CN103378214A - Stack-based copper zinc tin sulfur selenide (CZTSSe) thin film solar cell and manufacturing method thereof - Google Patents
Stack-based copper zinc tin sulfur selenide (CZTSSe) thin film solar cell and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides a stack-based copper zinc tin sulfur selenide (CZTSSe) thin film solar cell and a manufacturing method of the stack-based CZTSSe thin film solar cell. The manufacturing method of the stack-based CZTSSe thin film solar cell sequentially includes: sequentially forming a sulfide layer, a cuprous selenide layer and a zinc stannide layer on a back electron layer, manufacturing a selenide layer containing sulfur compounds and a selenium sulfide solar energy absorbing layer after selenylation and sulfuration, and depositing an n-type buffering layer and a top electron layer to manufacture the stack-based CZTSSe thin film solar cell, wherein the selenium sulfide solar energy absorbing layer comprises a low-energy-gap copper zinc tin selenide (CZTSe) layer arranged between two high-energy-gap CZTSSe layers in a clamping mode to form a stack-based solar energy absorbing layer. Besides, the invention further provides the stack-based CZTSSe thin film solar cell. Due to the fact that the stack-based solar energy absorbing layer improves the light absorbing rate and reduces the recombination rate of electrons/holes, the photoelectric property of the stack-based CZTSSe thin film solar cell is improved.
Description
Technical field
The invention relates to a kind of stack copper-zinc-tin-selenium S film solar battery, espespecially a kind of stack copper-zinc-tin-selenium S film solar battery that contains stack solar absorbing layer structure.
In addition, the present invention is also about a kind of manufacture method of stack copper-zinc-tin-selenium S film solar battery.
Background technology
Thin-film solar cells can be divided into amorphous silicon thin-film solar cell, multi-crystal silicon film solar battery and multi-element compounds thin-film solar cells etc. according to the difference of material.
The multi-element compounds thin-film solar cells that has developed on the market at present, for example: copper-indium-galliun-selenium film solar cell (Copper Indium Gallium Selenide thin-film solar cell, CIGS thin-film solar cell), copper-zinc-tin-sulfur film solar cell (Copper Zinc Tin Sulfide thin-film solar cell, CZTS thin-film solar cell) or copper-zinc-tin-selenium thin-film solar cells (Copper Zinc Tin Selenide thin-film solar cell, CZTSe thin-film solar cell).
Take the CZTSe thin-film solar cells as example, the method of making at present the multi-element compounds thin-film solar cells has two kinds: (1) uses copper, zinc, tin and four kinds of independent evaporation sources of selenium, mode with coevaporation forms the CZTSe solar absorbing layer on the substrate with dorsum electrode layer, sequentially deposit N-shaped resilient coating and top electrode layer again and make the CZTSe thin-film solar cells; (2) use zinc selenide, stannic selenide and copper selenide as sputtering source, mode with layering sequentially forms copper zinc-tin precursor layer in the substrate that has on the dorsum electrode layer, again through forming the CZTSe solar absorbing layer behind the selenylation reaction, then sequentially deposit N-shaped resilient coating and top electrode layer, make the CZTSe thin-film solar cells.
Yet, in the prepared traditional C ZTSe thin-film solar cells of aforementioned two kinds of manufacture methods, only can form the solar absorbing layer structure of single semiconductor energy gap, and can't on dorsum electrode layer, form ohmic contact layer.Therefore, electronics unpredictably moves toward dorsum electrode layer easily, in the phenomenon of dorsum electrode layer and solar absorption interlayer generation electron/hole-recombination (electron/hole recombination), and the generation of reduction photoelectric current.
In addition, because sunlight is comprised of the light of various different-energies, short wavelength, the common penetration depth of high-octane light are more shallow, and long wavelength, the common penetration depth of low-energy light are darker.When traditional C ZTSe thin-film solar cells only has the solar absorbing layer structure of single semiconductor energy gap, just can't effectively absorb the more shallow short-wavelength light of penetration depth, and reduce traditional C ZTSe thin-film solar cells to the Optical Absorption rate.
Summary of the invention
Because the existing defective of prior art, main purpose of the present invention is to promote the copper-zinc-tin-selenium S film solar battery to the Optical Absorption rate, and reduce the phenomenon of dorsum electrode layer and selenium sulfuration solar absorption interlayer generation electron/hole-recombination, use the photoelectric conversion efficiency that promotes stack copper-zinc-tin-selenium S film solar battery.
For reaching above-mentioned purpose, the present invention provides a kind of manufacture method of stack copper-zinc-tin-selenium S film solar battery, comprising: a substrate (A) is provided, is formed with a dorsum electrode layer on this substrate; (B) on this dorsum electrode layer, form a sulfur-containing compound layer; (C) on this sulfur-containing compound layer, form a Berzeline layer (Cu
2Se layer); (D) on this Berzeline layer, form a tin zinc layer (SnZn layer), include the solar energy precursor layer of Berzeline layer and tin zinc layer with formation one on this sulfur-containing compound layer; (E) this sulfur-containing compound layer of selenizing and this solar energy precursor layer, to make this sulfur-containing compound layer be transformed into a selenizing sulfur-containing compound layer, and make this solar energy precursor layer be transformed into a selenizing solar absorbing layer, wherein this selenizing sulfur-containing compound layer is formed on this dorsum electrode layer, and this selenizing solar absorbing layer is formed on this selenizing sulfur-containing compound layer; (F) vulcanize this selenizing solar absorbing layer, to make it be transformed into selenium sulfuration solar absorbing layer, wherein this selenium sulfuration solar absorbing layer includes one first copper-zinc-tin-selenium sulphur layer, a copper-zinc-tin-selenium layer and one second copper-zinc-tin-selenium sulphur layer, wherein this first copper-zinc-tin-selenium sulphur layer is formed at the bottom of this selenium sulfuration solar absorbing layer, and this copper-zinc-tin-selenium layer is formed between this first copper-zinc-tin-selenium sulphur layer and this second copper-zinc-tin-selenium sulphur layer; And (G) on this selenium sulfuration solar absorbing layer, form a N-shaped resilient coating, and on this N-shaped resilient coating, form a top electrode layer, to make stacked type copper-zinc-tin-selenium S film solar battery.
In this, because the energy gap of copper-zinc-tin-selenium sulphur layer is higher than the copper-zinc-tin-selenium layer, when below that larger the first copper-zinc-tin-selenium sulphur layer of energy gap and the second copper-zinc-tin-selenium sulphur layer are formed at respectively the copper-zinc-tin-selenium layer and top, can make stack copper-zinc-tin-selenium S film solar battery of the present invention contain the structure of stack solar absorbing layer, and be improved its photoelectric conversion efficiency.
In other words, the first copper-zinc-tin-selenium sulphur layer of adjacent back electrode layer can make electronics be difficult for diffusing to dorsum electrode layer, and then reduces the phenomenon of dorsum electrode layer and selenium sulfuration solar absorption interlayer generation electron/hole-recombination; The second copper-zinc-tin-selenium sulphur layer of adjacent top electrodes layer then can effectively absorb low penetration degree, short wavelength and high-octane light, and then improves the absorptivity of stack copper-zinc-tin-selenium S film solar battery, even improve the generation of photoelectric current.
In addition, in order further to reduce the phenomenon of dorsum electrode layer and selenium sulfuration solar absorption interlayer generation electron/hole-recombination, the present invention forms a sulfur-containing compound layer on dorsum electrode layer.Better, this sulfur-containing compound layer can be the copper bearing sulphide layer, contains the zinc sulfurized layer, stanniferous sulfurized layer, contain the combination of molybdenum sulphide layer or its etc.Described copper bearing sulphide layer, for example: cuprous sulfide layer (Cu
2S layer); Contain the zinc sulfurized layer, for example: zinc sulfide layer (ZnS layer); Stanniferous sulfurized layer, for example: stannic disulfide layer (SnS
2Layer); Contain the molybdenum sulphide layer, for example: curing molybdenum layer (MoS
2But be not limited only to this layer).In addition, dorsum electrode layer can be the molybdenum electrode layer.Behind the selenylation reaction of sulfur-containing compound layer through step (E) that is formed on the dorsum electrode layer, can form a kind of as two (selenium, sulphur) change molybdenum layer (Mo (Se, S)
2Layer) selenizing sulfur-containing compound layer.
In this, because two (selenium, sulphur) energy gap of change molybdenum layer is to be higher than copper-zinc-tin-selenium sulphur layer, and the energy gap of copper-zinc-tin-selenium sulphur layer is higher than again the copper-zinc-tin-selenium layer, therefore, two (selenium, sulphur) are changed the phenomenon that molybdenum layer can further reduce dorsum electrode layer and selenium sulfuration solar absorption interlayer generation electron/hole-recombination, increase electronics toward the probability of top electrode layer conduction, even improve the generation of photoelectric current.
In addition, formed two (selenium, sulphur) are changed molybdenum layer and also be can be used as an ohmic contact layer, and then can reduce the contact resistance value of stack copper-zinc-tin-selenium S film solar battery.
Described " stack " refers to that the different compound layer of material, composition or energy gap arranges in the mode of intersecting mutually.For example: the copper-zinc-tin-selenium layer is folded in the structure that two-layer copper-zinc-tin-selenium sulphur layer is a kind of stack.
Described " the first copper-zinc-tin-selenium sulphur layer " reaches " the second copper-zinc-tin-selenium sulphur layer " and refers to that one contains the nonwoven fabric from filaments of the selenium sulfide of copper zinc-tin, and the chemical expression formula is such as Cu
2ZnSn (Se, S)
4Shown in.Wherein, in the first copper-zinc-tin-selenium sulphur layer and the second copper-zinc-tin-selenium sulphur layer, copper atom content account for copper, zinc, tin, selenium and sulphur atom content and ratio (Cu/ (Cu+Zn+Sn+Se+S)) be between 0.15 to 0.3; Zinc atom content account for copper, zinc, tin, selenium and sulphur atom content and ratio (Zn/ (Cu+Zn+Sn+Se+S)) be between 0.1 to 0.2; Tin atom content account for copper, zinc, tin, selenium and sulphur atom content and ratio (Sn/ (Cu+Zn+Sn+Se+S)) be between 0.05 to 0.15; Selenium atom content account for copper, zinc, tin, selenium and sulphur atom content and ratio (Se/ (Cu+Zn+Sn+Se+S)) be between 0.2 to 0.25; Sulphur atom content account for copper, zinc, tin, selenium and sulphur atom content and ratio (S/ (Cu+Zn+Sn+Se+S)) be between 0.25 to 0.3.
Described " copper-zinc-tin-selenium layer " refers to that one contains the nonwoven fabric from filaments of the selenium sulfide of copper zinc-tin, and the chemical expression formula is such as Cu
2ZnSnSe
4Shown in.Wherein, in independent copper-zinc-tin-selenium layer, copper atom content account for copper, zinc, tin and selenium atom content and ratio (Cu/ (Cu+Zn+Sn+Se)) be between 0.15 to 0.3; Zinc atom content account for copper, zinc, tin and selenium atom content and ratio Zn/ (Cu+Zn+Sn+Se)) be between 0.1 to 0.2; Tin atom content account for copper, zinc, tin and selenium atom content and ratio (Sn/ (Cu+Zn+Sn+Se)) be between 0.05 to 0.15; Selenium atom content account for copper, zinc, tin and selenium atom content and ratio (Se/ (Cu+Zn+Sn+Se)) be between 0.45 to 0.55.
Described " two (selenium, sulphur) are changed molybdenum layer " refers to that one contains the nonwoven fabric from filaments of the selenium sulfide of molybdenum, and the chemical expression formula is such as Mo (Se, S)
2Shown in.Wherein, selenium atom is about 1 to 2.3 to the atomic ratio of sulphur atom.
Better, in the step (B) of the manufacture method of above-mentioned stack copper-zinc-tin-selenium S film solar battery, comprise with heat treating process and vulcanize this molybdenum electrode layer, use and on the surface of molybdenum electrode layer, form a curing molybdenum layer.Wherein, the temperature of vulcanization reaction can be between 300 ℃ to 600 ℃, and the thickness of curing molybdenum layer can be between 10 nanometers (nm) between the 200nm.
Better, in the step (C) of the manufacture method of above-mentioned stack copper-zinc-tin-selenium S film solar battery, comprise and use a Berzeline target (Cu
2Se target) form this Berzeline layer, and the selenium atom of this Berzeline target is preferably between 0.4 to 0.6 to the atomic ratio of copper atom.
Better, in the step (D) of the manufacture method of above-mentioned stack copper-zinc-tin-selenium S film solar battery, comprise and use a tin zinc target (ZnSn target) to form this tin zinc layer, and the tin atom of this tin zinc target is preferably the atomic ratio of zinc atom and is higher than more than 1, better is between 1.2 and 1.5, make tin atom in the tin zinc layer to the atomic ratio of zinc atom near 1: 1.
Better, in the step (E) of the manufacture method of above-mentioned stack copper-zinc-tin-selenium S film solar battery, comprise and use the selenium element that contains selenium material or hydrogen selenide gas, with this sulfur-containing compound layer of heat treating process selenizing and this solar energy precursor layer.The described selenium material that contains can be selenium ingot or selenium powder, and the temperature of selenylation reaction can be between 400 ℃ to 600 ℃.
Better, in the step (F) of the manufacture method of above-mentioned stack copper-zinc-tin-selenium S film solar battery, comprise the element sulphur that uses sulphurous materials or hydrogen sulfide gas, vulcanize this selenizing solar energy precursor layer with heat treating process.Described sulphurous materials can be sulphur ingot or sulphur powder, and the temperature of vulcanization reaction can be between 300 ℃ to 600 ℃.
For reaching above-mentioned purpose, the present invention also provides a kind of stack copper-zinc-tin-selenium S film solar battery, and it comprises: a substrate; One dorsum electrode layer, it is formed on this substrate; One selenium sulfuration solar absorbing layer, it is formed on this dorsum electrode layer, and this selenium sulfuration solar absorbing layer includes one first copper-zinc-tin-selenium sulphur layer, a copper-zinc-tin-selenium layer and one second copper-zinc-tin-selenium sulphur layer, wherein this first copper-zinc-tin-selenium sulphur layer is formed at the bottom of this selenium sulfuration solar absorbing layer, and this copper-zinc-tin-selenium layer is formed between this first copper-zinc-tin-selenium sulphur layer and this second copper-zinc-tin-selenium sulphur layer; One N-shaped resilient coating, it is formed on this second copper-zinc-tin-selenium sulphur layer of this selenium sulfuration solar absorbing layer; And a top electrode layer, this top electrode layer is formed on this N-shaped resilient coating.
Better, stack copper-zinc-tin-selenium S film solar battery of the present invention can be obtained by above-mentioned manufacture method, makes it have the structure of stack solar absorbing layer.Better, more include a selenizing sulfur-containing compound layer between dorsum electrode layer and this selenium sulfuration solar absorbing layer in the stack copper-zinc-tin-selenium S film solar battery of the present invention.
Better, comprise a copper-zinc-tin-selenium layer in the selenium sulfuration solar absorbing layer of stack copper-zinc-tin-selenium S film solar battery of the present invention, other has " the first copper-zinc-tin-selenium sulphur layer " to reach below and top that " the second copper-zinc-tin-selenium sulphur layer " lays respectively at this copper-zinc-tin-selenium layer.Wherein, in the first copper-zinc-tin-selenium sulphur layer and the second copper-zinc-tin-selenium sulphur layer, the atom content ratio of Cu/ (Cu+Zn+Sn+Se+S) is between 0.15 to 0.3; The atom content ratio of Zn/ (Cu+Zn+Sn+Se+S) is between 0.1 to 0.2; The atom content ratio of Sn/ (Cu+Zn+Sn+Se+S) is between 0.05 to 0.15; The atom content ratio of Se/ (Cu+Zn+Sn+Se+S) is between 0.2 to 0.25; And the atom content ratio of S/ (Cu+Zn+Sn+Se+S) is between 0.25 to 0.3.
In addition, in independent copper-zinc-tin-selenium layer, the atom content ratio of Cu/ (Cu+Zn+Sn+Se) is between 0.15 to 0.3; The atom content ratio of Zn/ (Cu+Zn+Sn+Se) is between 0.1 to 0.2; The atom content ratio of Sn/ (Cu+Zn+Sn+Se) is between 0.05 to 0.15; And the atom content ratio of Se/ (Cu+Zn+Sn+Se) is between 0.45 to 0.55.
Better, the thickness of the first copper-zinc-tin-selenium sulphur layer can be between between the 50nm to 300nm, and the thickness of this second copper-zinc-tin-selenium sulphur layer can be between between the 50nm to 200nm, and the thickness of this copper-zinc-tin-selenium layer can be between between the 700nm to 2500nm.
In stack copper-zinc-tin-selenium S film solar battery of the present invention, better, this dorsum electrode layer can be the molybdenum electrode layer.Better, further including two (selenium, sulphur) between this dorsum electrode layer and this selenium sulfuration solar absorbing layer and change molybdenum layer, its thickness is between between the 10nm to 200nm.
Described substrate can be glass substrate, soda-lime glass substrate, polymeric substrate, flexible metal substrate or flexible alloying metal substrate.
The material of described N-shaped resilient coating can be zinc oxide film, zinc (oxygen, sulphur, hydrogen-oxygen) compound (Zn (O, S, OH)
x), zinc sulphide, cadmium sulfide, (selenium, hydrogen-oxygen) changes zinc (Zn (Se, OH)), zinc selenide, selenium indium compound (In
xSe
y), zinc indium selenides (ZnIn
xSe
y), indium (hydrogen-oxygen, sulphur) compound (In
x(OH, S)
y), indium trisulfide (In
2S
3), three selenizings, two indium (In
2Se
3) or zinc-magnesium oxide (ZnMgO
x).
The material of described this top electrode layer can be zinc oxide aluminum (Aluminum Zinc Oxide layer, AZO), tin indium oxide (Indium Tin Oxide, IZO) or indium zinc oxide (Indium Zinc Oxide, IZO).
Accordingly, the invention provides a kind of stack copper-zinc-tin-selenium S film solar battery and preparation method thereof, utilize the lower copper-zinc-tin-selenium layer of the higher copper-zinc-tin-selenium sulphur layer of energy gap and energy gap to form the structure of stack solar absorbing layer, and then improve generation and the photoelectric conversion efficiency of photoelectric current.
Description of drawings
Fig. 1 is the flow chart that the present invention makes stack copper-zinc-tin-selenium S film solar battery.
Fig. 2 is the structural representation of traditional C ZTSe thin-film solar cells.
Fig. 3 is the graph of a relation of the external quantum efficiency-energy gap of embodiment 1 and comparative example 1.
Drawing reference numeral:
11 substrates, 12 dorsum electrode layers
13 sulfur-containing compound layer 13A selenizing sulfur-containing compound layers
14 solar energy precursor layer, 141 Berzeline layers
142 tin zinc layers, 151 first copper-zinc-tin-selenium sulphur layer
152 copper-zinc-tin-selenium layers, 153 second copper-zinc-tin-selenium sulphur layer
15A selenizing solar absorbing layer 15B selenium sulfuration solar absorbing layer
16n type resilient coating 17 top electrode layer
21 substrates, 22 molybdenum electrode layers
23 copper-zinc-tin-selenium solar absorbing layer 24n type cadmium sulfide resilient coatings
25 aluminum zinc oxide electrode layers
Embodiment
Below, will be by each specific embodiment explanation embodiments of the present invention, those skilled in the art can understand advantage and the effect that the present invention can reach easily via the content of this specification, and under not departing from spirit of the present invention, carry out various modifications and change, to implement or to use content of the present invention.
Embodiment 1:
Below, will cooperate shown in Figure 1ly, describe the making flow process that the present invention makes stack copper-zinc-tin-selenium S film solar battery in detail.
At first, provide clean substrate 11.Utilize sputter process on substrate 11, to form a dorsum electrode layer 12.In present embodiment, substrate 11 is the soda-lime glass substrate, and dorsum electrode layer 12 is the molybdenum electrode layer, and the thickness of molybdenum electrode layer is about 400nm to 1000nm.
Then, at low vacuum in 10
-2In the vacuum cavity of holder (torr), utilize the element sulphur of hydrogen sulfide gas, vulcanization reaction is carried out on the surface of dorsum electrode layer 12, on dorsum electrode layer 12, to form a sulfur-containing compound layer 13.In present embodiment, through behind the vulcanization reaction, can form on the surface of molybdenum electrode layer the curing molybdenum layer that a thickness is about 10nm to 200nm.
Then, in low vacuum in 10
-2In the vacuum cavity of torr, use purity to be higher than 95% Berzeline target, at sulfur-containing compound layer 13 deposition one Berzeline layer 141; And in the vacuum cavity of same sputter environment, use purity to be higher than 95% tin zinc target, at this Berzeline layer 141 deposition one tin zinc layer 142, use and on sulfur-containing compound layer 13, form a solar energy precursor layer 14 that includes Berzeline layer 141 and tin zinc layer 142.
In this, in order to control the content ratio between each element in the solar energy precursor layer 14, the selenium atom of Berzeline target of the present invention is between 0.4 to 0.6 to the atomic ratio of copper atom, and the tin atom of tin zinc target is between 1.2 to 1.5 to the atomic ratio of zinc atom.
Afterwards, in low vacuum in 10
-2In the vacuum cavity of torr, utilize the selenium element of hydrogen selenide gas, simultaneously sulfur-containing compound layer 13 and solar energy precursor layer 14 are carried out selenylation reaction with 400 ℃ to 600 ℃ high temperature and reach 0.5 to 1 hour, use and form a selenizing sulfur-containing compound layer 13A (namely, two (selenium, sulphur) are changed molybdenum layer) and a selenizing solar absorbing layer 15A.
Wherein, selenizing sulfur-containing compound layer 13A is formed on the dorsum electrode layer 12, selenizing solar absorbing layer 15A is formed on the selenizing sulfur-containing compound layer 13A, and selenizing solar absorbing layer 15A includes one and is formed at copper-zinc-tin-selenium sulphur layer 151 and on the selenizing sulfur-containing compound layer 13A and is formed at copper-zinc-tin-selenium layer 152 on the copper-zinc-tin-selenium sulphur layer 151.
Because two (selenium, sulphur) energy gap of the selenizing sulfur-containing compound layer 13A of change molybdenum layer is higher than copper-zinc-tin-selenium sulphur layer 151, and the energy gap of copper-zinc-tin-selenium sulphur layer 151 is higher than again copper-zinc-tin-selenium layer 152, therefore, stack copper-zinc-tin-selenium S film solar battery of the present invention can pass through two (selenium, sulphur) change the phenomenon that molybdenum layer and copper-zinc-tin-selenium sulphur layer reduce dorsum electrode layer and selenium sulfuration solar absorption interlayer generation electron/hole-recombination, increase electronics toward the probability and the generation that improves photoelectric current of top electrode layer conduction.
Then, in low vacuum in 10
-2In the vacuum cavity of torr, utilize the element sulphur of hydrogen sulfide gas, with 300 ℃ to 600 ℃ high temperature selenizing solar absorbing layer 15A was carried out vulcanization reaction 0.1 to 0.5 hour, be transformed into selenium sulfuration solar absorbing layer 15B to make it.
In this, described vulcanization reaction mainly is that high-temperature heat treatment is carried out on the surface of selenizing solar absorbing layer 15A, and the surface conversion of using copper-zinc-tin-selenium layer 152 is the second copper-zinc-tin-selenium sulphur layer 153.
Accordingly, the copper-zinc-tin-selenium layer 152 that energy gap is lower is formed between the first higher copper-zinc-tin-selenium sulphur layer 151 of energy gap and this second copper-zinc-tin-selenium sulphur layer 153.Therefore, manufacture method of the present invention through aforesaid selenizing and vulcanization reaction after, can obtain to contain the stack copper-zinc-tin-selenium S film solar battery of the structure of stack solar absorbing layer.
In this, because the position is higher than copper-zinc-tin-selenium layer 152 at the energy gap of the second copper-zinc-tin-selenium sulphur layer 153 on surface, therefore can improve the absorptivity to low penetration degree, short wavelength and high-energy light, and then promote the photoelectric conversion efficiency of stack copper-zinc-tin-selenium S film solar battery of the present invention.
At last, with the chemical bath depositon method, in the upper deposition of selenium sulfuration solar absorbing layer 15B N-shaped resilient coating 16, on N-shaped resilient coating 16, deposit one with sputtering method again and have the top electrode layer 17 of window structure, namely finish the making of stack copper-zinc-tin-selenium S film solar battery of the present invention.
Via aforesaid manufacture method, stack copper-zinc-tin-selenium S film solar battery of the present invention sequentially includes from the bottom to top: substrate 11, dorsum electrode layer 12, selenizing sulfur-containing compound layer 13A, selenium sulfuration solar absorbing layer 15B, N-shaped resilient coating 16 and top electrode layer 17.
Wherein, selenium sulfuration solar absorbing layer 15B more sequentially is formed with the first copper-zinc-tin-selenium sulphur layer 151, copper-zinc-tin-selenium layer 152 and the second copper-zinc-tin-selenium sulphur layer 153 from the bottom to top, wherein copper-zinc-tin-selenium sulphur layer 151 is formed at the bottom of this selenium sulfuration solar absorbing layer 15B, and this copper-zinc-tin-selenium layer 152 is formed between copper-zinc-tin-selenium sulphur layer 151 and another copper-zinc-tin-selenium sulphur layer 153, so that contain the structure of stack solar absorbing layer in the stack copper-zinc-tin-selenium S film solar battery of the present invention.
In present embodiment, the thickness of copper-zinc-tin-selenium sulphur layer 151 is about between the 50nm to 300nm among the selenium sulfuration solar absorbing layer 15B, the thickness of copper-zinc-tin-selenium layer 152 is about between the 700nm to 2500nm, and the thickness of copper-zinc-tin-selenium sulphur layer 153 is about between the 50nm to 200nm.N-shaped resilient coating 15 is N-shaped cadmium sulfide resilient coating, and its thickness is about between the 30nm to 100nm; Top electrode layer 16 is the aluminum zinc oxide layer, and its thickness is about between the 1000nm to 3000nm.
In addition, detect the content ratio of copper, zinc, tin, selenium and element sulphur in the stack copper-zinc-tin-selenium S film solar battery of the present invention by energy dissipation spectrum measuring system (Energy Dispersive Spectroscopy, EDS).
In the first copper-zinc-tin-selenium sulphur layer and the second copper-zinc-tin-selenium sulphur layer, the atom content ratio of Cu/ (Cu+Zn+Sn+Se+S) is between 0.15 to 0.3; The atom content ratio of Zn/ (Cu+Zn+Sn+Se+S) is between 0.1 to 0.2; The atom content ratio of Sn/ (Cu+Zn+Sn+Se+S) is between 0.05 to 0.15; The atom content ratio of Se/ (Cu+Zn+Sn+Se+S) is between 0.2 to 0.25; And the atom content ratio of S/ (Cu+Zn+Sn+Se+S) is between 0.25 to 0.3.
In the copper-zinc-tin-selenium layer, the atom content ratio of Cu/ (Cu+Zn+Sn+Se) is between 0.15 to 0.3; The atom content ratio of Zn/ (Cu+Zn+Sn+Se) is between 0.1 to 0.2; The atom content ratio of Sn/ (Cu+Zn+Sn+Se) is between 0.05 to 0.15; And the atom content ratio of Se/ (Cu+Zn+Sn+Se) is between 0.45 to 0.55.
Embodiment 2:
Present embodiment is to make stack copper-zinc-tin-selenium S film solar battery as embodiment 1 described manufacturing method thereof haply.
Its main difference point is, utilizes sputter process to form a sulfur-containing compound layer at the molybdenum electrode layer.This sulfur-containing compound layer is the cuprous sulfide layer.In enforcement aspect of the present invention, described sulfur-containing compound layer also can be the combination of zinc sulfide layer, artificial gold layer or its etc.
Afterwards, as embodiment 1 described manufacture method, sequentially deposit Berzeline layer and tin zinc layer.Described Berzeline layer and tin zinc layer are the solar energy precursor layer, and this solar energy precursor layer is formed on the cuprous sulfide layer.
Then, as embodiment 1 described manufacture method, described sulfur-containing compound layer and solar absorption precursor layer foundation are carried out selenizing and vulcanization reaction, deposit again N-shaped cadmium sulfide resilient coating and aluminum zinc oxide electrode layer, can make stack copper-zinc-tin-selenium S film solar battery of the present invention.
Via aforesaid manufacture method, the prepared stack copper-zinc-tin-selenium of present embodiment S film solar battery also sequentially includes from the bottom to top: substrate, molybdenum electrode layer, two (selenium, sulphur) are changed molybdenum layer, the first copper-zinc-tin-selenium sulphur layer, copper-zinc-tin-selenium layer, the second copper-zinc-tin-selenium sulphur layer, N-shaped cadmium sulfide resilient coating and aluminum zinc oxide electrode layer.
Test case:
Below, will be with the prepared stack copper-zinc-tin-selenium of above-mentioned manufacture method S film solar battery as embodiment, with traditional C ZTSe thin-film solar cells as a comparative example, advantage and the effect of proved invention stack copper-zinc-tin-selenium S film solar battery.
Wherein, traditional C ZTSe thin-film solar cells is a kind of copper zinc-tin zinc thin-film solar cells that only has the solar absorbing layer structure of single semiconductor energy gap and do not have ohmic contact layer.As shown in Figure 2, this traditional C ZTSe thin-film solar cells sequentially comprises from the bottom to top: substrate 21, molybdenum electrode layer 22, copper-zinc-tin-selenium solar absorbing layer 23, N-shaped cadmium sulfide resilient coating 24, aluminum zinc oxide electrode layer 25.Wherein, the thickness of copper-zinc-tin-selenium solar absorbing layer 23 is about 2500nm.
1. the stack solar absorbing layer is on the impact of thin-film solar cells
Table 1: the photoelectric characteristic result of stack copper-zinc-tin-selenium S film solar battery of the present invention and traditional C ZTSe thin-film solar cells
As above shown in the table, the photoelectric conversion efficiency (CE) of stack copper-zinc-tin-selenium S film solar battery of the present invention is 8.60%, open circuit voltage (V
Oc) be 0.44V, short circuit current (J
Sc) be 40.1mA/cm
2, fill factor, curve factor (FF) is 0.48, maximum power magnitude of voltage (V
Max) be 0.3V, maximum power current value (J
Max) be 27.7mA/cm
2, and peak power output density value (P
Max) be 8.60mW/cm
2, those photoelectric characteristics all are better than traditional C ZTSe thin-film solar cells, confirm that the stack solar absorbing layer can significantly promote the photoelectric characteristic of stack copper-zinc-tin-selenium S film solar battery of the present invention.
2. high energy gap copper-zinc-tin-selenium sulphur layer is on the impact of Optical Absorption rate
Stack copper-zinc-tin-selenium S film solar battery of the present invention is that its absorption coefficient of light is greater than 5x10 under 400 to 1100nm the illumination in optical wavelength
3Cm
-1Especially, be that the absorption coefficient of light is greater than 3x10 under 385 to 475nm the illumination in optical wavelength
4Cm
-1Compared to traditional C ZTSe thin-film solar cells, be that the absorption coefficient of light is about 1x10 only under 385 to 475nm the illumination in optical wavelength
4Cm
-1Experimental result confirms: the copper-zinc-tin-selenium sulphur layer that high energy gap is set in the adjacent top electrodes layer can promote stack copper-zinc-tin-selenium S film solar battery for the absorptivity of short-wavelength light, and then improves the generation of photoelectric current.
See also shown in Figure 3, stack copper-zinc-tin-selenium S film solar battery of the present invention (embodiment 1) is higher than the external quantum efficiency of traditional C ZTSe thin-film solar cells at the external quantum efficiency (external quantum efficiency) of high energy gap scope (that is, (being equivalent to wavelength between the light of 387nm to 495nm) between the 2.5eV to 3.2eV).
Experimental result confirms: stack copper-zinc-tin-selenium S film solar absorbed layer of the present invention excites in identical number of photons and really can change out than polyelectron down, thereby has the effect that promotes photoelectric conversion efficiency.
3. two (selenium, sulphur) are changed molybdenum layer to the impact of contact resistance value
Be not formed with two (selenium on the dorsum electrode layer, sulphur) the forward bias resistance rate of the traditional C ZTSe thin-film solar cells of change molybdenum layer is 43 Ω, compared to stack copper-zinc-tin-selenium S film solar battery of the present invention, its forward bias resistance rate significantly reduces most 11 Ω.Experimental result confirms: two (selenium, sulphur) are changed molybdenum layer and really be can be used as an ohmic contact layer, effectively reduce the contact resistance value in the stack copper-zinc-tin-selenium S film solar battery.
In sum, the present invention forms the structure of stack solar absorbing layer by the lower copper-zinc-tin-selenium layer of the higher copper-zinc-tin-selenium sulphur layer of energy gap and energy gap, and further pass through two (selenium of higher energy gap, sulphur) change the phenomenon that molybdenum layer reduces dorsum electrode layer and selenium sulfuration solar absorption interlayer generation electron/hole-recombination, promote stack copper-zinc-tin-selenium S film solar battery photoelectric characteristic of the present invention and photoelectric conversion efficiency.
Above-described embodiment is only given an example for convenience of description, and the interest field that the present invention advocates should be as the criterion so that claim is described certainly, but not only limits to above-described embodiment.
Claims (13)
1. the manufacture method of a stack copper-zinc-tin-selenium S film solar battery is characterized in that, the manufacture method of described stack copper-zinc-tin-selenium S film solar battery comprises:
(A) provide a substrate, be formed with a dorsum electrode layer on the described substrate;
(B) on described dorsum electrode layer, form a sulfur-containing compound layer;
(C) on described sulfur-containing compound layer, form a Berzeline layer;
(D) on described Berzeline layer, form a tin zinc layer, include the solar energy precursor layer of Berzeline layer and tin zinc layer with formation one on described sulfur-containing compound layer;
(E) the described sulfur-containing compound layer of selenizing and described solar energy precursor layer, to make described sulfur-containing compound layer be transformed into a selenizing sulfur-containing compound layer, and make described solar energy precursor layer be transformed into a selenizing solar absorbing layer, wherein said selenizing sulfur-containing compound layer is formed on the described dorsum electrode layer, and described selenizing solar absorbing layer is formed on the described selenizing sulfur-containing compound layer;
(F) the described selenizing solar absorbing layer of sulfuration, to make it be transformed into selenium sulfuration solar absorbing layer, wherein said selenium sulfuration solar absorbing layer includes one first copper-zinc-tin-selenium sulphur layer, a copper-zinc-tin-selenium layer and one second copper-zinc-tin-selenium sulphur layer, wherein said the first copper-zinc-tin-selenium sulphur layer is formed at the bottom of described selenium sulfuration solar absorbing layer, and described copper-zinc-tin-selenium layer is formed between described the first copper-zinc-tin-selenium sulphur layer and described the second copper-zinc-tin-selenium sulphur layer; And
(G) on described selenium sulfuration solar absorbing layer, form a N-shaped resilient coating, and on described N-shaped resilient coating, form a top electrode layer, to make stacked type copper-zinc-tin-selenium S film solar battery.
2. manufacture method as claimed in claim 1 is characterized in that, described sulfur-containing compound layer is the copper bearing sulphide layer, contain zinc sulfurized layer, stanniferous sulfurized layer, contain the combination of molybdenum sulphide layer or its etc.
3. manufacture method as claimed in claim 1 is characterized in that, described dorsum electrode layer is the molybdenum electrode layer, and described step (B) comprises the molybdenum electrode layer that vulcanizes described base material, uses to form one contain the molybdenum sulphide layer on described molybdenum electrode layer.
4. such as each described manufacture method in the claims 1 to 3, it is characterized in that in step (E) afterwards, described selenizing sulfur-containing compound layer is that two (selenium, sulphur) are changed molybdenum layer.
5. manufacture method as claimed in claim 1 is characterized in that, described step (C) comprises uses a Berzeline target to form described Berzeline layer; And described step (D) comprises uses a tin zinc target to form described tin zinc layer.
6. manufacture method as claimed in claim 5, it is characterized in that, the selenium atom of described Berzeline target is between 0.4 to 0.6 to the atomic ratio of copper atom, and tin atom is between 1.2 and 1.5 to the atomic ratio of zinc atom in the described tin zinc target.
7. a stack copper-zinc-tin-selenium S film solar battery is characterized in that, described stack copper-zinc-tin-selenium S film solar battery comprises:
One substrate;
One dorsum electrode layer, it is formed on the described substrate;
One selenium sulfuration solar absorbing layer, it is formed on the described dorsum electrode layer, and described selenium sulfuration solar absorbing layer includes one first copper-zinc-tin-selenium sulphur layer, a copper-zinc-tin-selenium layer and one second copper-zinc-tin-selenium sulphur layer, wherein said the first copper-zinc-tin-selenium sulphur layer is formed at the bottom of described selenium sulfuration solar absorbing layer, and described copper-zinc-tin-selenium layer is formed between described the first copper-zinc-tin-selenium sulphur layer and described the second copper-zinc-tin-selenium sulphur layer;
One N-shaped resilient coating, it is formed on the second copper-zinc-tin-selenium sulphur layer of described selenium sulfuration solar absorbing layer; And
One top electrode layer, described top electrode layer are formed on the described N-shaped resilient coating.
8. stack copper-zinc-tin-selenium S film solar battery as claimed in claim 7, it is characterized in that, in the first copper-zinc-tin-selenium sulphur layer and the second copper-zinc-tin-selenium sulphur layer of described selenium sulfuration solar absorbing layer, the atom content ratio of Cu/ (Cu+Zn+Sn+Se+S) is between 0.15 to 0.3; The atom content ratio of Zn/ (Cu+Zn+Sn+Se+S) is between 0.1 to 0.2; The atom content ratio of Sn/ (Cu+Zn+Sn+Se+S) is between 0.05 to 0.15; The atom content ratio of Se/ (Cu+Zn+Sn+Se+S) is between 0.2 to 0.25; And the atom content ratio of S/ (Cu+Zn+Sn+Se+S) is between 0.25 to 0.3.
9. stack copper-zinc-tin-selenium S film solar battery as claimed in claim 7, it is characterized in that, in the copper-zinc-tin-selenium layer of described selenium sulfuration solar absorbing layer, the atom content ratio of Cu/ (Cu+Zn+Sn+Se) is between 0.15 to 0.3, the atom content ratio of Zn/ (Cu+Zn+Sn+Se) is between 0.1 to 0.2, the atom content ratio of Sn/ (Cu+Zn+Sn+Se) is between 0.05 to 0.15, and the atom content ratio of Se/ (Cu+Zn+Sn+Se) is between 0.45 to 0.55.
10. stack copper-zinc-tin-selenium S film solar battery as claimed in claim 7, it is characterized in that, the thickness of described the first copper-zinc-tin-selenium sulphur layer is between the 300nm between 50 nanometers, the thickness of described the second copper-zinc-tin-selenium sulphur layer is between 50 to 200nm, and the thickness of described copper-zinc-tin-selenium layer is between 700 to 2500nm.
11. stack copper-zinc-tin-selenium S film solar battery as claimed in claim 7 is characterized in that described dorsum electrode layer is the molybdenum electrode layer, and more includes one or two (selenium, sulphur) change molybdenum layer between described molybdenum electrode layer and the described selenium sulfuration solar absorbing layer.
12. stack copper-zinc-tin-selenium S film solar battery as claimed in claim 11 is characterized in that, the thickness that described two (selenium, sulphur) are changed molybdenum layer is between between the 10nm to 200nm.
13. stack copper-zinc-tin-selenium S film solar battery as claimed in claim 7 is characterized in that, described stack copper-zinc-tin-selenium S film solar battery is by obtained such as each described manufacture method in a kind of claim 1 to 6.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103606573A (en) * | 2013-11-27 | 2014-02-26 | 中国科学院上海硅酸盐研究所 | Intermediate band absorbing material of chalcopyrite structure and preparing method thereof |
| CN105039926A (en) * | 2015-06-15 | 2015-11-11 | 岭南师范学院 | Method for preparing CZTSSe film with liquid-tin heating continuous sulfuration and selenization method, CZTSSe film prepared through method and application of CZTSSe film |
| CN104701394B (en) * | 2013-12-09 | 2017-02-15 | 北京有色金属研究总院 | Cu2ZnSn (S1-xSex) 4 thin film with preferred orientation effect |
| US10014423B2 (en) | 2016-09-30 | 2018-07-03 | International Business Machines Corporation | Chalcogen back surface field layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752453A (en) * | 2008-12-04 | 2010-06-23 | 上海空间电源研究所 | Preparation method of glass-substrate double-side CIGS thin film solar cell module |
| WO2011090728A2 (en) * | 2009-12-28 | 2011-07-28 | David Jackrel | Low cost solar cells formed using a chalcogenization rate modifier |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752453A (en) * | 2008-12-04 | 2010-06-23 | 上海空间电源研究所 | Preparation method of glass-substrate double-side CIGS thin film solar cell module |
| WO2011090728A2 (en) * | 2009-12-28 | 2011-07-28 | David Jackrel | Low cost solar cells formed using a chalcogenization rate modifier |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103606573A (en) * | 2013-11-27 | 2014-02-26 | 中国科学院上海硅酸盐研究所 | Intermediate band absorbing material of chalcopyrite structure and preparing method thereof |
| CN104701394B (en) * | 2013-12-09 | 2017-02-15 | 北京有色金属研究总院 | Cu2ZnSn (S1-xSex) 4 thin film with preferred orientation effect |
| CN105039926A (en) * | 2015-06-15 | 2015-11-11 | 岭南师范学院 | Method for preparing CZTSSe film with liquid-tin heating continuous sulfuration and selenization method, CZTSSe film prepared through method and application of CZTSSe film |
| US10014423B2 (en) | 2016-09-30 | 2018-07-03 | International Business Machines Corporation | Chalcogen back surface field layer |
| US10790398B2 (en) | 2016-09-30 | 2020-09-29 | International Business Machines Corporation | Chalcogen back surface field layer |
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