
| CN104278238A (en) | Preparation method of high-quality copper-zinc-tin sulphur semiconductor film | |
| US20140326317A1 (en) | Method of fabricating copper indium gallium selenide (cigs) thin film for solar cell using simplified co-vacuum evaporation and copper indium gallium selenide (cigs) thin film for solar cell fabricated by the same | |
| KR101265967B1 (en) | Apparatus for making the photovoltaic absorber layer | |
| KR101160487B1 (en) | Thick film typed cigs solar cell and manufacturing method thereof | |
| Tuttle et al. | Investigations into alternative substrate, absorber and buffer layer processing for Cu (In, Ga) Se/sub 2/-based solar cells | |
| CN102097522A (en) | Selenizing method for light absorption layer of copper-indium-gallium-selenium (CIGS) thin-film solar cell | |
| CN101510574A (en) | Method for preparing narrow bandgap film photovoltaic material beta-FeSi2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180206 Termination date: 20201027 |