CN102738291B - Silicon-based heterojunction double-side solar cell and preparation method thereof - Google Patents
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Abstract
The invention discloses a silicon-based heterojunction double-side solar cell and a preparation method of the silicon-based heterojunction double-side cell. The conventional amorphous-silicon thin-film is replaced by the amorphous-silicon germanium alloy as an emitting diode of the heterojunction cell, at the same time, an intrinsic microcrystalline silicon germanium thin-film is used as an interface buffer layer of the cell, so that valence-band offset caused by the heterojunction band mismatch can be reduced effectively, the block influence on the holes is decreased, and the collection of the photovoltaic minority carrier holes is facilitated, furthermore the photovoltaic performance index of the solar cell is increased. The intrinsic microcrystalline silicon germanium thin film, a P-type doped amorphous-silicon germanium thin film, an intrinsic amorphous-silicon thin-film and an N+ type doped amorphous-silicon thin-film are prepared on two sides of the N-type microcrystalline silicon wafer by the radio frequency plasma enhanced chemical vapor deposition, the purpose of effectively collecting a photovoltaic carrier is achieved. The heterojunction double-side solar cell with 14.62% of photoelectric conversion efficiency is prepared on the double-side polished FZ-type microcrystalline silicon wafer by the process.
Description
Technical field
The present invention relates to the two-sided hetero-junction solar cell of field of photovoltaic power generation, particularly a kind of amorphous silicon germanium/crystallite SiGe/crystal silicon heterojunction double-sided solar battery and preparation method thereof.
Background technology
Thin film silicon/crystalline silicon heterojunction solar cell is a kind of a kind of photovoltaic solar cell of the advantage separately that combines first generation crystal silicon cell and second generation hull cell, it mainly leans on crystalline silicon as absorbed layer, thin layer is just in order to form PN heterojunction to collect photo-generated carrier, thereby the thickness of thin layer is not high, make the light durability of this kind of battery high; Battery preparation process is exactly mainly the deposition process of film simultaneously, and making technology temperature is low, approximately 180 ~ 220 DEG C, has avoided the pyroprocess of crystal silicon cell, thereby has been conducive to control the cost of technique; In addition, due to the advantage separately in conjunction with two battery eliminators, thereby photovoltaic efficiency between two battery eliminators, and closer to first generation crystal silicon cell, peak efficiency has reached 21% left and right, " HIT " battery of producing by SANYO GS company is kept.This battery product, comprise the design that numerous in the world research institutions carries out, be with amorphous silicon membrane as the emitter of battery to form PN heterojunction, collect photo-generated carrier and produce photovoltaic effect, but the shortcoming of this design is, between emitter amorphous silicon and base stage crystalline silicon, can be with mismatch larger, and the energy gap potential barrier of generation plays the effect of obstruction for the collection of photoproduction minority carrier, be unfavorable for collecting, thereby affected its photovoltaic performance.
Summary of the invention
The object of the present invention is to provide a kind of amorphous silicon germanium/crystallite SiGe/crystal silicon heterojunction double-sided solar battery, the mismatch of being with realizing between film emitter and crystalline silicon base stage reduces, collection inhibition to charge carrier weakens, thereby is conducive to improve the photovoltaic performance of battery.
The present invention provides the preparation method of a kind of amorphous silicon germanium/crystallite SiGe/crystal silicon heterojunction double-sided solar battery simultaneously.
The object of the invention is to be achieved by the following technical programs, a kind of amorphous silicon germanium/crystallite SiGe/crystal silicon heterojunction double-sided solar battery, the material that forms PN heterojunction is P type amorphous silicon germanium thin film and n type single crystal silicon, by laminated layer sequence from top to bottom, be followed successively by positive electrode titanium, palladium, silver-colored compound grid, nesa coating AZO, the amorphous silicon germanium thin film P-a-SiGe of P type doping, intrinsic micro crystal silicon germanium film I-mc-SiGe, N-type twin polishing monocrystalline silicon piece N-c-Si, intrinsic amorphous silicon film I-a-Si, N
+heavily doped amorphous silicon membrane N
+-a-Si, back side nesa coating AZO, aluminum back electrode, wherein amorphous silicon germanium thin film P-a-SiGe, the intrinsic micro crystal silicon germanium film I-mc-SiGe of the doping of P type and N-type twin polishing monocrystalline silicon piece N-c-Si form the positive PN heterojunction of solar cell device, N-type twin polishing monocrystalline silicon piece N-c-Si, intrinsic amorphous silicon film I-a-Si and N
+heavily doped amorphous silicon membrane N
+-a-Si forms the back of the body surface field layer of solar cell device, forms P (a-SiGe)-I (mc-SiGe)-N (c-Si)-I (a-Si)-N
+(a-Si) structure, wherein a-SiGe represents amorphous silicon germanium, and mc-SiGe represents crystallite SiGe, and c-Si represents monocrystalline silicon, and a-Si represents amorphous silicon; Wherein said titanium, palladium, silver-colored compound gate are 0.012 ~ 0.015mm, grid line width is 0.020 ~ 0.025mm, spacing between grid line is 4 ~ 5mm, the thickness of described nesa coating AZO is 125 ~ 150nm, and the amorphous silicon germanium thin film thickness of described P type doping is 16 ~ 20nm, and described intrinsic micro crystal silicon germanium film thickness is 10 ~ 12nm, described N-type twin polishing monocrystalline silicon piece thickness is 0.200 ~ 0.220mm, conductivity is 1 ~ 2S/cm, and described intrinsic amorphous silicon film thickness is 5 ~ 8nm, described N
+heavily doped amorphous silicon membrane thickness is 20 ~ 25nm, and described back side nesa coating AZO thickness is 125 ~ 150nm, described aluminum back electrode, and thickness is 0.015 ~ 0.025mm.
The very amorphous silicon germanium thin film P-a-SiGe of P type doping of transmitting that forms PN heterojunction, its bandwidth is 1.3 ~ 1.4eV.
Adopt intrinsic micro crystal silicon germanium film I-mc-SiGe to carry out passivation heterojunction boundary as heterojunction boundary resilient coating, reduce boundary defect state, the bandwidth of described intrinsic micro crystal silicon germanium film (2) is 1.1 ~ 1.2eV.
Described N
+heavily doped amorphous silicon membrane N
+the bandwidth of-a-Si is 1.8 ~ 1.9eV.
The preparation method of amorphous silicon germanium/crystallite SiGe/crystal silicon heterojunction double-sided solar battery, the process route of the method is as follows:
(1) preparation of positive PN heterojunction
(a) with silane SiH
4, hydrogen H
2, germane GeH
4for reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, first deposit in the one side of N-type twin polishing monocrystalline silicon piece the intrinsic micro crystal silicon germanium film I-mc-SiGe that preparation a layer thickness is 10 ~ 12nm;
(b) with silane SiH
4, hydrogen H
2, germane GeH
4, trimethyl borine TMB is reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, on above-mentioned intrinsic amorphous silicon germanium film, the amorphous silicon germanium thin film P-SiGe of the P type doping that deposition preparation a layer thickness is 16 ~ 20nm again, forms heterojunction P(a-SiGe)-I(mc-SiGe)-N(c-Si);
(2) preparation of reverse side back of the body surface field layer N-I-N+
(a) with silane SiH
4, hydrogen H
2for reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, first deposit at the another side of N-type twin polishing monocrystalline silicon piece the intrinsic amorphous silicon film I-a-Si that a layer thickness is 5 ~ 8nm;
(b) with silane SiH
4, hydrogen H
2, phosphine PH
3, methane CH
4for reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, the N that deposition preparation a layer thickness is 20 ~ 25nm again on above-mentioned intrinsic amorphous silicon film 4
+the heavily doped amorphous silicon membrane N of type
+-a-Si, forms back of the body surface field N(c-Si)-I(a-Si)-N+(a-Si);
(3) preparation of nesa coating AZO
Adopt magnetron sputtering technique, on above-mentioned heterojunction surface, the back of the body surface field layer surface plate respectively nesa coating and back side nesa coating, its thickness is 125 ~ 150nm, transmitance is 88% ~ 90%, square resistance is 60 ~ 80 ohm of every squares;
(4) preparation of titanium, palladium, silver-colored compound grid
Reactive evaporation technique, prepares titanium, palladium, silver-colored compound grid 9, and thickness is 0.012 ~ 0.015mm, and grid line width is 0.020 ~ 0.025mm, and the spacing between grid line is 4 ~ 5mm;
(5) the above-mentioned two-sided hetero-junction solar cell device preparing carries out edge cuts processing, to eliminate the impact of edge shorting.
Beneficial effect of the present invention:
1, in the silicon heterogenous battery of routine, use more amorphous silicon membrane for emitter, the present invention replaces with the amorphous silicon membrane of mixing germanium, replace the resilient coating passivation heterojunction boundary of amorphous silicon membrane as interface using microcrystalline silicon-germanium film simultaneously, make interface resilient coating and the emitter of hetero-junction solar cell with microcrystal silicon germanium alloy+Amorphous Si-Ge Alloy, because amorphous silicon germanium thin film bandwidth is 1.3 ~ 1.4eV, microcrystalline silicon-germanium film bandwidth is 1.1 ~ 1.2eV, 1.12 eV are comparatively approaching with crystalline silicon bandwidth, launch very amorphous silicon and amorphous silicon germanium from Fig. 2, energy band diagram when interface resilient coating is two kinds of different thin layers of amorphous silicon and crystallite SiGe relatively can be found out, due to the relatively low bandwidth of crystallite SiGe, very approaching with monocrystalline silicon, make the valence band band rank DE at film and grain boundary place
v1compare DE
v2little, also the inhibition in photoproduction minority carrier hole is weakened, be more conducive to photohole cross potential barrier arrive emitter be collected, be conducive to the raising of battery current.
(2) back of the body surface field preparation technology in the present invention is than traditional high-sintering process, and temperature is only 200 DEG C of left and right, replaces high-temperature diffusion process by the thin film deposition of low temperature, and this cost control for industrialization has positive effect.
(3) in the present invention, what front electrode adopted is titanium, palladium, silver electrode composite, and this is than single silver electrode, is more conducive to form good ohmic contact between the amorphous silicon germanium of P type doping, reduce the series resistance of battery, improve battery conversion efficiency.
The present invention proposes a kind of new PN heterojunction structure: amorphous silicon germanium+crystallite SiGe/crystalline silicon.By Amorphous Si-Ge Alloy and microcrystal silicon germanium alloy, replace amorphous silicon membrane, by microcrystal silicon germanium alloy as interface resilient coating, reach the object of narrow energy gap width, and alternative traditional amorphous silicon, the mismatch of being with realizing between film emitter and crystalline silicon base stage reduces, and the collection inhibition of charge carrier is weakened, thereby be conducive to improve the photovoltaic performance of battery.Adopting technique of the present invention is on the twin polishing FZ type monocrystalline silicon piece of 1cm2 (square that the length of side is 1cm) at area, the heterojunction double-sided solar battery that to have prepared photoelectric conversion efficiency be 14.62%, the method that the present invention proposes is chilling process, cost is low, easy to operate, process route simple possible.
Brief description of the drawings
Fig. 1 is the structure diagram of amorphous silicon germanium of the present invention/crystallite SiGe/crystal silicon heterojunction double-sided solar battery;
Fig. 2 is amorphous silicon germanium/crystallite SiGe/crystalline silicon and the comparison of amorphous silicon/crystal silicon cell PN heterojunction energy band diagram;
Fig. 3 is that area is amorphous silicon germanium/crystallite SiGe/crystal silicon heterojunction double-sided solar battery J-V curve of 1cm2 (square that the length of side is 1cm).
Embodiment
(1) adopt silicon chip standard cleaning step, i.e. RCA cleaning process, the N-type twin polishing monocrystalline silicon piece 1 that FZ method is made carries out standard cleaning, and in experiment, the thickness of choosing N-type twin polishing monocrystalline silicon piece 1 is 0.220mm, and conductivity is 1 ~ 2S/cm, and area is 4cm
2(square that the length of side is 2cm);
(2) cleaned N-type twin polishing monocrystalline silicon piece 1 being immersed to concentration is in 2% hydrofluoric acid aqueous solution, keeps for 10 seconds, is removed with the silicon dioxide oxide-film of guaranteeing monocrystalline silicon surface, also can not cause the overetch of hydrofluoric acid to silicon face simultaneously.Then rapidly the N-type twin polishing monocrystalline silicon piece 1 of handling well is put into vacuum cavity, pumping high vacuum, is set in 180 DEG C by underlayer temperature;
(3), in the time that vacuum degree reaches 2.0e-4Pa, start positive technique.First process the front of N-type twin polishing monocrystalline silicon piece 1 with the plasma bombardment of pure hydrogen atmosphere, to remove surperficial dangling bonds, to reduce blemish state.Then, taking hydrogen, silane, germane as reacting gas, utilize RF-PECVD technology to prepare one deck intrinsic micro crystal silicon germanium film 2 in the front of N-type twin polishing monocrystalline silicon piece 1 deposition, thickness is 12nm, and conductivity is 5 ' 10
-5s/cm; And then taking hydrogen, silane, germane, trimethyl borine as reacting gas, on above-mentioned intrinsic micro crystal silicon germanium film 2, then deposit the amorphous silicon germanium thin film 3 that one deck P type adulterates, and thickness is 18 nm, conductivity is 3.3 ' 10
-4s/cm, bandwidth control is 1.35eV; So far, complete the preparation of positive heterogeneous P-I-N knot;
(4) battery sample of the above-mentioned preparation that completes positive heterogeneous P-I-N knot is taken out from vacuum, and rapidly its reverse side is become to depositional plane, to continue the preparation of battery back of the body surface field layer.This process is wanted rapidly, to reduce the oxidation of atmosphere to monocrystalline silicon reverse side as far as possible, should be controlled at 1 minute taking interior as best.Then rapid pumping high vacuum, to carry out the back process of battery device;
(5) when degree reaches 2.0e-4Pa, start back process, first process the surface (being now the back side of silicon chip) of monocrystalline silicon with the plasma bombardment of pure hydrogen atmosphere, to remove oxide on surface, dangling bonds, reduction blemish state.Then, taking hydrogen, silane as reacting gas, utilize RF-PECVD technology to prepare one deck intrinsic amorphous silicon film 4 in monocrystalline silicon surface (being now the back side of silicon chip) deposition, thickness is 6nm, and conductivity is 10
-6s/cm; And then taking hydrogen, silane, phosphine, methane as reacting gas, on above-mentioned intrinsic amorphous silicon film 4, then deposit one deck N
+heavily doped amorphous silicon membrane 5, thickness is 20 nm, conductivity is 10
-2s/cm, bandwidth control is 1.85eV; So far, completed the preparation of reverse side battery back of the body surface field layer;
(6) completed on the sample of battery positive and negative technique, adopted magnetron sputtering technique, plated respectively nesa coating AZO in battery positive and negative, wherein the thickness of front nesa coating 6 is 130 nm, and square resistance is 60 ohm of every squares, and transmitance is 90%; The thickness of back side nesa coating 7 is 140 nm, and square resistance is 50 ohm of every squares, and transmitance is 80%; Follow on nesa coating 7 overleaf and plate one deck aluminum back electrode 8 with magnetron sputtering technique again, thickness is 0.020mm;
(7) reactive evaporation technique, prepares titanium, palladium, silver-colored compound grid 9, and thickness is 0.013mm, and grating spacing is 4mm.
(8) the above-mentioned two-sided hetero-junction solar cell device preparing carries out edge cuts processing, and to eliminate the impact of edge shorting, the battery device area cutting into is 1 ' 1 cm
2;
(9) the photovoltaic J-V curve of amorphous silicon germanium/crystal silicon heterojunction double-sided solar battery that technique prepares as shown in Figure 3, wherein short-circuit current density J
sC=38.32mA/cm
2; Open circuit voltage V
oC=568.5mV; Fill factor, curve factor FF=0.671; Battery conversion efficiency Effi=14.62%.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction.Although the present invention discloses as above with preferred embodiment, but not in order to limit the present invention.Any those of ordinary skill in the art, do not departing from technical solution of the present invention scope situation, all can utilize method and the technology contents of above-mentioned announcement to make many possible variations and modification to technical solution of the present invention, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not depart from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, be equal to replacements, equivalence change and modify, all still belong to technical solution of the present invention protect scope in.
Claims (5)
1. a silicon based hetero-junction double-sided solar battery, it is characterized in that, by laminated layer sequence from top to bottom, be followed successively by positive electrode titanium, palladium, silver-colored compound grid (9), nesa coating AZO(6), the amorphous silicon germanium thin film (3) of P type doping, intrinsic micro crystal silicon germanium film (2), N-type twin polishing monocrystalline silicon piece (1), intrinsic amorphous silicon film (4), N
+heavily doped amorphous silicon membrane (5), back side nesa coating AZO (7), aluminum back electrode (8);
Wherein, amorphous silicon germanium thin film (3), intrinsic micro crystal silicon germanium film (2) and the N-type twin polishing monocrystalline silicon piece (1) of P type doping forms the positive PN heterojunction of solar cell device, N-type twin polishing monocrystalline silicon piece (1), intrinsic amorphous silicon film (4) and N
+heavily doped amorphous silicon membrane (5) forms the back of the body surface field layer of solar cell device;
The thickness of described titanium, palladium, silver-colored compound grid (9) is 0.012 ~ 0.015mm, grid line width is 0.020 ~ 0.025mm, spacing between grid line is 4 ~ 5mm, described nesa coating AZO(6) thickness be 125 ~ 150nm, the thickness of the amorphous silicon germanium thin film (3) of described P type doping is 16 ~ 20nm, the thickness of described intrinsic micro crystal silicon germanium film (2) is 10 ~ 12nm, described N-type twin polishing monocrystalline silicon piece (1) thickness is 0.200 ~ 0.220mm, conductivity is 1 ~ 2S/cm, described intrinsic amorphous silicon film (4) thickness is 5 ~ 8nm, described N
+heavily doped amorphous silicon membrane (5) thickness is 20 ~ 25nm, described back side nesa coating AZO(7) thickness is 125 ~ 150nm, described aluminum back electrode (8) thickness is 0.015 ~ 0.025mm.
2. a kind of silicon based hetero-junction double-sided solar battery according to claim 1, is characterized in that, forms the very amorphous silicon germanium thin film (3) of P type doping of transmitting of PN heterojunction, and its bandwidth is 1.3 ~ 1.4eV.
3. a kind of silicon based hetero-junction double-sided solar battery according to claim 1, it is characterized in that, adopt intrinsic micro crystal silicon germanium film (2) to carry out passivation heterojunction boundary as heterojunction boundary resilient coating, reduce boundary defect state, the bandwidth of described intrinsic micro crystal silicon germanium film (2) is 1.1 ~ 1.2eV.
4. a kind of silicon based hetero-junction double-sided solar battery according to claim 1, is characterized in that described N
+the bandwidth of heavily doped amorphous silicon membrane (5) is 1.8 ~ 1.9eV.
5. a preparation method for silicon based hetero-junction double-sided solar battery, is characterized in that, the process route of the method is as follows:
(1) preparation of positive PN heterojunction
(a) with silane SiH
4, hydrogen H
2, germane GeH
4for reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, first deposit in the one side of N-type twin polishing monocrystalline silicon piece (1) the intrinsic micro crystal silicon germanium film I-mc-SiGe(2 that preparation a layer thickness is 10 ~ 12nm);
(b) with silane SiH
4, hydrogen H
2, germane GeH
4, trimethyl borine TMB is reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, the amorphous silicon germanium thin film (3) of the P type doping that deposition preparation a layer thickness is 16 ~ 20nm again on above-mentioned intrinsic micro crystal silicon germanium film (2), forms heterojunction;
(2) reverse side back of the body surface field layer N-I-N
+preparation
(a) with silane SiH
4, hydrogen H
2for reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, first deposit at the another side of N-type twin polishing monocrystalline silicon piece (1) the intrinsic amorphous silicon film I-a-Si(4 that a layer thickness is 5 ~ 8nm);
(b) with silane SiH
4, hydrogen H
2, phosphine PH
3, methane CH
4for reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, the N that deposition preparation a layer thickness is 20 ~ 25nm again on above-mentioned intrinsic amorphous silicon film (4)
+the heavily doped amorphous silicon membrane N of type
+-a-Si(6), form back of the body surface field layer N-I-N
+;
(3) preparation of nesa coating AZO
Adopt magnetron sputtering technique, on above-mentioned heterojunction surface, the back of the body surface field layer surface plate respectively nesa coating AZO(6) and back side nesa coating AZO(7), described nesa coating AZO(6) and back side nesa coating AZO(7) thickness is 125 ~ 150nm, transmitance is 88% ~ 90%, and square resistance is 60 ~ 80 ohm of every squares;
(4) preparation of titanium, palladium, silver-colored compound grid
Reactive evaporation technique, prepares titanium, palladium, silver-colored compound grid (9), and thickness is 0.012 ~ 0.015mm, and grid line width is 0.020 ~ 0.025mm, and the spacing between grid line is 4 ~ 5mm;
(5) the above-mentioned two-sided hetero-junction solar cell device preparing carries out edge cuts processing, to eliminate the impact of edge shorting.
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| CN104701411A (en) * | 2013-12-10 | 2015-06-10 | 泉州市博泰半导体科技有限公司 | Edge insulating method used during manufacturing of silicon-based heterojunction battery piece |
| CN106449850B (en) * | 2015-08-05 | 2018-07-13 | 钧石(中国)能源有限公司 | A kind of efficient silicon based hetero-junction double-side cell and preparation method thereof |
| CN105932075B (en) * | 2016-05-12 | 2017-07-11 | 南昌大学 | One kind back of the body crystalline silicon heterojunction solar cell and preparation method thereof |
| CN106057926A (en) * | 2016-08-24 | 2016-10-26 | 常州天合光能有限公司 | Passivated emitting electrode solar cell with laminated heterojunction structure and preparation method thereof |
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| CN109004053B (en) * | 2017-06-06 | 2024-03-29 | 通威太阳能（成都）有限公司 | Crystalline silicon/thin film silicon heterojunction solar cell with double-sided light receiving function and manufacturing method thereof |
| CN110620163B (en) * | 2019-10-28 | 2024-05-24 | 通威太阳能(金堂)有限公司 | Heterojunction solar cell, laminated tile assembly and manufacturing method thereof |
| CN111029424B (en) * | 2019-12-12 | 2022-02-15 | 中建材浚鑫科技有限公司 | Silicon-based double-diode double-sided solar cell and preparation method thereof |
| CN114497260B (en) * | 2022-02-08 | 2024-01-09 | 理想万里晖半导体设备(上海)股份有限公司 | Method for manufacturing heterojunction solar cell and heterojunction solar cell |
| CN116177550B (en) * | 2023-03-09 | 2024-02-27 | 浙江大学 | Surface passivation method and application of silicon nano material |
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| US6521883B2 (en) * | 2000-07-18 | 2003-02-18 | Sanyo Electric Co., Ltd. | Photovoltaic device |
| JP3490964B2 (en) * | 2000-09-05 | 2004-01-26 | 三洋電機株式会社 | Photovoltaic device |
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| CN101866973A (en) * | 2010-06-09 | 2010-10-20 | 中国科学院电工研究所 | Thin film silicon/crystalline silicon heterogenous pn junction structure for solar cell |
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