CN108155256B - Copper-zinc-tin-sulfur thin-film solar cell with absorption layer having element gradient and preparation method thereof - Google Patents
Copper-zinc-tin-sulfur thin-film solar cell with absorption layer having element gradient and preparation method thereof Download PDFInfo
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 59
- 239000010409 thin film Substances 0.000 title claims abstract description 44
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 37
- 238000004544 sputter deposition Methods 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000013077 target material Substances 0.000 claims description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000010949 copper Substances 0.000 abstract description 41
- 239000011701 zinc Substances 0.000 abstract description 40
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000005477 sputtering target Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 229910003310 Ni-Al Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
- H01L31/0327—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4 characterised by the doping material
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L31/065—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the graded gap type
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- 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
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Abstract
The invention discloses a suckerA copper zinc tin sulfide thin-film solar cell with a collected layer having element gradient and a preparation method thereof. The solar cell comprises a substrate, a back electrode layer, a CZTS absorption layer, a buffer layer, a transparent conductive oxide layer and a top electrode which are sequentially stacked, wherein the CZTS absorption layer has Cu and Zn element gradients in the thickness direction, and the chemical formula of the CZTS absorption layer is CuaZnbSnScWherein a is more than or equal to 1.6 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 1.35, and c is more than or equal to 3.8 and less than or equal to 4.5. In the process of depositing the copper-zinc-tin-sulfur of the absorption layer of the cell, the gradient distribution of Cu (Zn) and Zn elements is formed in the thickness direction of the absorption layer by changing the deposition amount of the Cu (Zn) elements at different depths, so that the copper-zinc-tin-sulfur thin film solar cell with a gradient band gap structure is constructed. The method can effectively increase the short-circuit current of the battery, and further improve the photoelectric conversion efficiency of the battery.
Description
Technical Field
The invention relates to a copper-zinc-tin-sulfur thin-film solar cell with an absorption layer having an element gradient and a preparation method thereof, belonging to the technical field of photovoltaics.
Background
The structure of the copper-zinc-tin-sulfur (CZTS) thin film solar cell is very similar to that of a copper-indium-gallium-selenium (CIGS) thin film cell, the difference between the copper-zinc-tin-sulfur (CZTS) thin film solar cell and the CIGS thin film cell is only In the material of an absorption layer, the CZTS cell replaces expensive rare metals In and Ga In the CIGS cell by cheap Zn and Sn elements, and the cost of the cell is greatly reduced. At present, the highest photoelectric conversion efficiency of a pure CZTS thin film battery is only 9.2% [ Kato t.et al, 27th European Photovoltaic Solar Energy conversion and inhibition, 2236(2012) ], and there is a great difference from the theoretical efficiency of 32.2% [ Guo q.et al, j.am.chem.soc., 131(2009), 11672], so that the optimization of the performance of the CZTS thin film Solar battery is one of the research hotspots in the Photovoltaic field in recent years.
Studies have shown that CZTS carrier lifetimes are low [ Dhakal t.p.et al, sol.energy, 100(2014), 23; repins i.et al, sol. energy mater. sol. cells, 101(2012), 154; barkhouse d.a.r.et., prog.photoblast: res.appl., 20(2012), 6]Battery short circuit current density (J)sc) Small (3-20 mA/cm)2)[Chen S.et al.，Adv.Mater.，25(2013)，1522]Is one of the main causes of the low battery efficiency. Research on CIGS thin film batteries has great reference significance for solving the above-mentioned problems of CZTS batteries [ conteras m.a. et al, Proceedings of the First World Conference on photo voltaic energy conversion, 68-75 (1994); gabor a.m.et al, sol.energy mate.sol.cells, 41(1996), 247; gorji n.e.et al, sol.energy, 86(2012), 920; powalla m.et al, sol.energy mater.sol.cells, 119(2013), 51]. In a CIGS thin film battery, a gradient band gap structure can be constructed In an absorption layer by controlling the gradient distribution of elements In and Ga In CIGS of the absorption layer, and the gradient band gap structure can effectively improve the service life of photogenerated carriers and the J of the batteryscAnd further improve the photoelectric conversion efficiency of the cell. In view of this, some international research institutes have conducted research work on CZTS thin-film solar cells with element gradients, and currently mainly focus on the following two aspects: 1) se is doped into CZTS, S is replaced by Se, and the influence of a gradient band gap structure generated by gradient distribution of Se and S on the performance of the CZTS battery is researched [ Woo K.et al., Sci.Rep., 3(2013), 3069; hironiwa d.et al, jpn.j.appl.phys, 53(2014), 071201](ii) a 2) Ge was doped in CZTS, Sn was replaced by Ge, and the influence of the gradient bandgap structure generated by the gradient distribution of Ge and Sn [ Kim I.et al, chem. Mater., 26(2014), 3957 ] was studied]. Although the research is advanced to a certain extent, the CZTS material system is more complicated due to the doping of Se and Ge, the controllability of the battery preparation is greatly reduced, and the application of the battery is restricted to a certain extent due to the toxicity of Se compared with S.
It has been shown that the change of the content of the metal element in CZTS can have an important effect on the band structure. Experimental results show that as the Cu content increases, the CZTS bandgap gradually decreases [ Tanaka k.et al, sol.energymater.sol.cells, 95(2011), 838; inamdar a.i.et al, sol. energy, 91(2013), 196; sugimoto H.et al, IEEE Photoviral specialties Conference, 2(2013), 3208 ]; the calculations show that in the Zn-rich region in the phase diagram, the CZTS band gap gradually decreases with increasing Zn content [ Xiao w.et al, sol. energy, 116(2015), 125 ]. In view of the experimental and theoretical results, the CZTS thin-film solar cell with the gradient band gap structure is prepared by controlling the gradient distribution of Cu and Zn elements in the CZTS absorption layer, so that the photoelectric conversion performance of the cell is improved, and the feasibility is high. However, related studies are still rarely reported at present.
Disclosure of Invention
The invention aims to provide a copper-zinc-tin-sulfur thin film solar cell with an absorption layer with element gradient, which adopts a CZTS thin film with Cu and Zn element gradient as an absorption layer material of the cell, thereby improving the J of the cellscAnd photoelectric efficiency.
The invention also aims to provide a preparation method of the copper-zinc-tin-sulfur thin film solar cell with the element gradient.
In order to achieve the purpose, the invention adopts the following technical scheme:
the copper-zinc-tin-sulfur thin-film solar cell with the absorption layer having the element gradient comprises a substrate, a back electrode layer, a CZTS absorption layer, a buffer layer, a transparent conductive oxide layer and a top electrode which are sequentially stacked, wherein the CZTS absorption layer has Cu and Zn element gradients in the thickness direction, and the chemical formula of the CZTS absorption layer is CuaZnbSnScWherein a is more than or equal to 1.6 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 1.35, and c is more than or equal to 3.8 and less than or equal to 4.5.
In the copper-zinc-tin-sulfur thin film solar cell with the absorption layer provided by the invention having the element gradient, Cu is used as the absorption layeraZnbSnScThe absorbent layers a, b and c are set within the above range mainly for the following reasons: (1) the CZTS thin film battery with the composition interval in the Cu-poor Zn-rich region in the phase diagram has high photoelectric efficiency, so that a and b of the CZTS are arranged in the Cu-poor Zn-rich composition range, namely the upper limit of a and the lower limit of b are limited; (2) excessive depletion of film composition by Cu-Zn-rich can lead to ZnS and SnxSyAnd the formation of harmful impure phases, therefore, the lower limit of a and the upper limit of b in CZTS must be limited to avoid the formation of harmful impure phases; (3) after the ranges of a and b are defined, the range of c can be determined, but c cannot be less than 3.8, and when c is less than 3.8, the absorption layerAnd thus, the performance of the battery is deteriorated due to the occurrence of anion vacancies therein, and studies have shown that the film is slightly rich in sulfur when the vulcanization of the absorption layer is complete, and thus, the range of c is defined as 3.8. ltoreq. c.ltoreq.4.5.
A preparation method of the copper-zinc-tin-sulfur thin-film solar cell with the absorption layer having the element gradient comprises the following steps:
(1) forming a back electrode layer on a substrate;
(2) forming a precursor film on the back electrode layer, and forming gradient distribution of Cu and Zn elements in the thickness direction of the absorption layer by changing the deposition amount of the Cu and Zn elements at different depths;
(3) carrying out vulcanization heat treatment on the precursor film to obtain a crystallized CZTS absorption layer with Cu and Zn element gradients;
(4) forming a buffer layer on the CZTS absorption layer;
(5) forming a transparent conductive oxide layer on the buffer layer;
(6) and forming a top electrode on the transparent conductive oxide layer to obtain the CZTS thin-film solar cell.
In the preparation process of the CZTS precursor film, the required Cu (Cu) (Zn) element gradient can be formed in the thickness direction of the absorbing layer by controlling the deposition amount of Cu (Zn) elements at different depths, and meanwhile, the preparation method of the precursor film is selected from one or a combination of a plurality of sputtering methods, evaporation methods, pulse laser deposition methods, electroplating methods, sol-gel methods and nanocrystalline coating methods. For example, a CZTS precursor film with Cu and Zn element gradients can be obtained by gradually changing the sputtering power of a Cu-containing target (a Zn-containing target) in the process of preparing the CZTS precursor film by magnetron sputtering, gradually changing the evaporation rate of a Cu source (a Zn source) in the process of preparing the CZTS precursor film by evaporation, sequentially spin-coating various colloids with different Cu: Zn ratios in the process of preparing the CZTS precursor film by a sol-gel method, and the like.
The invention has the advantages that:
according to the invention, the CZTS thin-film solar cell with a gradient band gap structure is prepared by controlling the gradient distribution of the elements Cu and Zn in the absorption layer of the CZTS thin-film solar cell, so that the CZTS thin film is improvedJ of Membrane cellscAnd photoelectric conversion efficiency.
Drawings
Fig. 1 is a structural diagram of a copper zinc tin sulfide thin film solar cell with an absorption layer having an element gradient according to the present invention.
FIG. 2 is a process flow diagram of the present invention for preparing a CZTS thin film solar cell with an absorption layer having an element gradient.
Fig. 3 is an element distribution diagram of the absorption layer CZTS of the copper zinc tin sulfide thin-film solar cell with an element gradient in the absorption layer obtained in example 1 of the present invention.
Fig. 4 is an element distribution diagram of the absorption layer CZTS of the copper zinc tin sulfide thin-film solar cell with an absorption layer having an element gradient obtained in example 2 of the present invention.
Detailed Description
The invention is further illustrated below with reference to the figures and examples, but the embodiments of the invention are not limited thereto.
As shown in fig. 1, the Cu-Zn-sn-sulfide thin film solar cell having an absorption layer with an element gradient according to the present invention includes a substrate 100, a back electrode layer 110, a CZTS absorption layer 120 having an element gradient of Cu and Zn, a buffer layer 130, a transparent conductive oxide layer 140, and a top electrode 150, which are sequentially stacked.
As shown in fig. 2, the method for preparing a copper zinc tin sulfide thin-film solar cell with an absorption layer having an element gradient sequentially comprises the following steps:
(1) forming a back electrode layer on a substrate;
(2) forming a precursor film on the back electrode layer, and forming gradient distribution of Cu and Zn elements in the thickness direction of the absorption layer by changing the deposition amount of the Cu and Zn elements at different depths;
(3) carrying out vulcanization heat treatment on the precursor film to obtain a crystallized CZTS absorption layer with Cu and Zn element gradients;
(4) forming a buffer layer on the CZTS absorption layer;
(5) forming a transparent conductive oxide layer on the buffer layer;
(6) and forming a top electrode on the transparent conductive oxide layer to obtain the CZTS thin-film solar cell.
According to the invention, the gradient distribution of elements Cu and Zn in the absorption layer of the CZTS thin-film solar cell is controlled to prepare the CZTS thin-film solar cell with a gradient band gap structure, so that the J of the CZTS thin-film solar cell is improvedscAnd photoelectric conversion efficiency.
Example 1
The copper-zinc-tin-sulfur thin film solar cell with the absorption layer having the element gradient comprises a substrate, a back electrode layer, a CZTS absorption layer with Cu and Zn element gradients, a buffer layer, a transparent conductive oxide layer and a top electrode which are sequentially stacked, wherein the chemical formula of the absorption layer can be expressed as Cu1.72Zn1.21SnS4.44. The preparation process comprises the following steps:
step 1: preparation of Mo back electrode layer
Mo is used as a sputtering target material, and a Mo back electrode layer with the thickness of 1 mu m is deposited on the cleaned soda-lime glass substrate by adopting a single-target sputtering mode.
Step 2: precursor film preparation
By magnetron sputtering technique with Cu2S, ZnS and SnS2Preparing a copper-zinc-tin-sulfur precursor film for sputtering a target material by three-target co-sputtering, wherein the sputtering gas is Ar gas, the sputtering pressure is 0.25Pa, and ZnS and SnS are adopted in the sputtering process2The sputtering power of the target material is kept unchanged, and is respectively 70W, 23W and Cu2The sputtering power of the S target is gradually increased from 63W to 72W, the sputtering power is increased by 1W every 2min, and the sputtering time is 20min in total.
And step 3: precursor film heat treatment
And carrying out vulcanization heat treatment on the copper-zinc-tin-sulfur precursor film. Putting the precursor film in a tube furnace, simultaneously loading a quartz boat containing S powder into the quartz tube, respectively heating the film and the quartz boat with N2As a sulfidation carrier gas. The heating temperature of the quartz boat is 125 ℃, and the film is heated to 550 ℃ and is kept for 5 min. After the heat treatment is finished, naturally cooling to room temperature, wherein N is generated in the cooling process2The flow is not changed, the airflow is stable, and the crystallized copper-zinc-tin-sulfur absorption layer with Cu and Zn element gradients is finally prepared. The film composition profile is shown in fig. 3, from which it can be seen that,the thickness of the CZTS absorption layer prepared by the embodiment is 1 μm, the film has obvious Cu and Zn element gradients in the thickness direction, the bottom of the film is richer in Cu and leaner in Zn than the top of the film, and the Sn element has no gradient basically in the thickness direction of the film.
And 4, step 4: buffer layer preparation
And (3) adopting a magnetron sputtering technology, taking CdS and ZnO as sputtering target materials, and sequentially preparing CdS and ZnO buffer layers on the CZTS absorption layer after heat treatment, wherein the thickness of the CdS layer is 50nm, and the thickness of the ZnO layer is 80 nm.
And 5: preparation of zinc-aluminum oxide transparent conductive oxide layer
Preparing a zinc-aluminum oxide transparent conductive oxide layer by adopting a magnetron sputtering technology and taking zinc-aluminum oxide as a sputtering target material, wherein Al in the target material2O33 at% of doping, and the thickness of the zinc-aluminum oxide transparent conductive oxide layer is 0.8 μm.
Step 6: top electrode preparation
And preparing a Ni-Al top electrode on the transparent conductive oxide layer by adopting magnetron sputtering. In the sputtering process, Ni and Al are used as sputtering targets, a Ni layer is deposited first, then an Al layer is deposited, and in the finally prepared Ni-Al top electrode, the thickness of the Ni layer is 0.05 mu m, and the thickness of the Al layer is 1.95 mu m.
According to the copper-zinc-tin-sulfur thin film solar cell prepared by the process, the short-circuit current of the cell is 24.4mA/cm2The cell efficiency was 5.78%.
Example 2
The copper-zinc-tin-sulfur thin film solar cell with the absorption layer having the element gradient comprises a substrate, a back electrode layer, a CZTS absorption layer with Cu and Zn element gradients, a buffer layer, a transparent conductive oxide layer and a top electrode which are sequentially stacked, wherein the chemical formula of the absorption layer can be expressed as Cu1.68Zn1.12SnS4.28. The preparation process comprises the following steps:
step 1: preparation of Mo back electrode layer
Mo is used as a sputtering target material, and a Mo back electrode layer with the thickness of 1 mu m is deposited on the cleaned soda-lime glass substrate by adopting a single-target sputtering mode.
Step 2: precursor film preparation
Adopting magnetron sputtering techniqueSurgery with Cu2S, ZnS and SnS2Preparing a copper-zinc-tin-sulfur precursor film for sputtering a target material by three-target co-sputtering, wherein the sputtering gas is Ar gas, the sputtering pressure is 0.25Pa, and Cu is adopted in the sputtering process2S and SnS2The sputtering power of the target was kept constant at 67W and 23W, respectively, and the sputtering power of the ZnS target was gradually increased from 64W to 78W, 2W every 2.5min, and the sputtering time was 20min in total.
And step 3: precursor film heat treatment
And carrying out vulcanization heat treatment on the copper-zinc-tin-sulfur precursor film. Putting the precursor film in a tube furnace, simultaneously loading a quartz boat containing S powder into the quartz tube, respectively heating the film and the quartz boat with N2As a sulfidation carrier gas. The heating temperature of the quartz boat is 125 ℃, and the film is heated to 550 ℃ and is kept for 5 min. After the heat treatment is finished, naturally cooling to room temperature, wherein N is generated in the cooling process2The flow is not changed, the airflow is stable, and the crystallized copper-zinc-tin-sulfur absorption layer with Cu and Zn element gradients is finally prepared. The composition distribution curve of the film is shown in fig. 4, and it can be seen from the graph that the thickness of the CZTS absorbing layer prepared in this example is 1 μm, the film has a significant gradient of Cu and Zn elements in the thickness direction, the Zn element content gradually decreases from the top to the bottom of the film, the Cu element content gradually increases, and the Cu element content basically changes linearly, while the Sn element has no gradient in the thickness direction of the film.
And 4, step 4: buffer layer preparation
And (3) adopting a magnetron sputtering technology, taking CdS and ZnO as sputtering target materials, and sequentially preparing CdS and ZnO buffer layers on the CZTS absorption layer after heat treatment, wherein the thickness of the CdS layer is 50nm, and the thickness of the ZnO layer is 80 nm.
And 5: preparation of zinc-aluminum oxide transparent conductive oxide layer
Preparing a zinc-aluminum oxide transparent conductive oxide layer by adopting a magnetron sputtering technology and taking zinc-aluminum oxide as a sputtering target material, wherein Al in the target material2O33 at% of doping, and the thickness of the zinc-aluminum oxide transparent conductive oxide layer is 0.8 μm.
Step 6: top electrode preparation
And preparing a Ni-Al top electrode on the transparent conductive oxide layer by adopting magnetron sputtering. In the sputtering process, Ni and Al are used as sputtering targets, a Ni layer is deposited first, then an Al layer is deposited, and in the finally prepared Ni-Al top electrode, the thickness of the Ni layer is 0.05 mu m, and the thickness of the Al layer is 1.95 mu m.
According to the copper-zinc-tin-sulfur thin film solar cell prepared by the process, the short-circuit current of the cell is 25.3mA/cm2The cell efficiency was 5.92%.
Claims (2)
1. The copper-zinc-tin-sulfur thin-film solar cell with the absorption layer having the element gradient is characterized by comprising a substrate, a back electrode layer, a CZTS absorption layer, a buffer layer, a transparent conductive oxide layer and a top electrode which are sequentially stacked, wherein the CZTS absorption layer has the element gradient of Cu and Zn in the thickness direction, and the chemical formula of the CZTS absorption layer is CuaZnbSnScWherein a is more than or equal to 1.6 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 1.35, and c is more than or equal to 3.8 and less than or equal to 4.5; the preparation method of the copper-zinc-tin-sulfur thin film solar cell comprises the following steps:
(1) forming a back electrode layer on a substrate;
(2) magnetron sputtering technology is adopted on the back electrode layer, and Cu is used2S, ZnS and SnS2For sputtering a target material, preparing a CZTS precursor film by three-target co-sputtering, and forming gradient distribution of Cu and Zn elements in the thickness direction of the absorption layer by changing the deposition amount of the Cu and Zn elements at different depths;
(3) carrying out vulcanization heat treatment on the precursor film to obtain a crystallized CZTS absorption layer with Cu and Zn element gradients;
(4) forming a buffer layer on the CZTS absorption layer;
(5) forming a transparent conductive oxide layer on the buffer layer;
(6) and forming a top electrode on the transparent conductive oxide layer to obtain the CZTS thin-film solar cell.
2. The CZTS thin-film solar cell with the absorption layer having the element gradient according to claim 1, wherein in the step (2), the sputtering gas is Ar gas, and Cu is used in the sputtering process2S and SnS2The sputtering power of the target material is kept unchanged, the sputtering power of the ZnS target material is gradually increased,or maintaining ZnS and SnS during sputtering2Sputtering power of the target material is not changed, Cu2The sputtering power of the S target gradually increases.
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