CN102738291A - Silicon-based heterojunction double-side solar cell and preparation method thereof - Google Patents
Silicon-based heterojunction double-side solar cell and preparation method thereof Download PDFInfo
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- CN102738291A CN102738291A CN201210233534XA CN201210233534A CN102738291A CN 102738291 A CN102738291 A CN 102738291A CN 201210233534X A CN201210233534X A CN 201210233534XA CN 201210233534 A CN201210233534 A CN 201210233534A CN 102738291 A CN102738291 A CN 102738291A
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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 heterojunction battery 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
The thin film silicon/crystalline silicon heterojunction solar cell is a kind of a kind of photovoltaic solar cell that combines the advantage separately of 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, makes the light durability of this kind battery high; The cell preparation process mainly is exactly the depositing of thin film process simultaneously, and the making technology temperature is low, about 180 ~ 220 ℃, has avoided the pyroprocess of crystal silicon cell, thereby has helped controlling the cost of technology; In addition, owing to combine the advantage separately of two battery eliminators, thereby photovoltaic efficiency and more approaches first generation crystal silicon cell between two battery eliminators, and peak efficiency has reached about 21%, and " HIT " battery of producing by SANYO GS company is kept.This battery product comprises numerous in the world designs that research institution carried 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, can be with mismatch bigger between emitter amorphous silicon and the base stage crystalline silicon, 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 influenced 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; Realize that the mismatch of being with between film emitter and the crystalline silicon base stage reduces; Collection inhibition to charge carrier weakens, thereby helps improving 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 objective of the invention is to be achieved through following technical scheme, a kind of amorphous silicon germanium/crystallite SiGe/crystal silicon heterojunction double-sided solar battery, the material that constitutes 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, P type doped amorphous silicon germanium film P-a-SiGe; 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 P type doped amorphous silicon germanium film P-a-SiGe, intrinsic micro crystal silicon germanium film I-mc-SiGe 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 the 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, and the grid line width is 0.020 ~ 0.025mm, and the spacing between the grid line is 4 ~ 5mm; The thickness of said nesa coating AZO is 125 ~ 150nm, and said P type doped amorphous silicon germanium film thickness is 16 ~ 20nm, and said intrinsic micro crystal silicon germanium film thickness is 10 ~ 12nm; Said N type twin polishing monocrystalline silicon piece thickness is 0.200 ~ 0.220mm; Conductivity is 1 ~ 2S/cm, and said intrinsic amorphous silicon film thickness is 5 ~ 8nm, said N
+Heavily doped amorphous silicon membrane thickness is 20 ~ 25nm, and said back side nesa coating AZO thickness is 125 ~ 150nm, and said aluminum back electrode, thickness are 0.015 ~ 0.025mm.
The emission of formation PN heterojunction is P type doped amorphous silicon germanium film P-a-SiGe very, and its bandwidth is 1.3 ~ 1.4eV.
Adopt intrinsic micro crystal silicon germanium film I-mc-SiGe to come the passivation heterojunction boundary as the heterojunction boundary resilient coating, reduce the boundary defect attitude, the bandwidth of said intrinsic micro crystal silicon germanium film (2) is 1.1 ~ 1.2eV.
Said 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 this method is following:
(1) preparation of positive PN heterojunction
(a) with silane SiH
4, hydrogen H
2, germane GeH
4Be reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, at first depositing preparation one layer thickness in the one side of N type twin polishing monocrystalline silicon piece is the intrinsic micro crystal silicon germanium film I-mc-SiGe of 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; Deposition preparation one layer thickness is the P type doped amorphous silicon germanium film P-SiGe of 16 ~ 20nm again, promptly 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
2Be reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, at first deposit the intrinsic amorphous silicon film I-a-Si that a layer thickness is 5 ~ 8nm at the another side of N type twin polishing monocrystalline silicon piece;
(b) with silane SiH
4, hydrogen H
2, phosphine PH
3, methane CH
4Be reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, deposition preparation one layer thickness is the N of 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,, back of the body surface field laminar surface surperficial at above-mentioned heterojunction plates nesa coating and back side nesa coating respectively, and its thickness is 125 ~ 150nm, and 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 technology, preparation titanium, palladium, silver-colored compound grid 9, thickness is 0.012 ~ 0.015mm, and the grid line width is 0.020 ~ 0.025mm, and the spacing between the grid line is 4 ~ 5mm;
(5) the above-mentioned two-sided heterojunction battery device for preparing carries out the edge cuts processing, to eliminate the influence of edge shorting.
Beneficial effect of the present invention:
1, in the silicon heterogenous battery of routine, use more amorphous silicon membrane to be emitter; The present invention uses the amorphous silicon membrane of mixing germanium to replace; Replace the resilient coating passivation heterojunction boundary of amorphous silicon membrane with microcrystalline silicon-germanium film simultaneously, promptly make the interface resilient coating and the emitter of heterojunction battery, because the amorphous silicon germanium thin film bandwidth is 1.3 ~ 1.4eV with microcrystal silicon germanium alloy+amorphous silicon germanium alloy as the interface; The microcrystalline silicon-germanium film bandwidth is 1.1 ~ 1.2eV; 1.12 eV are comparatively approaching with the crystalline silicon bandwidth, and the energy band diagram when Fig. 2 launches that very amorphous silicon is amorphous silicon and two kinds of different thin layers of crystallite SiGe with amorphous silicon germanium, interface resilient coating relatively can be found out, because 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 promptly the inhibition in photoproduction minority carrier hole is weakened, more help photohole and cross potential barrier and arrive emitter and be collected, help the raising of battery current.
(2) back of the body surface field preparation technology among the present invention is than traditional high-sintering process, and temperature is merely about 200 ℃, i.e. thin film deposition through low temperature replaces high-temperature diffusion process, and this cost control for industrialization has positive effect.
(3) among the present invention; What front electrode adopted is titanium, palladium, silver electrode composite, and this is than single silver electrode, more help and P type doped amorphous silicon germanium between form good Ohmic contact; 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.Through amorphous silicon germanium alloy and microcrystal silicon germanium alloy; Replace amorphous silicon membrane, as the interface resilient coating, reach the purpose of narrow energy gap width by the microcrystal silicon germanium alloy; And alternative traditional amorphous silicon; Realize that the mismatch of being with between film emitter and the crystalline silicon base stage reduces, the collection inhibition of charge carrier is weakened, thereby help improving the photovoltaic performance of battery.Adopting technology of the present invention is on the twin polishing FZ type monocrystalline silicon piece of 1cm2 (length of side is the square of 1cm) at area; Prepared photoelectric conversion efficiency and be 14.62% heterojunction double-sided solar battery; The method that the present invention proposes is chilling process; Cost is low, and is easy to operate, the process route simple possible.
Description of 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 that amorphous silicon germanium/crystallite SiGe/crystalline silicon and amorphous silicon/crystal silicon cell PN heterojunction energy band diagram compare;
Fig. 3 is the amorphous silicon germanium/crystallite SiGe/crystal silicon heterojunction double-sided solar battery J-V curve of 1cm2 (length of side is the square of 1cm) for area.
Embodiment
(1) adopt silicon chip standard cleaning step, i.e. RCA cleaning process, the N type twin polishing monocrystalline silicon piece 1 that the FZ method is made carries out standard cleaning, and in the 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(length of side is the square of 2cm);
(2) cleaned N type twin polishing monocrystalline silicon piece 1 being immersed concentration is in 2% the 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.Rapidly the N type twin polishing monocrystalline silicon piece of handling well 1 is put into vacuum cavity then, pumping high vacuum is set in 180 ℃ with underlayer temperature;
(3) when vacuum degree reaches 2.0e-4Pa, begin positive technology.Handle the front of N type twin polishing monocrystalline silicon piece 1 earlier with the plasma bombardment of pure hydrogen atmosphere, to remove surperficial dangling bonds, to reduce the blemish attitude.Then, be reacting gas with hydrogen, silane, germane, deposition prepares one deck intrinsic micro crystal silicon germanium film 2 in the front of N type twin polishing monocrystalline silicon piece 1 to utilize the RF-PECVD technology, and thickness is 12nm, and conductivity is 5 ' 10
-5S/cm; And then be reacting gas with hydrogen, silane, germane, trimethyl borine, on above-mentioned intrinsic micro crystal silicon germanium film 2, depositing one deck P type doped amorphous silicon germanium film 3 again, thickness is 18 nm, conductivity is 3.3 ' 10
-4S/cm, bandwidth is controlled to be 1.35eV; So far, accomplish the preparation of positive heterogeneous P-I-N knot;
(4) battery sample with the preparation of the positive heterogeneous P-I-N knot of above-mentioned completion takes out from vacuum, and rapidly its reverse side is become depositional plane, to continue the preparation of battery back of the body surface field layer.This process is wanted rapidly, and to reduce the oxidation of atmosphere to the monocrystalline silicon reverse side as far as possible, should be controlled at 1 minute is best with in.Rapid then pumping high vacuum is to carry out the back process of battery device;
When (5) degree reaches 2.0e-4Pa, the beginning back process, the surface (be silicon chip back this moment) of handling monocrystalline silicon earlier with the plasma bombardment of pure hydrogen atmosphere is to remove oxide on surface, dangling bonds, reduction blemish attitude.Then, be reacting gas with hydrogen, silane, utilize the RF-PECVD technology at monocrystalline silicon surface (being silicon chip back this moment) deposition preparation one deck intrinsic amorphous silicon film 4, thickness is 6nm, conductivity is 10
-6S/cm; And then be reacting gas with hydrogen, silane, phosphine, methane, on above-mentioned intrinsic amorphous silicon film 4, deposit one deck N again
+Heavily doped amorphous silicon membrane 5, thickness are 20 nm, and conductivity is 10
-2S/cm, bandwidth is controlled to be 1.85eV; So far, accomplished the preparation of reverse side battery back of the body surface field layer;
(6) accomplished on the sample of battery positive and negative technology, adopted magnetron sputtering technique, plated nesa coating AZO respectively in the 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 the nesa coating 7 overleaf and plate layer of aluminum back electrode 8 with magnetron sputtering technique again, thickness is 0.020mm;
(7) reactive evaporation technology, preparation titanium, palladium, silver-colored compound grid 9, thickness is 0.013mm, grating spacing is 4mm.
(8) the above-mentioned two-sided heterojunction battery device for preparing carries out the edge cuts processing, and to eliminate the influence of edge shorting, the battery device area that cuts into is 1 ' 1 cm
2
(9) the photovoltaic J-V curve of amorphous silicon germanium/crystal silicon heterojunction double-sided solar battery of obtaining of prepared is as shown in Figure 3, wherein short-circuit current density J
SC=38.32mA/cm
2Open circuit voltage V
OC=568.5mV; Fill factor, curve factor FF=0.671; Battery conversion efficiency Effi=14.62%.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction.Though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention.Any those of ordinary skill in the art; Do not breaking away under the technical scheme scope situation of the present invention; All the method for above-mentioned announcement capable of using and technology contents are made many possible changes and modification to technical scheme of the present invention, or are revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical scheme of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, be equal to replacement, equivalence changes and modify, all still belong in the scope that technical scheme of the present invention protects.
Claims (5)
1. a silicon based hetero-junction double-sided solar battery 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), P type doped amorphous silicon germanium film (3); 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, P type doped amorphous silicon germanium film (3), intrinsic micro crystal silicon germanium film (2) and N type twin polishing monocrystalline silicon piece (1) form 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 said titanium, palladium, silver-colored compound grid (9) is 0.012 ~ 0.015mm; The grid line width is 0.020 ~ 0.025mm, and the spacing between the grid line is 4 ~ 5mm, and the thickness of said nesa coating AZO (6) is 125 ~ 150nm; The thickness of said P type doped amorphous silicon germanium film (3) is 16 ~ 20nm; The thickness of said intrinsic micro crystal silicon germanium film (2) is 10 ~ 12nm, and said N type twin polishing monocrystalline silicon piece (1) thickness is 0.200 ~ 0.220mm, and conductivity is 1 ~ 2S/cm; Said intrinsic amorphous silicon film (4) thickness is 5 ~ 8nm, said N
+Heavily doped amorphous silicon membrane (5) thickness is 20 ~ 25nm, and said back side nesa coating AZO (7) thickness is 125 ~ 150nm, and said 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, the emission of formation PN heterojunction is P type doped amorphous silicon germanium film (3) very, 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 come the passivation heterojunction boundary as the heterojunction boundary resilient coating; Reduce the boundary defect attitude, the bandwidth of said 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 said N
+The bandwidth of heavily doped amorphous silicon membrane (5) is 1.8 ~ 1.9eV.
5. the preparation method of a silicon based hetero-junction double-sided solar battery is characterized in that, the process route of this method is following:
(1) preparation of positive PN heterojunction
(a) with silane SiH
4, hydrogen (H
2, germane GeH
4Be reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, the one side of N type twin polishing monocrystalline silicon piece (1) at first deposit preparation one layer thickness be 10 ~ 12nm intrinsic micro crystal silicon germanium film (2) (I-mc-SiGe);
(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; Deposition preparation one layer thickness is the P type doped amorphous silicon germanium film (3) of 16 ~ 20nm again on above-mentioned intrinsic micro crystal silicon germanium film (2), forms heterojunction;
(2) preparation of reverse side back of the body surface field layer N-I-N+
(a) with silane SiH
4, hydrogen H
2Be reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, at first deposit the intrinsic amorphous silicon film I-a-Si (4) that a layer thickness is 5 ~ 8nm at the another side of N type twin polishing monocrystalline silicon piece (1);
(b) with silane SiH
4, hydrogen H
2, phosphine PH
3, methane CH
4Be reacting gas, adopt radio frequency plasma to strengthen chemical vapor deposition method RF-PECVD, deposition preparation one layer thickness is the N of 20 ~ 25nm again on above-mentioned intrinsic amorphous silicon film (4)
+The heavily doped amorphous silicon membrane N of type
+-a-Si (6) forms back of the body surface field layer N-I-N+;
(3) preparation of nesa coating AZO
Adopt magnetron sputtering technique;, back of the body surface field laminar surface surperficial at above-mentioned heterojunction plates nesa coating AZO (6) and back side nesa coating AZO (7) respectively; Its thickness is 125 ~ 150nm, and 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 technology, preparation titanium, palladium, silver-colored compound grid 9, thickness is 0.012 ~ 0.015mm, and the grid line width is 0.020 ~ 0.025mm, and the spacing between the grid line is 4 ~ 5mm;
(5) the above-mentioned two-sided heterojunction battery device for preparing carries out the edge cuts processing, to eliminate the influence of edge shorting.
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| CN105932075A (en) * | 2016-05-12 | 2016-09-07 | 南昌大学 | Back crystal silicon heterojunction solar cell and preparation method thereof |
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