CN105590973A - Flexible thin film solar cell having high-adhesion absorbing layer - Google Patents
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Abstract
The present invention relates to a flexible thin film solar cell having a high-adhesion absorbing layer, and belongs to the technical field of CIGS thin film solar cells. The flexible thin film solar cell is characterized by comprising a multilayer structure, wherein the multilayer structure successively comprises a flexible substrate, a Mo electrode layer, a stress buffer layer, a CIGS absorbing layer, a CdS buffer layer, a transparent conductive window layer, and a Ni-Al gate electrode; the stress buffer layer is arranged between the CIGS absorbing layer and the Mo electrode layer, so as to improve the binding force of the CIGS absorbing layer grown on the flexible substrate. The flexible thin film solar cell of the present invention has the advantages that the flexible thin film solar cell can obtain the CIGS absorbing layer with high adhesion, can effectively avoid the problems of cracking even detachment of a CIGS thin film on the flexible substrate due to internal stress, and can improve electrical property of the absorbing layer.
Description
Technical field
The invention belongs to CIGS thin-film solar cell technical field, particularly relate to a kind of high-bond absorbed layer of havingFlexible thin-film solar cell.
Background technology
At present, flexible substrate CIGS (Cu (In, Ga) Se2, being called for short CIGS) and thin film solar cell has quality and compares powerThe advantages, particularly flexible substrate CIGS hull cell such as high, capability of resistance to radiation strong, good stability, its quality is than power oneAs be greater than 600W/kg, and battery component is applicable to volume to volume preparation and monolithic is integrated, aspect producing in batches and reducing costsHave very large potentiality, range of application is (than rigid substrate) more extensively. At present, restrict that such battery performance improvesKey issue and technological difficulties are deposition techniques of high-performance CIGS absorbed layer.
CIGS absorbed layer is the core of such solar cell, improves CIGS absorbed layer crystalline quality, optimizes its photoelectric property and isIn laboratory, obtain the key of high efficiency CIGS thin film solar cell, be also to commercially produce middle raising battery component to become simultaneouslyProduct rate, the basis reducing costs. But, for flexible substrate, particularly polyimide plastic substrate (Polyimide,Be called for short PI substrate), except absorbent layer structure and photoelectric property, the adhesion between CIGS film and substrate and hearth electrodeAlso be one of key factor affecting battery performance. Previously there is patent (patent No.: CN200610016182.7) to provide softThe typical structure of property CIGS thin film solar cell is: flexible substrate/Mo electrode layer/CIGS absorbed layer/CdS cushion/transparentConductive window layer/Ni-Al gate electrode/antireflective coating. This patent does not consider to deposit on PI substrate adhering to of CIGS absorbed layerProperty problem. Because the difference of thermal expansion coefficients between thin layer is larger, as shown in table 1, in CIGS absorbed layer growth course,The generation deformation of being heated of PI substrate, the larger stress that made CIGS film inner accumulation. According to the hull cell structure of accompanying drawing 1,The CIGS absorbed layer slight crack obtaining is more, even occurs obscission from Mo/PI substrate, as shown in Fig. 3 (a). CIGSAbsorbed layer is in the subsequent technique such as chemical bath, sputtering sedimentation is processed, and the problem of coming off can be more serious, to the performance of battery andYield rate makes a big impact.
The thermal coefficient of expansion of table 1 flexible substrate and related semiconductor material
Summary of the invention
The present invention provides a kind of flexible thin with high-bond absorbed layer for solving the technical problem existing in known technologyFilm solar cell.
The object of this invention is to provide one and can obtain high-bond CIGS absorbed layer, effectively avoided in flexible substrateCIGS film, because of problems such as internal stress ftracture, even comes off, has improved the high knot of having of the features such as absorbed layer electrical propertiesThe flexible thin-film solar cell of absorbed layer with joint efforts.
The flexible thin-film solar cell structure that the present invention has high-bond absorbed layer is: flexible substrate/Mo electrode layer/stressCushion/CIGS absorbed layer/CdS cushion/electrically conducting transparent Window layer/Ni-Al gate electrode/antireflective coating. Than existingThe disclosed flexible CIGS thin-film solar cell structure of patent, the feature of this structure be CIGS absorbed layer and Mo electrode layer itBetween designed a stress-buffer layer, improved the adhesion of the CIGS absorbed layer of growing in flexible substrate, effectively avoidedThe problem that comes off of absorbed layer, can improve performance and the yield rate of flexible CIGS thin film solar cell.
Flexible CIGS thin film solar cell of the present invention comprises sandwich construction, as shown in Figure 1. Adopt flexible substrate (to comprisePI substrate, metal substrate etc.), on it, structure is followed successively by: (thickness is about 0.5～1 μ m) to Mo hearth electrode; Stress bufferLayer (In1-x,Gax)2Se3Film (thickness is about 100nm～1000nm, is called for short IGS); P-type CIGS absorbed layer (thicknessBetween 1～3 μ m); N-shaped CdS cushion (thickness is about 50nm); I-ZnO layer and ZnO:Al Window layer (thicknessBe respectively 50nm and 300～500nm); Ni/Al metal gate electrode. For small size CIGS thin film solar cell, forReduce because battery surface reflects the optical absorption loss causing, improve battery performance, at the surface deposition one of above-mentioned battery structureLayer thickness is about the MgF of 100nm2Antireflection layer, as shown in Figure 2.
Prepare stress-buffer layer (In1-x,Gax)2Se3The concrete technology of film (being called for short IGS film) is: whole chamberBackground vacuum pressure reaches 1 × 10-4Pa, before CIGS film absorption layer deposition, adopts coevaporation In, Ga and Se unitElement deposition IGS film. In deposition process, underlayer temperature keeps constant, evaporation cavity in scope between 350 DEG C～480 DEG CIn chamber, remain enough Se atmosphere, fully react with Se element with the In, the Ga element that ensure to deposit on substrate,Form (In1-x,Gax)2Se3Phase. The temperature of Ga, In evaporation source is constant is respectively 900 DEG C-1100 DEG C, 800 DEG C-1000 DEG C,Se evaporation source keeps constant within the scope of 250 DEG C～350 DEG C. Film deposition rate is about 15nm/min, obtains thickness and is about(the In of 100-1000nm1-x,Gax)2Se3Film (0.2 < x < 0.8), then deposits CIGS absorbed layer. IGS thin film depositionThe vacuum pressure of journey middle chamber remains on 1 × 10-3Pa left and right.
The present invention has the technical scheme that the flexible thin-film solar cell of high-bond absorbed layer takes:
A flexible thin-film solar cell with high-bond absorbed layer, is characterized in: have the soft of high-bond absorbed layerProperty thin film solar cell comprises sandwich construction, and sandwich construction is followed successively by flexible substrate, Mo electrode layer, stress-buffer layer, CIGSAbsorbed layer, CdS cushion, electrically conducting transparent Window layer, Ni-Al gate electrode, establish between CIGS absorbed layer and Mo electrode layerThere is stress-buffer layer, improve the adhesion of the CIGS absorbed layer of flexible substrate growth.
The flexible thin-film solar cell that the present invention has high-bond absorbed layer can also adopt following technical scheme:
The described flexible thin-film solar cell with high-bond absorbed layer, is characterized in: have high-bond absorbed layerFlexible thin-film solar cell comprise sandwich construction, at surface deposition one deck MgF of battery structure2Antireflection layer.
The described flexible thin-film solar cell with high-bond absorbed layer, is characterized in: MgF2Antireflection layer thickness is90-110nm。
The described flexible thin-film solar cell with high-bond absorbed layer, is characterized in: Mo electrode layers thickness is 0.5～1 μ m, p-type CIGS absorber thickness is 1～3 μ m, N-shaped CdS buffer layer thickness is 45-55nm.
The described flexible thin-film solar cell with high-bond absorbed layer, is characterized in: stress-buffer layer is(In1-x,Gax)2Se3Film 0.2 < x < 0.8 stress-buffer layer.
The described flexible thin-film solar cell with high-bond absorbed layer, is characterized in: (In1-x,Gax)2Se3FilmStress buffer layer thickness is 100nm～1000nm.
Advantage and good effect that the present invention has are:
There is the flexible thin-film solar cell of high-bond absorbed layer owing to having adopted the brand-new technical scheme of the present invention, with existingTechnology is compared, and the present invention has following characteristics:
1, the present invention designs one deck IGS stress-buffer layer between CIGS absorbed layer and hearth electrode Mo. At deposition CIGSBefore absorbed layer, first deposit certain thickness IGS stress-buffer layer, its thermal coefficient of expansion and PI substrate and CIGS materialBetween difference less, stronger than CIGS absorbed layer with the adhesion of Mo electrode. In the time that PI substrate is heated generation deformation, IGSLayer has effectively been alleviated the internal stress accumulating in CIGS film nucleation, crystallization process, and the CIGS that has obtained high-bond absorbsLayer, the problem of having avoided the CIGS film in flexible substrate to ftracture, even come off because of internal stress, as shown in Figure 3.
2, the present invention designs one deck IGS stress-buffer layer between CIGS absorbed layer and hearth electrode Mo, at deposition cushionTime can evaporate NaF, obtain the IGS film containing Na. Na atom is by diffusing into the CIGS of subsequent depositionIn film, improve the electrical properties of absorbed layer. Avoided independent deposition NaF layer to CIGS film and PI/Mo lining simultaneouslyThe impact that bear building-up is made a concerted effort.
Brief description of the drawings
Fig. 1 is the flexible CIGS thin-film solar cell structure with high-bond absorbed layer;
Fig. 2 is the small size flexible CIGS thin-film solar cell structure with high-bond absorbed layer;
In figure: 1-gate electrode; 2-i-ZnO&ZnO:Al Window layer; 3-n type CdS cushion; 4-CIGS absorbed layer;5-IGS stress-buffer layer; 6-Mo hearth electrode; 7-flexible substrate; 8-antireflection layer.
Fig. 3 is the photo of the CIGS absorbed layer exterior appearance that deposits in PI substrate/Mo structure, (a) CIGS film in figureDirect precipitation, on PI substrate/Mo electrode, (b) designs in figure between CIGS film and PI substrate/Mo electrode structureIGS stress-buffer layer.
Detailed description of the invention
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples, and coordinate accompanying drawingBe described in detail as follows:
Embodiment 1
There is a flexible thin-film solar cell for high-bond absorbed layer, consult accompanying drawing 1. Large area flexible CIGSThe structure of thin film solar cell comprises: flexible substrate 7, Mo hearth electrode 6, IGS stress-buffer layer 5, CIGS absorbed layer 4,CdS cushion 3, i-ZnO&ZnO:Al Window layer 2, Ni-Al gate electrode 1, wherein flexible substrate is tinsel, asTi paillon foil, stainless steel substrates, Cu paillon foil etc., substrate thickness is 50-100 μ m.
In flexible thin-film solar cell structure, IGS stress-buffer layer is between CIGS absorbed layer and Mo electrode, and thickness is100nm-1000nm. Tinsel using thickness as 50-100 μ m, as substrate, before deposition absorbed layer, first adoptsVolume to volume coevaporation process deposits IGS stress buffer layer film. In deposition process, in chamber, vacuum pressure remains on1 × 10-3Pa left and right, underlayer temperature keeps constant in scope between 350 DEG C～480 DEG C, keeps enough Se atmosphere.The temperature of Ga, In evaporation source is constant is respectively 900 DEG C-1100 DEG C, 800 DEG C-1000 DEG C, and Se evaporation source is at 250 DEG C～350 DEG CIn scope, keep constant. Substrate with the speed of 50mm/min successively by Ga and In evaporation source. IGS film deposition rate approximatelyFor 20nm/min, finally obtaining thickness is the IGS stress-buffer layer of 100-1000nm. Close In and Ga evaporation source baffle plate,Se continues to keep constant evaporation rate. Adjust underlayer temperature, Cu, In, the each evaporation source evaporation rate of Ga, continued CIGSAbsorbed layer deposition.
The CdS cushion with volume to volume chemical bath method deposition 50nm thickness successively on CIGS absorbed layer, penetrates by volume to volumeFrequently magnetron sputtering method deposition i-ZnO/ZnO:Al Window layer, the thickness of double-layer films is respectively 50nm and 500nm. Finally makePrepare Ag or Al gate electrode with volume to volume silk-screen printing technique, Ag or Al thickness are 2 μ m, obtain large area flexible metalSubstrate CIGS thin film solar cell.
Embodiment 2
There is a flexible thin-film solar cell for high-bond absorbed layer, refer to accompanying drawing 1. Large area flexible CIGSThe structure of thin film solar cell comprises: flexible substrate 7, Mo hearth electrode 6, IGS stress-buffer layer 5, CIGS absorbed layer 4,CdS cushion 3, i-ZnO&ZnO:Al Window layer 2, Ni-Al gate electrode 1, wherein flexible substrate is plastics, as polyamidesImines films etc., substrate thickness is 25-50 μ m.
In flexible thin-film solar cell structure, IGS stress-buffer layer is between CIGS absorbed layer and Mo electrode, and thickness is100nm-1000nm. Polyimides using thickness as 25-50 μ m, as substrate, before deposition absorbed layer, first adoptsVolume to volume coevaporation process deposits IGS stress buffer layer film. In deposition process, in chamber, vacuum pressure remains on1×10-3Pa left and right, underlayer temperature keeps constant in scope between 350 DEG C～480 DEG C, keeps enough Se atmosphere. Ga,The temperature of In evaporation source is constant is respectively 900 DEG C-1100 DEG C, 800 DEG C-1000 DEG C, and Se evaporation source is at 250 DEG C～350 DEG C modelsEnclose interior maintenance constant. Substrate with the speed of 50mm/min successively by Ga and In evaporation source. IGS film deposition rate is about20nm/min, finally obtaining thickness is the IGS stress-buffer layer of 100-1000nm. Close In and Ga evaporation source baffle plate,Se continues to keep constant evaporation rate. Adjust underlayer temperature, Cu, In, the each evaporation source evaporation rate of Ga, continued CIGSAbsorbed layer deposition.
Experimental result as shown in Figure 3, certain thickness IGS cushion has effectively improved CIGS absorbed layer and has served as a contrast at PITack on the end/Mo film, has avoided the problem that comes off of CIGS absorbed layer.
On CIGS absorbed layer, successively with the CdS cushion of volume to volume chemical bath method deposition 50nm thickness, use volume to volumeRadio-frequency magnetron sputter method deposition i-ZnO/ZnO:Al Window layer, the thickness of double-layer films is respectively 50nm and 500nm. FinallyUse volume to volume silk-screen printing technique to prepare Ag or Al gate electrode, Ag or Al thickness are 2 μ m, obtain large area flexiblePI substrate CIGS thin film solar cell.
Embodiment 3
There is a flexible thin-film solar cell for high-bond absorbed layer, refer to accompanying drawing 2. Small size flexible copper indium gallium selenideThe structure of thin film solar cell comprises: flexible substrate 7, Mo hearth electrode 6, IGS stress-buffer layer 5, CIGS absorbed layer 4,CdS cushion 3, i-ZnO&ZnO:Al Window layer 2, Ni-Al gate electrode 1, MgF2Antireflection layer 8, wherein flexible substrateFor tinsel, as Ti paillon foil, stainless steel substrates, Cu paillon foil etc., substrate thickness is 50-100 μ m; Also can be plastics,As Kapton etc., substrate thickness is 25-50 μ m.
In flexible thin-film solar cell structure, IGS stress-buffer layer is between CIGS absorbed layer and Mo electrode, and thickness is100nm-1000nm. Adopt low temperature coevaporation process deposits small size CIGS absorbed layer. First, Co-evaporated Deposition IGS shouldPower buffer layer thin film. In chamber, vacuum pressure remains on 1 × 10-3Pa left and right, underlayer temperature is model between 350 DEG C～480 DEG CEnclose interior maintenance constant, keep enough Se atmosphere. The temperature of Ga, In evaporation source respectively constant be 800 DEG C-1000 DEG C,700 DEG C-900 DEG C, Se evaporation source keeps constant within the scope of 220 DEG C～280 DEG C. In deposition cushion, evaporate NaF,Evaporating temperature is 600 DEG C-800 DEG C. IGS film deposition rate is about 40nm/min, obtains IGS suitable thickness, that contain NaFilm, closes In, Ga and NaF evaporation source baffle plate, and Se continues to keep constant evaporation rate. Then, adjust underlayer temperature,Cu, In, the each evaporation source evaporation rate of Ga complete the deposition of CIGS absorbed layer on IGS film.
On CIGS absorbed layer, successively with the CdS cushion of chemical bath method deposition 50nm thickness, use radio-frequency magnetron sputter methodDeposition i-ZnO/ZnO:Al Window layer, the thickness of double-layer films is respectively 50nm and 300nm. Finally evaporate Ni-Al grid electricityThe utmost point, the thickness of Ni and Al is respectively 0.05 μ m and 3 μ m, finally adopts evaporation technology deposit thickness to be about the MgF of 100nm2Antireflection layer, obtains small size flexible CIGS thin film solar cell.
With coming to the same thing of embodiment 1 and example 2, certain thickness IGS cushion has effectively improved CIGS absorbed layer at PITack on substrate/Mo film, has avoided the problem that comes off of CIGS absorbed layer. Meanwhile, grew at CIGS absorbed layerCheng Zhong, Na atom diffuses in CIGS film by IGS stress-buffer layer, makes the carrier concentration of CIGS absorbed layerFrom 3 × 1016cm-3Bring up to 2 × 1017cm-3(having improved nearly 7 times), has significantly improved the electrical properties of this layer film, phaseAnswer the open-circuit voltage of CIGS hull cell to improve 10%, fill factor, curve factor has improved 10%-20%. This slow by IGS stressPunching layer mixes the mode of Na and has avoided the impact of independent deposition NaF layer on CIGS film and PI/Mo substrate adhesion.
The present embodiment has described can obtain high-bond CIGS absorbed layer, has effectively avoided the CIGS in flexible substrateFilm, because of problems such as internal stress ftracture, even comes off, has improved the good effects such as absorbed layer electrical properties.
Claims (6)
1. a flexible thin-film solar cell with high-bond absorbed layer, is characterized in that: have high-bond absorbed layerFlexible thin-film solar cell comprises sandwich construction, and sandwich construction is followed successively by flexible substrate, Mo electrode layer, stress bufferLayer, CIGS absorbed layer, CdS cushion, electrically conducting transparent Window layer, Ni-Al gate electrode, CIGS absorbed layer and MoBetween electrode layer, be provided with stress-buffer layer, improve the adhesion of the CIGS absorbed layer of flexible substrate growth.
2. the flexible thin-film solar cell with high-bond absorbed layer according to claim 1, is characterized in that: haveThe flexible thin-film solar cell of high-bond absorbed layer comprises sandwich construction, at surface deposition one deck MgF of battery structure2Antireflection layer.
3. the flexible thin-film solar cell with high-bond absorbed layer according to claim 2, is characterized in that: MgF2Antireflection layer thickness is 90-110nm.
4. the flexible thin-film solar cell with high-bond absorbed layer according to claim 1 and 2, is characterized in that:Mo electrode layers thickness is 0.5～1 μ m, and p-type CIGS absorber thickness is 1～3 μ m, N-shaped CdS buffer layer thicknessFor 45-55nm.
5. according to the flexible thin-film solar cell with high-bond absorbed layer described in claim 1,2 or 3, it is characterized in that:Stress-buffer layer is (In1-x,Gax)2Se3Film 0.2 < x < 0.8 stress-buffer layer.
6. the flexible thin-film solar cell with high-bond absorbed layer according to claim 5, is characterized in that:(In1-x,Gax)2Se3Membrane stress buffer layer thickness is 100nm～1000nm.
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| CN107994079A (en) * | 2017-08-11 | 2018-05-04 | 北京汉能光伏投资有限公司 | Flexible thin-film battery and preparation method thereof |
| CN114843354A (en) * | 2022-04-21 | 2022-08-02 | 福州大学 | Flexible CZTSSe solar cell based on ultrathin CdS/ZTO double buffer layers and preparation method thereof |
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| CN103311357A (en) * | 2013-06-18 | 2013-09-18 | 天津理工大学 | Copper-indium-gallium-selenium solar battery device and preparation method thereof |
| CN103400896A (en) * | 2013-07-24 | 2013-11-20 | 中国科学院上海高等研究院 | CuInGaSe flexible thin-film solar cell and preparation method thereof |
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| CN103311357A (en) * | 2013-06-18 | 2013-09-18 | 天津理工大学 | Copper-indium-gallium-selenium solar battery device and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107994079A (en) * | 2017-08-11 | 2018-05-04 | 北京汉能光伏投资有限公司 | Flexible thin-film battery and preparation method thereof |
| CN114843354A (en) * | 2022-04-21 | 2022-08-02 | 福州大学 | Flexible CZTSSe solar cell based on ultrathin CdS/ZTO double buffer layers and preparation method thereof |
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Application publication date: 20160518 |