CN102956738A - Compound semiconductor laminated film solar cell - Google Patents
Compound semiconductor laminated film solar cell Download PDFInfo
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- CN102956738A CN102956738A CN2012104974263A CN201210497426A CN102956738A CN 102956738 A CN102956738 A CN 102956738A CN 2012104974263 A CN2012104974263 A CN 2012104974263A CN 201210497426 A CN201210497426 A CN 201210497426A CN 102956738 A CN102956738 A CN 102956738A
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- Y—GENERAL 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a compound semiconductor laminated film solar cell, comprising a copper indium gallium selenide cell (CIGS) bottom cell with a low bandgap and a copper gallium selenide (CGS) top cell with a high bandgap. The compound semiconductor laminated film solar cell is characterized in that the bottom cell and the top cell are internally connected in series into a whole through a connecting layer; and the connecting layer is composed of a transparent metal oxide conductive layer positioned at the bottom cell and a nanometer metal conductive layer positioned at the top cell. According to the compound semiconductor laminated film solar cell, the combination of transparent metal oxide and a nanometer metal film is used as the connecting layer of the bottom cell and the top cell, so that the technological compatibility problem of the bottom cell and the top cell is solved, the internal electrical connection of the bottom cell and the top cell is realized, the manufacturing process of the cell is simplified, the manufacturing cost of the cell is reduced, and the cell is simple in structure.
Description
Technical field
The invention belongs to the thin film solar cell technical field, particularly relate to a kind of compound semiconductor laminated film solar battery.
Background technology
At present, the solar cell of using on the market is still take first generation monocrystalline silicon/polycrystal silicon cell as main, but second generation thin film solar cell is acknowledged as the main direction of following solar cell development.It is one of effective way of decrease solar cell cost at the solar cell that the material of micron dimension is prepared into that thin film solar cell refers to thickness.In numerous thin film solar cells, I-III-VI compound semiconductor copper indium (gallium) selenium film solar battery (claims again Cu (In, Ga) Se
2(be called for short CIGS) thin film solar cell) becomes the study hotspot of photovoltaic circle with advantages such as its conversion efficiency are high, long-time stability are good, capability of resistance to radiation is strong, be expected to become follow-on cheap solar cell.No matter be which is for solar cell, the limit (31%) that all has an energy transformation ratio, Shockley and Queisser have analyzed the reason that has the conversion ratio limit: after the photon that is higher than band-gap energy produced charge carrier, the unnecessary energy of charge carrier lost in the mode of Phonon emission (1); (2) photon that is lower than band-gap energy is not absorbed.One of approach that addresses this problem is exactly to widen photovoltaic material to the absorption region of solar spectrum energy, as adopts many knot laminations or multi-band gap structure, minute energy absorption or realization Multiphoton Absorbtion.
The stacked solar cell, cascade solar cell concept is proposed by Jackson in nineteen fifty-five the earliest, and present three knot GaAs efficiency of solar cell surpass 40%, are higher than traditional single junction cell far away.Stacked solar cell, cascade solar cell has been successfully applied to the preparation of different materials battery, the exactly III-V compounds of group multijunction cell take GaAs representative that technique is the most ripe, having reached 41.1% such as the GaInP/GaInAs/Ge three junction batteries conversion efficiency under 454 times of optically focused conditions that is connected by tunnel junction, is present the most efficient solar cell.In addition, also extensively concerned to the research of pellicular cascade solar cell, the basic structure of its three junction amorphous silicons stacked solar cell, cascade solar cell is α-Si/ α-SiGe/ α-SiGe.Can obtain more efficiently stacked solar cell, cascade solar cell by amorphous silicon and amorphous germanium silicon being carried out hydrogenation treatment, its structure is α-Si:H/ α-SiGe:H/ α-SiGe:H, has obtained 15.39% conversion efficiency at present.
Owing to utilize distribution ratio can effectively regulate optical band gap, so I-III-VI family chalcopyrite compound semiconductor is in the unique advantage in stacked solar cell, cascade solar cell field.In I-III-VI compound semiconductor system, the optical band gap of Cu base chalcopyrite compound is 0.9-2.9eV, and Ag base chalcopyrite compound band gap is 0.6-3.1eV, and so wide optical band gap scope is very potential in the application of stacked solar cell, cascade solar cell.
The existing pellicular cascade solar cell total that relates to is to be together in series by a plurality of tunnel junctions, and consequently whole battery structure only has two contacts or claims " two ends ".In order to obtain the folded type solar cell of efficient polycrystal film, the top battery must have wide bandgap semiconductor materials, and transparent conductive material is as back of the body contact.Just because of this, contact becomes imperative as the back of the body with transparent conductive oxide.Present known I-III-VI family chalcopyrite compound semiconductor binode thin film solar cell, realized that the top battery adopts wide bandgap semiconductor materials, transparent conductive oxide as back of the body contact, improved the conversion efficiency of solar cell, but because I-III-VI family chalcopyrite compound can't be realized tunnel junction, processing compatibility between end battery and the top battery is poor, directly inner connection the between end battery and the top battery, the outer cascade system of many employings, the whole battery of result needs three or four contacts, so that battery structure is complicated, improved the cost of manufacture of battery.
Summary of the invention
The present invention for solve the technical problem that exists in the known technology provide a kind of simple in structure, cost of manufacture is low, and the high compound semiconductor laminated film solar battery of battery conversion efficiency.
The following technical scheme of the present invention is:
The compound semiconductor laminated film solar battery comprises the copper gallium selenium top battery of battery and a broad-band gap at the bottom of the Copper Indium Gallium Selenide of a narrow band gap, and be characterized in: battery of the described end and top battery are become one by the articulamentum internal series-connection; Described articulamentum is made of the transparent metal oxide conductive layer that is positioned at end battery and the nano metal conductive layer that is positioned at the top battery.
The present invention can also adopt following technical measures:
Described transparent metal oxide conductive layer is a kind of of the TCO film that forms of the thick Al of 300-600nm, Ga or In doping ZnO, or ito thin film; The Mo film that described nano metal conductive layer is thickness 30-50nm.
At the bottom of the Copper Indium Gallium Selenide of described narrow band gap battery comprise from bottom to top the thick Mo film of 600nm-800nm as the thick CIGS film of back electrode Mo1,1.5-2.0 μ m as the N-shaped CdS film of end cell p type absorbed layer, 30-50nm as the thick native oxide zinc film of end battery N-shaped resilient coating and 50-60nm at the bottom of battery intrinsic the Window layer Copper Indium Gallium Selenide and the cadmium sulfide hetero-junction solar cell that consist of.
The copper gallium selenium top battery of described broad-band gap comprises copper gallium selenium and the cadmium sulfide hetero-junction solar cell that ZnAO film that the thick CGS film of 1-1.5 μ m forms as top battery intrinsic Window layer, Al doping ZnO that 400-600nm is thick as the thick intrinsic ZnO film of top battery N-shaped resilient coating, 50-60nm as the thick N-shaped CdS film of top cell p type absorbed layer, 30-50nm or ito thin film consist of as electrode layer as top battery conductive Window layer and the thick Al of 2-4 μ m from bottom to top.
The advantage that the present invention has and good effect:
1, the combination of the present invention by transparent metal oxide and nanometer metallic film is as the articulamentum of end battery and top battery, solved the processing compatibility problem between end battery and the top battery, realized that the inner electrical between end battery and the top battery connects, simplified cell making process, reduced the cost of manufacture of battery, battery structure is simple;
2, the present invention has adopted ultrathin nanometer metal M o to carry out transition between transparent metal oxide and top battery obsorbing layer, namely solved both directly reef knot phenomenons of causing of contact, has brought into play again the advantage that the Mo film is beneficial to growth I-III-VI family material;
3, top of the present invention battery obsorbing layer has adopted the low temperature process deposition process, effectively reduces the top battery preparation technique to the impact of end battery performance.
Description of drawings
Fig. 1 is the binode laminated film solar battery structural representation that the present invention prepares.
Label among the figure is respectively: 1-back electrode Mo; Cell p type absorbed layer at the bottom of the 2-; Battery N-shaped resilient coating at the bottom of the 3-; Battery intrinsic Window layer at the bottom of the 4-; The 5-articulamentum; 6-top cell p type absorbed layer; 7-top battery N-shaped resilient coating; 8-top battery intrinsic Window layer; 9-top battery conductive Window layer; The 10-electrode layer.
Embodiment
For further disclosing summary of the invention of the present invention, Characteristic, also be elaborated by reference to the accompanying drawings as follows especially exemplified by following instance.
The compound semiconductor laminated film solar battery comprises the copper gallium selenium top battery of battery and a broad-band gap at the bottom of the Copper Indium Gallium Selenide of a narrow band gap.
Innovative point of the present invention is:
Battery of the described end and top battery are become one by the articulamentum internal series-connection; Described articulamentum is made of the transparent metal oxide conductive layer that is positioned at end battery and the nano metal conductive layer that is positioned at the top battery; Described transparent metal oxide conductive layer is a kind of of the TCO film that forms of the thick Al of 300-600nm, Ga or In doping ZnO, or ito thin film; The Mo film that described nano metal conductive layer is thickness 30-50nm; At the bottom of the Copper Indium Gallium Selenide of described narrow band gap battery comprise from bottom to top the thick Mo film of 600nm-800nm as the thick CIGS film of back electrode Mo, 1.5-2.0 μ m as the N-shaped CdS film of end cell p type absorbed layer, 30-50nm as the thick native oxide zinc film of end battery N-shaped resilient coating and 50-60nm at the bottom of battery intrinsic the Window layer Copper Indium Gallium Selenide and the cadmium sulfide hetero-junction solar cell that consist of; The copper gallium selenium top battery of described broad-band gap comprises copper gallium selenium and the cadmium sulfide hetero-junction solar cell that ZnAO film that the thick CGS film of 1-1.5 μ m forms as top battery intrinsic Window layer, Al doping ZnO that 400-600nm is thick as the thick intrinsic ZnO film of top battery N-shaped resilient coating, 50-60nm as the thick N-shaped CdS film of top cell p type absorbed layer, 30-50nm or ito thin film consist of as electrode layer as top battery conductive Window layer and the thick Al of 2-4 μ m from bottom to top.
The preparation process of compound semiconductor laminated film solar battery:
Step 1: direct current magnetron sputtering process prepares back electrode Mo at substrate:
⑴ under the room temperature, adopting first base vacuum is＜5 * 10
-3Pa, operating pressure is that hyperbar, the sputtering power of 1-2Pa is the low-power of 60W, Deposited By Dc Magnetron Sputtering Mo on the flexible polyimide substrate, sedimentation time is 60min, forming ground floor thickness on the substrate is the Mo film of 0.05-0.1 μ m;
⑵ adopt base vacuum is＜5 * 10
-3Pa, operating pressure is that low pressure, the sputtering power of 0.2-0.4Pa is the high power of 150W, Deposited By Dc Magnetron Sputtering Mo on ground floor Mo film, sedimentation time is 150min, form second layer Mo film, the double-deck Mo film that two-layer Mo film formation gross thickness is 600-800nm is as back electrode Mo1;
Step 2: three-step approach prepares end cell p type absorbed layer at back electrode Mo:
(1) first step: underlayer temperature is heated to 380-400 ℃, at In, Ga and the Se element formation (In of back electrode Mo evaporation 90%
0.7Ga
0.3)
2Se
3Initialization layer, Se/ (In+Ga) flow-rate ratio is greater than 3, and the Temperature Setting of each evaporation source is as follows: T
In=810 ℃, T
Ga=850 ℃, T
Se=240 ℃, evaporation time is 12-15min;
⑵ second step: underlayer temperature is risen to 450-550 ℃, and at initialization layer evaporation Cu and Se element, the Temperature Setting of each evaporation source is as follows: T
Cu=1050 ℃, T
Se=240 ℃, until the evaporation that the cooling point finishes Cu occurs;
⑶ the 3rd step: keeping underlayer temperature is 450-550 ℃, evaporation In, Ga and Se element, and the Temperature Setting of each evaporation source is as follows: T
In=810 ℃, T
Ga=850 ℃, T
Se=240 ℃, evaporation time is 2-3min; The upper thick narrow band gap CIGS film of 1.5-2.0 μ m that forms of back electrode Mo is as end cell p type absorbed layer 2;
Step 3: chemical bath method (CBD) prepares end battery N-shaped resilient coating at end cell p type absorbed layer:
Select (CH
3COO)
2Cd=0.001M, SC (NH
2)
2=0.01M, CH
3COONH
4=0.03M, NH
4OH=0.003M is mixed with reaction solution; The pH value of reaction solution is adjusted to 8-9, and bath temperature is 60 ℃-70 ℃, and the water-bath time is 30min, at the thick N-shaped CdS film of end cell p type absorbed layer growth 30-50nm as end battery N-shaped resilient coating 3;
Step 4: radio-frequency magnetron sputter method prepares end battery intrinsic Window layer at end battery N-shaped resilient coating:
It is＜8 * 10 that base vacuum is set
-4Pa regulates O
2: Ar is than being 80:1, and operating pressure is 0.7-0.8Pa, and Sputtering power density is 2.0-2.5W/cm
2, sputtering time is 20-40min; The intrinsic ZnO film that rf magnetron sputtering 50-60nm is thick on end battery N-shaped resilient coating is as end battery intrinsic Window layer 4;
Step 5: radio-frequency magnetron sputter method prepares articulamentum in end battery intrinsic Window layer:
⑴ at end battery intrinsic Window layer preparation transparent metal oxide conductive layer
Base vacuum is＜8 * 10
-4Pa, operating pressure is 0.4-0.6Pa, Sputtering power density is 2.5-2.8W/cm
2, sputtering time is 100-150min, rf magnetron sputtering Al is ZnO thin film doped on end battery intrinsic Window layer, forms the ZAO film of thickness 300-600nm on the end battery intrinsic Window layer as the transparent metal oxide conductive layer;
⑵ transparent metal oxide conductive layer prepares the nano metal conductive layer
Base vacuum is＜5 * 10
-3Pa, operating pressure is 0.2-0.8Pa, and sputtering power is 120-130W, and sputtering time is 10min, and rf magnetron sputtering thickness is that the Mo film of 30-50nm is as the nano metal conductive layer on the ZAO film;
Transparent metal oxide conductive layer and nano metal conductive layer namely consist of the articulamentum 5 of end battery and top battery;
Step 6: three-step approach prepares top cell p type absorbed layer at articulamentum:
⑴ the first step: evaporate Ga on the Mo film of articulamentum
2Se
3Initialization layer
During 380 ± 10 ℃ of underlayer temperatures, T
Ga=850 ℃, T
Se=240 ℃, at Ga and the Se element of Mo film evaporation 90%, evaporation time is 10-12min, and Se/ (In+Ga) flow-rate ratio is greater than forming Ga on 3, the Mo film
2Se
3Initialization layer;
⑵ second step: underlayer temperature is risen to 450 ± 10 ℃, T
Cu=1050 ℃, T
Se=240 ℃, at Ga
2Se
3Evaporation Cu and Se element on the initialization layer, evaporation time is 8-10min;
⑶ the 3rd step: keeping underlayer temperature is 450 ± 10 ℃, T
Ga=850 ℃, T
Se=240 ℃, on the second step basis, evaporate again Ga and Se element, evaporation time is 2-3min; Coevaporation goes out the broad-band gap CGS film of 1-1.5 μ m as top cell p type absorbed layer 6 on the Mo film;
Step 7: the chemical bath method prepares top battery N-shaped resilient coating at top cell p type absorbed layer:
Select (CH
3COO)
2Cd=0.001M, SC (NH
2)
2=0.01M, CH
3COONH
4=0.03M, NH
4OH=0.003M is mixed with reaction solution; The pH value of reaction solution is adjusted to 8-9, and bath temperature is 60 ℃-70 ℃, and the water-bath time is 30min, at the N-shaped CdS film of top cell p type absorbed layer growth 30-50nm as top battery N-shaped resilient coating 7;
Step 8: radio-frequency magnetron sputter method prepares top battery intrinsic Window layer at top battery N-shaped resilient coating:
It is＜8 * 10 that base vacuum is set
-4Pa regulates O
2: Ar is than being 80:1, and operating pressure is 0.8Pa, and Sputtering power density is 2.0-2.5W/cm
2, sputtering time is 25-35min; Rf magnetron sputtering thickness is that the ZnO film of 50-60nm is as top battery intrinsic Window layer 8 on the battery N-shaped resilient coating of top;
Step 9: radio-frequency magnetron sputter method prepares top battery conductive Window layer in top battery intrinsic Window layer:
It is＜8 * 10 that base vacuum is set
-4Pa, operating pressure is 0.4-0.6Pa, Sputtering power density is 2.5-2.8W/cm
2, sputtering time is 120-150min, rf magnetron sputtering thickness is that the ZAO film that forms of the Al doping ZnO of 400-600nm is as top battery conductive Window layer 9 on the battery intrinsic Window layer of top;
Step 10: direct current magnetron sputtering process prepares electrode layer in top battery conductive Window layer:
It is＜5 * 10 that base vacuum is set
-3Pa, operating pressure is 0.6Pa, Sputtering power density is 2W/cm
2Sputtering time is 50-80min, on the battery conductive Window layer of top magnetically controlled DC sputtering thickness be the Al of 2-4 μ m as electrode layer 10, namely finish as shown in Figure 1 the semiconductor laminated thin film solar cell of internal series-connection all-in-one-piece compound of the CGS/CdS heterojunction top battery that battery and step 6-step 10 are made at the bottom of the CIGS/CdS heterojunction of step 1-step 4 being made by articulamentum.
Although the above is described the preferred embodiments of the present invention by reference to the accompanying drawings; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away from the scope situation that aim of the present invention and claim protect, can also make a lot of forms.These all belong within protection scope of the present invention.
Claims (4)
1. compound semiconductor laminated film solar battery comprises the copper gallium selenium top battery of battery and a broad-band gap at the bottom of the Copper Indium Gallium Selenide of a narrow band gap, and it is characterized in that: battery of the described end and top battery are become one by the articulamentum internal series-connection; Described articulamentum is made of the transparent metal oxide conductive layer that is positioned at end battery and the nano metal conductive layer that is positioned at the top battery.
2. compound semiconductor laminated film solar battery according to claim 1 is characterized in that: described transparent metal oxide conductive layer is a kind of of the TCO film that forms of the thick Al of 300-600nm, Ga or In doping ZnO, or ito thin film; The Mo film that described nano metal conductive layer is thickness 30-50nm.
3. compound semiconductor laminated film solar battery according to claim 1 is characterized in that: at the bottom of the Copper Indium Gallium Selenide of described narrow band gap battery comprise from bottom to top the thick Mo film of 600nm-800nm as the thick CIGS film of back electrode Mo1,1.5-2.0 μ m as the N-shaped CdS film of end cell p type absorbed layer, 30-50nm as the thick native oxide zinc film of end battery N-shaped resilient coating and 50-60nm at the bottom of battery intrinsic the Window layer Copper Indium Gallium Selenide and the cadmium sulfide hetero-junction solar cell that consist of.
4. compound semiconductor laminated film solar battery according to claim 1 is characterized in that: the copper gallium selenium top battery of described broad-band gap comprises copper gallium selenium and the cadmium sulfide hetero-junction solar cell that ZnAO film that the thick CGS film of 1-1.5 μ m forms as top battery intrinsic Window layer, Al doping ZnO that 400-600nm is thick as the thick intrinsic ZnO film of top battery N-shaped resilient coating, 50-60nm as the thick N-shaped CdS film of top cell p type absorbed layer, 30-50nm or ito thin film consist of as electrode layer as top battery conductive Window layer and the thick Al of 2-4 μ m from bottom to top.
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| CN105742390A (en) * | 2014-12-12 | 2016-07-06 | 北京汉能创昱科技有限公司 | Laminated thin film solar battery and preparation method thereof |
| CN105870210A (en) * | 2016-04-13 | 2016-08-17 | 黄广明 | CIGS/CGS double-junction laminated thin film solar cell |
| CN107482073A (en) * | 2017-07-19 | 2017-12-15 | 旭科新能源股份有限公司 | A kind of molybdenum layer preparation method of CIGS flexible thin-film battery |
| CN111725332A (en) * | 2020-06-11 | 2020-09-29 | 中山德华芯片技术有限公司 | High-performance three-junction gallium arsenide solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105742390A (en) * | 2014-12-12 | 2016-07-06 | 北京汉能创昱科技有限公司 | Laminated thin film solar battery and preparation method thereof |
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| CN105870210A (en) * | 2016-04-13 | 2016-08-17 | 黄广明 | CIGS/CGS double-junction laminated thin film solar cell |
| CN107482073A (en) * | 2017-07-19 | 2017-12-15 | 旭科新能源股份有限公司 | A kind of molybdenum layer preparation method of CIGS flexible thin-film battery |
| CN111725332A (en) * | 2020-06-11 | 2020-09-29 | 中山德华芯片技术有限公司 | High-performance three-junction gallium arsenide solar cell |
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