CN101752454B - Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure - Google Patents
Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure Download PDFInfo
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Abstract
The invention discloses a preparation method of an ultrathin Cu-In-Ga-Se thin film solar cell with a light trap structure, comprising the following steps: a back electrode Mo film (11), an Ag film (12), transparent electric-conduction ZnO, an Al film (13), an MoSe2 film (14), an adsorption layer (15), a Zn (S, O, OH) buffer layer (16), a transparent window layer SnO2, In (17), an electrode Ni/Al laminated film (18) and an antireflection layer MgF2 film (19) are sequentially deposited on a substrate, the thickness of the adsorption layer (15) is 0.3mum-1mum; V-shaped band gap graded distribution is generated in the film of the cell adsorption layer (15), so as to realize the preparation of the light trap structure of the ultrathin Cu-In-Ga-Se thin film solar cell; by adopting the invention, the optical and electrical loss caused by thinning of the adsorption layer can be reduced, and the cell conversion efficiency is improved. The preparation method has the beneficial effects of simple process, low material cost and no pollution and the like.
Description
Technical field
The present invention relates to photovoltaic cell manufacture method, especially a kind of preparation method with the ultra-thin CIGS thin-film solar cell of light trapping structure.
Background technology
CIGS thin-film solar cell, since middle 1970s starting, has just been subject to people's generally attention with its superior performance, develop very fastly, is one of the most rising thin film solar cell.Its typical structure is substrate/back electrode/absorbed layer/resilient coating/Window layer/top electrode/antireflection layer that heap is built successively.
In battery structure, the Copper Indium Gallium Selenide (CuIn that absorbed layer is direct band gap
1-xga
x(Se
1-ys
y)
2) film, thickness is generally in 1.5 μ m～2 μ m scopes.Keeping under the prerequisite that electricity conversion is constant, the thickness of attenuate absorbed layer, reduces sedimentation time and material cost as much as possible, is the main trend that develops in the world such battery technology at present.
Thinning absorber thickness (thickness < 1 μ m), one side can reduce the consumption of the noble metals such as In, Ga, reduces the cost of material and technique; Can significantly reduce battery weight on the other hand, expand the application of battery.But, for the absorbed layer of thickness thinning, there is luminous energy greatly can see through absorbed layer, cannot be absorbed, cause significant battery performance decay.In order to improve the utilance of sunlight, back electrode film must have good optical reflection performance, unabsorbed solar energy is reflected back in absorbed layer and recycles.
At present, copper indium gallium selenide film battery structure adopts metal M o thin-film material as back electrode conventionally, but its optical reflectivity is not high, cannot meet the requirement of slimline battery.And there is the metal A g thin-film material of very high optical reflectivity, in the preparation process of absorbed layer, Ag can be diffused in a large number and in absorbed layer, form dephasign compound, and reduces battery performance.Therefore, for ultra-thin CIGS thin-film solar cell, a kind of light trapping structure with interface stability between high optical reflectivity, low-resistivity and film be must design, thereby the thickness thinning of absorbed layer and the contradiction between cell conversion efficiency decay effectively solved.
Do not find at present explanation or the report of technology similar to the present invention, not yet collect both at home and abroad similarly data yet.
Summary of the invention
In order to solve the thickness thinning of prior art absorbed layer and the problems such as contradiction between cell conversion efficiency decay, the object of the present invention is to provide a kind of preparation method with the ultra-thin CIGS thin-film solar cell of light trapping structure.The light trapping structure of the solar cell that application the inventive method is made is comprised of back reflection composite bed and absorbed layer, in the situation that battery obsorbing layer thickness is less than 1 μ m, can fully absorb solar spectrum, has greatly improved battery efficiency.
In order to reach foregoing invention object, the present invention is that the technical scheme that its technical problem of solution adopts is to provide a kind of manufacture method with the ultra-thin CIGS thin-film solar cell of glass substrate of light trapping structure, comprises the steps:
Step 1, on cleaned common soda-lime glass substrate, sputtering sedimentation back electrode Mo film, thickness is 0.5 μ m～1.0 μ m; Step 2, on back electrode, sputtering sedimentation has the Ag film of suede degree, and thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃; Step 3, employing sputtering method deposit transparent conducting ZnO: Al film, thickness is 0.15 μ m～0.25 μ m, underlayer temperature is 150 ℃～250 ℃; The Mo film that step 4, sputtering sedimentation thickness are 3nm～20nm, adopts solid-state selenium source selenizing method to its selenizing, the MoSe that formation thickness is 5nm～25nm
2film; Step 5, utilize coevaporation method deposition to there is the Copper Indium Gallium Selenide (CuIn that " V " type band gap gradient distributes
1-xga
x(Se
1-ys
y)
2, atomic ratio y=0) and absorbed layer, at MoSe
2on film, first deposit broad-band gap Copper Indium Gallium Selenide (atomic ratio x > 0.7, y=0) film, thickness is 0.05 μ m～0.12 μ m, deposit again narrow band gap CIGS thin-film (atomic ratio 0.35>=x>=0.22, y=0), by technological parameter, regulate and control, in absorbed layer, form " V " type band gap gradient and distribute; The thickness of absorbed layer is 0.3 μ m～1.0 μ m; In absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃; After absorbed layer deposition finishes, it is carried out to the heat treatment that original position is evaporated appropriate NaF material, make the content of Na atom in absorbed layer remain on 0.1%; Step 6, use chemical bath method, deposit Zn (S, O, OH) resilient coating on absorbed layer, thickness is 30nm～70nm; Under step 7, the condition that do not heat at substrate, sputtering sedimentation transparent window layer SnO
2: In film, thickness is 0.2 μ m～0.4 μ m; Step 8, in transparent window layer hydatogenesis top electrode Ni/Al laminated film, thickness is 2.5 μ m～3 μ m; Step 9, hydatogenesis antireflection layer MgF
2film, thickness is 100nm～130nm.
In order to reach foregoing invention object, the present invention is that another technical scheme that its technical problem of solution adopts is to provide a kind of manufacture method with the ultra-thin CIGS thin-film solar cell of flexible substrate of light trapping structure, it is characterized in that, the method comprises the steps:
Step 1, in cleaned flexible substrate, sputtering sedimentation a layer thickness is the SiO of 0.5 μ m～1.0 μ m
2film; Sputtering sedimentation back electrode Mo film on this film, thickness is 0.5 μ m～1.0 μ m; Step 2, on back electrode, sputtering sedimentation has the Ag film of suede degree, and thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃; Step 3, employing sputtering method deposit transparent conducting ZnO: Al film, thickness is 0.15 μ m～0.25 μ m, underlayer temperature is 150 ℃～250 ℃; The Mo film that step 4, sputtering sedimentation thickness are 3nm～20nm, adopts solid-state selenium source selenizing method to its selenizing, the MoSe that formation thickness is 5nm～25nm
2film; Step 5, utilize coevaporation method deposition to there is the Copper Indium Gallium Selenide (CuIn that " V " type band gap gradient distributes
1-xga
x(Se
1-ys
y)
2, atomic ratio y=0) and absorbed layer [15], at MoSe
2on film, first deposit broad-band gap Copper Indium Gallium Selenide (atomic ratio x > 0.7, y=0) film, thickness is 0.05 μ m～0.12 μ m, deposit again narrow band gap CIGS thin-film (atomic ratio 0.35>=x>=0.22, y=0), by technological parameter, regulate and control, in absorbed layer, form " V " type band gap gradient and distribute; The thickness of absorbed layer is 0.3 μ m～1.0 μ m; In absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃; After absorbed layer deposition finishes, it is carried out to the heat treatment that original position is evaporated appropriate NaF material, make the content of Na atom in absorbed layer remain on 0.1%; Step 6, use chemical bath method, deposit Zn (S, O, OH) resilient coating on absorbed layer, thickness is 30nm～70nm; Step 7, under substrate is not had a mind to the condition of heating, sputtering sedimentation transparent window layer SnO
2: In film, thickness is 0.2 μ m～0.4 μ m; Step 8, in transparent window layer hydatogenesis top electrode Ni/Al laminated film, thickness is 2.5 μ m～3 μ m; Step 9, hydatogenesis antireflection layer MgF
2film, thickness is 100nm～130nm.
The present invention has the preparation method of the ultra-thin CIGS thin-film solar cell of light trapping structure, owing to taking above-mentioned technical scheme, adopt ultra-thin absorbent layer structure (thickness is 0.3 μ m～1.0 μ m), reduce on the one hand the consumption of the noble metals such as In, Ga, reduced the battery manufacture costs such as material, technique; Significantly reduce on the other hand the weight of hull cell, expanded the application of battery.Meanwhile, back reflection composite bed forms light trapping structure jointly with the absorbed layer that " V " type gradient band gap distributes, and reduces as far as possible optics and electricity loss that absorbed layer thinning causes, has greatly improved cell conversion efficiency.And resilient coating adopts Zn (S, O, OH) film to replace the conventional CdS film using, and has avoided the pollution of heavy metal Cd element to environment.Therefore, the present invention has that technique is simple, the cost of material is low, free of contamination feature, can significantly reduce the manufacturing cost of thin film solar cell.
Accompanying drawing explanation
Fig. 1 is the structural representation of the ultra-thin CIGS thin-film solar cell of glass substrate with light trapping structure of application the inventive method manufacture;
Fig. 2 is the structural representation of the ultra-thin CIGS thin-film solar cell of flexible substrate with light trapping structure of application the inventive method manufacture.
Embodiment
Fig. 1 is the structural representation of the ultra-thin CIGS thin-film solar cell of glass substrate with light trapping structure of application the inventive method manufacture; As shown in Figure 1, this solar cell comprises: heap is built successively common soda-lime glass substrate 10, back electrode Mo film 11, Ag film 12, transparent conducting ZnO: Al film 13, MoSe
2film 14, absorbed layer 15, resilient coating 16, transparent window layer SnO
2: In film 17, electrode Ni/Al laminated film 18, antireflection layer MgF
2film 19.
Fig. 2 is the structural representation of the ultra-thin CIGS thin-film solar cell of flexible substrate with light trapping structure of application manufacture of the present invention; As shown in Figure 2, this solar cell comprises: heap is built successively flexible substrate 20, SiO
2film 21, back electrode Mo film 11, Ag film 12, transparent conducting ZnO: Al film 13, MoSe
2film 14, absorbed layer 15, resilient coating 16, transparent window layer SnO
2: In film 17, electrode Ni/Al laminated film 18, antireflection layer MgF
2film 19.
In above-mentioned solar cell, on back electrode, deposit successively Ag film, transparent conductive oxide film and MoSe
2film, forms back reflection composite bed.Back reflection composite bed and absorbed layer form light trapping structure jointly.Wherein Ag film is as reflector, and Ag film has very high optical reflectivity, and the Ag film surface of deposition has certain suede degree, makes the solar photon that sees through absorbed layer by the effect of back reflection composite bed, can return to absorbed layer interior and be maximized absorption.Because Ag is easy to the elements such as In, Ga, Se and forms dephasign compound, therefore on Ag film surface, needing deposition layer of transparent conductive oxide film, can be Zinc-oxide-based film (ZnO:Al, ZnO:B, ZnO:Ga, ZnO:Mg) or tin oxide class film (SnO
2: F, SnO
2: In), it can stop that Ag atom, to absorbed layer diffusion inside, improves the interface stability between Ag film and absorbed layer.On sull surface, form skim MoSe
2, can stop oxide to the diffusion of absorbed layer inside, accurate ohmic contact that again can be between the two, improves battery performance.Therefore, back reflection composite bed of the present invention has the feature of interface stability between high optical reflectivity, low-resistivity and film.Simultaneously, utilize in Copper Indium Gallium Selenide (atomic ratio 0.15≤y≤0.3) film of selenizing/sulfuration method deposition after Copper Indium Gallium Selenide (atomic ratio y=0) film of coevaporation method deposition or splash-proofing sputtering metal initialization layer, to there is " V " type band gap gradient and distribute, thereby maximally utilise solar spectrum.The formed light trapping structure of back reflection composite bed and absorbed layer, can increase the collection of light path and photo-generated carrier effectively, reduces the various losses that absorbed layer thinning causes, and improves significantly the transformation efficiency of ultra-thin CIGS thin-film solar cell.
Above-described ultra-thin CIGS thin-film solar cell, substrate is common soda-lime glass or flexible material (metal stainless steel foil, titanium foil, polyimides).For flexible substrate, before deposition back electrode, first wanting sputtering sedimentation a layer thickness is the SiO of 0.5 μ m～1.0 μ m
2film, stops the various objectionable impurities elements in substrate to spread in absorbed layer, and reduces the surface roughness of backing material, is conducive to improve the thin-film material quality of subsequent growth.And for glass substrate, need not this technique.Absorbed layer (CuIn
1-xga
x(Se
1-ys
y)
2) deposition finish after, its original position is evaporated to appropriate NaF material and heat-treats, make the content of Na atom in absorbed layer remain on 0.1% left and right, played the effect of passivation grain boundary defects and purifying impurity.
Below in conjunction with drawings and Examples, to the present invention, the manufacture method of above-mentioned two kinds of solar cells is described in detail.
Embodiment 1
Fig. 1 has provided the structural representation of the ultra-thin CIGS thin-film solar cell of glass substrate with light trapping structure, and according to the present invention, the manufacture method of this solar cell comprises following step:
Step 1, on cleaned common soda-lime glass substrate 10, sputtering sedimentation back electrode Mo film 11, thickness is 0.5 μ m～1.0 μ m.
Step 2, on back electrode 11, sputtering sedimentation has the Ag film 12 of certain suede degree, and thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃.
Step 3, employing sputtering method deposit transparent conducting ZnO: Al film 13, thickness is 0.15 μ m～0.25 μ m, underlayer temperature is 150 ℃～250 ℃.
The Mo film that step 4, sputtering sedimentation thickness are 3nm～20nm, adopts solid-state selenium source selenizing method to its selenizing, the MoSe that formation thickness is 5nm～25nm
2film 14.
Step 5, utilize coevaporation method deposition to there is the Copper Indium Gallium Selenide (CuIn that " V " type band gap gradient distributes
1-xga
x(Se
1-ys
y)
2, atomic ratio y=0) and absorbed layer 15.At MoSe
2on film 14, first deposit broad-band gap Copper Indium Gallium Selenide (atomic ratio x > 0.7, y=0) film, thickness is 0.05 μ m～0.12 μ m, deposit again narrow band gap CIGS thin-film (atomic ratio 0.35>=x>=0.22, y=0), by technological parameter, regulate and control, in absorbed layer, form " V " type band gap gradient and distribute.The thickness of absorbed layer is 0.3 μ m～1.0 μ m.In absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃.After absorbed layer deposition finishes, it is carried out to the heat treatment that original position is evaporated appropriate NaF material, make the content of Na atom in absorbed layer remain on 0.1% left and right.
Step 6, use chemical bath method, deposit Zn (S, O, OH) resilient coating 16 on absorbed layer 15, thickness is 30nm～70nm.
Step 7, under substrate is not had a mind to the condition of heating, sputtering sedimentation transparent window layer SnO
2: In film 17, thickness is 0.2 μ m～0.4 μ m.
Step 8, in transparent window layer 17 hydatogenesis top electrode Ni/Al laminated film 18, thickness is 2.5 μ m～3 μ m.
Step 9, hydatogenesis antireflection layer MgF
2film 19, thickness is 100nm～130nm.
Embodiment 2
Above-mentioned steps three or step 4, can be at the surperficial Direct precipitation MoSe of Ag film 12
2film 14, realizing back reflection composite bed is double-layer compound film structure.All the other steps are with embodiment 1.
Embodiment 3
Above-mentioned steps five, can be with the Copper Indium Gallium Selenide (CuIn that " V " type band gap gradient distributes that gets everything ready of selenizing/sulfuration legal system after splash-proofing sputtering metal initialization layer
1-xga
x(Se
1-ySy)
2, atomic ratio 0.15≤y≤0.3) and absorbed layer 15.At MoSe
2on film 14, sputter CuGa target (Ga content is 22wt.%) and In target, preparing thickness is the Cu-In-Ga metal initialization layer of 0.12 μ m～0.4 μ m.Then adopt solid-state selenium source, solid-state sulphur source successively metal initialization layer to be carried out to selenizing and vulcanizing treatment, preparation has Copper Indium Gallium Selenide (atomic ratio 0.22≤x≤0.35, the 0.15≤y≤0.3) film that " V " type band gap gradient distributes.In selenizing and vulcanizing treatment process, underlayer temperature is 400 ℃～510 ℃.Prepared absorber thickness is 0.3 μ m～1.0 μ m.After absorbed layer deposition finishes, the heat treatment that it is carried out to original position evaporation NaF material, makes the content of Na atom in absorbed layer remain on 0.1% left and right.All the other steps are with embodiment 1.
Embodiment 4
Above-mentioned steps three or step 4, back reflection composite bed is double-layer compound film structure, can be at Ag film surface Direct precipitation MoSe
2film.All the other steps are with embodiment 3.
Embodiment 5
Fig. 2 has provided the structural representation of the ultra-thin CIGS thin-film solar cell of flexible substrate with light trapping structure; The manufacture method of this solar cell comprises following step:
Step 1, in cleaned flexible substrate 20, sputtering sedimentation a layer thickness is the SiO of 0.5 μ m～1.0 μ m
2film 21, then on film 21 sputtering sedimentation back electrode Mo film 11, thickness is 0.5 μ m～1.0 μ m;
Step 2～step 9, identical to step 9 with the step 2 of embodiment 1.
Embodiment 6
In the ultra-thin CIGS thin-film solar cell of the flexible substrate described in embodiment 5, back reflection composite bed is double-layer compound film structure, at the surperficial Direct precipitation MoSe of Ag film 12
2film 14.All the other steps are with embodiment 5.
Embodiment 7
In the ultra-thin CIGS thin-film solar cell of the flexible substrate described in embodiment 5, before deposition back electrode, in flexible substrate, sputtering sedimentation a layer thickness is the SiO of 0.5 μ m～1.0 μ m
2film.All the other steps are with embodiment 3.
Embodiment 8
In the ultra-thin CIGS thin-film solar cell of the flexible substrate described in embodiment 5, back reflection composite bed is double-layer compound film structure, at Ag film surface Direct precipitation MoSe
2film.All the other steps are with embodiment 7.
In above-mentioned two kinds of solar cells, glass substrate is that thickness is the common soda-lime glass of 2mm～3mm, and flexible substrate is that thickness is the flexible material (metal stainless steel foil, titanium foil, polyimides) of 20 μ m～50 μ m.
Back reflection composite bed, for double-deck or three layers of complex thin film structure, by Ag film/MoSe
2film or Ag film/transparent conductive oxide film/MoSe
2film forms, and has the characteristic of interface stability between high optical reflectivity, low-resistivity and film.
In absorbed layer material, from incident sunlight one side to back electrode side, there is " V " type band gap gradient.
Transparent window layer described in above-mentioned steps seven is the transparent conductive oxide film of sputtering sedimentation, can be Zinc-oxide-based film (ZnO:Al, ZnO:B, ZnO:Ga, ZnO:Mg) or tin oxide class film (SnO
2: F, SnO
2: In).It is characterized in that: at substrate, do not have a mind under heating condition, sputter obtains the transparent conductive film that thickness is 0.2 μ m～0.4 μ m.
Transparent conductive oxide film described in above-mentioned steps three is Zinc-oxide-based film (ZnO:Al, ZnO:B, ZnO:Ga, ZnO:Mg) or the tin oxide class film (SnO of sputtering sedimentation
2: F, SnO
2: In).It is characterized in that: at underlayer temperature, be that under the condition of 150 ℃～250 ℃, sputter obtains the transparent conductive film that thickness is 0.15 μ m～0.25 μ m.
Claims (7)
1. a manufacture method with the ultra-thin CIGS thin-film solar cell of glass substrate of light trapping structure, is characterized in that, the method comprises the steps:
Step 1, upper at cleaned common soda-lime glass substrate [10], sputtering sedimentation back electrode Mo film [11], thickness is 0.5 μ m～1.0 μ m;
Step 2, at the upper sputtering sedimentation of back electrode [11], have the Ag film [12] of suede degree, thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃;
Step 3, employing sputtering method deposit transparent conducting ZnO: A1 film [13], thickness is 0.15 μ m～0.25 μ m, underlayer temperature is 150 ℃～250 ℃;
The Mo film that step 4, sputtering sedimentation thickness are 3nm～20nm, adopts solid-state selenium source selenizing method to its selenizing, the MoSe that formation thickness is 5nm～25nm
2film [14];
Step 5, utilize coevaporation method deposition to have the CuInGaSe absorbed layer [15] that " V " type band gap gradient distributes, the chemical formula of described Copper Indium Gallium Selenide is CuIn
1-xga
x(Se
1-ys
y)
2, atomic ratio y=0, at MoSe
2film first deposits broad-band gap CIGS thin-film on [14], and the chemical formula of described Copper Indium Gallium Selenide is CuIn
1-xga
x(Se
1-ys
y)
2, atomic ratio x > 0.7, y=0, thickness is 0.05 μ m～0.12 μ m, then deposits narrow band gap CIGS thin-film, the chemical formula of described Copper Indium Gallium Selenide is CuIn
1-xga
x(Se
1-ys
y, atomic ratio 0.35>=x>=0.22, y=0, regulates and controls by technological parameter, forms " V " type band gap gradient and distribute in absorbed layer; The thickness of absorbed layer is 0.3 μ m～1.0 μ m; In absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃; After absorbed layer deposition finishes, it is carried out to the heat treatment that original position is evaporated appropriate NaF material, make the content of Na atom in absorbed layer remain on 0.1%;
Step 6, use chemical bath method, at the upper deposition of absorbed layer [15] Zn (S, O, OH) resilient coating [16], thickness is 30nm～70nm;
Step 7, under substrate is not had a mind to the condition of heating, sputtering sedimentation transparent window layer SnO
2: In film [17], thickness is 0.2 μ m～0.4 μ m;
Step 8, at the upper hydatogenesis top electrode Ni/A1 laminated film [18] of transparent window layer [17], thickness is 2.5 μ m～3 μ m;
Step 9, hydatogenesis antireflection layer MgF
2film [19], thickness is 100nm～130nm.
2. the manufacture method of the ultra-thin CIGS thin-film solar cell of glass substrate as claimed in claim 1, is characterized in that: at the surperficial Direct precipitation MoSe of Ag film [12]
2film [14] replaces step 3 and step 4, and realizing back reflection composite bed is double-layer compound film structure.
3. the manufacture method of the ultra-thin CIGS thin-film solar cell of glass substrate as claimed in claim 1, is characterized in that: at Ag film surface Direct precipitation MoSe
2film, realizing back reflection composite bed is that double-layer compound film structure replaces step 3 and step 4; With the get everything ready Cu-In-Ga-Se-S absorbed layer [15] of " V " type band gap gradient of selenizing/sulfuration legal system after splash-proofing sputtering metal initialization layer, replace step 5, the chemical formula of described Cu-In-Ga-Se-S is CuIn
1-xga
x(Se
1-ys
y)
2, atomic ratio 0.15≤y≤0.3, at MoSe
2the upper sputter CuGa target of film [14] and In target, wherein the Ga content of CuGa target is 22wt.%, preparing thickness is the Cu-In-Ga metal initialization layer of 0.12 μ m～0.4 μ m; Then adopt solid-state selenium source, solid-state sulphur source successively metal initialization layer to be carried out to selenizing and vulcanizing treatment, preparation has the Cu-In-Ga-Se-S thin film that " V " type band gap gradient distributes, and the chemical formula of described Cu-In-Ga-Se-S is CuIn
1-xga
x(Se
1-ys
y)
2, atomic ratio 0.22≤x≤0.35,0.15≤y≤0.3; In selenizing and vulcanizing treatment process, underlayer temperature is 400 ℃～510 ℃, and prepared absorber thickness is 0.3 μ m～1.0 μ m; After absorbed layer deposition finishes, the heat treatment that it is carried out to original position evaporation NaF material, makes the content of Na atom in absorbed layer remain on 0.1%.
4. a manufacture method with the ultra-thin CIGS thin-film solar cell of flexible substrate of light trapping structure, is characterized in that, the method comprises the steps:
Step 1, in the upper sputtering sedimentation a layer thickness of cleaned flexible substrate [20], be the SiO of 0.5 μ m～1.0 μ m
2film [21]; At the upper sputtering sedimentation back electrode Mo film [11] of film [21], thickness is 0.5 μ m～1.0 μ m again;
Step 2, at the upper sputtering sedimentation of back electrode [11], have the Ag film [12] of suede degree, thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃;
Step 3, employing sputtering method deposit transparent conducting ZnO: A1 film [13], thickness is 0.15 μ m～0.25 μ m, underlayer temperature is 150 ℃～250 ℃;
The Mo film that step 4, sputtering sedimentation thickness are 3nm～20nm, adopts solid-state selenium source selenizing method to its selenizing, the MoSe that formation thickness is 5nm～25nm
2film [14];
Step 5, utilize coevaporation method deposition to have the CuInGaSe absorbed layer [15] that " V " type band gap gradient distributes, the chemical formula of described Copper Indium Gallium Selenide is CuIn
1-xga
x(Se
1-ys
y)
2, atomic ratio y=0, at MoSe
2film first deposits broad-band gap CIGS thin-film on [14], and the chemical formula of described Copper Indium Gallium Selenide is CuIn
1-xga
x(Se
1-ys
y)
2, atomic ratio x > 0.7, y=0, thickness is 0.05 μ m～0.12 μ m, then deposits narrow band gap CIGS thin-film, the chemical formula of described Copper Indium Gallium Selenide is CuIn
1-xga
x(Se
1-ys
y) 2, atomic ratio 0.35>=x>=0.22, y=0, regulates and controls by technological parameter, forms " V " type band gap gradient and distribute in absorbed layer; The thickness of absorbed layer is 0.3 μ m～1.0 μ m; In absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃; After absorbed layer deposition finishes, it is carried out to the heat treatment that original position is evaporated appropriate NaF material, make the content of Na atom in absorbed layer remain on 0.1%;
Step 6, use chemical bath method, at the upper deposition of absorbed layer [15] Zn (S, O, OH) resilient coating [16], thickness is 30nm～70nm;
Step 7, under substrate is not had a mind to the condition of heating, sputtering sedimentation transparent window layer SnO
2: In film [17], thickness is 0.2 μ m～0.4 μ m;
Step 8, at the upper hydatogenesis top electrode Ni/A1 laminated film [18] of transparent window layer [17], thickness is 2.5 μ m～3 μ m;
Step 9, hydatogenesis antireflection layer MgF
2film [19], thickness is 100nm～130nm.
5. the manufacture method of the ultra-thin CIGS thin-film solar cell of flexible substrate as claimed in claim 4, is characterized in that: at the surperficial Direct precipitation MoSe of Ag film [12]
2film [14] replaces step 3 and step 4, and realizing back reflection composite bed is double-layer compound film structure.
6. the manufacture method of the ultra-thin CIGS thin-film solar cell of flexible substrate as claimed in claim 4, it is characterized in that: with the Cu-In-Ga-Se-S absorbed layer [15] that " V " type band gap gradient distributes of getting everything ready of selenizing/sulfuration legal system after splash-proofing sputtering metal initialization layer, replace step 5, the chemical formula of described Cu-In-Ga-Se-S is CuIn
1-xga
x(Se
1-ys
y)
2, atomic ratio 0.15≤y≤0.3, at MoSe
2the upper sputter CuGa target of film [14] and In target, the Ga content of described CuGa target is 22wt.%, preparing thickness is the Cu-In-Ga metal initialization layer of 0.12 μ m～0.4 μ m; Then adopt solid-state selenium source, solid-state sulphur source successively metal initialization layer to be carried out to selenizing and vulcanizing treatment, preparation has the Cu-In-Ga-Se-S thin film that " V " type band gap gradient distributes, and the chemical formula of described Cu-In-Ga-Se-S is CuIn
1-xga
x(Se
1-ys
y)
2, atomic ratio 0.22≤x≤0.35,0.15≤y≤0.3; In selenizing and vulcanizing treatment process, underlayer temperature is 400 ℃～510 ℃, and prepared absorber thickness is 0.3 μ m～1.0 μ m; After absorbed layer deposition finishes, the heat treatment that it is carried out to original position evaporation NaF material, makes the content of Na atom in absorbed layer remain on 0.1%.
7. the manufacture method of ultra-thin CIGS thin-film solar cell according to claim 6, is characterized in that: in described absorbed layer material, have " V " type band gap gradient distribute from incident sunlight one side to back electrode side.
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| TW201227980A (en) * | 2010-12-30 | 2012-07-01 | Univ Nat Cheng Kung | Thin film solar cell and method for manufacturing the same |
| CN102956722B (en) * | 2011-08-19 | 2015-05-27 | 比亚迪股份有限公司 | Thin-film solar cell |
| CN103022161A (en) * | 2011-09-22 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | Back electrode for manufacturing island-shaped growth structure with high electric conduction, high light reflection and low light loss |
| CN103022225A (en) * | 2011-09-22 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | Method for manufacturing island-shaped growth structure back electrode |
| FR2983642B1 (en) | 2011-12-05 | 2014-01-03 | Nexcis | IMPROVED INTERFACE BETWEEN A LAYER I-III-VI2 AND A REAR CONTACT LAYER IN A PHOTOVOLTAIC CELL. |
| US9935211B2 (en) | 2012-04-25 | 2018-04-03 | Guardian Glass, LLC | Back contact structure for photovoltaic devices such as copper-indium-diselenide solar cells |
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| CN102956754B (en) * | 2012-11-28 | 2017-02-08 | 中国电子科技集团公司第十八研究所 | Preparation method of absorbing layer of thin-film solar cell |
| US8703524B1 (en) * | 2012-11-29 | 2014-04-22 | Tsmc Solar Ltd. | Indium sputtering method and materials for chalcopyrite-based material usable as solar cell absorber layers |
| US9178103B2 (en) * | 2013-08-09 | 2015-11-03 | Tsmc Solar Ltd. | Apparatus and method for forming chalcogenide semiconductor absorber materials with sodium impurities |
| CN104681644A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院大连化学物理研究所 | Structure and preparing method of flexible film solar battery |
| CN104716207A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Structure and manufacturing technology of flexible thin film solar cell |
| CN104752557A (en) * | 2013-12-31 | 2015-07-01 | 中国电子科技集团公司第十八研究所 | Preparation method of light trapping structure type copper indium gallium diselenide thin film solar cell |
| TW201607054A (en) * | 2014-08-04 | 2016-02-16 | Chih-Huang Lai | Thin film solar cell and manufacturing method thereof |
| CN105405925A (en) * | 2015-11-10 | 2016-03-16 | 中建材光电装备（太仓）有限公司 | Method for controlling reaction of back electrode molybdenum and selenium in CIGS high temperature co-deposition process |
| CN108735861A (en) * | 2018-06-04 | 2018-11-02 | 北京铂阳顶荣光伏科技有限公司 | A kind of solar battery sheet and preparation method thereof, Preparation equipment and solar cell |
| CN112885503B (en) * | 2021-01-12 | 2022-06-21 | 南开大学 | Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film |
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