CN111354814B - Double-junction laminated solar cell and preparation method thereof - Google Patents
Double-junction laminated solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 33
- 230000031700 light absorption Effects 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 39
- 238000002161 passivation Methods 0.000 claims description 23
- 238000000137 annealing Methods 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000010549 co-Evaporation Methods 0.000 claims description 6
- 238000000231 atomic layer deposition Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims 2
- MUYUEDVRJJRNOO-UHFFFAOYSA-N selanylidene(sulfanylidene)antimony Chemical compound S=[Sb]=[Se] MUYUEDVRJJRNOO-UHFFFAOYSA-N 0.000 abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 239000010703 silicon Substances 0.000 abstract description 18
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
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- 239000010408 film Substances 0.000 description 17
- 239000011787 zinc oxide Substances 0.000 description 14
- 238000002207 thermal evaporation Methods 0.000 description 10
- 238000001755 magnetron sputter deposition Methods 0.000 description 7
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007888 film coating Substances 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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Abstract
The invention relates to a double-junction laminated solar cell and a preparation method thereof, wherein the cell comprises a crystal silicon cell and an antimony selenide sulfide cell which are arranged in a laminated manner, wherein the antimony selenide sulfide cell is provided with an antimony selenide sulfide light absorption layer and a buffer layer; sb used for preparing the antimony selenide sulfide light-absorbing layer 2 (Se x S 1–x ) 3 In the formula, x is more than or equal to 0 and less than or equal to 0.5; the buffer layer is made of Zn (O, S, OH) X One or more of CdS, ZnO or (Zn, Mg) O. The laminated cell can improve the efficient and sufficient absorption of solar spectrum and realize Sb 2 (Se x S 1‑x ) 3 The thin film absorbs light with the wavelength of 300-700nm, and the crystalline silicon absorbs light with the wavelength of 700-1200nm, so that the laminated cell has a wider spectral response value.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a novel double-junction laminated cell and a preparation method thereof.
Background
The crystalline silicon solar cell technology is the most mature photovoltaic power generation technology at present, and due to the advantages of the crystalline silicon solar cell technology in the aspects of comprehensive cost and conversion efficiency, other types of solar cells such as CIGS, OPV, gallium arsenide and other thin film cells are difficult to replace crystalline silicon cells in a short time, the performance of the crystalline silicon cells is continuously improved, and the technology is continuously optimized, so that the method has important significance in reducing the cost. However, the conventional crystalline silicon cell has some limitations in material and process, and the forbidden band width of crystalline silicon is 1.12eV and is an indirect band gap; in addition, the conventional crystalline silicon battery needs high temperature in the diffusion and sintering process, minority carrier recombination is aggravated in the high temperature processes, and the influence of auger recombination is more obvious in the thermal diffusion process, so that the open-circuit voltage limit value of the crystalline silicon battery is about 750mV, the theoretical limit efficiency of the crystalline silicon battery is about 29%, and the efficiency of the crystalline silicon battery is difficult to greatly improve. Therefore, a new heterojunction cell with upper and lower double absorption layers formed by materials with excellent optical and electrical properties and silicon is found, and the heterojunction cell has important significance for improving the spectral absorption rate and further improving the efficiency of the solar cell.
Antimony selenide sulfide Sb 2 (Se x S 1-x ) 3 The material is a V-VI family direct band gap semiconductor material with stable properties, and the earth crust is rich in content, safe and nontoxic. And has high light absorption coefficient, moderate band gap width and easy regulation (1.1-1.8eV), so the material is regarded as one of the most promising solar cell materials. The forbidden band widths of antimony selenide sulfide and crystalline silicon can be well complemented, the absorption spectrum of the solar cell is widened, and the double-junction laminated cell is very suitable for being manufactured; however, no research report about antimony selenide sulfide and a crystalline silicon tandem cell exists at present, and the research on the specific structure and the preparation method of the double-junction tandem cell is very little.
Disclosure of Invention
The invention aims to provide a double-junction laminated solar cell, which comprises a crystalline silicon cell and an antimony selenide sulfide cell which are arranged in a laminated manner, wherein the antimony selenide sulfide cell is internally provided with an antimony selenide sulfide light absorption layer and a buffer layer;
preparation of said Sb 2 (Se x S 1–x ) 3 Material Sb of light-absorbing layer 2 (Se x S 1–x ) 3 In the formula, x is more than or equal to 0 and less than or equal to 0.5;
the buffer layer is made of Zn (O, S, OH) X One or more of CdS, ZnO or (Zn, Mg) O.
For Sb 2 (Se x S 1–x ) 3 And in addition, when x is more than or equal to 0 and less than or equal to 0.5, and the buffer layer prepared by the material is arranged on the surface of the light absorption layer, the antimony selenide sulfide and the crystalline silicon battery can play a better matching role, and the overall efficiency of the battery is improved.
In the invention, (Zn, Mg) O is magnesium-doped zinc oxide, and in the preparation process, Zn and Mg are jointly used as film coating materials to carry out film coating by adopting a conventional process. The relative amounts of Zn and Mg used herein are not particularly limited as long as a (Zn, Mg) O film usable in the art can be formed.
Zn(O,S,OH) X The zinc oxide is hydrogen and sulfur doped zinc oxide, and Zn, S and H are jointly used as film coating materials to carry out film coating by adopting a conventional process in the preparation process. Here, the relative amounts of Zn, S and H are not particularly limited as long as Zn (O, S, OH) usable in the art can be formed X And (5) film forming.
Preferably, the buffer layer includes a first buffer layer and a second buffer layer;
the first buffer layer is attached to the surface of the antimony selenide sulfide light absorption layer, and the second buffer layer is attached to the first buffer layer far away from Sb 2 (Se x S 1–x )3 surface of light absorbing layer. Compared with a single-layer buffer layer, the double-buffer layer is arranged, so that the transmission and collection efficiency of carriers can be effectively improved.
Further preferably, the first buffer layer material is Zn (O, S, OH) X Or CdS, and the material of the second buffer layer is ZnO or (Zn, Mg) O. Zn (O, S, OH) X Or the band gap of CdS is lower than that of ZnO or (Zn, Mg) O, so that the CdS is more suitable for being used as the first buffer layer.
Preferably, the material of the first buffer layer is Zn (O, S, OH) X The material of the second buffer layer is (Zn, Mg) O; or the first buffer layer is CdS, and the second buffer layer is ZnO. The prepared battery has better performance by adopting the matching as the first buffer layer or the second buffer layer.
As a further preferable mode, the light absorption layer material is Sb 2 (Se 0.1 S 0.9 ) 3 The first buffer layer is CdS; the second buffer layer is ZnO.
Or the light absorption layer is made of Sb 2 (Se 0.25 S 0.75 ) 3 The first buffer layer is Zn (O, S, OH) X (ii) a The second buffer layer is (Zn, Mg) O.
Preferably, said Sb is 2 (Se x S 1–x ) 3 The thickness of the light absorption layer is 200-1000 nm;
preferably, the thickness of the first buffer layer is 10-80 nm;
preferably, the thickness of the second buffer layer is 50 to 100 nm.
Preferably, the antimony selenide sulfide light absorption layer is located between the crystalline silicon battery and the first buffer layer, and the antimony selenide sulfide light absorption layer is attached to the surface of the crystalline silicon battery.
Preferably, the antimony selenide sulfide cell further comprises a TCO transparent conducting layer and an antireflection layer; the first surface of the TCO transparent conducting layer is attached to the surface, far away from the first buffer layer, of the second buffer layer, and the antireflection layer is attached to the second surface of the TCO transparent conducting layer.
Preferably, the material of the TCO transparent conductive layer is one of ITO, FTO, IZO, AZO, GZO, or graphene thin film.
Preferably, the antireflection film is MgF 2 Or Si 3 N 4 。
Preferably, the thickness of the TCO transparent conductive layer is 50-200 nm.
Preferably, the thickness of the antireflection film is 50 to 100 nm.
As a preferred scheme, the antimony selenide sulfide battery comprises an antimony selenide sulfide light absorption layer, a first buffer layer, a second buffer layer, a TCO layer and an antireflection film;
the first buffer layer is attached to the first surface of the antimony sulfide light absorption layer, and the second buffer layer is attached to the first buffer layer far away from Sb 2 (Se x S 1–x )3, the first surface of the TCO transparent conductive layer is attached to the surface, away from the first buffer layer, of the second buffer layer, the antireflection layer is attached to the second surface of the TCO transparent conductive layer, and the first surface and the second surface of the TCO transparent conductive layer are oppositely arranged;
the Sb 2 (Se x S 1–x ) 3 The thickness of the light absorption layer is 200-1000nm, the thickness of the first buffer layer is 10-80nm, the thickness of the second buffer layer is 50-100nm, the thickness of the TCO transparent conductive layer is 50-200nm, and the thickness of the antireflection film is 50-100 nm; the thickness of the second buffer layer is 25-40 nm greater than that of the first buffer layer.
The Sb is 2 (Se x S 1–x ) 3 X is more than or equal to 0 and less than or equal to 0.5 in the light absorption layer material, and the first buffer layer material is Zn (O, S, OH) X Or CdS, the second buffer layer is made of ZnO or (Zn, Mg) O, the TCO transparent conductive layer is made of one of ITO, FTO, IZO, AZO, GZO or graphene films, and the antireflection film is MgF 2 Or Si 3 N 4 。
The antimony selenide sulfur battery with the structure is compounded with the crystalline silicon battery, so that the conversion efficiency of the battery can be effectively improved.
Preferably, the crystalline silicon cell comprises Si arranged in a stacked manner in sequence 3 N 4 Passivation layer, Al 2 O 3 Passivation layer, p/n type crystalline silicon substrate and SiO 2 Layer n + poly-Si layer, ITO layer and MoO x A layer; the MoO x The layer is attached to the surface of the antimony selenide sulfur light absorption layer far away from the first buffer layer.
Preferably, the ITO layer is made of Sn-doped In 2 O 3 ；
Preferably, the MoO x X in the layer is 3;
preferably, said Si is 3 N 4 The thickness of the passivation layer is 20-100 nm;
preferably, the Al is 2 O 3 The thickness of the passivation layer is 20-100 nm;
preferably, the thickness of the p/n type crystalline silicon substrate is 150-;
preferably, the SiO 2 The thickness of the layer is 1.0-2.0 nm;
preferably, said n + The deposition thickness of the poly-Si layer is 100-300 nm;
preferably, the thickness of the ITO layer is 20-100 nm;
preferably, the MoO x The thickness of the layer is 50-300 nm.
The laminated layer of the invention also comprises Si 3 N 4 A back electrode of a passivation layer and a positive electrode at the anti-reflection film.
Another object of the invention is to protect the process for the preparation of the material according to the invention, comprising the following steps:
by double source vacuum co-evaporation with Sb 2 S 3 Powder and Sb 2 Se 3 Forming the Sb on the surface of a substrate as a raw material 2 (Se x S 1–x ) 3 A light absorbing layer;
chemical water bath deposition method is adopted to deposit on the Sb 2 (Se x S 1–x ) 3 Forming the first buffer layer on the light absorption layer;
and forming the second buffer layer on the first buffer layer by adopting an atomic layer deposition method.
Preferably, the Sb is formed by adopting a double-source vacuum co-evaporation method 2 (Se x S 1–x ) 3 In the process of the light absorption layer, the vacuum degree is set to 10 -3 -10 -6 Pa, the evaporation temperature is 300-700 ℃, and the substrate surface temperature is 200-400 ℃.
Preference is given toOf (1) forming said Sb 2 (Se x S 1–x ) 3 Annealing the light absorbing layer at the temperature of 300-500 ℃ for 0.5-2.0 h;
and/or, after the second buffer layer is formed, annealing is carried out for 0.5-2.0h under the condition of the temperature of 100-300 ℃.
Preferably, a TCO transparent conductive layer is prepared on the surface of the second buffer layer by a magnetron sputtering method, and an antireflection layer is prepared on the surface of the TCO transparent conductive layer by a thermal evaporation method.
Preferably, the preparation method further comprises the preparation of the crystalline silicon battery, and comprises the following steps:
1) preparing SiO on the front side of a silicon wafer by adopting a high-temperature thermal oxidation method 2 A layer; then adopting Low Pressure Chemical Vapor Deposition (LPCVD) to form SiO 2 Surface deposition of a layer n + A poly-Si layer, performing high temperature annealing;
2) at said n + performing magnetron sputtering on the surface of the poly-Si layer to form an ITO transparent conductive film; sequentially preparing Al on the back of the silicon wafer by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method 2 O 3 And Si 3 N 4 A passivation layer;
3) preparing MoO on the surface of the ITO by adopting a thermal evaporation method x A layer.
Preferably, the temperature of the high-temperature thermal oxygen oxidation in the step 1) is 200-500 ℃.
Preferably, the annealing temperature in the step 1) is 800-1150 ℃.
As a preferred scheme, the preparation method of the invention comprises the following steps:
1) preparing SiO on the front side of a silicon wafer by adopting a high-temperature thermal oxidation method 2 A layer; then adopting Low Pressure Chemical Vapor Deposition (LPCVD) to form SiO 2 Surface deposition of a layer n + A poly-Si layer, performing high-temperature annealing;
2) at said n + performing magnetron sputtering on the surface of the poly-Si layer to form an ITO transparent conductive film; sequentially preparing Al on the back of the silicon wafer by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method 2 O 3 And Si 3 N 4 A passivation layer;
3) MoO is prepared on the ITO layer on the front side of the silicon wafer by adopting a thermal evaporation method x A layer.
4) Vacuum degree 10 of vacuum thermal evaporation equipment -3 -10 -6 Pa, selecting Sb 2 S 3 Powder and Sb 2 Se 3 Powder is used as an evaporation source, the evaporation temperature is 300-700 ℃, the substrate surface temperature is 200-400 ℃, and the MoO is subjected to a codeposition method x Surface preparation of Sb 2 (Se x S 1–x ) 3 A light absorbing layer; after the deposition is finished, annealing;
5) by chemical water bath deposition method, the Sb is treated 2 (Se x S 1–x ) 3 Preparing a first buffer layer on the surface of the light absorption layer;
6) and preparing a second buffer layer on the surface of the first buffer layer by adopting an atomic layer deposition method, and annealing to obtain the buffer layer.
The invention has the following beneficial effects:
1) the laminated cell can improve the efficient and sufficient absorption of the solar spectrum, and realizes that the antimony selenide sulfide film absorbs light with the wavelength of 300-700nm, and the crystalline silicon absorbs light with the wavelength of 700-1200nm, so that the laminated cell has a wider spectral response value;
2) the preparation process of the laminated cell can fully utilize the mature process and equipment of the existing crystalline silicon and thin film cell, does not need to replace or increase production equipment, reduces the capital investment of products, and has rich raw materials of antimony sulfide and antimony selenide and lower cell production cost.
Drawings
Fig. 1 is a schematic view of the structure of the laminated cell of the present invention.
In the figure: 1. p/n type crystal silicon base, 2, SiO 2 Layer, 3, n + poly-Si layer, 4, Al 2 O 3 Passivation layer, 5, Si 3 N 4 A passivation layer; 6. back electrode, 7, ITO layer, 8, MoO x Layer, 9, Sb 2 (Se x S 1–x ) 3 A light absorption layer 10, a first buffer layer 11, a second buffer layer 12, and a TCO transparent conductive layer; 13. an anti-reflective layer; 14. and a positive electrode.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment relates to Sb 2 (Se 0.1 S 0.9 ) 3 The structure of the/Si double-junction laminated cell comprises from bottom to top: ag electrode, Si 3 N 4 Passivation layer, Al 2 O 3 Passivation layer, p-type crystalline silicon substrate and SiO 2 Layer n + poly-Si layer, ITO layer, MoO x Layer, Sb 2 (Se 0.1 S 0.9 ) 3 Light absorption layer, first buffer layer CdS, second buffer layer ZnO, transparent conducting layer AZO and antireflection layer MgF 2 And an Au electrode;
said Si 3 N 4 And Al 2 O 3 The thickness of the passivation layer is 50 nm; the thickness of the p-type crystalline silicon substrate is 180 mu m, and the SiO is 2 The layer thickness was 1.5 nm; n is + The deposition thickness of the poly-Si layer is 150nm, and the thickness of the ITO layer is 20 nm; the MoO x Layer thickness of 150nm, said Sb 2 (Se 0.1 S 0.9 ) 3 The band gap of the light absorption layer material is 1.72eV, and the thickness of the light absorption layer material is 500 nm; the thickness of the first buffer layer CdS is 20 nm; the thickness of the second buffer layer ZnO is 50 nm; the thickness of the AZO layer is 100 nm; the antireflection layer is MgF 2 Is 50 nm; the thickness of the Ag electrode is 800nm, and the thickness of the Au electrode is 300 nm. The structure schematic diagram is shown in figure 1;
the embodiment also relates to a preparation method of the battery, which comprises the following steps:
1) cleaning p-type silicon wafer, and preparing SiO by thermal oxidation of the front surface of the silicon wafer at 500 DEG C 2 A layer; then adopting a low-pressure chemical vapor deposition method to continuously deposit n + Annealing the poly-Si layer at 900 ℃ for half an hour; at said n + performing magnetron sputtering on the surface of the poly-Si layer to form a layer of ITO transparent conductive film;
2) sequentially preparing Al on the back of the silicon wafer by adopting a PECVD method 2 O 3 And Si 3 N 4 A passivation layer;
3) MoO is prepared on the surface of ITO by adopting a thermal evaporation method x A layer;
4) in the MoO x Preparing Sb on the surface of the layer by adopting a double-source vacuum co-evaporation method 2 (Se x S 1–x ) 3 The light absorption layer comprises the following specific steps: vacuum degree of 1 × 10 by using vacuum thermal evaporation equipment -6 Pa, the evaporation source is Sb 2 S 3 Powder and Sb 2 Se 3 Powder, wherein the evaporation temperature is 500 ℃, and the substrate surface temperature during deposition is 300 ℃; after the deposition is finished, continuously annealing for 2.0h at 300 ℃ to improve the performance of the film;
5) in Sb 2 (Se x S 1–x ) 3 Preparing a first buffer layer CdS on the light absorption layer by adopting a chemical water bath deposition method, preparing a second buffer layer ZnO by adopting an atomic layer deposition method, and annealing at 200 ℃ for 1.0 h;
6) preparing an AZO transparent conductive layer on the surface of the second buffer layer ZnO by adopting a magnetron sputtering method, and sequentially preparing an antireflection layer MgF by adopting a thermal evaporation method 2 A front electrode Au and a back electrode Ag.
Example 2
The embodiment relates to Sb 2 (Se 0.25 S 0.75 ) 3 The structure of the/Si double-junction laminated cell comprises from bottom to top: al electrode, Si 3 N 4 Passivation layer, Al 2 O 3 Passivation layer, n-type crystalline silicon substrate and SiO 2 Layer n + poly-Si layer, ITO layer, MoO x Layer, Sb 2 (Se 0.25 S 0.75 ) 3 Light absorbing layer, first buffer layer Zn (O, S, OH) X A second buffer layer (Zn, Mg) O, a transparent conductive layer FTO and an antireflection layer Si 3 N 4 And Ag/Cu electrodes.
Said Si 3 N 4 And Al 2 O 3 The thickness of the passivation layer is 20nm, the thickness of the n-type crystalline silicon substrate is 160 mu m, and the SiO is 2 The layer thickness is 1.7nm, n + The deposition thickness of the poly-Si layer is 200nm, the thickness of the ITO layer is 35nm, and the MoO is x Layer thickness 200nm, said Sb 2 (Se 0.25 S 0.75 ) 3 Light absorbing layer materialThe band gap is 1.65eV, and the thickness is 350 nm; the first buffer layer Zn (O, S, OH) X Is 45 nm; the thickness of the second buffer layer (Zn, Mg) O is 75 nm; the thickness of the FTO layer is 85 nm; the antireflection film is Si 3 N 4 Is 80 nm; the thickness of the Al electrode is 1000nm, and the thickness of the Ag/Cu electrode is 500 nm.
The embodiment also relates to a preparation method of the battery, which comprises the following steps:
1) firstly, cleaning an n-type silicon wafer, and preparing SiO by thermally oxidizing the front surface of the silicon wafer at 300 DEG C 2 A layer; then adopting a low-pressure chemical vapor deposition method to deposit n on the front surface + Annealing the poly-Si layer for 1 hour at 850 ℃; on the front side of the silicon wafer (n) + poly-Si layer) magnetron sputtering a layer of ITO transparent conductive film;
2) preparing Al on the back of the silicon wafer by adopting a PECVD method 2 O 3 And Si 3 N 4 A passivation layer;
3) MoO is prepared on the ITO layer on the front side of the silicon wafer by adopting a thermal evaporation method x A layer;
4) sb preparation by double-source vacuum co-evaporation method 2 (Se 0.25 S 0.75 ) 3 The light absorption layer is specifically as follows: vacuum degree of 2X 10 is set by adopting vacuum thermal evaporation equipment -3 Pa, the evaporation source is Sb 2 S 3 Powder and Sb 2 Se 3 Powder, wherein the evaporation temperature is 650 ℃, and the substrate surface temperature during deposition is 250 ℃; after the deposition is finished, continuously annealing for 2.0h at 350 ℃ to improve the performance of the film;
5) in Sb 2 (Se 0.25 S 0.75 ) 3 Preparing a first buffer layer Zn (O, S, OH) on the light absorption layer by adopting a chemical water bath deposition method in sequence X Preparing a second buffer layer (Zn, Mg) O by adopting an atomic layer deposition method, and annealing at the annealing temperature of 150 ℃ for 1.5 h;
6) finally, preparing a FTO transparent conductive layer by adopting a magnetron sputtering method, and sequentially preparing an antireflection layer Si by adopting a thermal evaporation method 3 N 4 The front electrode is made of Ag/Cu alloy, and the back electrode is made of Al.
Example 3
The present example differs from example 1 in that:
the light absorption layer is made of Sb 2 (Se 0.5 S 0.5 ) 3 The band gap is 1.42eV, and the thickness is 750 nm;
the first buffer layer Zn (O, S, OH) X Is 75 nm;
the thickness of the second buffer layer (Zn, Mg) O is 100 nm;
in the preparation process, the vacuum degree is set to be 1 multiplied by 10 in the step 4) -5 Setting the evaporation temperature to 650 ℃, setting the substrate surface temperature to 400 ℃ during deposition, and annealing for 1.0h at 450 ℃;
step 5) the first buffer layer is Zn (O, S, OH) X The second buffer layer is (Zn, Mg) O, the annealing temperature is 300 ℃, and the annealing time is 0.5 h.
Example 4
This example differs from example 1 in that:
the light absorption layer is made of Sb 2 S 3 The band gap is 1.8eV, and the thickness is 1000 nm;
step 4) setting the vacuum degree to 10 -4 The evaporation temperature is set to 350 ℃, the substrate surface temperature during deposition is 280 ℃, and annealing is carried out for 1.0h at 350 ℃.
Example 5
The difference from embodiment 1 is that the first buffer layer is CdS and the second buffer layer is (Zn, Mg) O.
Example 6
The difference compared to example 1 is that the first buffer layer is Zn (O, S, OH) X The second buffer layer is ZnO
Example 7
This example differs from example 1 in that: the antimony selenide sulfur battery is only provided with one buffer layer which is CdS.
Comparative example 1
Compared with the embodiment 1, the difference is that the antimony selenide sulfide light-absorbing layer material is Sb 2 (Se 0.8 S 0.2 ) 3 A band gap of 1.3eV
Comparative example 2
The embodiment relates to a crystalThe silicon cell had the same structure as the crystalline silicon cell in example 1, and was composed of an Ag back electrode and an Si back electrode in this order from bottom to top 3 N 4 Passivation layer, Al 2 O 3 Passivation layer, p-type crystalline silicon substrate and SiO 2 Layer n + poly-Si layer, Ag front electrode
Examples of the experiments
At room temperature, AM1.5G, 100 mW. cm -2 The examples were tested under conditions, with the main test equipment: the efficiency of the cell was measured using a solar simulator, standard silicon detector, Keithley 2400 source meter, IV tester, etc. The specific test results are shown in table 1:
TABLE 1
| Battery with a battery cell | Distribution of forbidden band width of battery | Conversion efficiency |
| Example 1 | 1.72eV/1.12eV | 28.5％ |
| Example 2 | 1.65eV/1.12eV | 30.8％ |
| Example 3 | 1.42eV/1.12eV | 27.2％ |
| Example 4 | 1.8eV/1.12eV | 26.7％ |
| Example 5 | 1.72eV/1.12eV | 25.8％ |
| Example 6 | 1.65eV/1.12eV | 25.2％ |
| Example 7 | 1.72eV/1.12eV | 25.0％ |
| Comparative example 1 | 1.3eV/1.12eV | 21.5％ |
| Comparative example 2 | 1.12eV | 24.5％ |
As can be seen from the data in the above table, Sb in examples 1, 2, 3 and 4 2 (Se x S 1-x ) 3 The photoelectric conversion efficiency of the/Si double-junction laminated cell is greatly improved compared with that of the existing monocrystalline silicon cell, and the photoelectric conversion efficiency of the/Si double-junction laminated cell is also improved to a certain extent in the embodiments 5-7. The reason is that the forbidden bandwidth distribution of the antimony selenide sulfide cell and the crystalline silicon cell keeps better matching with the solar cell spectrum, and the solar spectrum can be better utilized compared with the monocrystalline silicon cell.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (4)
1. A double-junction tandem solar cell, characterized in that its structure comprises from bottom to top: ag electrode, Si 3 N 4 Passivation layer, Al 2 O 3 Passivation layer, p-type crystalline silicon substrate and SiO 2 Layer n + poly-Si layer, ITO layer, MoO x Layer, Sb 2 (Se 0.1 S 0.9 ) 3 Light absorption layer, CdS first buffer layer, ZnO second buffer layer, AZO transparent conductive layer and MgF antireflection layer 2 And an Au electrode; wherein Sb 2 (Se 0.1 S 0.9 ) 3 The thickness of the light absorption layer is 500nm, the thickness of the CdS first buffer layer is 20nm, and the thickness of the ZnO second buffer layer is 50 nm;
or the structure comprises from bottom to top: al electrode, Si 3 N 4 Passivation layer, Al 2 O 3 Passivation layer, n-type crystalline silicon substrate and SiO 2 Layer n + poly-Si layer, ITO layer, MoO x Layer, Sb 2 (Se 0.25 S 0.75 ) 3 Light absorbing layer, first buffer layer Zn (O, S, OH) X A second buffer layer (Zn, Mg) O, a transparent conductive layer FTO and an antireflection layer Si 3 N 4 And Ag/Cu electrodes; wherein Sb 2 (Se 0.25 S 0.75 ) 3 The thickness of the light absorption layer is 350 nm; first buffer layer Zn (O, S, OH) X Is 45 nm; the thickness of the second buffer layer (Zn, Mg) O was 75 nm.
2. The method of fabricating a dual junction tandem solar cell of claim 1, comprising:
by double source vacuum co-evaporation with Sb 2 S 3 Powder and Sb 2 Se 3 Forming Sb on the surface of a substrate as a raw material 2 (Se x S 1–x ) 3 X =0.1 or 0.25 light absorbing layer;
and preparing a buffer layer.
3. The method of fabricating a dual junction tandem solar cell according to claim 2, comprising:
chemical water bath deposition method is adopted to deposit on the Sb 2 (Se x S 1–x ) 3 X =0.1 or 0.25 light absorbing layer on which the first buffer layer is formed;
and forming the second buffer layer on the first buffer layer by adopting an atomic layer deposition method.
4. The method according to claim 2, wherein said Sb is formed by a double source vacuum co-evaporation method 2 (Se x S 1–x ) 3 In the process of x =0.1 or 0.25 light absorbing layer, when x =0.1, the degree of vacuum is set to 1 × 10 -6 Pa, the evaporation temperature is 500 ℃, the surface temperature of the substrate is 300 ℃, and annealing is continued for 2.0h at 300 ℃ after deposition is finished; when x =0.25, the vacuum degree was set to 2 × 10 -3 Pa, the evaporation temperature is 650 ℃, the substrate surface temperature is 250 ℃, and after the deposition is finished, the annealing is continued for 2.0 hours at 350 ℃;
after the second buffer layer is formed, annealing is carried out for 0.5-2.0h under the condition of the temperature of 100-300 ℃.
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| CN105810772B (en) * | 2016-05-30 | 2017-07-14 | 中南大学 | A kind of antimony trisulfide/silicon stacked solar cell, cascade solar cell and preparation method thereof |
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| EP0297644A2 (en) * | 1987-07-01 | 1989-01-04 | ENIRICERCHE S.p.A. | Process for preparing thin films of crystalline metals or semiconductors on amorphous substrates, and thin-film electroluminescent device obtainable by means of such a process |
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