CN105826425A - Preparation method for preparing copper-zinc-tin-sulfide (Cu-Zn-Sn-S) thin film solar cell - Google Patents
Preparation method for preparing copper-zinc-tin-sulfide (Cu-Zn-Sn-S) thin film solar cell Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000010409 thin film Substances 0.000 title abstract description 26
- 238000004544 sputter deposition Methods 0.000 claims abstract description 30
- 238000000151 deposition Methods 0.000 claims abstract description 29
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910004576 Cd1-xZnxS Inorganic materials 0.000 claims abstract description 13
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 22
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 22
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000002207 thermal evaporation Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 239000011686 zinc sulphate Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 7
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000238 buergerite Inorganic materials 0.000 description 1
- IGUWUAGBIVHKDA-UHFFFAOYSA-N cadmium;sulfanylidenezinc Chemical compound [Zn].[Cd]=S IGUWUAGBIVHKDA-UHFFFAOYSA-N 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical group S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a preparation method for preparing a copper-zinc-tin-sulfide (Cu-Zn-Sn-S) thin film solar cell. The thin film solar cell comprises a soda-lime glass substrate, a metal back electrode molybdenum (Mo) layer, a p-type Cu2ZnSnS4 absorption layer, an n-type Cd1-xZnxS buffer layer, a ZnO window layer, and an Al electrode. The method for preparing the p-type Cu2ZnSnS4 absorption layer comprises the steps of adopting a quaternary compound copper-zinc-tin-sulfur target and conducting the one-step sputtering deposition without any subsequent vulcanization process. The n-type Cd1-xZnxS buffer layer reduces the usage amount of Cd and also reduces the environmental pollution. Meanwhile, the short-wave absorption of the solar cell is improved, and the photoelectric conversion efficiency of the solar cell is increased. The elements of the thin film solar cell are non-toxic, pollution-free and rich in reserve volume. The solar cell is simple in preparation process, high in photoelectric conversion efficiency and low in cost, thus being suitable for industrial production.
Description
Technical field
The present invention relates to the preparation method of a kind of copper-zinc-tin-sulfur film solar cell with cadmium zinc sulfur cushion, belong to technical field of new energies.
Background technology
Along with the traditional fossil energy such as oil, coal is petered out, the development and utilization of regenerative resource is increasingly subject to the attention of people.Solar energy, as a kind of cleaning, the regenerative resource of safety, has great advantages for development and potentiality.Solar energy power generating is one of modal Solar use form.People are made that the biggest effort in research, exploitation and the industrialization of solar cell.While body material cell development, thin film solar cell is relatively low due to cost, becomes the development trend of following solar cell.The material being currently used for absorption layer of thin film solar cell mainly has: non-crystalline silicon, cadmium telluride (CdTe) and CIGS (CuInGaSe2).
The cost of amorphous silicon material and preparation technology is relatively low, it is easy to accomplish large-scale production, and the low light level effect of non-crystalline silicon is preferable.But the photoelectric transformation efficiency of amorphous silicon film solar battery is relatively low, in laboratory, the stable photoelectric transformation efficiency of battery is the highest by only about 13%, and in actual production, its efficiency is less than 10%.This is that the short circuit current causing battery is the lowest owing to there is substantial amounts of defect in amorphous material, becoming the complex centre of carrier；Meanwhile, amorphous silicon material has photo attenuation effect, becomes the maximum obstruction limiting its development.
CdTe is a kind of efficient, stable and the thin film solar cell of advantage of lower cost.But, heavy metal element Cd can be to environment.Although CdTe is relatively stable and nontoxic under room temperature, but in actual preparation technology, and not all Cd2+Thin film will be deposited into, after discharging along with waste liquid, environment and human health are had adverse effect.
CuInGaSe2It it is one of novel thin film solar cell the most most with prospects.In August, 2010, Germany's solar energy and Hydrogen Energy research center (ZSW) have prepared the CuInGaSe that laboratory photoelectric transformation efficiency is the highest2Thin film solar cell, its conversion efficiency reaches 20.3%.But, In, Ga are rare element, greatly limit CuInGaSe2The large-scale industrial production of thin film solar cell.
There is the quaternary compound semiconductor copper-zinc-tin-sulfur (Cu of stannite structure2ZnSnS4) it is direct band-gap semicondictor material, absorptance is bigger；Its energy gap is 1.51eV, and energy gap optimal with solar cell absorbed layer (1.5eV) is sufficiently close to.Additionally, Cu2ZnSnS4Without toxic element, and each element rich reserves in the earth's crust.Therefore, Cu2ZnSnS4It is to be expected to most substitute CuInGaSe2Absorbed layer material.2013, American I BM company and solarFrontier, Tokyo answered the Wang Neng photoelectricity company joint development in chemical industry and Taiwan to go out the Cu that photoelectric transformation efficiency is 12.6%2ZnSnS4Thin film solar cell, becomes current Cu2ZnSnS4The whole world of solar cell high conversion efficiency.Preparation Cu2ZnSnS4The main method of thin film has: electron-beam vapor deposition method, Vacuum sublimation, spray pyrolysis, electrochemical deposition method, magnetron sputtering method etc..Wherein, magnetron sputtering method has film forming compactness height, utilization rate of raw materials is high, technological parameter easily regulates and controls, easily realizes the advantages such as large area industrialized production, is to prepare Cu at present2ZnSnS4One of the most promising method of thin film.
The most frequently used cushioning layer material of CZTS thin film solar cell is cadmium sulfide (CdS), but CdS can produce poisonous Cd in preparation process2+Ion.Additionally, the defect state density of CdS film is relatively big, thin film exists the defects such as substantial amounts of dislocation, fault, not only have impact on carrier lifetime, but also can extend in absorbed layer material, affect the photoelectric transformation efficiency of battery.Cd1-xZnxS is direct band-gap semicondictor material, has sphalerite and two kinds of crystal structures of buergerite, and its energy gap is 3.66eV, than CdS(2.42eV) much broader, can increase CZTS thin film solar cell short-wave absorption, the spectrum improving battery utilizes scope, and then improves the photoelectric transformation efficiency of battery.Cd1-xZnxCompared with S with CdS, there is the best electric property, but decrease the usage amount of Cd, protect environment.Cd1-xZnxS is as cushion, compared with the CZTS solar cell using CdS cushion, can increase the short-wave absorption of battery on the basis of keeping preferable electric property; the spectrum providing battery utilizes scope; improve the photoelectric transformation efficiency of battery, also reduce the usage amount of Cd, protect environment.
Summary of the invention
It is an object of the invention to provide a kind of novel C u2ZnSnS4The preparation method of thin film solar cell.Its method uses one-step method list target magnetic control sputtering depositing operation to prepare Cu2ZnSnS4Thin film, it is not necessary to follow-up sulfuration, saves preparation cost, and simplifies technological process.Meanwhile, the H can being effectively prevented from sulfuration process2S gas pollution on the environment.This solar cell uses Cd1-xZnxS, as cushion, i.e. improves photoelectric transformation efficiency, decreases again the pollution of Cd ion pair environment.
The Cu of the present invention2ZnSnS4Thin film solar cell includes: the soda-lime glass substrate that sets gradually from bottom to top, metal back electrode molybdenum (Mo) layer, p-type Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS cushion, intrinsic ZnO and Al adulterate ZnO(AZO) Window layer, Al top electrode.Feature is: described p-type Cu2ZnSnS4Absorbed layer is by compound target sputtering preparation, and its thickness is 1000 ~ 1500nm, and N-type buffer layer is Cd1-xZnxS。
Above-mentioned Cu2ZnSnS4The preparation method of thin film solar cell comprises the following steps:
1) substrate cleans
Soda-lime glass is selected to be followed successively by as substrate, cleaning step: chloroazotic acid (HNO3: HCl=1:3) boil 20min, acetone ultrasonic cleaning 20min, dehydrated alcohol ultrasonic cleaning 20min, deionized water ultrasonic cleaning 20min, put into dry for standby in 70 DEG C of baking ovens.
2) pulse direct current (or direct current) sputtering sedimentation metal back electrode Mo layer
Use single target pulsed dc magnetron sputtering deposition metal back electrode Mo layer on a glass substrate.Target is the metal Mo target of 99.99% purity.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa, sputtering power is 80W, and underlayer temperature is 600 DEG C, and sputtering time is 60min, and institute's deposited film thickness is 1000nm.
3) r. f. magnetron sputtering p-type Cu2ZnSnS4Absorbed layer
Single target radio frequency magnetron is used to sputter at depositing p-type Cu on metal back electrode Mo layer2ZnSnS4Absorbed layer.Target is Cu2ZnSnS4Compound target.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa, sputtering power is 70W, and underlayer temperature is 500 DEG C, and sputtering time is 1.5h.Film thickness is 1000 ~ 1500nm.
4) chemical bath method depositing n-type Cd1-xZnxS cushion
Use chemical bath method in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS cushion.With zinc sulfate (ZnSO4), thiourea (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, and sedimentation time is 1h, and film thickness is 80nm.
5) r. f. magnetron sputtering ZnO Window layer
Use rf magnetron sputtering at N-shaped Cd1-xZnxZnO Window layer is deposited, including intrinsic ZnO and Al doping ZnO(AZO on S cushion), sputtering power is 70W, and underlayer temperature is 200 DEG C, and sputtering time is 1.5h.Intrinsic zno layer thickness be 200nm, AZO layer thickness be 600nm.
6) thermal evaporation deposition Al electrode
ZnO Window layer is added a cover palisade mask plate, uses thermal evaporation depositing Al electrode in Window layer.
Accompanying drawing illustrates:
Fig. 1. Cu of the present invention2ZnSnS4The structural representation of thin film solar cell；
Fig. 2 .p type Cu2ZnSnS4The X-ray diffraction spectrum of absorbed layer thin film；
Fig. 3 .n type Cd1-xZnxThe X-ray diffraction spectrum of S cushion.
Detailed description of the invention:
Example 1:
The Cu of the present invention2ZnSnS4Thin film solar cell includes: soda-lime glass substrate, metal back electrode Mo layer, p-type Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS cushion, ZnO Window layer, Al electrode.Wherein, described p-type Cu2ZnSnS4Absorbed layer is prepared by rf magnetron sputtering, and its film thickness is 1000 ~ 1500nm.
Concrete preparation technology is as follows:
1) soda-lime glass substrate is cleaned.Glass substrate is put into chloroazotic acid (HNO3: HCl=1:3) in boil 20min, then with acetone ultrasonic cleaning 20min, then with dehydrated alcohol ultrasonic cleaning 20min, finally with deionized water ultrasonic cleaning 20min, put into dry for standby in 70 DEG C of baking ovens；
2) pulsed dc magnetron sputtering sedimentation metal back electrode Mo layer is used at glass substrate surface.Target is the metal Mo target of 99.99% purity.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa, sputtering power is 80W, and underlayer temperature is 600 DEG C, and sputtering time is 1h, and institute's deposited film thickness is 100nm；
3) copper-zinc-tin-sulfur target is loaded magnetron sputtering plating intracavity, the substrate depositing metal back electrode Mo layer is put into plated film intracavity, is evacuated to 5 × 10-4Pa, sputtering power is 70W, and underlayer temperature 500 DEG C is down to room temperature after sputtering sedimentation 1.5h, takes out, p-type Cu from plated film chamber2ZnSnS4Absorbed layer preparation is formed, and its thickness is 1000nm；
4) use chemical bath method in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS cushion.With zinc sulfate (ZnSO4), thiourea (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, and sedimentation time is 1h, and film thickness is 80nm；
5) use rf magnetron sputtering at N-shaped Cd1-xZnxDepositing ZnO Window layer on S cushion, this Window layer is laminated construction, uses radio-frequency magnetron sputter method, first deposition intrinsic ZnO, and its thickness is 200nm, redeposited Al doping ZnO(AZO), its thickness is 600nm；
6) in ZnO Window layer, add palisade mask plate, use thermal evaporation depositing Al electrode in ZnO Window layer.
Example 2:
The Cu of the present invention2ZnSnS4Thin film solar cell includes: soda-lime glass substrate, metal back electrode Mo layer, p-type Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS cushion, ZnO Window layer, Al electrode.Wherein, described p-type Cu2ZnSnS4Absorbed layer is prepared by rf magnetron sputtering, and its film thickness is 1000 ~ 1500nm.
Concrete preparation technology is as follows:
1) soda-lime glass substrate is cleaned.Glass substrate is put into chloroazotic acid (HNO3: HCl=1:3) in boil 20min, then with acetone ultrasonic cleaning 20min, then with dehydrated alcohol ultrasonic cleaning 20min, finally with deionized water ultrasonic cleaning 20min, put into dry for standby in 70 DEG C of baking ovens；
2) pulsed dc magnetron sputtering sedimentation metal back electrode Mo layer is used at glass substrate surface.Target is the metal Mo target of 99.99% purity.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa, sputtering power is 80W, and underlayer temperature is 600 DEG C, and sputtering time is 1h, and institute's deposited film thickness is 100nm；
3) copper-zinc-tin-sulfur target is loaded magnetron sputtering plating intracavity, the substrate depositing metal back electrode Mo layer is put into plated film intracavity, is evacuated to 5 × 10-4Pa, sputtering power is 70W, and underlayer temperature 500 DEG C is down to room temperature after sputtering sedimentation 1.5h, takes out, p-type Cu from plated film chamber2ZnSnS4Absorbed layer preparation is formed, and its thickness is 1300nm；
4) use chemical bath method in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS cushion.With zinc sulfate (ZnSO4), thiourea (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, and sedimentation time is 1h, and film thickness is 80nm；
5) use rf magnetron sputtering at N-shaped Cd1-xZnxDepositing ZnO Window layer on S cushion, this Window layer is laminated construction, uses radio-frequency magnetron sputter method, first deposition intrinsic ZnO, and its thickness is 200nm, redeposited Al doping ZnO(AZO), its thickness is 600nm；
6) in ZnO Window layer, add palisade mask plate, use thermal evaporation depositing Al electrode in ZnO Window layer.
Example 3:
The Cu of the present invention2ZnSnS4Thin film solar cell includes: soda-lime glass substrate, metal back electrode Mo layer, p-type Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS cushion, ZnO Window layer, Al electrode.Wherein, described p-type Cu2ZnSnS4Absorbed layer is prepared by rf magnetron sputtering, and its film thickness is 1000 ~ 1500nm.
Concrete preparation technology is as follows:
1) soda-lime glass substrate is cleaned.Glass substrate is put into chloroazotic acid (HNO3: HCl=1:3) in boil 20min, then with acetone ultrasonic cleaning 20min, then with dehydrated alcohol ultrasonic cleaning 20min, finally with deionized water ultrasonic cleaning 20min, put into dry for standby in 70 DEG C of baking ovens；
2) pulsed dc magnetron sputtering sedimentation metal back electrode Mo layer is used at glass substrate surface.Target is the metal Mo target of 99.99% purity.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa, sputtering power is 80W, and underlayer temperature is 600 DEG C, and sputtering time is 1h, and institute's deposited film thickness is 100nm；
3) copper-zinc-tin-sulfur target is loaded magnetron sputtering plating intracavity, the substrate depositing metal back electrode Mo layer is put into plated film intracavity, is evacuated to 5 × 10-4Pa, sputtering power is 70W, and underlayer temperature 500 DEG C is down to room temperature after sputtering sedimentation 1.5h, takes out, p-type Cu from plated film chamber2ZnSnS4Absorbed layer preparation is formed, and its thickness is 1500nm；
4) use chemical bath method in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS cushion.With zinc sulfate (ZnSO4), thiourea (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, and sedimentation time is 1h, and film thickness is 80nm；
5) use rf magnetron sputtering at N-shaped Cd1-xZnxDepositing ZnO Window layer on S cushion, this Window layer is laminated construction, uses radio-frequency magnetron sputter method, first deposition intrinsic ZnO, and its thickness is 200nm, redeposited Al doping ZnO(AZO), its thickness is 600nm；
6) in ZnO Window layer, add palisade mask plate, use thermal evaporation depositing Al electrode in ZnO Window layer.
Claims (2)
1. a copper-zinc-tin-sulfur film solar cell, including: the soda-lime glass substrate that sets gradually from bottom to top, metal back electrode molybdenum (Mo) layer, p-type Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS cushion, intrinsic ZnO and Al adulterate ZnO(AZO) Window layer, Al electrode.Feature is: described p-type Cu2ZnSnS4Absorbed layer is by the sputtering preparation of copper zincium tin sulfur compound target one step, and its thickness is 1000 ~ 1500nm.
2. the preparation method of a copper-zinc-tin-sulfur film solar cell as claimed in claim 1, it is characterised in that: the method includes step in detail below:
1) substrate cleans
Soda-lime glass is selected to be followed successively by as substrate, cleaning step: chloroazotic acid (HNO3: HCl=1:3) boil 20min, acetone ultrasonic cleaning 20min, dehydrated alcohol ultrasonic cleaning 20min, deionized water ultrasonic cleaning 20min, put into dry for standby in 70 DEG C of baking ovens.
2) pulse direct current sputtering sedimentation metal back electrode Mo layer
Use single target pulsed dc magnetron sputtering deposition metal back electrode Mo layer on a glass substrate.Target is the metal Mo target of 99.99% purity.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa, sputtering power is 80W, and underlayer temperature is 600 DEG C, and sputtering time is 1h, and institute's deposited film thickness is 1100nm.
3) r. f. magnetron sputtering p-type Cu2ZnSnS4Absorbed layer
Single target radio frequency magnetron is used to sputter at depositing p-type Cu on metal back electrode Mo layer2ZnSnS4Absorbed layer.Target is Cu2ZnSnS4Compound list target.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa, sputtering power is 70W, and underlayer temperature is 500 DEG C, and sputtering time is 1.5h.Film thickness is 1000 ~ 1500nm.
4) chemical bath method depositing n-type Cd1-xZnxS cushion
Use chemical bath method in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS cushion.With zinc sulfate (ZnSO4), thiourea (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, and sedimentation time is 1h, and film thickness is 80nm.
5) r. f. magnetron sputtering ZnO Window layer
Use rf magnetron sputtering at N-shaped Cd1-xZnxZnO Window layer is deposited, including intrinsic ZnO and Al doping ZnO(AZO on S cushion), sputtering power is 120W, and underlayer temperature is 200 DEG C, and sputtering time is 1.5h.Intrinsic zno layer thickness be 200nm, AZO layer thickness be 600nm.
6) thermal evaporation deposition Al electrode
ZnO Window layer is added a cover palisade mask plate, uses thermal evaporation method depositing Al electrode in Window layer.
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