CN102157622A - Method for manufacturing serial uniwafer integrated multi-junction thin film solar cell - Google Patents
Method for manufacturing serial uniwafer integrated multi-junction thin film solar cell Download PDFInfo
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Abstract
The invention relates to the manufacturing field of a serial uniwafer integrated multi-junction thin film solar cell. The manufacturing method comprises the following steps: depositing a multi-junction p-n junction serial solar cell epitaxy material comprising at least an insulating layer, a lower contact layer, a tunnel junction, a multi-junction p-n junction structure and a top contact layer which are grown upwards from the substrate and are connected sequentially by utilizing a molecular epitaxy or metallorganics chemical vapor deposition method; corroding to form a lower contact layer table board by utilizing a photoetching technology and an etching technology, and etching the corrosion table board to the lower isolating layer; growing and passivating the insulating layer is at the frontage of the solar cell epitaxy material by utilizing a deposition method, and manufacturing an electrode window and a light in window by utilizing the photoetching and etching technologies; and manufacturing an electric connecting layer on the electrode window and the passivated insulating layer by utilizing the photoetching and film coating technologies, and forming the electric connection between a top contact layer and the lower contact layer through a stripping technology and an annealing process. The solar cell has the characteristics of high efficiency, high-voltage output, light weight and flexibility.
Description
Technical field
The present invention relates to the manufacturing field of the integrated multi-knot thin film solar cell of a kind of tandem monolithic.
Background technology
Existing volume production solar cell mainly adopts material such as polysilicon, amorphous silicon.Because the band gap of silicon has only 1.1eV, and belongs to the indirect gap semiconductor material, so photoelectric conversion efficiency is not high, only has about 16%.If adopt many knots form, absorb sunlight by multijunction structure, then can increase efficient greatly, can reach more than 40%.
Existing multijunction solar cell all is single separate structures, and output voltage has only several volts, can not satisfy high-voltage applications; And owing to use hard substrate, causing battery is rigidity, can not satisfy arcuate surfaces such as balloon are arranged, the application on the dirigible; Remove and cause solar cell weight bigger in addition, epitaxial loayer only has about 10 μ m effective, and the substrate that supports has 300-500 μ m thick, and it is invalid making the weight of conventional solar cell more than 95%.Therefore, manufacture the single chip integrated multi-junction solar hull cell of a kind of tandem and have realistic meaning.
Summary of the invention
The present invention provides the manufacture method of the single chip integrated multi-knot thin film solar cell of a kind of tandem in order to overcome above deficiency.
To achieve the object of the present invention, the manufacture method of the single chip integrated multi-knot thin film solar cell of this tandem may further comprise the steps:
1, solar cell epitaxial material growth link, use molecular beam epitaxy or metal-organic chemical vapor deposition equipment method depositing solar cell epitaxial material on substrate, the solar cell epitaxial material comprise at least from substrate up generate and the separator that connects successively, down contact layer, tunnel junction, tie p-n junction structure, top contact layer more, this technical scheme can obtain high-quality solar cell epitaxial material;
2, use photoetching technique and lithographic technique to erode away down the contact layer table top, form the solar cell that the monolithic integrated array is arranged;
3, use photoetching technique and lithographic technique will descend the contact layer mesa etch, make adjacent solar battery form good electric isolation to lower floor's separator;
4, use deposition process at the positive growth of passivation insulating barrier of solar cell epitaxial material;
5, on passivation insulation, use photoetching technique and lithographic technique to leave electrode window through ray and go into light window;
6, use photoetching technique and coating technique on electrode window through ray and passivation insulation, to prepare electric connection layer;
7, use lift-off technology and annealing process, realize being electrically connected by electric connection layer between top contact layer and the following contact layer.
Solar cell epitaxial material growth link also comprises the corrosion sacrifice layer that is grown directly upon on the substrate, and the corrosion sacrifice layer is between substrate and separator.
Backing material is a GaAs material, many knot p-n junction structures are gallium indium phosphorus/GaAs binode or GaAs/germanium binode or gallium indium phosphorus/GaAs/germanium three knots, top contact layer and following contact layer are highly doped semi-conducting materials, highly doped semi-conducting material is highly doped GaAs, separator is that semi insulating semiconductor or p-n junction are isolated, and tunnel junction is meant the highly doped and very thin p-n junction structure layer of growth on following contact layer.So far formed the solar cell epitaxial material of the multiple semiconductor p-n junction series connection that energy gap from top to down reduces successively, can repeatedly absorb sunlight and realize the high efficiency opto-electronic conversion.
Lithographic technique is inductively coupled plasma etching or reactive ion etching or wet etching or plasma etching.
Deposition process is plasma enhanced CVD or microwave electron cyclotron resonance-chemical vapour deposition (CVD).
Passivation insulation is nano oxidized silicon thin film or nano silicon nitride silicon thin film.
Coating technique is electron beam evaporation evaporation or sputter coating.
Utilize substrate desquamation and film transfer technology in conjunction with the ad hoc corrosion sacrifice layer process of this technology, gallium arsenide substrate is peeled off, simultaneously the solar cell epitaxial material is transferred on the fexible film substrate, the combination of solar cell epitaxial material and fexible film substrate can be Van der Waals for or the bonding mode of bonding agent, and fexible film is polytetrafluoroethylene film or polyimide film or aluminium foil.
The invention has the advantages that, realize the high efficiency opto-electronic conversion by repeatedly absorption to sunlight, only a metal deposition can be finished solar cell and is connected in series, can realize voltage output on a large scale and high voltage output flexibly, satisfy arcuate surfaces such as balloon are arranged, the application on the dirigible, solar cell weight significantly reduces, and realizes efficient, high pressure output, light weight and flexibility, can be applied in specialized field such as space flight; The innovation of manufacture craft makes that this solar cell cost performance is higher, has more the market competitiveness.
Description of drawings
Fig. 1 is the solar cell material structural representation.
Fig. 2 is following contact layer mesa etch schematic diagram.
Fig. 3 is a solar cell mesa-isolated etching schematic diagram.
Fig. 4 is the structural representation of p-n junction separator.
Fig. 5 is passivation deposition and opening schematic diagram.
Fig. 6 is adjacent two solar cell cascaded structure schematic diagrames.
Fig. 7 is the solar battery structure schematic diagram of yi word pattern series connection.
Fig. 8 is the solar battery structure schematic diagram of S type series connection.
Fig. 9 is the solar cell material structural representation that black wax supports.
Figure 10 is the structural representation of solar cell epitaxial material and fexible film substrate.
Figure 11 is the structural representation of the integrated multi-knot thin film solar cell of tandem monolithic of the present invention.
Embodiment
The present invention is further described with embodiment below in conjunction with accompanying drawing:
The integrated multi-knot thin film solar cell of this tandem monolithic of present embodiment mainly consists of the following components: 1, substrate, 2, separator, 3, contact layer down, 4, tunnel junction, 5, tie the p-n junction structure, 6, the top contact layer more, 7, passivation insulation, 8, electric connection layer.
The manufacture method of the integrated multi-knot thin film solar cell of this tandem monolithic mainly may further comprise the steps:
1, use molecular beam epitaxy or the metal-organic chemical vapor deposition equipment method one deck corrosion sacrifice layer 2 of growing as shown in Figure 1 on GaAs (GaAs) substrate 1, this corrosion sacrifice layer 2 is aluminium arsenide (AlAs) materials.Deposition multijunction solar cell epitaxial material 8 on corrosion sacrifice layer 2 simultaneously, this solar cell epitaxial material 8 comprise at least from gallium arsenide substrate 1 and up generate and the separator 3, following contact layer 4, the tunnel junction 5 that connect successively, tie p-n junction structure 6 and top contact layer 7 more.Many knot p-n junction structures can be gallium indium phosphorus (GaInP)/GaAs (GaAs) binode, GaAs (GaAs)/germanium (Ge) binode or gallium indium phosphorus (GaInP)/GaAs (GaAs)/germanium (Ge) three knot materials, top contact layer and following contact layer are highly doped semi-conducting materials (highly doped GaAs), separator can be semi insulating semiconductor or p-n junction isolated material, and tunnel junction is the highly doped and very thin p-n junction structure layer of growth on following contact layer; Thereby formed the multiple semiconductor p-n junction series connection that energy gap from top to down reduces successively, realized the conversion of high efficiency luminous point by absorption repeatedly to sunlight.
2, following contact layer etching.At first on solar cell epitaxial material 8 shown in Figure 1, make figure by lithography, use coupled plasma etching (ICP dry method) or wet etching technique to erode away down contact layer table top 9 then, form solar cell epitaxial material structure 14 shown in Figure 2.Thereby form single chip integrated series connected battery array, form several array arrangements to hundreds of above batteries, this structure efficiently with battery integrated-solar battery structure of monolithic, according to using the arrange quantity of battery of needs adjustable array, make that the making of solar cell is more flexible; Remove and to save the material of making solar cell in addition, reduce production costs, improve the competitiveness of product in market.
3, mesa-isolated etching.In conjunction with Fig. 2 to Fig. 4, on the basis of solar cell epitaxial material structure 14 shown in Figure 2, make figure by lithography, use coupled plasma etching (ICP dry method) or wet etching technique will descend contact layer table top 9 to etch into lower floor's separator 3, form separator table top 10 and form solar cell epitaxial material structure 15 shown in Figure 3.In order to realize the electric isolation between single battery, separator can be selected semi insulating semiconductor or p-n junction isolated material for use; When separator 3 was the semi insulating semiconductor material, when etching into separator 3, the separator 3 of high impedance had been isolated single battery; When separator 3 is the p-n junction isolated material, p-n junction isolated material structure comprises the P-type material 11 of top layer, the n type material 12 of bottom and the depletion region 13 that is positioned at the middle high resistant of p-n junction isolated material that is formed by P-type material 11 and n type material 12 as shown in Figure 4, when etching into n type material when following, the depletion region of high resistant is separated single battery.This technical scheme makes the good electric isolation of formation between single battery, solar cell have the electricity security performance of height, has guaranteed the work that solar cell is stable.
4, passivation insulation deposition and opening.With reference to figure 5, at first use plasma enhanced CVD or microwave electron cyclotron resonance-chemical vapour deposition technique superficial growth passivation insulation 17 at solar cell epitaxial material structure 15 shown in Figure 5, this passivation insulation 17 is nano oxidized silicon thin film or nano silicon nitride silicon thin film, then on passivation insulation 17, deposit photoresist, make graph window then by lithography, use reactive ion etching or wet etching are left electrode window through ray and are gone into light window, form solar cell epitaxial material structure 16, electrode window through ray comprises top contact layer electrode window through ray 18 and following contact layer electrode window through ray 19.
5, electric connection layer forms and connects with battery.By solar cell epitaxial material structure 20 shown in Figure 6 as can be known, this solar cell is provided with tunnel junction 5, just, make the top contact layer 7 of solar cell, the doping polarity unanimity of following contact layer 4 electrodes can be all n type or p type in response to having used semiconductor tunnel junction technology; Therefore, can realize top contact layer 7, the ohmic contact of following contact layer 4 electrodes and the end to end series connection of solar cell by a metal deposition.Concrete technology is: at first make electric connection layer 21 figures by lithography, with top contact layer electrode window through ray 18, contact layer electrode window through ray 19 and the exposure of the coupling part between them down, the photoresist of this part is removed; Then make deposited by electron beam evaporation evaporation or sputter coating technology metal on evaporation on the exposure area, make metal directly be deposited on the chip, form top contact layer 7 and be connected with the electrode of following contact layer 4, and the zone of other (photoresist is arranged), metal deposition is on photoresist; After using acetone to remove photoresist then, the removal of the photoresist of metal below it in these (photoresist are arranged) zone is removed, and is formed into light window, goes into the zone that light window had both received sunlight.Use this technology to realize the head and the tail series connection of solar cell, according to design and practical needs, the quantity of control series-connected solar cells, but the quantity of series-connected solar cells several to hundreds of, make solar cell to export and reach the above voltage of 400V, obtain the requirement of high pressure output.The connected mode of the series connection of solar cell 25 and quantity can be provided with control by photolithography plate, can be in-line arrangement shown in Figure 7 or S font shown in Figure 8 and arrange, and realize voltage output on a large scale and high voltage output flexibly.
6, substrate desquamation and film transfer.Corrosion sacrifice layer 2 in the material is used for substrate desquamation and transfer.At first on the front of solar cell epitaxial material 20 shown in Figure 9, use black wax 22 to support, use the selective corrosion corrosion to fall to corrode sacrifice layer 2 then, and 20 layers of other solar cell epitaxial materials are unaffected; Because corrosion sacrifice layer 2 is aluminium arsenide materials in this execution mode, selective corrosion liquid can be selected hydrofluoric acid solution, hydrofluoric acid solution can dissolve aluminium arsenide corrosion sacrifice layer 2 in room temperature, and reaction unit is simple plastics or poly-tetrafluoro beaker, and normal temperature leaves standstill and can corrode after 6-8 hour fully.Like this, by removing corrosion sacrifice layer 2, gallium arsenide substrate 1 realizes separating with solar cell epitaxial material 20.As shown in figure 10, the solar cell epitaxial material 20 that black wax 22 is supported is transferred to fexible film substrate 23, and fexible film substrate 23 can be polytetrafluoroethylene film substrate or polyimide film substrate or aluminum substrates; Solar cell epitaxial material 20 can be Van der Waals for or the bonding mode of bonding agent with the combination of fexible film substrate.Re-use the dewax solvent at last black wax 22 is removed the solar cell 24 that obtains as shown in figure 11.Aluminium arsenide substrate after the separation can be recycled in the growth of material once more, meets environmental protection design and the theory of producing.This technical scheme makes that solar cell can be in the application that has on arcuate surfaces such as balloon, the dirigible, removing in addition, the weight of solar cell itself has also obtained significantly reducing, remedied the defective of existing solar cell aspect flexible and light weight, the service efficiency of solar cell get a qualitative improvement.
Claims (14)
1. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic is characterized in that: may further comprise the steps:
(1), solar cell epitaxial material growth link, use molecular beam epitaxy or metal-organic chemical vapor deposition equipment method depositing solar cell epitaxial material on substrate, the solar cell epitaxial material comprise at least from substrate up generate and the separator that connects successively, down contact layer, tunnel junction, tie p-n junction structure, top contact layer more;
(2), use photoetching technique and lithographic technique to erode away down the contact layer table top;
(3), use photoetching technique and lithographic technique will descend the contact layer mesa etch to lower floor's separator;
(4), use deposition process at the positive growth of passivation insulating barrier of solar cell epitaxial material;
(5), on passivation insulation, use photoetching technique and lithographic technique to leave electrode window through ray and go into light window;
(6), use photoetching technique and coating technique on electrode window through ray and passivation insulation, to prepare electric connection layer;
(7), use lift-off technology and annealing process, realize electrical connection by electric connection layer between top contact layer and the following contact layer.
2. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1, it is characterized in that: described backing material is a GaAs material.
3. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described many knot p-n junction structures are gallium indium phosphorus/GaAs binode or GaAs/germanium binode or gallium indium phosphorus/GaAs/germanium three knots.
4. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described top contact layer and following contact layer are highly doped semi-conducting materials.
5. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 3 is characterized in that: described highly doped semi-conducting material is highly doped GaAs.
6. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described separator is that semi insulating semiconductor or p-n junction are isolated.
7. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described tunnel junction is meant the highly doped and very thin p-n junction structure layer of growth on following contact layer.
8. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described lithographic technique is inductively coupled plasma etching or reactive ion etching or wet etching or plasma etching.
9. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described deposition process is plasma enhanced CVD or microwave electron cyclotron resonance-chemical vapour deposition (CVD).
10. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described passivation insulation is nano oxidized silicon thin film or nano silicon nitride silicon thin film.
11. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described coating technique is electron beam evaporation evaporation or sputter coating.
12. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1 is characterized in that: described solar cell epitaxial material growth link also comprises the corrosion sacrifice layer that is grown directly upon on the substrate.
13. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 1, it is characterized in that: also comprise and utilize substrate desquamation and film transfer technology in conjunction with the ad hoc corrosion sacrifice layer process of this technology, with substrate desquamation, simultaneously the solar cell epitaxial material is transferred on the fexible film substrate.
14. the manufacture method of the integrated multi-knot thin film solar cell of tandem monolithic according to claim 13 is characterized in that: described fexible film substrate is polytetrafluoroethylene film substrate or polyimide film substrate or aluminum substrates.
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| CN103000739A (en) * | 2011-09-16 | 2013-03-27 | 深圳光启高等理工研究院 | Electronic device and circuit power unit therefor |
| CN103066159A (en) * | 2013-01-11 | 2013-04-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monolithic coupling assembly preparation method based on thermophotovoltaic battery |
| WO2014036917A1 (en) * | 2012-09-04 | 2014-03-13 | 厦门市三安光电科技有限公司 | Flip solar cell chip and preparation method thereof |
| CN104009047A (en) * | 2013-02-27 | 2014-08-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Laser photovoltaic battery of upside-down mounting structure, and manufacturing method thereof |
| CN104201231A (en) * | 2014-09-11 | 2014-12-10 | 六安市大宇高分子材料有限公司 | Hybrid three-junction compound photovoltaic cell |
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| CN103000739A (en) * | 2011-09-16 | 2013-03-27 | 深圳光启高等理工研究院 | Electronic device and circuit power unit therefor |
| WO2014036917A1 (en) * | 2012-09-04 | 2014-03-13 | 厦门市三安光电科技有限公司 | Flip solar cell chip and preparation method thereof |
| CN103066159A (en) * | 2013-01-11 | 2013-04-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monolithic coupling assembly preparation method based on thermophotovoltaic battery |
| CN104009047B (en) * | 2013-02-27 | 2017-10-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of laser photovoltaic cell of inverted structure and preparation method thereof |
| CN104009047A (en) * | 2013-02-27 | 2014-08-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Laser photovoltaic battery of upside-down mounting structure, and manufacturing method thereof |
| CN104201231A (en) * | 2014-09-11 | 2014-12-10 | 六安市大宇高分子材料有限公司 | Hybrid three-junction compound photovoltaic cell |
| US10483316B2 (en) | 2016-01-13 | 2019-11-19 | mPower Technology, Inc. | Fabrication and operation of multi-function flexible radiation detection systems |
| US10892372B2 (en) | 2016-12-09 | 2021-01-12 | mPower Technology, Inc. | High performance solar cells, arrays and manufacturing processes therefor |
| CN106611799A (en) * | 2017-01-12 | 2017-05-03 | 合肥海润光伏科技有限公司 | Inkjet-printed double-sided crystalline silicon solar cell and preparation method thereof |
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| CN111276550A (en) * | 2019-11-11 | 2020-06-12 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Flexible solar cell with graphene transparent electrode and manufacturing method thereof |
| CN111524984A (en) * | 2020-04-20 | 2020-08-11 | 中山德华芯片技术有限公司 | Flexible gallium arsenide solar cell chip and manufacturing method thereof |
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