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 PDF

Info

Publication number
CN101752454A
CN101752454A CN200810204035A CN200810204035A CN101752454A CN 101752454 A CN101752454 A CN 101752454A CN 200810204035 A CN200810204035 A CN 200810204035A CN 200810204035 A CN200810204035 A CN 200810204035A CN 101752454 A CN101752454 A CN 101752454A
Authority
CN
China
Prior art keywords
film
thickness
layer
absorbed layer
band gap
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN200810204035A
Other languages
Chinese (zh)
Other versions
CN101752454B (en
Inventor
徐传明
曹章轶
马贤芳
王小顺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Space Power Sources
Original Assignee
Shanghai Institute of Space Power Sources
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Space Power Sources filed Critical Shanghai Institute of Space Power Sources
Priority to CN200810204035.1A priority Critical patent/CN101752454B/en
Publication of CN101752454A publication Critical patent/CN101752454A/en
Application granted granted Critical
Publication of CN101752454B publication Critical patent/CN101752454B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Photovoltaic Devices (AREA)

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

Preparation method with ultra-thin CIGS thin-film solar cell of light trapping structure
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 2 Film 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 2 Film 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.
CN200810204035.1A 2008-12-04 2008-12-04 Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure Expired - Fee Related CN101752454B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200810204035.1A CN101752454B (en) 2008-12-04 2008-12-04 Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200810204035.1A CN101752454B (en) 2008-12-04 2008-12-04 Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure

Publications (2)

Publication Number Publication Date
CN101752454A true CN101752454A (en) 2010-06-23
CN101752454B CN101752454B (en) 2014-08-13

Family

ID=42479118

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200810204035.1A Expired - Fee Related CN101752454B (en) 2008-12-04 2008-12-04 Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure

Country Status (1)

Country Link
CN (1) CN101752454B (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569442A (en) * 2010-12-30 2012-07-11 彭洞清 Thin film solar cell and manufacturing method thereof
CN102956752A (en) * 2012-11-28 2013-03-06 中国电子科技集团公司第十八研究所 Preparation method of flexible copper indium gallium selenium thin film solar battery
CN102956754A (en) * 2012-11-28 2013-03-06 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
CN102956722A (en) * 2011-08-19 2013-03-06 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
CN103474505A (en) * 2012-06-06 2013-12-25 尚越光电科技有限公司 Alkali metal doping method in large-scale production of CIGS (copper, indium, gallium, selenium) thin-film solar cell
CN103855249A (en) * 2012-11-29 2014-06-11 台积太阳能股份有限公司 METHOD and material FOR INDIUM SPUTTERING AND FOR FORMING CHALCOPYRITE-BASED SOLAR CELL ABSORBER LAYERS
CN104342634A (en) * 2013-08-09 2015-02-11 台积太阳能股份有限公司 Apparatus and method for forming chalcogenide semiconductor absorber materials with sodium impurities
CN104396020A (en) * 2012-04-25 2015-03-04 葛迪恩实业公司 Back contact structure for photovoltaic devices such as copper-indium-diselenide solar cells
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
CN105322051A (en) * 2014-08-04 2016-02-10 赖志煌 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
US9478695B2 (en) 2011-12-05 2016-10-25 Nexcis Interface between a I/III/VI2 layer and a back contact layer in a photovoltaic cell
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
CN112885503A (en) * 2021-01-12 2021-06-01 南开大学 Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101097968A (en) * 2007-06-27 2008-01-02 华东师范大学 Highly-effective laminate solar battery and method for making same
CN101295743A (en) * 2008-04-15 2008-10-29 福建钧石能源有限公司 Thin film, its forming method and solar battery with the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101097968A (en) * 2007-06-27 2008-01-02 华东师范大学 Highly-effective laminate solar battery and method for making same
CN101295743A (en) * 2008-04-15 2008-10-29 福建钧石能源有限公司 Thin film, its forming method and solar battery with the same

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569442A (en) * 2010-12-30 2012-07-11 彭洞清 Thin film solar cell and manufacturing method thereof
CN102569442B (en) * 2010-12-30 2014-08-13 彭洞清 Thin film solar cell and manufacturing method thereof
CN102956722A (en) * 2011-08-19 2013-03-06 比亚迪股份有限公司 Thin-film solar cell
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
US9478695B2 (en) 2011-12-05 2016-10-25 Nexcis Interface between a I/III/VI2 layer and a back contact layer in a photovoltaic cell
CN104396020A (en) * 2012-04-25 2015-03-04 葛迪恩实业公司 Back contact structure for photovoltaic devices such as copper-indium-diselenide solar cells
CN104396020B (en) * 2012-04-25 2018-04-24 葛迪恩实业公司 Rear contact structures for the photovoltaic device of similar copper and indium The sub-salt acid solar 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
CN103474505A (en) * 2012-06-06 2013-12-25 尚越光电科技有限公司 Alkali metal doping method in large-scale production of CIGS (copper, indium, gallium, selenium) thin-film solar cell
CN103474505B (en) * 2012-06-06 2016-07-20 尚越光电科技有限公司 Alkali-metal-doped method in copper-indium-galliun-selenium film solar cell large-scale production
CN102956752A (en) * 2012-11-28 2013-03-06 中国电子科技集团公司第十八研究所 Preparation method of flexible copper indium gallium selenium thin film solar battery
CN102956754A (en) * 2012-11-28 2013-03-06 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
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
CN102956752B (en) * 2012-11-28 2016-12-21 中国电子科技集团公司第十八研究所 The preparation method of flexible CIGS thin-film solar cell
CN103855249B (en) * 2012-11-29 2016-11-23 台湾积体电路制造股份有限公司 Can be used as indium sputtering method and the material of the material based on Chalkopyrite of solar battery obsorbing layer
CN103855249A (en) * 2012-11-29 2014-06-11 台积太阳能股份有限公司 METHOD and material FOR INDIUM SPUTTERING AND FOR FORMING CHALCOPYRITE-BASED SOLAR CELL ABSORBER LAYERS
CN104342634A (en) * 2013-08-09 2015-02-11 台积太阳能股份有限公司 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
CN105322051A (en) * 2014-08-04 2016-02-10 赖志煌 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
CN112885503A (en) * 2021-01-12 2021-06-01 南开大学 Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film
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

Also Published As

Publication number Publication date
CN101752454B (en) 2014-08-13

Similar Documents

Publication Publication Date Title
CN101752454B (en) Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure
US20130037100A1 (en) Thin Film Photovoltaic Solar Cells
CN104882495B (en) Transparent conductive window layer for solar cell, and CIGS-base thin-film solar cell
EP2777075B1 (en) Conducting substrate for photovoltaic cell
CN103915516B (en) A kind of sodium doping method of CIGS base film photovoltaic material
EP1836736A2 (en) Process and photovoltaic device using an akali-containing layer
US9935211B2 (en) Back contact structure for photovoltaic devices such as copper-indium-diselenide solar cells
Cooray et al. Large area ZnO films optimized for graded band-gap Cu (InGa) Se2-based thin-film mini-modules
WO2011074685A1 (en) Process for production of cis-based thin-film solar cell
KR20090123645A (en) High-efficiency cigs solar cells and manufacturing method thereof
CN106024937A (en) CIGS-based thin-film solar cell and preparation method thereof
KR20120080045A (en) Manufacturing method of solar cell
CN101752453A (en) Preparation method of glass-substrate double-side CIGS thin film solar cell module
EP2702615B1 (en) Method of preparing a solar cell
CN105261660A (en) CIGS-based thin-film solar cell
TW201914044A (en) Solar cell and method of manufacturing same
CN105023958B (en) CIGS based thin film solar cell and preparation method thereof
US9034686B2 (en) Manufacturing methods for semiconductor devices
CN104882508A (en) Chalcopyrite type film photovoltaic cell and manufacturing method thereof
CN102956722A (en) Thin-film solar cell
JP2017059656A (en) Photoelectric conversion element and solar battery
CN105261666A (en) Thin-film solar cell
KR101315311B1 (en) Back contact and cis-based solar cell comprising the same
US20220173262A1 (en) See-through thin film solar cell module and method of manufacturing the same
JP2011249686A (en) Method for manufacturing photoelectric conversion element and photoelectric conversion element

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140813

Termination date: 20191204