CN105826425B - A kind of preparation method of copper-zinc-tin-sulfur film solar cell - Google Patents
A kind of preparation method of copper-zinc-tin-sulfur film solar cell Download PDFInfo
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- CN105826425B CN105826425B CN201510984120.4A CN201510984120A CN105826425B CN 105826425 B CN105826425 B CN 105826425B CN 201510984120 A CN201510984120 A CN 201510984120A CN 105826425 B CN105826425 B CN 105826425B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 238000004544 sputter deposition Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910004576 Cd1-xZnxS Inorganic materials 0.000 claims abstract description 14
- 238000004062 sedimentation Methods 0.000 claims abstract description 14
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 22
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 22
- 238000000151 deposition Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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 6
- 230000008021 deposition Effects 0.000 claims description 6
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water 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
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 27
- 239000010409 thin film Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000005987 sulfurization reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 8
- 229910000368 zinc sulfate Inorganic materials 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
- 238000007747 plating Methods 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 239000011686 zinc sulphate Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002210 silicon-based material Substances 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
- 230000033228 biological regulation 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
- 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
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 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
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052984 zinc sulfide 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
- H01L31/18—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
Abstract
The invention discloses a kind of preparation method of copper-zinc-tin-sulfur film solar cell, which includes soda-lime glass substrate, metal back electrode molybdenum (Mo) layer, p-type Cu2ZnSnS4Absorbed layer, N-shaped Cd1‑xZnxS buffer layer, ZnO Window layer, Al electrode；The p-type Cu2ZnSnS4The preparation method of absorbed layer is: using quaternary compound copper-zinc-tin-sulfur target, using a step sputtering sedimentation, is not necessarily to subsequent sulfuration process.The N-shaped Cd1‑xZnxS buffer layer reduces the usage amount of Cd, reduces the pollution to environment, while increasing the short-wave absorption of battery, improves the photoelectric conversion efficiency of battery.Thin film solar cell of the invention has many advantages, such as that nontoxic and pollution-free each element, rich reserves, preparation process are simple, photoelectric conversion efficiency is higher, cost is relatively low, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of copper-zinc-tin-sulfur film solar cell with cadmium zinc sulphur buffer layer, belong to new energy
Source technology field.
Background technique
As the traditional fossil energies such as petroleum, coal are petered out, the development and utilization of renewable energy is increasingly subject to people
Attention.Solar energy has great advantages for development and potentiality as a kind of cleaning, the renewable energy of safety.Solar energy
Photovoltaic power generation is one of most common Solar use form.People make in the research, exploitation and industrialization of solar cell
Very big effort.While body material cell continues to develop, thin film solar cell becomes the following sun electricity since cost is relatively low
The development trend in pond.Material currently used for absorption layer of thin film solar cell mainly has: amorphous silicon, cadmium telluride (CdTe) and copper and indium
Gallium selenium (CuInGaSe2).
Cost is relatively low by amorphous silicon material and preparation process, it is easy to accomplish large-scale production, and the dim light effect of amorphous silicon
Preferably.But the photoelectric conversion efficiency of amorphous silicon film solar battery is lower, and the stabilization photoelectric conversion efficiency of battery is most in laboratory
Height only has 13% or so, its efficiency is less than 10% in actual production.This is because there are a large amount of defect in amorphous material, at
For the complex centre of carrier, cause the short circuit current of battery very low；Meanwhile amorphous silicon material has photo attenuation effect, at
It is hindered to limit the maximum of its development.
CdTe is a kind of efficient, stable and advantage of lower cost thin film solar cell.However, heavy metal element Cd can be right
Environment pollutes.Although CdTe is relatively stable and nontoxic under room temperature, in practical preparation process, and not all Cd2+Capital
It is deposited into film, environment and human health are had adverse effect after being discharged with waste liquid.
CuInGaSe2It is one of novel thin film solar cell most with prospects at present.In August, 2010, the German sun
The highest CuInGaSe of laboratory photoelectric conversion efficiency can be prepared with Hydrogen Energy research center (ZSW)2Thin film solar cell,
Transfer efficiency is up to 20.3%.However, In, Ga are rare element, CuInGaSe is greatly limited2Thin film solar cell it is extensive
Industrialized production.
Quaternary compound semiconductor copper-zinc-tin-sulfur (Cu with stannite structure2ZnSnS4) it is direct band-gap semicondictor material
Material, absorption coefficient are larger；Its forbidden bandwidth is 1.51eV, is tapped with the best forbidden bandwidth of solar cell absorbed layer (1.5eV) ten
Closely.In addition, Cu2ZnSnS4Without toxic element, and each element rich reserves in the earth's crust.Therefore, Cu2ZnSnS4It is most to be expected to
Substitute CuInGaSe2Absorption layer material.2013, chemical industry and platform were answered in IBM Corporation, the U.S. and solar Frontier, Tokyo
The Wang Neng photoelectricity company joint development in gulf has gone out the Cu that photoelectric conversion efficiency is 12.6%2ZnSnS4Thin film solar cell becomes mesh
Preceding Cu2ZnSnS4The global highest transfer efficiency of solar cell.Prepare Cu2ZnSnS4The main method of film has: electron beam evaporation
Method, Vacuum sublimation, spray pyrolysis, electrochemical deposition method, magnetron sputtering method etc..Wherein, magnetron sputtering method has film forming
The advantages that compactness is high, utilization rate of raw materials is high, technological parameter is easy regulation, Yi Shixian large area industrialized production, is current
Prepare Cu2ZnSnS4One of most promising method of film.
The most common cushioning layer material of CZTS thin film solar cell is cadmium sulfide (CdS), but CdS can be produced during the preparation process
Raw toxic Cd2+Ion.In addition, the defects of defect state density of CdS film is larger, and there are a large amount of dislocations, fault in film,
Carrier lifetime is not only affected, but also can extend to and absorb in layer material, influences the photoelectric conversion efficiency of battery.Cd1- xZnxS is direct band-gap semicondictor material, have two kinds of crystal structures of zincblende and buergerite, forbidden bandwidth 3.66eV, than
CdS(2.42eV) much broader, CZTS thin film solar cell short-wave absorption can be increased, improve the spectrum utilization scope of battery, into
And improve the photoelectric conversion efficiency of battery.Cd1-xZnxS has same good electric property, but reduces Cd compared with CdS
Usage amount, protect environment.Cd1-xZnxS is as buffer layer, can be with compared with the CZTS solar cell for using CdS buffer layer
The short-wave absorption for increasing battery on the basis of keeping preferable electric property, provides the spectrum utilization scope of battery, improves electricity
The photoelectric conversion efficiency in pond also reduces the usage amount of Cd, protects environment.
Summary of the invention
The object of the present invention is to provide a kind of novel C u2ZnSnS4The preparation method of thin film solar cell.Its method uses one
Footwork list target magnetic control sputtering depositing operation prepares Cu2ZnSnS4Film is not necessarily to subsequent vulcanization, saves preparation cost, and simplify
Process flow.Meanwhile the H in sulfuration process can be effectively avoided2S gas pollution on the environment.This solar cell makes
Use Cd1-xZnxS improves photoelectric conversion efficiency as buffer layer, and reduce the pollution of Cd ion pair environment.
Cu of the invention2ZnSnS4Thin film solar cell includes: soda-lime glass substrate, the metal set gradually from bottom to top
Back electrode molybdenum (Mo) layer, p-type Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS buffer layer, intrinsic ZnO and Al adulterate ZnO(AZO) window
Mouth layer, Al top electrode.Feature is: the p-type Cu2ZnSnS4Absorbed layer is sputtered by compound target and is prepared, with a thickness of 1000 ~
1500nm, N-type buffer layer Cd1-xZnxS。
Above-mentioned Cu2ZnSnS4The preparation method of thin film solar cell the following steps are included:
1) substrate cleans
Select soda-lime glass as substrate, cleaning step is successively are as follows: chloroazotic acid (HNO3: HCl=1:3) 20min is boiled, acetone is super
Sound clean 20min, dehydrated alcohol be cleaned by ultrasonic 20min, deionized water be cleaned by ultrasonic 20min, be put into 70 DEG C of baking ovens dry it is standby
With.
2) Mo layers of sputtering sedimentation metal back electrode of pulse direct current (or direct current)
Using deposited metal back electrode Mo layers on a glass substrate of single target pulsed dc magnetron sputtering.Target is 99.99% pure
The metal Mo target of degree.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa splashes
Penetrating power is 80W, and underlayer temperature is 600 DEG C, sputtering time 60min, and institute's deposited film thickness is 1000nm.
3) r. f. magnetron sputtering p-type Cu2ZnSnS4Absorbed layer
Depositing p-type Cu on metal back electrode Mo layer is sputtered at using single target radio frequency magnetron2ZnSnS4Absorbed 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 70W, underlayer temperature are 500 DEG C, sputtering time 1.5h.Film thickness is 1000 ~ 1500nm.
4) chemical water bath depositing n-type Cd1-xZnxS buffer layer
Using chemical water bath in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS buffer layer.With zinc sulfate
(ZnSO4), thiocarbamide (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, sedimentation time 1h,
Film thickness is 80nm.
5) r. f. magnetron sputtering ZnO Window layer
Using rf magnetron sputtering in N-shaped Cd1-xZnxZnO Window layer is deposited on S buffer layer, including intrinsic ZnO and Al mix
Miscellaneous ZnO(AZO), sputtering power 70W, underlayer temperature is 200 DEG C, sputtering time 1.5h.Intrinsic zno layer with a thickness of 200nm,
AZO layers with a thickness of 600nm.
6) thermal evaporation deposition Al electrode
In ZnO Window layer cover palisade mask plate, using thermal evaporation in Window layer depositing Al electrode.
Detailed description of the invention:
Fig. 1 Cu of the present invention2ZnSnS4The structural schematic diagram of thin film solar cell；
Fig. 2 p-type Cu2ZnSnS4Absorb the X-ray diffraction spectrum of layer film；
Fig. 3 .n type Cd1-xZnxThe X-ray diffraction spectrum of S buffer layer.
Specific embodiment:
Example 1:
Cu of the invention2ZnSnS4Thin film solar cell includes: soda-lime glass substrate, Mo layers of metal back electrode, p-type
Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS buffer layer, ZnO Window layer, Al electrode.Wherein, the p-type Cu2ZnSnS4Absorbed layer
It is prepared by rf magnetron sputtering, film thickness is 1000 ~ 1500nm.
Specific preparation process 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 use acetone
It is cleaned by ultrasonic 20min, is then cleaned by ultrasonic 20min with dehydrated alcohol, is finally cleaned by ultrasonic 20min with deionized water, is put into 70
It is dried for standby in DEG C baking oven；
2) Mo layers of pulsed dc magnetron sputtering sedimentation metal back electrode are used in glass substrate surface.Target is 99.99% pure
The metal Mo target of degree.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa splashes
Penetrating power is 80W, and underlayer temperature is 600 DEG C, sputtering time 1h, and institute's deposited film thickness is 100nm；
3) copper-zinc-tin-sulfur target loading magnetron sputtering plating is intracavitary, deposited metal back electrode Mo layers of substrate is put into
Plated film is intracavitary, is evacuated to 5 × 10-4Pa, sputtering power 70W, are down to room temperature after sputtering sedimentation 1.5h by 500 DEG C of underlayer temperature,
It is taken out from plating membrane cavity, p-type Cu2ZnSnS4Absorbed layer prepares to be formed, with a thickness of 1000nm；
4) using chemical water bath in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS buffer layer.With zinc sulfate
(ZnSO4), thiocarbamide (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, sedimentation time 1h,
Film thickness is 80nm；
5) using rf magnetron sputtering in N-shaped Cd1-xZnxZnO Window layer is deposited on S buffer layer, this Window layer is lamination knot
Structure, using radio-frequency magnetron sputter method, first deposition intrinsic ZnO, with a thickness of 200nm, redeposited Al adulterates ZnO(AZO), thickness
For 600nm；
6) in ZnO Window layer plus palisade mask plate, using thermal evaporation in ZnO Window layer depositing Al electrode.
Example 2:
Cu of the invention2ZnSnS4Thin film solar cell includes: soda-lime glass substrate, Mo layers of metal back electrode, p-type
Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS buffer layer, ZnO Window layer, Al electrode.Wherein, the p-type Cu2ZnSnS4Absorbed layer
It is prepared by rf magnetron sputtering, film thickness is 1000 ~ 1500nm.
Specific preparation process 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 use acetone
It is cleaned by ultrasonic 20min, is then cleaned by ultrasonic 20min with dehydrated alcohol, is finally cleaned by ultrasonic 20min with deionized water, is put into 70
It is dried for standby in DEG C baking oven；
2) Mo layers of pulsed dc magnetron sputtering sedimentation metal back electrode are used in glass substrate surface.Target is 99.99% pure
The metal Mo target of degree.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa splashes
Penetrating power is 80W, and underlayer temperature is 600 DEG C, sputtering time 1h, and institute's deposited film thickness is 100nm；
3) copper-zinc-tin-sulfur target loading magnetron sputtering plating is intracavitary, deposited metal back electrode Mo layers of substrate is put into
Plated film is intracavitary, is evacuated to 5 × 10-4Pa, sputtering power 70W, are down to room temperature after sputtering sedimentation 1.5h by 500 DEG C of underlayer temperature,
It is taken out from plating membrane cavity, p-type Cu2ZnSnS4Absorbed layer prepares to be formed, with a thickness of 1300nm；
4) using chemical water bath in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS buffer layer.With zinc sulfate
(ZnSO4), thiocarbamide (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, sedimentation time 1h,
Film thickness is 80nm；
5) using rf magnetron sputtering in N-shaped Cd1-xZnxZnO Window layer is deposited on S buffer layer, this Window layer is lamination knot
Structure, using radio-frequency magnetron sputter method, first deposition intrinsic ZnO, with a thickness of 200nm, redeposited Al adulterates ZnO(AZO), thickness
For 600nm；
6) in ZnO Window layer plus palisade mask plate, using thermal evaporation in ZnO Window layer depositing Al electrode.
Example 3:
Cu of the invention2ZnSnS4Thin film solar cell includes: soda-lime glass substrate, Mo layers of metal back electrode, p-type
Cu2ZnSnS4Absorbed layer, N-shaped Cd1-xZnxS buffer layer, ZnO Window layer, Al electrode.Wherein, the p-type Cu2ZnSnS4Absorbed layer
It is prepared by rf magnetron sputtering, film thickness is 1000 ~ 1500nm.
Specific preparation process 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 use acetone
It is cleaned by ultrasonic 20min, is then cleaned by ultrasonic 20min with dehydrated alcohol, is finally cleaned by ultrasonic 20min with deionized water, is put into 70
It is dried for standby in DEG C baking oven；
2) Mo layers of pulsed dc magnetron sputtering sedimentation metal back electrode are used in glass substrate surface.Target is 99.99% pure
The metal Mo target of degree.Sputter gas is high-purity argon gas (99.999%), gas flow 20mL/min.It is evacuated to 5 × 10-4Pa splashes
Penetrating power is 80W, and underlayer temperature is 600 DEG C, sputtering time 1h, and institute's deposited film thickness is 100nm；
3) copper-zinc-tin-sulfur target loading magnetron sputtering plating is intracavitary, deposited metal back electrode Mo layers of substrate is put into
Plated film is intracavitary, is evacuated to 5 × 10-4Pa, sputtering power 70W, are down to room temperature after sputtering sedimentation 1.5h by 500 DEG C of underlayer temperature,
It is taken out from plating membrane cavity, p-type Cu2ZnSnS4Absorbed layer prepares to be formed, with a thickness of 1500nm；
4) using chemical water bath in p-type Cu2ZnSnS4Depositing n-type Cd on absorbed layer1-xZnxS buffer layer.With zinc sulfate
(ZnSO4), thiocarbamide (SC (NH2)2), cadmium acetate Cd (CH3COO)2As reactant, bath temperature is 80 DEG C, sedimentation time 1h,
Film thickness is 80nm；
5) using rf magnetron sputtering in N-shaped Cd1-xZnxZnO Window layer is deposited on S buffer layer, this Window layer is lamination knot
Structure, using radio-frequency magnetron sputter method, first deposition intrinsic ZnO, with a thickness of 200nm, redeposited Al adulterates ZnO(AZO), thickness
For 600nm；
6) in ZnO Window layer plus palisade mask plate, using thermal evaporation in ZnO Window layer depositing Al electrode.
Claims (2)
1. a kind of copper-zinc-tin-sulfur film solar cell, comprising: soda-lime glass substrate, the metal back electrode set gradually from bottom to top
Mo layers, p type Cu2ZnSnS4 absorbed layer, n type Cd 1-xZnxS buffer layer, intrinsic ZnO and Al adulterate ZnO window
Layer, Al electrode, it is characterised in that: the p type Cu2ZnSnS4 absorbed layer is sputtered by one step of copper zincium tin sulfur compound target and made
It is standby, with a thickness of 1000 ~ 1500nm, Mo layers of metal back electrode with a thickness of 1100nm, the thickness of N-shaped Cd1-xZnxS buffer layer
For 80nm, intrinsic zno layer with a thickness of 200nm, Al doped zno layer with a thickness of 600nm.
2. a kind of preparation method of the copper-zinc-tin-sulfur film solar cell as described in claim 1, it is characterised in that: this method
Comprising the following specific steps
1) substrate cleans
Select soda-lime glass as substrate, cleaning step is successively are as follows: chloroazotic acid boils 20min, and acetone is cleaned by ultrasonic 20min, anhydrous
EtOH Sonicate cleans 20min, and deionized water is cleaned by ultrasonic 20min, is put into 70 DEG C of baking ovens and is dried for standby；
2) Mo layers of pulse direct current sputtering sedimentation metal back electrode
Using deposited metal back electrode Mo layers on a glass substrate of single target pulsed dc magnetron sputtering, target is 99.99% pure
The metal Mo target of degree, sputter gas are high-purity argon gas, and gas flow 20mL/min is evacuated to 5 × 10-4Pa sputters function
Rate is 80W, and underlayer temperature is 600 DEG C, sputtering time 1h, and institute's deposited film thickness is 1100nm；
3) r. f. magnetron sputtering p type Cu2ZnSnS4 absorbed layer
Sputtering at deposition p type Cu2ZnSnS4 absorbed layer, target on metal back electrode Mo layer using single target radio frequency magnetron is
Cu2ZnSnS4 compound list target, sputter gas are high-purity argon gas, and gas flow 20mL/min is evacuated to 5 × 10-4Pa splashes
Penetrating power is 70W, and underlayer temperature is 500 DEG C, sputtering time 1.5h, and film thickness is 1000 ~ 1500nm；
4) chemical water bath deposits n type Cd1-xZnxS buffer layer
N type Cd 1-xZnxS buffer layer is deposited on p type Cu2ZnSnS4 absorbed layer using chemical water bath, with sulfuric acid
As reactant, bath temperature is 80 DEG C, sedimentation time 1h, film thickness 80nm for zinc, thiocarbamide, cadmium acetate；
5) r. f. magnetron sputtering ZnO Window layer
ZnO Window layer is deposited on n type Cd1-xZnxS buffer layer using rf magnetron sputtering, including intrinsic ZnO and
Al adulterates ZnO, sputtering power 120W, underlayer temperature be 200 DEG C, sputtering time 1.5h, intrinsic ZnO layers with a thickness of
200nm, AZO layers with a thickness of 600nm；
6) thermal evaporation deposition Al electrode
In ZnO Window layer cover palisade mask plate, using thermal evaporation method in Window layer depositing Al electrode.
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| CN108039388B (en) * | 2018-01-08 | 2024-03-26 | 广东工业大学 | Cu (copper) alloy 2 ZnSn(S,Se) 4 Thin film solar cell and preparation method thereof |
| CN108389934A (en) * | 2018-03-08 | 2018-08-10 | 西南石油大学 | A method of preparing CIGS solar cell with a step sputtering method |
| CN109473495B (en) * | 2018-11-19 | 2020-11-10 | 中国科学院兰州化学物理研究所 | Method for preparing CdZnS buffer layer film step by step |
| CN109904256A (en) * | 2019-01-09 | 2019-06-18 | 云南师范大学 | A kind of copper-zinc-tin-sulfur film preparation method |
| CN110224037A (en) * | 2019-06-03 | 2019-09-10 | 深圳先进技术研究院 | Copper-zinc-tin-sulfur film solar cell and preparation method thereof |
| CN111312854A (en) * | 2020-02-21 | 2020-06-19 | 云南师范大学 | Magnesium-doped copper-zinc-tin-sulfur thin film solar cell and preparation method thereof |
| CN113964221B (en) * | 2021-10-12 | 2023-09-05 | 闽都创新实验室 | Electronic synaptic device and its making method |
| CN115498052B (en) * | 2022-09-22 | 2024-02-09 | 深圳先进技术研究院 | CIGS solar cell preparation method |
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| US5112410A (en) * | 1989-06-27 | 1992-05-12 | The Boeing Company | Cadmium zinc sulfide by solution growth |
| CN102610673A (en) * | 2012-03-23 | 2012-07-25 | 华东师范大学 | Copper zinc tin sulfur compound thin-film solar cell and preparation method thereof |
| CN104485369A (en) * | 2014-09-30 | 2015-04-01 | 天津理工大学 | Copper zinc tin sulfide thin film solar cell device and preparation method thereof |
| CN105023961A (en) * | 2015-08-24 | 2015-11-04 | 中国工程物理研究院材料研究所 | Flexible Cu2ZnSnS4 thin-film solar cell and preparation method thereof |
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| CN102610673A (en) * | 2012-03-23 | 2012-07-25 | 华东师范大学 | Copper zinc tin sulfur compound thin-film solar cell and preparation method thereof |
| CN104485369A (en) * | 2014-09-30 | 2015-04-01 | 天津理工大学 | Copper zinc tin sulfide thin film solar cell device and preparation method thereof |
| CN105023961A (en) * | 2015-08-24 | 2015-11-04 | 中国工程物理研究院材料研究所 | Flexible Cu2ZnSnS4 thin-film solar cell and preparation method thereof |
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