CN109560159A - A kind of copper-zinc-tin-sulfur film solar cell - Google Patents
A kind of copper-zinc-tin-sulfur film solar cell Download PDFInfo
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- CN109560159A CN109560159A CN201811301706.6A CN201811301706A CN109560159A CN 109560159 A CN109560159 A CN 109560159A CN 201811301706 A CN201811301706 A CN 201811301706A CN 109560159 A CN109560159 A CN 109560159A
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- copper
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 20
- 230000008021 deposition Effects 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 57
- 239000011787 zinc oxide Substances 0.000 claims description 33
- 238000004544 sputter deposition Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 13
- 239000005083 Zinc sulfide Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 113
- 239000010408 film Substances 0.000 description 52
- 238000010438 heat treatment Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 229910052774 Proactinium Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005477 sputtering target Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- 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
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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of copper-zinc-tin-sulfur film solar cells, including sequentially connected glass substrate, back electrode, absorbed layer, the second middle layer, buffer layer, electrically conducting transparent Window layer and top electrode, wherein the back electrode is Mo film, with a thickness of 1 μm；The absorbed layer is the copper-zinc-tin-sulfur film of magnetron sputtering deposition, with a thickness of 900-1500nm；Second middle layer is ZnS film, with a thickness of 10nm；The buffer layer is CdS film, with a thickness of 30 ~ 50nm；The ZnO:Al film of i-ZnO film and 500 ~ 600nm that the electrically conducting transparent Window layer is 50 ~ 80nm being sequentially depositing；It is described to power on extremely evaporation silver-coated electrode.The present invention introduces two middle layers from design, increase copper-zinc-tin-sulfur crystallite dimension, reduce molybdenum disulfide resistive formation thickness, reduce decomposition caused by copper-zinc-tin-sulfur is spread because of Mo, reduce Interface composites and boundary defect at most important two in copper-zinc-tin-sulfur battery, surface dark current is reduced, minority carrier life time is extended, improves the collection efficiency of minority carrier.
Description
Technical field
The present invention relates to area of solar cell, and in particular to a kind of copper-zinc-tin-sulfur (CZTS) thin film solar cell.
Background technique
The problem of deteriorating with global energy shortage and amblent air temperature is increasingly aggravated, the mankind there is an urgent need to recent decades it
It inside finds one kind and is capable of the renewable and clean energy resource of substitute fossil fuels, and can be realized large-scale application to adapt to mankind society
It can develop to energy increasing need.Solar energy resources wide, cleanliness without any pollution, resourceful, never with its distributional region
The advantages that exhausted is optimal renewable energy.Solar energy power generating is one of preferred plan of Solar use, and low
Cost, pollution-free, high conversion efficiency solar cell are always the target pursued.
Copper-zinc-tin-sulfur (Cu2ZnSnS4, CZTS) thin film solar cell is because it is at low cost, incident photon-to-electron conversion efficiency is high, inhales
Receipts coefficient is high, forbidden bandwidth is suitable and advantages of environment protection, becomes the hot spot of hull cell research in recent years.
It is well known that being easy to produce between back electrode and CZTS absorbed layer in the good CZTS cell process of processability
Molybdenum disulfide causes CZTS to decompose and generates secondary phase, these secondary phases become Trapping Centers, reduce less sub- collection rate, cause out
Road voltage reduces, and finally results in battery efficiency reduction.And the means that Traditional control secondary phase generates are only to rely on technical staff
Experience pass through control preformed layer elemental ratio, the comprehensive regulations factor such as chamber pressure, temperature, time when vulcanization, without quantitative
Execute data.Because up to 7% lattice mismatch also leads to a large amount of heterogeneous interface between CZTS absorbed layer and CdS buffer layer
Crystal dislocation generates Interface composites center, reduces minority carrier life time and diffusion length, it is unfavorable to cause to the collection of minority carrier
It influences.
Summary of the invention
The object of the present invention is to provide a kind of copper-zinc-tin-sulfur film solar cells, effectively improve the current-carrying of CZTS hull cell
Sub- service life and few sub- collection rate, finally improve the performance of CZTS device.
Copper-zinc-tin-sulfur film solar cell of the present invention, including sequentially connected glass substrate, back electrode, absorption
Layer, the second middle layer, buffer layer, electrically conducting transparent Window layer and top electrode, wherein the back electrode is Mo film, with a thickness of 1 μ
m；The absorbed layer is the CZTS film of magnetron sputtering deposition, with a thickness of 900-1500nm；Second middle layer is that ZnS is thin
Film, with a thickness of 10nm；The buffer layer is CdS film, with a thickness of 30 ~ 50nm；Electrically conducting transparent Window layer (6) include one layer 50 ~
The ZnO:Al film of the i-ZnO film of 80nm and one layer of 500 ~ 600nm, wherein i-ZnO film is connect with buffer layer (5)；It is described
Power on extremely evaporation silver-coated electrode.
Further, the absorbed layer be (112), (220), the CZTS film of (312) height preferred orientation, by
After being sequentially depositing the first middle layer and copper-zinc-tin-sulfur preformed layer on back electrode, under 560 ± 10 DEG C of sulphur atmosphere be heat-treated 45 ~
It being made after 60min, wherein the first middle layer is that ZnO film deposits to obtain using zinc oxide target as target using magnetron sputtering,
With a thickness of 10 ~ 20nm；Copper-zinc-tin-sulfur preformed layer is using zinc sulphide target and copper-tin alloy target as target, using magnetron sputtering stepped depositions
It obtains, with a thickness of 700-800nm.
The preparation method of above-mentioned copper-zinc-tin-sulfur film solar cell, includes the following steps:
(1) back electrode Mo film, the first middle layer are successively deposited on a glass substrate in same cavity using magnetron sputtering method
ZnO film, copper-zinc-tin-sulfur preformed layer；
(2) after above-mentioned sample is heat-treated 45 ~ 60min under 560 ± 10 DEG C of sulphur atmosphere, the first middle layer ZnO film and copper
Zinc-tin sulphur preformed layer, which reacts, generates absorbed layer copper-zinc-tin-sulfur film；
(3) the second middle layer ZnS film is deposited on absorbed layer using magnetron sputtering method；
(4) chemical water domain method (CBD) buffer layer CdS film in the second middle layer is used；
(5) i-ZnO film and ZnO:Al film are sequentially depositing as electrically conducting transparent window using magnetron sputtering method on the buffer layer
Layer；
(6) top electrode silver-coated electrode is prepared on the ZnO:Al film of electrically conducting transparent Window layer using electron beam evaporation deposition method.
Preferably, target purity used in magnetron sputtering is not less than 99.99%, and working gas purity is not less than
99.999%, chamber base vacuum is 5.0 × 10-4Pa, Ar gas flow are 30sccm, and the distance of substrate to sputtering target material is
10cm。
Preferably, it in step (1), when using Mo target material deposition back electrode (2), is sputtered at air pressure 1.2Pa respectively
15min sputters 50min at air pressure 0.3Pa, and loading power is direct current, and sputtering power 200W, deposition thickness is 1 μm.
Preferably, in step (1), when depositing the first middle layer (301) using zinc oxide target, target loading power is to penetrate
Frequently, sputtering power 50W, deposition thickness are 10 ~ 20nm.
Preferably, in step (1), using zinc sulphide target and copper-tin alloy target stepped depositions copper-zinc-tin-sulfur preformed layer (302)
When, loading power is radio frequency, and sputtering power 50W, deposition thickness is 700 ~ 800nm.
Preferably, in step (3), when depositing the second middle layer (4) using zinc sulphide target, target loading power is radio frequency,
Sputtering power is 50W, deposition thickness 10nm.
Preferably, in step (5), the i-ZnO film and 500 ~ 600nm of 50 ~ 80nm are sequentially depositing using magnetron sputtering
When the film of ZnO:Al is as electrically conducting transparent Window layer (6), sputtering power 80W.
Preferably, in step (2), annealing temperature is 560 ± 10 DEG C, and initial temperature is room temperature, 25 DEG C/min of heating rate,
Detailed process is as follows: when being warming up to 250 ± 10 DEG C, being passed through sulfur vapor and chamber temperature is made to maintain air pressure in 3000Pa, reach
Cooled to room temperature after 560 ± 10 DEG C of 45 ~ 60min of heat preservation.
Compared with prior art, the present invention has the advantage that
(1) present invention introduces two middle layers from design, increases CZTS crystallite dimension, reduces molybdenum disulfide resistive formation
Thickness reduces decomposition caused by CZTS is spread because of Mo, reduces Interface composites and interface at most important two in CZTS battery
Defect reduces surface dark current, extends minority carrier life time, improves the collection efficiency of minority carrier.
(2) present invention uses magnetron sputtering disposable depositing inter-layer and CZTS film under a high vacuum, avoids contact with sky
Conductance causes device contamination.
(3) present invention uses magnetron sputtering middle layer, accurately controls the deposition rate of middle layer, guarantees that middle layer reaches
To ideal thickness, the first middle layer is made to disappear after curing, the second middle layer in device fabrication process still.
It should be appreciated that as long as aforementioned concepts and all combinations additionally conceived described in greater detail below are at this
It can be viewed as a part of the subject matter of the disclosure in the case that the design of sample is not conflicting.In addition, required guarantor
All combinations of the theme of shield are considered as a part of the subject matter of the disclosure.
Can be more fully appreciated from the following description in conjunction with attached drawing present invention teach that the foregoing and other aspects, reality
Apply example and feature.The features and/or benefits of other additional aspects such as illustrative embodiments of the invention will be below
Description in it is obvious, or learnt in practice by the specific embodiment instructed according to the present invention.
Detailed description of the invention
Attached drawing is not intended to drawn to scale.In the accompanying drawings, identical or nearly identical group each of is shown in each figure
It can be indicated by the same numeral at part.For clarity, in each figure, not each component part is labeled.
Now, example will be passed through and the embodiments of various aspects of the invention is described in reference to the drawings, in which:
Fig. 1 is the structural schematic diagram of copper-zinc-tin-sulfur film solar cell of the present invention.
Fig. 2 is copper-zinc-tin-sulfur film solar battery structure design diagram before the present invention makes annealing treatment.
Fig. 3 is the scanning electron microscope exterior view of CZTS film prepared by embodiment 1.
Fig. 4 is the Raman map of CZTS film prepared by embodiment 1.
Fig. 5 is the XRD spectrum of CZTS film prepared by embodiment 1.
Fig. 6 is the J-V curve comparison figure of CZTS battery prepared by embodiment 2 and tradition CZTS battery.
Fig. 7 is the J-V curve comparison figure of CZTS battery prepared by embodiment 3 and tradition CZTS battery.
Label in attached drawing are as follows: 1- glass substrate, 2- back electrode, the first middle layer of 301-, 302- copper-zinc-tin-sulfur preformed layer,
3- absorbed layer, the second middle layer of 4-, 5- buffer layer, 6- electrically conducting transparent Window layer, 7- top electrode.
Specific embodiment
In order to make the contents such as sedimentary sequence of the invention be easier to be understood, below according to specific embodiment and combine
Attached drawing, the present invention is described in further detail.
Various aspects with reference to the accompanying drawings to describe the present invention in the present invention, shown in the drawings of the embodiment of many explanations.
It is not intended to cover all aspects of the invention for embodiment disclosed by the invention.It should be appreciated that a variety of designs presented hereinbefore
And embodiment, and those of describe in more detail below design and embodiment can in many ways in any one come
Implement, this is to should be conception and embodiment disclosed in this invention to be not limited to any embodiment.In addition, disclosed by the invention
Some aspects can be used alone, or otherwise any appropriately combined use with disclosed by the invention.
The principle of the invention is: first middle layer participates in generating copper zinc in copper-zinc-tin-sulfur preformed layer sulfidation
Tin sulphur absorbed layer and reacted completely, reduce the phase counterdiffusion of most of Mo and S before reaction completely, be not only greatly reduced
MoS 2It generates, more reduces the decomposition of CZTS, to reduce ZnS, SnS, Cu2The formation of the secondary phases such as S and CZTS Hole.
There is the adhesive force for reducing CZTS and back electrode in hole, and it is well known that doping of the Na ion in CZTS can effectively increase
The crystallite dimension of big CZTS, but the presence of hole reduces diffusion path of the Na ion to CZTS, and makes the diffusion of Na not
Uniformly, to make that CZTS crystal grain becomes smaller and size is uneven, so the first middle layer can also promote CZTS crystal grain to become larger and
It is even.There are the arrangement of the conduction band of cliff of displacement formula, conduction bands between traditional copper-zinc-tin-sulfur solar battery CZTS absorbed layer and CdS buffer layer
Band offset value reaches 0.14eV or so, causes open-circuit voltage lower.The lattice mismatch of CZTS and CdS reaches between 7%, CZTS and CdS
There are a large amount of face dislocations and defects, reduce service life, diffusion length and the collection efficiency of few son.CZTS and ZnS lattice mismatch is only
It is 0.5%, and without the conduction band of cliff of displacement formula arrangement, reduces and absorb the existing problems for influencing battery performance in bed boundary.It adopts
It, can be to avoid, in CZTS Surface Creation ZnS, the ZnS of disperse is in CZTS in traditional sulfidation with the second middle layer is sputtered
In in vivo in the presence of, the Zener pinning due to caused by the obstruction to grain boundary.
In conjunction with Fig. 1, copper-zinc-tin-sulfur film solar cell of the present invention, from the bottom to top by sequentially connected glass substrate
1, back electrode 2, absorbed layer 3, the second middle layer 4, buffer layer 5, electrically conducting transparent Window layer 6 and top electrode 7 form, wherein described
Back electrode 2 is Mo film, with a thickness of 1 μm；The absorbed layer 3 is the CZTS film of magnetron sputtering deposition, with a thickness of 900-
1500nm；Second middle layer 4 is ZnS film, with a thickness of 10nm；The buffer layer 5 is CdS film, with a thickness of 30 ~
50nm；The ZnO:Al of i-ZnO film and 500 ~ 600nm that the electrically conducting transparent Window layer 6 is 50 ~ 80nm being sequentially depositing is thin
Film；The top electrode 7 is evaporation silver-coated electrode.
In conjunction with Fig. 2, the processing step of copper-zinc-tin-sulfur film solar cell of the present invention are as follows:
A. with laundry clothes and cleanser clean glass substrate 1 repeatedly twice, after cleaned with deionized water；Use alcohol and third respectively again
Ketone, which floods substrate, to carry out being ultrasonically treated each 30min twice, after cleaned with deionized water；Substrate is impregnated for 24 hours with potassium bichromate solution,
It is cleaned afterwards with deionized water, oxygen purging substrate surface and in 80 DEG C of dry 20min, cleaning of the completion to substrate.
B. cleaned glass substrate 1 is put into magnetron sputtering apparatus chamber, in glass substrate 1, sputtering sedimentation Mo film
As back electrode 2, sputtering pressure is that 1.2Pa and 0.3Pa sputters 15min and 50min respectively, and loading power is direct current, sputters function
Rate is 200W.
C. the first middle layer 301 is sputtered using zinc oxide target, with a thickness of 10-20nm, target loading power is radio frequency, sputtering
Power is 50W.
D. use zinc sulphide target and copper-tin alloy target substep sputtering sedimentation a layer thickness for the copper-zinc-tin-sulfur preformed layer of 800nm
302, loading power is radio frequency, sputtering power 50W.
E. the copper-zinc-tin-sulfur preformed layer 302 Step d sputtered carries out in-situ annealing, and 550 DEG C of annealing temperature, starting is warm
Degree is room temperature, and 25 DEG C/min of heating rate when being warming up to 260 DEG C, is passed through sulfur vapor and makes chamber temperature that air pressure be maintained to exist
3000Pa, the cooled to room temperature after reaching 550 DEG C of heat preservation 40min.
F. the second middle layer 4 is sputtered using zinc sulphide target, with a thickness of 10nm, target loading power is radio frequency, sputtering power
For 50W.
G. it uses chemical water domain method (CBD) buffer layer 5 in the second middle layer 4: cadmium sulfate 0.4617g being taken to add
10ml deionized water ultrasound 30min goes thiocarbamide 2.28g to add 20ml deionized water ultrasonic；350ml is added in sample obtained in e
Deionized water is heated to 80 DEG C of holding 3min；The cadmium sulfate solution for taking ammonium hydroxide 30ml to cross with ultrasound is added where sample after mixing
Water in；Sample solution is added after taking 10ml hydrogen peroxide to mix with the thiourea solution after ultrasound.At 83 DEG C after the above process
Heat preservation 12 minutes, takes out sample afterwards, dry in drying box,.
H. the sample after drying is put into magnetron sputtering chamber, 70nm is sequentially depositing using magnetron sputtering on buffer layer 5
I-ZnO film and 500nm ZnO:Al film as electrically conducting transparent Window layer 6, power 80W.
I. above-mentioned sample is taken out into the mask plate in ZnO:Al surface cover, electron beam evaporation deposition machine cavity room is put into, transparent
Silver-coated electrode is evaporated on conducting window layer 6 as top electrode 7.
Target purity used in above-mentioned all target as sputter is not less than 99.99%, and working gas purity is not less than
99.999%, chemical agent purity is not less than 99.98%, and chamber base vacuum is 5.0 × 10-4Pa, Ar gas flow is
30sccm, the distance of substrate to sputtering target material are 10cm.
Embodiment 1
It observes, the crystal grain distribution and crystalline quality of battery structure described in the present embodiment.
(a) it is followed successively by glass substrate, back electrode, the first middle layer, copper-zinc-tin-sulfur preformed layer from the bottom to top.In the standard of using
In the glass substrate of clean process, the Mo film of 1 μ m thick of sputtering sedimentation is as back electrode, respectively at air pressure 1.2Pa
15min is sputtered, 50min is sputtered at air pressure 0.3Pa, loading power is direct current, sputtering power 200W.Sputtering sedimentation later
One middle layer, the first middle layer are ZnO film, and with a thickness of 10 ~ 20nm, target loading power is radio frequency, sputtering power 50W.
Finally use zinc sulphide target and copper-tin alloy target substep sputtering sedimentation a layer thickness for the copper-zinc-tin-sulfur preformed layer of 800nm, load
Power supply is radio frequency, sputtering power 50W.The present embodiment sputters target purity used and is not less than 99.99%, and work other purity
It is not less than 99.999%, chamber base vacuum is 5.0 × 10-4Pa, Ar gas flow are 30sccm, substrate to sputtering target material
Distance is 10cm.
(b) the copper-zinc-tin-sulfur preformed layer of deposition is placed in tubular annealing furnace and is heat-treated under 560 DEG C of sulphur atmosphere
45min, be absorbed a layer copper-zinc-tin-sulfur film.The other conditions of heat treatment are as follows: sulphur source used, which is that single sulphur of solid-state is heated, to be produced
Raw sulfur vapor source, sulphur area are located in the middle part of tubular heater, and sulphur steam directly results from the graphite boat that preformed layer is placed.Heat
Processing heating rate is 25 DEG C/min, CZTS film natural cooling after heat treatment process.
Embodiment result: in conjunction with Fig. 3, electron scanning micrograph shows the crystal grain distribution after the first middle layer is added
Uniformly, average grain size 900nm, film is without obvious hole.In conjunction with Fig. 4, Raman test specimens, which have found, to be significantly located at
288cm-1,338cm-1And 373cm-1The CZTS standard scattering peak at place.In conjunction with Fig. 5, XRD test is also indicated that, is being added among first
(112) have been prepared after layer, (220), the CZTS film of the highly crystalline quality of (312) height preferred orientation.Raman and XRD is surveyed
Attempt the peak for being all displayed without oxide, it was demonstrated that oxygen is reacted completely.
Embodiment 2
Whether the thin-film device incident photon-to-electron conversion efficiency after observation the second middle layer of addition meets expection.
The second middle layer is sputtered on the basis of being added without the conventional suction layer of the first middle layer.It is sputtered using zinc sulphide target
The second middle layer is deposited, with a thickness of 10nm, target loading power is radio frequency, sputtering power 50W.The present embodiment sputters target used
Material purity is not less than 99.99%, other purity that work are not less than 99.999%, and chamber base vacuum is 5.0 × 10-4Pa, Ar
Gas flow is 30sccm, and the distance of substrate to sputtering target material is 10cm.
Blocked up ZnS can make the conduction band offset that needle pattern (spike) is generated between CZTS and ZnS, and increase series resistance,
Reduce short circuit current and external quantum efficiency.Using the sputtering thickness of 10nm, in the case where excess, CZTS and CdS is not isolated in ZnS,
Reduce face dislocation caused by high lattice mismatch between the two, reduces boundary defect and complex centre.
The absorbed layer for sputtering the second middle layer is successively sputtered into buffer layer CdS film again, with a thickness of 30 ~ 50nm；It is transparent
Conductive layer is the film that the ZnO:AL of the i-ZnO and 500 ~ 600nm of 50 ~ 80nm is sequentially depositing；Evaporate silver-coated electrode.
Embodiment result: in conjunction with the I-V curve comparison diagram of Fig. 6, embodiment 2 CZTS battery prepared and tradition CZTS battery
Show that the second middle layer behind efficiency, which is added, to be obviously improved, this proves the addition of ZnS, and CZTS and CdS is isolated really, reduces this
Face dislocation caused by high lattice mismatch between the two, generates surface passivation between CZTS and CdS, reduces the compound of surface,
Jsc is from 8.74mA/cm2Rise to 8.83mA/cm2, Voc rises to 508mV from 488mV, and Eff rises to 1.85% from 1.70%.
Embodiment 3
Whether the thin-film device incident photon-to-electron conversion efficiency after observation while the first middle layer of addition and the second middle layer meets.
On the soda-lime glass substrate using standard cleaning process, 1 μ m thick Mo back electrode sputtering pressure of sputtering is
1.2Pa and 0.3Pa sputters 15min and 50min respectively, and loading power is direct current, sputtering power 200W.Sputtering sedimentation later
One middle layer, the first middle layer are ZnO film, and 10 ~ 20nm of thickness, target loading power is radio frequency, sputtering power 50W.Most
Use zinc sulphide target and copper-tin alloy target substep sputtering sedimentation a layer thickness for the copper-zinc-tin-sulfur preformed layer of 800nm afterwards, load electricity
Source is radio frequency, sputtering power 50W.The present embodiment sputters target purity used and is not less than 99.99%, other purity that work are equal
Not less than 99.999%, chamber base vacuum is 5.0 × 10-4Pa, Ar gas flow be 30sccm, substrate to sputtering target material away from
From for 10cm.
The copper-zinc-tin-sulfur preformed layer of deposition is placed in tubular annealing furnace and is heat-treated under 560 DEG C of sulphur atmosphere
45min obtains CZTS film.The other conditions of heat treatment are as follows: sulphur source used is single sulphur of solid-state by thermogenetic sulfur vapor
Source, sulphur area are located in the middle part of tubular heater, and sulfur vapor directly results from the graphite boat that preformed layer is placed.Heat treatment heating speed
Rate is 25 DEG C/min, and absorbed layer CZTS film is made in CZTS film natural cooling after heat treatment process.
The second middle layer of sputtering sedimentation on the basis of above-mentioned absorbed layer.Second middle layer is sputtered using zinc sulphide target, it is thick
Degree is 10nm, and target loading power is radio frequency, sputtering power 50W.The present embodiment sputters target purity used and is not less than
99.99%, other purity that work are not less than 99.999%, and chamber base vacuum is 5.0 × 10-4Pa, Ar gas flow is
30sccm, the distance of substrate to sputtering target material are 10cm.
The absorbed layer for sputtering the second middle layer is successively sputtered into buffer layer CdS film again, with a thickness of 30 ~ 50nm；It is transparent
Conductive layer is the ZnO:Al THIN COMPOSITE of the i-ZnO and 500 ~ 600nm of 50 ~ 80nm.
Embodiment result: in conjunction with the I-V curve comparison diagram of Fig. 7, embodiment 3 CZTS battery prepared and tradition CZTS battery
Show that device made of the first middle layer and the second middle layer is added, both reduces MoS2Generation, reduce CZTS and Mo be anti-
Decomposition caused by answering, improves the quality of absorbed layer CZTS crystal generation, and improves caused by CZTS and CdS high lattice mismatch
The problems such as face dislocation.The defects of battery complex centre is effectively reduced, improves battery performance, Jsc is from 8.74mA/cm2Increase
Grow to 9.17mA/cm2, Voc rises to 584mV from 488mV, and Eff rises to 2.31% from 1.70%.
Above specific embodiment, has been further described the object, technical solutions and advantages of the present invention, institute
It should be understood that be not intended to restrict the invention the foregoing is merely specific implementation of the invention, it is all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of copper-zinc-tin-sulfur film solar cell, including sequentially connected glass substrate (1), back electrode (2), absorbed layer (3),
Second middle layer (4), buffer layer (5), electrically conducting transparent Window layer (6) and top electrode (7)；It is characterized by: among described second
Layer (4) is ZnS film.
2. solar cell as described in claim 1, it is characterised in that: absorbed layer (3) is copper-zinc-tin-sulfur film.
3. solar cell as described in claim 1, it is characterised in that: absorbed layer (3) is (112), and (220), (312) are highly selected
The copper-zinc-tin-sulfur film of excellent orientation.
4. the solar cell as described in claims 1 or 2 or 3, it is characterised in that: absorbed layer (3) by back electrode (2) according to
After the first middle layer of secondary deposition (301) and copper-zinc-tin-sulfur preformed layer (302), under 560 ± 10 DEG C of sulphur atmosphere in-situ annealing 45 ~
It is made after 60min, wherein the first middle layer (301) is ZnO film.
5. solar cell as claimed in claim 4, it is characterised in that: copper-zinc-tin-sulfur preformed layer (302) is with zinc sulphide target and copper
Tin alloy target is target, is obtained using magnetron sputtering stepped depositions, with a thickness of 700 ~ 800nm.
6. solar cell as claimed in claim 4, it is characterised in that: the first middle layer (301) is adopted using zinc oxide target as target
It deposits to obtain with magnetron sputtering, with a thickness of 10 ~ 20nm.
7. the solar cell as described in claim 1-4 is any, it is characterised in that: absorbed layer (3) is with a thickness of 900 ~ 1500nm.
8. a kind of preparation method of copper-zinc-tin-sulfur film solar cell characterized by comprising
(1) back electrode (2) Mo film, first are successively deposited on glass substrate (1) in same cavity using magnetron sputtering method
The step of middle layer (301) ZnO film, copper-zinc-tin-sulfur preformed layer (302)；
(2) after above-mentioned sample carries out in-situ annealing processing under sulphur atmosphere, the first middle layer (301) ZnO film and copper zinc
Tin sulphur preformed layer (302) reacts the step of generating absorbed layer (3) copper-zinc-tin-sulfur film；
(3) using magnetron sputtering method the step of depositing the second middle layer (4) ZnS film on absorbed layer (3)；
(4) using chemical water domain method buffer layer (5) CdS film on the second middle layer (4) the step of；
(5) i-ZnO film and ZnO:Al film are sequentially depositing as electrically conducting transparent window on buffer layer (5) using magnetron sputtering method
The step of mouth layer (6)；
(6) step of top electrode (7) is prepared on the ZnO:Al film of electrically conducting transparent Window layer (6) using electron beam evaporation deposition method
Suddenly.
9. method according to claim 8, which is characterized in that in step (1), when using Mo target material deposition back electrode (2), point
15min is not sputtered at air pressure 1.2Pa, 50min is sputtered at air pressure 0.3Pa, loading power is direct current, and sputtering power is
200W, deposition thickness are 1 μm.
10. method according to claim 8, which is characterized in that in step (1), deposit the first middle layer using zinc oxide target
(301) when, target loading power is radio frequency, and sputtering power 50W, deposition thickness is 10 ~ 20nm.
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