CN101752454A - 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 the photovoltaic cell manufacture method, especially a kind of preparation method with ultra-thin CIGS thin-film solar cell of light trapping structure.
Background technology
CIGS thin-film solar cell just has been subjected to people's generally attention with its superior performance since middle 1970s starting, develop very fastly, is one of the most rising thin film solar cell.Its typical structure is to pile substrate/back electrode/absorbed layer/resilient coating/Window layer/top electrode/antireflection layer of building successively.
In battery structure, absorbed layer is the Copper Indium Gallium Selenide (CuIn of direct band gap
1-xGa
x(Se
1-yS
y)
2) film, thickness is generally at 1.5 μ m～2 mu m ranges.Keeping under the constant prerequisite of electricity conversion, the thickness of attenuate absorbed layer makes sedimentation time and material cost reduce as much as possible, is the main trend that develops such battery technology at present in the world.
Thinning absorber thickness (thickness＜1 μ m), one side can reduce the consumption of noble metals such as In, Ga, reduces the cost of material and technology; 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, can't be absorbed, cause significant battery performance decay.In order to improve the utilance of sunlight, the back electrode film must have the good optical reflecting properties, makes unabsorbed solar energy be reflected back to carry out in the absorbed layer recycling.
At present, the CIGS thin-film battery structure adopts metal M o thin-film material as back electrode usually, but its optical reflectivity is not high, can't satisfy the requirement of slimline battery.And have 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 form the dephasign compound in the absorbed layer, and reduces battery performance.Therefore, for ultra-thin CIGS thin-film solar cell, must design and a kind ofly have the stable light trapping structure in interface between high optical reflectivity, low-resistivity and film, thereby solve the thickness thinning of absorbed layer and the contradiction between the cell conversion efficiency decay effectively.
Do not find at present the explanation or the report of technology similar to the present invention, do not collect both at home and abroad similarly data as yet yet.
Summary of the invention
Problems such as contradiction between the thickness thinning that solves the prior art absorbed layer and the cell conversion efficiency decay the object of the present invention is to provide a kind of preparation method with ultra-thin CIGS thin-film solar cell of light trapping structure.Use the light trapping structure of the solar cell that the inventive method makes and formed, can fully absorb solar spectrum under less than the situation of 1 μ m, improved battery efficiency greatly at battery obsorbing layer thickness by back reflection composite bed and absorbed layer.
In order to reach the foregoing invention purpose, the technical scheme that the present invention is adopted for its technical problem of solution provides a kind of manufacture method with 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 are 0.5 μ m～1.0 μ m; Step 2, sputtering sedimentation has the Ag film of suede degree on back electrode, and thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃; Step 3, employing sputtering method deposit transparent conducting ZnO: Al film, thickness are 0.15 μ m～0.25 μ m, and underlayer temperature is 150 ℃～250 ℃; Step 4, sputtering sedimentation thickness are the Mo film of 3nm～20nm, adopt solid-state selenium source selenizing method to its selenizing, and forming thickness is the MoSe of 5nm～25nm
2Film; Step 5, utilize coevaporation method deposition to have 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, promptly at MoSe
2(atomic ratio x＞0.7, y=0) film, thickness are 0.05 μ m～0.12 μ m to deposit the broad-band gap Copper Indium Gallium Selenide on the film earlier, deposit narrow band gap CIGS thin-film (atomic ratio 0.35 〉=x 〉=0.22 again, y=0), by the technological parameter regulation 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 the absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃; Absorbed layer deposition is carried out original position to it and is evaporated an amount of NaF material hot treatment after finishing, and makes that the Na atom content remains on 0.1% in the absorbed layer; Step 6, use the chemical bath method, (OH) resilient coating, thickness are 30nm～70nm for S, O to deposit Zn on absorbed layer; Step 7, under the condition that substrate does not heat, sputtering sedimentation transparent window layer SnO
2: In film, thickness are 0.2 μ m～0.4 μ m; Step 8, on 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 are 100nm～130nm.
In order to reach the foregoing invention purpose, another technical scheme that the present invention is adopted for its technical problem of solution provides a kind of manufacture method with ultra-thin CIGS thin-film solar cell of flexible substrate of light trapping structure, it is characterized in that this method comprises the steps:
Step 1, sputtering sedimentation one layer thickness is the SiO of 0.5 μ m～1.0 μ m on cleaned flexible substrate
2Film; Sputtering sedimentation back electrode Mo film on this film, thickness are 0.5 μ m～1.0 μ m; Step 2, sputtering sedimentation has the Ag film of suede degree on back electrode, and thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃; Step 3, employing sputtering method deposit transparent conducting ZnO: Al film, thickness are 0.15 μ m～0.25 μ m, and underlayer temperature is 150 ℃～250 ℃; Step 4, sputtering sedimentation thickness are the Mo film of 3nm～20nm, adopt solid-state selenium source selenizing method to its selenizing, and forming thickness is the MoSe of 5nm～25nm
2Film; Step 5, utilize coevaporation method deposition to have 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], promptly at MoSe
2(atomic ratio x＞0.7, y=0) film, thickness are 0.05 μ m～0.12 μ m to deposit the broad-band gap Copper Indium Gallium Selenide on the film earlier, deposit narrow band gap CIGS thin-film (atomic ratio 0.35 〉=x 〉=0.22 again, y=0), by the technological parameter regulation 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 the absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃; Absorbed layer deposition is carried out original position to it and is evaporated an amount of NaF material hot treatment after finishing, and makes that the Na atom content remains on 0.1% in the absorbed layer; Step 6, use the chemical bath method, (OH) resilient coating, thickness are 30nm～70nm for S, O to deposit Zn on absorbed layer; Step 7, under substrate is had a mind to the condition of heating, sputtering sedimentation transparent window layer SnO
2: In film, thickness are 0.2 μ m～0.4 μ m; Step 8, on 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 are 100nm～130nm.
The present invention has the preparation method of the ultra-thin CIGS thin-film solar cell of light trapping structure, owing to take above-mentioned technical scheme, adopt ultra-thin absorbent layer structure (thickness is 0.3 μ m～1.0 μ m), reduce the consumption of noble metals such as In, Ga on the one hand, reduced battery manufacturing costs such as material, technology; Significantly reduce the weight of hull cell on the other hand, expanded the application of battery.Simultaneously, the back reflection composite bed forms light trapping structure jointly with the absorbed layer that " V " type gradient band gap distributes, and reduces optics and electricity loss that the absorbed layer thinning causes as far as possible, has improved cell conversion efficiency greatly.And resilient coating adopts Zn, and (OH) film replaces the conventional CdS film that uses, and has avoided the pollution of heavy metal Cd element to environment for S, O.Therefore, the present invention has that technology is simple, the cost of material is low, free of contamination characteristics, can significantly reduce the manufacturing cost of thin film solar cell.
Description of drawings
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 manufacturing;
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 manufacturing.
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 manufacturing; As shown in Figure 1, this solar cell comprises: pile common soda-lime glass substrate 10, back electrode Mo film 11, Ag film 12, the transparent conducting ZnO of building successively: 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 manufacturing of the present invention; As shown in Figure 2, this solar cell comprises: pile flexible substrate 20, the SiO that builds successively
2 Film 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 the above-mentioned solar cell, on back electrode, deposit Ag film, transparent conductive oxide film and MoSe successively
2Film constitutes the back reflection composite bed.Back reflection composite bed and absorbed layer are formed light trapping structure jointly.Wherein the Ag film is as the reflector, and the Ag film has very high optical reflectivity, and the Ag film surface of deposition has certain suede degree, make to see through the effect of the solar photon of absorbed layer by the back reflection composite bed, and it is interior and be maximized absorption to return absorbed layer.Because Ag is easy to elements such as In, Ga, Se and forms the dephasign compound, therefore need deposition layer of transparent conductive oxide film on Ag film surface, 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 the Ag atom to the absorbed layer diffusion inside, improves the interface stability between Ag film and the absorbed layer.Form skim MoSe on the sull surface
2, can stop the diffusion of oxide to 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 stable characteristics in interface between high optical reflectivity, low-resistivity and film.Simultaneously, utilize to have " V " type band gap gradient in Copper Indium Gallium Selenide (atomic ratio 0.15≤y≤0.3) film of selenizing/sulfuration method deposition behind Copper Indium Gallium Selenide (atomic ratio y=0) film of coevaporation method deposition or the splash-proofing sputtering metal initialization layer 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 the absorbed layer thinning causes, and improves the transformation efficiency of ultra-thin CIGS thin-film solar cell significantly.
Above-described ultra-thin CIGS thin-film solar cell, substrate are common soda-lime glass or flexible material (metal stainless steel foil, titanium foil, polyimides).For flexible substrate, before the deposition back electrode, wanting sputtering sedimentation one layer thickness earlier is the SiO of 0.5 μ m～1.0 μ m
2Film stops the various objectionable impurities elements in the substrate to spread in absorbed layer, and reduces the surface roughness of backing material, helps improving the thin-film material quality of subsequent growth.And for glass substrate, need not this technology.Absorbed layer (CuIn
1-xGa
x(Se
1-yS
y)
2) after deposition finishes, its original position is evaporated an amount of NaF material heat-treat, make that the Na atom content remains on about 0.1% in the absorbed layer, played the effect of passivation grain boundary defects and purifying impurity.
To the present invention, the manufacture method of promptly above-mentioned two kinds of solar cells is described in detail below in conjunction with drawings and Examples.
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 are 0.5 μ m～1.0 μ m.
Step 2, sputtering sedimentation has the Ag film 12 of certain suede degree on back electrode 11, and thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃.
Step 3, employing sputtering method deposit transparent conducting ZnO: Al film 13, thickness are 0.15 μ m～0.25 μ m, and underlayer temperature is 150 ℃～250 ℃.
Step 4, sputtering sedimentation thickness are the Mo film of 3nm～20nm, adopt solid-state selenium source selenizing method to its selenizing, and forming thickness is the MoSe of 5nm～25nm
2Film 14.
Step 5, utilize coevaporation method deposition to have 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.Promptly at MoSe
2Deposit broad-band gap Copper Indium Gallium Selenide (atomic ratio x＞0.7 on the film 14 earlier, y=0) film, thickness is 0.05 μ m～0.12 μ m, deposit narrow band gap CIGS thin-film (atomic ratio 0.35 〉=x 〉=0.22 again, y=0), by the technological parameter regulation 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 the absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃.Absorbed layer deposition is carried out original position to it and is evaporated an amount of NaF material hot treatment after finishing, and makes that the Na atom content remains on about 0.1% in the absorbed layer.
Step 6, use the chemical bath method, (OH) resilient coating 16 for S, O, and thickness is 30nm～70nm to deposit Zn on absorbed layer 15.
Step 7, under substrate is had a mind to the condition of heating, sputtering sedimentation transparent window layer SnO
2: In film 17, thickness are 0.2 μ m～0.4 μ m.
Step 8, on 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 are 100nm～130nm.
Embodiment 2
Above-mentioned steps three or step 4 can directly deposit MoSe on Ag film 12 surfaces
2Film 14 realizes that the back reflection composite bed is the double-layer compound film structure.All the other steps are with embodiment 1.
Embodiment 3
Above-mentioned steps five can be with selenizing behind the splash-proofing sputtering metal initialization layer/sulfuration legal system Copper Indium Gallium Selenide (CuIn that " V " type band gap gradient distributes that gets everything ready
1-xGa
x(Se
1-ys
y)
2, atomic ratio 0.15≤y≤0.3) and absorbed layer 15.At MoSe
2On the 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.Adopt solid-state selenium source, solid-state sulphur source successively the metal initialization layer to be carried out selenizing and vulcanizing treatment then, 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, it is carried out original position evaporation NaF material hot treatment, make that the Na atom content remains on about 0.1% in the absorbed layer.All the other steps are with embodiment 1.
Embodiment 4
Above-mentioned steps three or step 4, back reflection composite bed are the double-layer compound film structure, promptly can directly deposit MoSe on Ag film surface
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, sputtering sedimentation one layer thickness is the SiO of 0.5 μ m～1.0 μ m on cleaned flexible substrate 20
2 Film 21, sputtering sedimentation back electrode Mo film 11 on film 21 again, 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 embodiment 5 described flexible substrate, the back reflection composite bed is the double-layer compound film structure, promptly directly deposits MoSe on Ag film 12 surfaces
2Film 14.All the other steps are with embodiment 5.
Embodiment 7
In the ultra-thin CIGS thin-film solar cell of embodiment 5 described flexible substrate, before the deposition back electrode, sputtering sedimentation one layer thickness is the SiO of 0.5 μ m～1.0 μ m on flexible substrate
2Film.All the other steps are with embodiment 3.
Embodiment 8
In the ultra-thin CIGS thin-film solar cell of embodiment 5 described flexible substrate, the back reflection composite bed is the double-layer compound film structure, promptly directly deposits MoSe on Ag film surface
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.
The back reflection composite bed is 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 is formed, and has interface stable properties between high optical reflectivity, low-resistivity and film.
In the absorbed layer material, has " V " type band gap gradient from incident sunlight one side to back electrode side.
Above-mentioned steps seven described transparent window layer are transparent conductive oxide films 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: under substrate was not had a mind to heating condition, sputter obtained the transparent conductive film that thickness is 0.2 μ m～0.4 μ m.
Above-mentioned steps three described transparent conductive oxide films are the 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: be that sputter obtains the transparent conductive film that thickness is 0.15 μ m～0.25 μ m under 150 ℃～250 ℃ the condition at underlayer temperature.
Claims (9)
1. the manufacture method with ultra-thin CIGS thin-film solar cell of glass substrate of light trapping structure is characterized in that this method comprises the steps:
Step 1, on cleaned common soda-lime glass substrate [10], sputtering sedimentation back electrode Mo film [11], thickness are 0.5 μ m～1.0 μ m;
Step 2, go up the Ag film [12] that sputtering sedimentation has the suede degree at back electrode [11], thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃;
Step 3, employing sputtering method deposit transparent conducting ZnO: Al film [13], thickness are 0.15 μ m～0.25 μ m, and underlayer temperature is 150 ℃～250 ℃;
Step 4, sputtering sedimentation thickness are the Mo film of 3nm～20nm, adopt solid-state selenium source selenizing method to its selenizing, and forming thickness is the MoSe of 5nm～25nm
2Film [14];
Step 5, utilize coevaporation method deposition to have 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], promptly at MoSe
2Film [14] is gone up deposition broad-band gap Copper Indium Gallium Selenide (atomic ratio x＞0.7 earlier, y=0) film, thickness is 0.05 μ m～0.12 μ m, deposit narrow band gap CIGS thin-film (atomic ratio 0.35 〉=x 〉=0.22 again, y=0), by the technological parameter regulation 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 the absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃; Absorbed layer deposition is carried out original position to it and is evaporated an amount of NaF material hot treatment after finishing, and makes that the Na atom content remains on 0.1% in the absorbed layer;
Step 6, use the chemical bath method, absorbed layer [15] go up deposition Zn (S, O, OH) resilient coating [16], thickness is 30nm～70nm;
Step 7, under substrate is had a mind to the condition of heating, sputtering sedimentation transparent window layer SnO
2: In film [17], thickness are 0.2 μ m～0.4 μ m;
Step 8, go up hydatogenesis top electrode Ni/Al laminated film [18] in transparent window layer [17], thickness is 2.5 μ m～3 μ m;
Step 9, hydatogenesis antireflection layer MgF
2Film [19], thickness are 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: described step 3 or step 4 can directly deposit MoSe on Ag film [12] surface
2Film [14] realizes that the back reflection composite bed is the 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, it is characterized in that: described step 5, can be with selenizing behind the splash-proofing sputtering metal initialization layer/sulfuration legal system Copper Indium Gallium Selenide (CuIn that " V " type band gap gradient distributes that gets everything ready
1-xGa
x(Se
1-yS
y)
2, atomic ratio 0.15≤y≤0.3) and absorbed layer [15], promptly at MoSe
2On the 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; Adopt solid-state selenium source, solid-state sulphur source successively the metal initialization layer to be carried out selenizing and vulcanizing treatment then, 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 ℃, and prepared absorber thickness is 0.3 μ m～1.0 μ m; After absorbed layer deposition finishes, it is carried out original position evaporation NaF material hot treatment, make that the Na atom content remains on 0.1% in the absorbed layer.
4. the manufacture method of the ultra-thin CIGS thin-film solar cell of glass substrate as claimed in claim 1 is characterized in that: described step 3 or step 4 can directly deposit MoSe on Ag film surface
2Film realizes that the back reflection composite bed is the double-layer compound film structure; Described step 5 can be with the get everything ready Copper Indium Gallium Selenide (CuIn of " V " type band gap gradient of selenizing behind the splash-proofing sputtering metal initialization layer/sulfuration legal system
1-xGa
x(Se
1-yS
y)
2, atomic ratio 0.15≤y≤0.3) and absorbed layer [15], promptly at MoSe
2On the 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; Adopt solid-state selenium source, solid-state sulphur source successively the metal initialization layer to be carried out selenizing and vulcanizing treatment then, 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 ℃, and prepared absorber thickness is 0.3 μ m～1.0 μ m; After absorbed layer deposition finishes, it is carried out original position evaporation NaF material hot treatment, make that the Na atom content remains on 0.1% in the absorbed layer.
5. the manufacture method with ultra-thin CIGS thin-film solar cell of flexible substrate of light trapping structure is characterized in that this method comprises the steps:
Step 1, to go up sputtering sedimentation one layer thickness in cleaned flexible substrate [20] be the SiO of 0.5 μ m～1.0 μ m
2Film [21]; Go up sputtering sedimentation back electrode Mo film [11] at film [21] again, thickness is 0.5 μ m～1.0 μ m;
Step 2, go up the Ag film [12] that sputtering sedimentation has the suede degree at back electrode [11], thickness is 50nm～150nm, and underlayer temperature is 150 ℃～300 ℃;
Step 3, employing sputtering method deposit transparent conducting ZnO: Al film [13], thickness are 0.15 μ m～0.25 μ m, and underlayer temperature is 150 ℃～250 ℃;
Step 4, sputtering sedimentation thickness are the Mo film of 3nm～20nm, adopt solid-state selenium source selenizing method to its selenizing, and forming thickness is the MoSe of 5nm～25nm
2Film [14];
Step 5, utilize coevaporation method deposition to have 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], promptly at MoSe
2Film [14] is gone up deposition broad-band gap Copper Indium Gallium Selenide (atomic ratio x＞0.7 earlier, y=0) film, thickness is 0.05 μ m～0.12 μ m, deposit narrow band gap CIGS thin-film (atomic ratio 0.35 〉=x 〉=0.22 again, y=0), by the technological parameter regulation 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 the absorbed layer film preparation process, underlayer temperature is controlled at 360 ℃～510 ℃; Absorbed layer deposition is carried out original position to it and is evaporated an amount of NaF material hot treatment after finishing, and makes that the Na atom content remains on 0.1% in the absorbed layer;
Step 6, use the chemical bath method, absorbed layer [15] go up deposition Zn (S, O, OH) resilient coating [16], thickness is 30nm～70nm;
Step 7, under substrate is had a mind to the condition of heating, sputtering sedimentation transparent window layer SnO
2: In film [17], thickness are 0.2 μ m～0.4 μ m;
Step 8, go up hydatogenesis top electrode Ni/Al laminated film [18] in transparent window layer [17], thickness is 2.5 μ m～3 μ m;
Step 9, hydatogenesis antireflection layer MgF
2Film [19], thickness are 100nm～130nm.
6. the manufacture method of the ultra-thin CIGS thin-film solar cell of flexible substrate as claimed in claim 5 is characterized in that: described step 3 or step 4 can directly deposit MoSe on Ag film [12] surface
2Film [14] realizes that the back reflection composite bed is the double-layer compound film structure.
7. the manufacture method of the ultra-thin CIGS thin-film solar cell of flexible substrate as claimed in claim 5, it is characterized in that: described step 5, can be with selenizing behind the splash-proofing sputtering metal initialization layer/sulfuration legal system Copper Indium Gallium Selenide (CuIn that " V " type band gap gradient distributes that gets everything ready
1-xGa
x(Se
1-yS
y)
2, atomic ratio 0.15≤y≤0.3) and absorbed layer [15], promptly at MoSe
2On the 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; Adopt solid-state selenium source, solid-state sulphur source successively the metal initialization layer to be carried out selenizing and vulcanizing treatment then, 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 ℃, and prepared absorber thickness is 0.3 μ m～1.0 μ m; After absorbed layer deposition finishes, it is carried out original position evaporation NaF material hot treatment, make that the Na atom content remains on 0.1% in the absorbed layer.
8. according to the manufacture method of the described ultra-thin CIGS thin-film solar cell of each claim in the claim 1 to 7, it is characterized in that:
Described glass substrate is that thickness is the common soda-lime glass of 2mm～3mm; Described flexible substrate is that thickness is 20 μ m～metal stainless steel foil of 50 μ m, titanium foil, polyimides flexible material; Described back reflection composite bed is double-deck or three layers of complex thin film structure, by Ag film/MoSe
2Film or Ag film/transparent conductive oxide film/MoSe
2Film is formed.
9. the manufacture method of ultra-thin CIGS thin-film solar cell according to claim 8 is characterized in that: in the described absorbed layer material, have " V " type band gap gradient from incident sunlight one side to back electrode side and distribute.
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