CN103779448B - The preparation method of the radial heterojunction solar cell of a kind of silicon nanowires - Google Patents

The preparation method of the radial heterojunction solar cell of a kind of silicon nanowires Download PDF

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CN103779448B
CN103779448B CN201410066901.0A CN201410066901A CN103779448B CN 103779448 B CN103779448 B CN 103779448B CN 201410066901 A CN201410066901 A CN 201410066901A CN 103779448 B CN103779448 B CN 103779448B
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董刚强
张海龙
刘丰珍
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University of Chinese Academy of Sciences
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Abstract

The present invention relates to the preparation method of the radial heterojunction solar cell of a kind of silicon nanowires, belong to field of photovoltaic technology.This method adopts hot-wire chemical gas-phase deposition technology, successively at N-shaped amorphous silicon membrane of originally seeking peace with conformal deposition on the monocrystalline silicon piece of nano wire, has prepared the radial heterojunction solar cell of nano wire that structure is n-α-Si:H/i-α-Si:H/p-c-SiNW.The atomic hydrogen process good by means of hot-wire chemical gas-phase deposition technology and intrinsic amorphous silicon passivation ability, make the performance of the radial heterojunction solar cell of the nano wire of preparation have and significantly improve.This solar battery structure is novel, function admirable, to have a wide range of applications value at photovoltaic art.

Description

The preparation method of the radial heterojunction solar cell of a kind of silicon nanowires
Technical field
The present invention relates to the preparation method of the radial heterojunction solar cell of a kind of silicon nanowires, belong to field of photovoltaic technology.
Background technology
The light absorption of conventional planar connection solar cell is parallel with carrier transport direction, both are simultaneously or a paradox: want fully to absorb light, just necessarily require material enough thick, and in electronic transport, in order to effective collection of charge carrier can be realized, require that material is enough thin.This shortcoming has had a strong impact on the further raising of conventional planar structure solar cell performance.Therefore, the research of new structure solar cell is imperative.Nano wire is prepared radial p-n junction solar cell, not only can utilize the sunken light effect that nano thread structure is good, the contradiction that conventional planar connection solar cell exists in light absorption and carrier transport can also be solved, greatly can improve the collection efficiency of charge carrier, be expected on cheap material, realize high photoelectric conversion efficiency.
At present, the correlative study work of the radial p-n junction solar cell of this new construction is carried out, but the high-temperature diffusion process that industrialization at present uses is difficult on nano wire, prepare radial p-n junction solar cell.Present applicant has proposed a kind of method (patent publication No. is CN201310395014) adopting low temperature shallow junction doping technique to prepare radial Homojeneous p-n Junction solar cell on silicon nanowires, adopt this technique greatly can improve short circuit current and the conversion efficiency of solar cell.But radially homogenous junction solar cell lacks good interface passivation, surface recombination is relatively more serious, and this makes the open circuit voltage of solar cell be not very high.Thin film silicon/crystalline silicon heterojunction solar battery is everybody confessed solar cell with high open circuit voltage characteristic, and the open circuit voltage of silicon based hetero-junction (HIT) solar cell of Japanese Panasonic company report reaches 750mV.The structure of silicon nanowires and heterojunction are combined, form the radial heterojunction solar cell of nano wire, can many-sided advantages such as high and radial p-n junction solar cell short circuit current is large in conjunction with heterojunction solar cell open circuit voltage, there is important scientific research and using value.At present You Duojia R&D institution begins one's study the radial heterojunction solar cell of silicon nanowires in the world, also report some results successively, but they are using plasma enhancing, and chemical vapour deposition (CVD) (PECVD) method prepares amorphous silicon membrane, this method is not only difficult on nano wire, realize good amorphous silicon membrane conformal deposition, and due to Ions Bombardment, the problems such as the plasma initial stage is unstable, make passivation effect undesirable, so the open circuit voltage of the radial heterojunction solar cell of the nano wire reported so far is not also more than 560mV, the conversion efficiency of battery is all less than 10%.
Hot-wire chemical gas-phase deposition (HWCVD) technology has low temperature depositing, experimentation is easy to control, a large amount of atomic hydrogen, without Ions Bombardment be easy to realize the advantages such as conformal deposition receiving in (micro-) rice structure.The more important thing is, hot-wire chemical gas-phase deposition technology is stronger than the passivation ability of plasma enhanced chemical vapor deposition, can reduce surface recombination, extremely be adapted at the radial heterojunction solar cell that processability on nano thread structure is excellent.
Summary of the invention
The object of the invention is the preparation method proposing the radial heterojunction solar cell of a kind of silicon nanowires, adopt hot-wire chemical gas-phase deposition technology, the surface of passivation nano thread structure, the N-shaped amorphous silicon membrane of originally seeking peace of depositing high-quality on nano wire, achieve the conformal deposition of amorphous silicon membrane, to improve open circuit voltage and the conversion efficiency of solar cell.
The preparation method of the radial heterojunction solar cell of the silicon nanowires that the present invention proposes, comprises the following steps:
(1) adopt wet etching method, the upper surface of p-type monocrystalline silicon piece formed erect, diameter is 20 ~ 2000 nanometers, is highly the nano wire of 100 ~ 10000 nanometers, and upper surface is clean with the Wafer Cleaning of nano wire;
(2) sample that step (1) obtains is put into the cavity of thermal evaporation apparatus, in cavity, vacuum reaches 3 × 10 -4after handkerchief, evaporation rafifinal, deposits at sample lower surface the metallic aluminium film that a layer thickness is 1 ~ 2 micron;
(3) sample that step (2) obtains is put into quartzy stove, pass into the mist of nitrogen and oxygen, wherein the volume ratio of nitrogen and oxygen is 95:5, keep 1 hour at 930 DEG C, make the metallic aluminium film of sample lower surface form aluminium back surface field layer, the upper surface of sample forms thermal oxide layer;
(4) sample levels step (3) obtained is placed, under the prerequisite that protection sample lower surface aluminium back surface field layer is not destroyed, hydrofluoric acid solution is dripped at sample upper surface, remove the oxide layer of sample upper surface, the percent by volume solubility of hydrofluoric acid solution is 5 ~ 15%, and the processing time is 1 ~ 3 minute;
(5) sample that step (4) obtains is put into the cavity of hot-filament chemical vapor deposition equipment, block sample with baffle plate, cavity is vacuumized, when chamber vacuum reaches 3 × 10 -4after handkerchief, light heated filament, the temperature of heated filament is 1500 ~ 1800 DEG C, passes into hydrogen, the flow of hydrogen is 20 standard milliliters/minute (sccm), under pressure is 1 ~ 20 handkerchief, remove baffle plate, atomic hydrogen process is carried out to sample, processing time is 0.5 ~ 3 minute, after process, block sample with baffle plate, close hydrogen;
(6) continue to pass into hydrogen and silane in cavity, hydrogen flowing quantity be 2 standard milliliters/minute, silane flow rate be 2 standard milliliters/minute, under pressure is 1 handkerchief, intrinsic amorphous silicon film is covered to cavity inner wall, cover time is 10 minutes, then removes baffle plate, to the intrinsic amorphous silicon film of silicon chip upper surface deposition 5 ~ 15 nanometer thickness with nano wire, deposition rate is 0.1 ~ 0.4 nm/sec, after deposition, block sample with baffle plate, close hydrogen and silane;
(7) continue to pass into silane and phosphine to cavity, silane flow rate be 2 standard milliliters/minute, phosphine flow be 2 standard milliliters/minute, under pressure is 2 handkerchiefs, cover N-shaped amorphous silicon membrane to cavity inner wall, cover time is 8 minutes, then remove baffle plate, to the N-shaped amorphous silicon membrane of upper surface deposition 10 ~ 30 nanometer thickness of the sample with intrinsic amorphous silicon film, deposition rate is 0.1 ~ 0.4 nm/sec, block sample with baffle plate, close silane and phosphine;
(8) sample that step (7) obtains is put into the cavity of thermal evaporation apparatus, block sample with baffle plate, cavity is vacuumized, when in cavity, vacuum reaches 5 × 10 -4after handkerchief, substrate bake temperature is made to be 220 DEG C, sample is toasted, pass into oxygen after baking, remove baffle plate, evaporation indium stannum alloy, under oxygen effect, the N-shaped amorphous silicon membrane of sample deposits the transparent conductive film of indium oxide layer tin material, and the transparent conductive film thickness of deposition is 80 ~ 150 nanometers, and sedimentation time is 2 ~ 4 minutes;
(9) sample that step (8) obtains is put into the cavity of another thermal evaporation apparatus, cavity is vacuumized, when chamber vacuum is less than 1 × 10 -3during handkerchief, evaporate titanium, palladium and ag material successively, in the sample upper surface titanium deposition-palladium-silver grating line of step (8), as the top electrode of solar cell, then, be less than 3 × 10 in chamber vacuum -3during handkerchief, evaporated metal aluminium, in the sample lower surface plated metal aluminium film of step (8), as the bottom electrode of solar cell.
The preparation method of the radial heterojunction solar cell of the silicon nanowires that the present invention proposes, has the following advantages:
1, the inventive method have employed hydrofluoric acid treatment, atomic hydrogen process, intrinsic amorphous silicon passivation technology combine, and reduces sample surfaces compound, reaches good interface passivation effect, for preparation high-performance solar cell provides prerequisite guarantee.
2, the inventive method adopts hot-wire chemical gas-phase deposition technology to prepare high-quality amorphous silicon membrane, instead of conventional plasma enhanced chemical vapor deposition technology, reduce the damage that Ions Bombardment brings, achieve the conformal deposition of amorphous silicon membrane, successfully prepare the radial heterojunction solar cell of nano wire that structure is N-shaped amorphous silicon/intrinsic amorphous silicon/p-type silicon nanowires (n-α-Si:H/i-α-Si:H/p-c-SiNW).
3, the radial heterojunction solar cell of the nano wire prepared of the inventive method, compared to conventional planar connection solar cell, short-circuit current density has had and has significantly improved, heterojunction is adopted to prepare solar cell with on the monocrystalline silicon piece of silicon nanowires, solve the shortcoming that the radial Homojeneous p-n Junction solar batteries of nano wire is low, the efficiency of final solar cell has had and has increased substantially, and has huge industrialization prospect.
Accompanying drawing explanation
Fig. 1 is the structural representation of the radial heterojunction solar cell of silicon nanowires prepared by the inventive method.
Fig. 2 is the scanning electron microscope (SEM) photograph of preparation method of the present invention on silicon nanowires after the nano amorphous silicon thin film of conformal deposition 60, and the upper left corner is enlarged drawing.
Fig. 3 is I-V curve and the battery parameter citing of the solar cell adopting the inventive method to prepare.
In Fig. 1,1 is bottom electrode, and 2 is aluminium back surface field layers, and 3 is upper surface p-type monocrystalline silicon pieces with nano wire, and 4 is intrinsic amorphous silicon films, and 5 is N-shaped amorphous silicon membranes, and 6 is transparent conductive films, and 7 is top electrodes, and 8 is nano wires.
Embodiment
The preparation method of the radial heterojunction solar cell of the silicon nanowires that the present invention proposes, the structure of this solar cell as shown in Figure 1, comprises the following steps:
(1) adopt wet etching method, the upper surface of p-type monocrystalline silicon piece 3 formed erect, diameter is 20 ~ 2000 nanometers, is highly the nano wire 8 of 100 ~ 10000 nanometers, and upper surface is clean with the Wafer Cleaning of nano wire;
(2) sample that step (1) obtains is put into the cavity of thermal evaporation apparatus, in cavity, vacuum reaches 3 × 10 -4after handkerchief, evaporation rafifinal, deposits at sample lower surface the metallic aluminium film that a layer thickness is 1 ~ 2 micron;
(3) sample that step (2) obtains is put into quartzy stove, pass into the mist of nitrogen and oxygen, wherein the volume ratio of nitrogen and oxygen is 95:5, keep 1 hour at 930 DEG C, make the metallic aluminium film of sample lower surface form aluminium back surface field layer 2, the upper surface of sample forms thermal oxide layer;
(4) sample levels step (3) obtained is placed, under the prerequisite that protection sample lower surface aluminium back surface field layer is not destroyed, hydrofluoric acid solution is dripped at sample upper surface, remove the oxide layer of sample upper surface, the percent by volume solubility of hydrofluoric acid solution is 5 ~ 15%, and the processing time is 1 ~ 3 minute;
(5) sample that step (4) obtains is put into the cavity of hot-filament chemical vapor deposition equipment, block sample with baffle plate, cavity is vacuumized, when chamber vacuum reaches 3 × 10 -4after handkerchief, light heated filament, the temperature of heated filament is 1500 ~ 1800 DEG C, passes into hydrogen, the flow of hydrogen is 20 standard milliliters/minute (sccm), under pressure is 1 ~ 20 handkerchief, remove baffle plate, atomic hydrogen process is carried out to sample, processing time is 0.5 ~ 3 minute, after process, block sample with baffle plate, close hydrogen;
(6) continue to pass into hydrogen and silane in cavity, hydrogen flowing quantity be 2 standard milliliters/minute, silane flow rate be 2 standard milliliters/minute, under pressure is 1 handkerchief, intrinsic amorphous silicon film is covered to cavity inner wall, cover time is 10 minutes, then removes baffle plate, to the intrinsic amorphous silicon film 4 of silicon chip upper surface deposition 5 ~ 15 nanometer thickness with nano wire, deposition rate is 0.1 ~ 0.4 nm/sec, after deposition, block sample with baffle plate, close hydrogen and silane;
(7) continue to pass into silane and phosphine to cavity, silane flow rate be 2 standard milliliters/minute, phosphine flow be 2 standard milliliters/minute, under pressure is 2 handkerchiefs, N-shaped amorphous silicon membrane is covered to cavity inner wall, cover time is 8 minutes, then baffle plate is removed, to the N-shaped amorphous silicon membrane 5 of upper surface deposition 10 ~ 30 nanometer thickness of the sample with intrinsic amorphous silicon film, deposition rate is 0.1 ~ 0.4 nm/sec, sample is blocked with baffle plate, close silane and phosphine, after depositing n-type amorphous silicon membrane, the monocrystalline silicon nano line of N-shaped amorphous silicon membrane and p-type defines radial heterojunction at the silicon chip upper surface with nano wire,
(8) sample that step (7) obtains is put into the cavity of thermal evaporation apparatus, block sample with baffle plate, cavity is vacuumized, when in cavity, vacuum reaches 5 × 10 -4after handkerchief, substrate bake temperature is made to be 220 DEG C, sample is toasted, pass into oxygen after baking, remove baffle plate, evaporation indium stannum alloy, under oxygen effect, the N-shaped amorphous silicon membrane of sample deposits the transparent conductive film 6 of indium oxide layer tin material, and the transparent conductive film thickness of deposition is 80 ~ 150 nanometers, and sedimentation time is 2 ~ 4 minutes;
(9) sample that step (8) obtains is put into the cavity of another thermal evaporation apparatus, cavity is vacuumized, when chamber vacuum is less than 1 × 10 -3during handkerchief, evaporate titanium, palladium and ag material successively, in the sample upper surface titanium deposition-palladium-silver grating line of step (8), as the top electrode 7 of solar cell, then, be less than 3 × 10 in chamber vacuum -3during handkerchief, evaporated metal aluminium, in the sample lower surface plated metal aluminium film of step (8), as the bottom electrode 1 of solar cell.
In preparation method of the present invention, the method that the upper surface of p-type monocrystalline silicon piece corrodes into silicon nanowires is used wet corrosion technique, the concrete preparation flow of this technique can see technology disclosed in Chinese patent ZL200610089728.1; Multiple other technologies are also had also to be used in preparation and grow nanowire on silicon chip, as methods such as reactive ion etching, photoetching technique, gas-liquid-solid (VLS), anodised aluminium (AAO) and electrochemical corrosion at present.The present invention can use above-mentioned any one method to prepare and grow nanowire on silicon chip.
In preparation method of the present invention, concrete technology silicon chip substrate with nano wire cleaned up is: first, the mixed solution of the concentrated sulfuric acid and hydrogen peroxide put into by sample, clean 30 minutes at 120 DEG C, remove organic contamination and the part metals ion of sample surfaces, wherein the Volume fraction of the concentrated sulfuric acid and hydrogen peroxide is 7:3, clean by washed with de-ionized water afterwards; Then, the mixed aqueous solution of ammoniacal liquor, hydrogen peroxide and isopropyl alcohol put into by sample, clean 10 minutes at 80 DEG C, clean by washed with de-ionized water afterwards, the Volume fraction of ammoniacal liquor wherein, hydrogen peroxide, isopropyl alcohol and water is 1:2:0.5:5, present invention optimizes traditional cleaning, add isopropyl alcohol, contribute to the pollution of nanowire sidewalls and bottom to clean up; Final sample puts into the aqueous solution of hydrochloric acid and hydrogen peroxide, and 80 DEG C of cleanings 7 minutes, thoroughly clean up for subsequent use with deionized water afterwards, the Volume fraction of hydrochloric acid wherein, hydrogen peroxide and water was 1:2:5.The silicon wafer parameters used in the present invention is: p-type is adulterated, zone melting single-crystal, <100> crystal orientation, resistivity 1 ~ 3 Ω cm.The parameter of the p-type doped monocrystalline silicon sheet wherein used, as doping content, resistivity, thickness etc. can be any one of the normal silicon chip used in photovoltaic industry, allow to adjust in right amount.
The purity of the hydrogen used in the inventive method is 99.9999%, and the concentration of silane is 50% (silane: hydrogen (v:v)=1:1), and the concentration of phosphine is 0.5% (phosphine: hydrogen (v:v)=0.5:99.5).
Below introduce the embodiment of the inventive method:
Embodiment one:
(1) adopt wet etching to p-type monocrystalline silicon piece (zone melting single-crystal, <100> crystal orientation, resistivity 1 ~ 3 Ω cm) upper surface corrodes, form nano wire, the height of nano wire is 6000 nanometers, sample is put into the mixed solution of the concentrated sulfuric acid and hydrogen peroxide, cleans 30 minutes at 120 DEG C, wherein the Volume fraction of the concentrated sulfuric acid and hydrogen peroxide is 7:3, clean by washed with de-ionized water afterwards; Then, the mixed aqueous solution of ammoniacal liquor, hydrogen peroxide and isopropyl alcohol put into by sample, clean 10 minutes at 80 DEG C, clean by washed with de-ionized water afterwards, the Volume fraction of ammoniacal liquor wherein, hydrogen peroxide, isopropyl alcohol and water was 1:2:0.5:5, and final sample puts into the aqueous solution of hydrochloric acid and hydrogen peroxide, 80 DEG C of cleanings 7 minutes, thoroughly clean up for subsequent use with deionized water afterwards, the Volume fraction of hydrochloric acid wherein, hydrogen peroxide and water is 1:2:5.After cleaning, sample nitrogen dries up for subsequent use.
(2) sample that step (1) obtains is put into the cavity of thermal evaporation apparatus, in cavity, vacuum is 2.5 × 10 -4under handkerchief, evaporation rafifinal, deposits at sample lower surface the metallic aluminium film that a layer thickness is 1.5 microns;
(3) sample that step (2) obtains is put into quartzy stove, pass into nitrogen and oxygen mixed gas, keep 1 hour, prepare aluminium back surface field layer at the sample back side at the temperature of 930 DEG C, the upper surface of sample forms thermal oxide layer;
(4) sample levels step (3) obtained is placed, and dripping percent by volume solubility at sample upper surface is the hydrofluoric acid solution of 12%, processing sample 2.5 minutes, removes the oxide layer of sample upper surface;
(5) sample that step (4) obtains being put into the cavity of hot-filament chemical vapor deposition equipment, block sample, vacuumize cavity with baffle plate, is 2.3 × 10 in vacuum -4under handkerchief, light heated filament, the temperature of heated filament is 1650 DEG C, then passes into hydrogen, the flow of hydrogen be 20 standard milliliters/minute, under pressure 5 handkerchief, remove baffle plate, atomic hydrogen process carried out to sample, processing time is 2 minutes, sample after atomic hydrogen process, closing baffle plate;
(6) continue to pass into hydrogen and silane in cavity, hydrogen flowing quantity be 2 standard milliliters/minute, silane flow rate be 2 standard milliliters/minute, under pressure is 1 handkerchief, intrinsic amorphous silicon film is covered to cavity inner wall, cover time is 10 minutes, then removes baffle plate, deposits the intrinsic amorphous silicon film of 12 nanometer thickness to the silicon chip upper surface with nano wire, deposition rate is 0.35 nm/sec, after deposition, block sample with baffle plate, close hydrogen and silane;
(7) continue to pass into silane and phosphine to cavity, silane flow rate be 2 standard milliliters/minute, phosphine flow be 2 standard milliliters/minute, under pressure is 2 handkerchiefs, cover N-shaped amorphous silicon membrane to cavity inner wall, cover time is 8 minutes, then remove baffle plate, the upper surface to the sample with intrinsic amorphous silicon film deposits the N-shaped amorphous silicon membrane of 24 nanometer thickness, and deposition rate is 0.3 nm/sec, block sample with baffle plate, close silane and phosphine;
(8) sample that step (7) obtains is put into the cavity of thermal evaporation apparatus, block sample with baffle plate, cavity is vacuumized, when vacuum in cavity is 3 × 10 -4after handkerchief, substrate bake temperature is made to be 220 DEG C, sample is toasted, pass into oxygen after baking, remove baffle plate, evaporation indium stannum alloy, under oxygen effect, the N-shaped amorphous silicon membrane of sample deposits the transparent conductive film of indium oxide layer tin material, and the transparent conductive film thickness of deposition is 135 nanometers, and sedimentation time is 3.5 minutes;
(9) sample that step (8) obtains is put into the cavity of another thermal evaporation apparatus, cavity is vacuumized, when chamber vacuum is 5 × 10 -4during handkerchief, evaporating titanium, palladium and ag material successively, at sample upper surface titanium deposition-palladium-silver grating line, as the top electrode of solar cell, then, is 1 × 10 in chamber vacuum -3during handkerchief, evaporated metal aluminium, in the sample lower surface plated metal aluminium film of step (8), as the bottom electrode of solar cell.
Embodiment two:
(1) adopt wet etching at p-type monocrystalline silicon piece (zone melting single-crystal, <100> crystal orientation, resistivity 1 ~ 3 Ω cm) upper surface corrosion nano wire, the height of nano wire is 1000 nanometers, sample is put into the mixed solution of the concentrated sulfuric acid and hydrogen peroxide, clean 30 minutes at 120 DEG C, wherein the Volume fraction of the concentrated sulfuric acid and hydrogen peroxide is 7:3, clean by washed with de-ionized water afterwards; Then, the mixed aqueous solution of ammoniacal liquor, hydrogen peroxide and isopropyl alcohol put into by sample, clean 10 minutes at 80 DEG C, clean by washed with de-ionized water afterwards, the Volume fraction of ammoniacal liquor wherein, hydrogen peroxide, isopropyl alcohol and water was 1:2:0.5:5, and final sample puts into the aqueous solution of hydrochloric acid and hydrogen peroxide, 80 DEG C of cleanings 7 minutes, thoroughly clean up for subsequent use with deionized water afterwards, the Volume fraction of hydrochloric acid wherein, hydrogen peroxide and water is 1:2:5.After cleaning, sample nitrogen dries up for subsequent use.
(2) sample that step (1) obtains is put into the cavity of thermal evaporation apparatus, in cavity, vacuum is 2.2 × 10 -4under handkerchief, evaporation rafifinal, deposits at sample lower surface the metallic aluminium film that a layer thickness is 2 microns;
(3) sample that step (2) obtains is put into quartzy stove, pass into nitrogen and oxygen mixed gas, keep 1 hour, prepare aluminium back surface field layer at the sample back side at the temperature of 930 DEG C, the upper surface of sample forms thermal oxide layer;
(4) sample levels step (3) obtained is placed, and dripping percent by volume solubility at sample upper surface is the hydrofluoric acid solution of 10%, processing sample 2 minutes, removes the oxide layer of sample upper surface;
(5) sample that step (4) obtains being put into the cavity of hot-filament chemical vapor deposition equipment, block sample, vacuumize cavity with baffle plate, is 2.2 × 10 in vacuum -4under handkerchief, light heated filament, the temperature of heated filament is 1750 DEG C, then passes into hydrogen, the flow of hydrogen be 20 standard milliliters/minute, under pressure 10 handkerchief, remove baffle plate, atomic hydrogen process carried out to sample, processing time is 1 minute, sample after atomic hydrogen process, closing baffle plate;
(6) continue to pass into hydrogen and silane in cavity, hydrogen flowing quantity be 2 standard milliliters/minute, silane flow rate be 2 standard milliliters/minute, under pressure is 1 handkerchief, intrinsic amorphous silicon film is covered to cavity inner wall, cover time is 10 minutes, then removes baffle plate, deposits the intrinsic amorphous silicon film of 10 nanometer thickness to the silicon chip upper surface with nano wire, deposition rate is 0.26 nm/sec, after deposition, block sample with baffle plate, close hydrogen and silane;
(7) continue to pass into silane and phosphine to cavity, silane flow rate be 2 standard milliliters/minute, phosphine flow be 2 standard milliliters/minute, under pressure is 2 handkerchiefs, cover N-shaped amorphous silicon membrane to cavity inner wall, cover time is 8 minutes, then remove baffle plate, the upper surface to the sample with intrinsic amorphous silicon film deposits the N-shaped amorphous silicon membrane of 20 nanometer thickness, and deposition rate is 0.26 nm/sec, block sample with baffle plate, close silane and phosphine;
(8) sample that step (7) obtains is put into the cavity of thermal evaporation apparatus, block sample with baffle plate, cavity is vacuumized, when vacuum in cavity is 2 × 10 -4after handkerchief, substrate bake temperature is made to be 220 DEG C, sample is toasted, pass into oxygen after baking, remove baffle plate, evaporation indium stannum alloy, under oxygen effect, the N-shaped amorphous silicon membrane of sample deposits the transparent conductive film of indium oxide layer tin material, and the transparent conductive film thickness of deposition is 120 nanometers, and sedimentation time is 3.3 minutes;
(9) sample that step (8) obtains is put into the cavity of thermal evaporation apparatus, cavity is vacuumized, when chamber vacuum is 3 × 10 -4during handkerchief, evaporating titanium, palladium and ag material successively, at sample upper surface titanium deposition-palladium-silver grating line, as the top electrode of solar cell, then, is 6 × 10 in chamber vacuum -4during handkerchief, evaporated metal aluminium, at sample lower surface plated metal aluminium film, as the bottom electrode of solar cell.
On nano wire, amorphous silicon parcel is good as seen from Figure 2, and the upper and lower diameter difference of nano wire is little, embodies the advantage of hot-wire chemical gas-phase deposition conformal deposition; Cleaned sample minority carrier life time initial value is 80 microseconds, and when after deposition 10 nanometer intrinsic amorphous silicon film, the minority carrier life time of sample reaches 160 microseconds, embodies the passivation effect that hot-wire chemical gas-phase deposition is good.Fig. 3 is I-V curve and the battery parameter citing of the battery adopting the inventive method embodiment to obtain.As can see from Figure 3, the open circuit voltage of the radial heterojunction solar cell of nano wire reaches 594mV, and short-circuit current density is 36.98mA/cm 2, conversion efficiency is 16.02%, and (open circuit voltage is 553mV, and short-circuit current density is 27.1mA/cm to compare at present the homogeneous structure solar cell of other scientific research groups report in the world 2, conversion efficiency is 8.03%; E.S.Ashour, M.Y.B.Sulaiman, M.H.RuslanandK.Sopian, Nanoscale.Res.Lett.8,466 (2013)), the conversion efficiency of solar cell improves nearly one times.

Claims (1)

1. a preparation method for the radial heterojunction solar cell of silicon nanowires, is characterized in that this preparation method comprises the following steps:
(1) adopt wet etching method, the upper surface of p-type monocrystalline silicon piece formed erect, diameter is 20 ~ 2000 nanometers, is highly the nano wire of 100 ~ 10000 nanometers, and upper surface is clean with the Wafer Cleaning of nano wire;
(2) sample that step (1) obtains is put into the cavity of thermal evaporation apparatus, in cavity, vacuum reaches 3 × 10 -4after handkerchief, evaporation rafifinal, deposits at sample lower surface the metallic aluminium film that a layer thickness is 1 ~ 2 micron;
(3) sample that step (2) obtains is put into quartzy stove, pass into the mist of nitrogen and oxygen, wherein the volume ratio of nitrogen and oxygen is 95:5, keeps 1 hour at 930 DEG C, make the metallic aluminium film of sample lower surface form aluminium back surface field layer, the upper surface of sample forms thermal oxide layer;
(4) sample levels step (3) obtained is placed, and drips hydrofluoric acid solution at sample upper surface, and remove the oxide layer of sample upper surface, the percent by volume solubility of hydrofluoric acid solution is 5 ~ 15%, and the processing time is 1 ~ 3 minute;
(5) sample that step (4) obtains is put into the cavity of hot-filament chemical vapor deposition equipment, block sample with baffle plate, cavity is vacuumized, when chamber vacuum reaches 3 × 10 -4after handkerchief, light heated filament, the temperature of heated filament is 1500 ~ 1800 DEG C, passes into hydrogen, the flow of hydrogen be 20 standard milliliters/minute, under pressure is 1 ~ 20 handkerchief, remove baffle plate, atomic hydrogen process carried out to sample, processing time is 0.5 ~ 3 minute, after process, blocks sample with baffle plate, closes hydrogen;
(6) continue to pass into hydrogen and silane in cavity, hydrogen flowing quantity be 2 standard milliliters/minute, silane flow rate be 2 standard milliliters/minute, under pressure is 1 handkerchief, intrinsic amorphous silicon film is covered to cavity inner wall, cover time is 10 minutes, then removes baffle plate, to the intrinsic amorphous silicon film of silicon chip upper surface deposition 5 ~ 15 nanometer thickness with nano wire, deposition rate is 0.1 ~ 0.4 nm/sec, after deposition, block sample with baffle plate, close hydrogen and silane;
(7) continue to pass into silane and phosphine to cavity, silane flow rate be 2 standard milliliters/minute, phosphine flow be 2 standard milliliters/minute, under pressure is 2 handkerchiefs, cover N-shaped amorphous silicon membrane to cavity inner wall, cover time is 8 minutes, then remove baffle plate, to the N-shaped amorphous silicon membrane of upper surface deposition 10 ~ 30 nanometer thickness of the sample with intrinsic amorphous silicon film, deposition rate is 0.1 ~ 0.4 nm/sec, block sample with baffle plate, close silane and phosphine;
(8) sample that step (7) obtains is put into the cavity of thermal evaporation apparatus, block sample with baffle plate, cavity is vacuumized, when in cavity, vacuum reaches 5 × 10 -4after handkerchief, substrate bake temperature is made to be 220 DEG C, sample is toasted, pass into oxygen after baking, remove baffle plate, evaporation indium stannum alloy, under oxygen effect, the N-shaped amorphous silicon membrane of sample deposits the transparent conductive film of indium oxide layer tin material, and the transparent conductive film thickness of deposition is 80 ~ 150 nanometers, and sedimentation time is 2 ~ 4 minutes;
(9) sample that step (8) obtains is put into the cavity of another thermal evaporation apparatus, cavity is vacuumized, when chamber vacuum is less than 1 × 10 -3during handkerchief, evaporate titanium, palladium and ag material successively, in the sample upper surface titanium deposition-palladium-silver grating line of step (8), as the top electrode of solar cell, then, be less than 3 × 10 in chamber vacuum -3during handkerchief, evaporated metal aluminium, in the sample lower surface plated metal aluminium film of step (8), as the bottom electrode of solar cell.
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