CN102005505B - Tin-doped crystalline silicon solar cell for inhibiting light attenuation and preparation method thereof - Google Patents

Tin-doped crystalline silicon solar cell for inhibiting light attenuation and preparation method thereof Download PDF

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CN102005505B
CN102005505B CN2010105099424A CN201010509942A CN102005505B CN 102005505 B CN102005505 B CN 102005505B CN 2010105099424 A CN2010105099424 A CN 2010105099424A CN 201010509942 A CN201010509942 A CN 201010509942A CN 102005505 B CN102005505 B CN 102005505B
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tin
silicon
solar cell
boron
preparation
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CN102005505A (en
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余学功
王朋
马向阳
杨德仁
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Zhejiang University ZJU
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Abstract

The invention discloses a tin-doped crystalline silicon solar cell for inhibiting light attenuation and a preparation method thereof. The preparation method of the tin-doped crystalline silicon solar cell comprises the following steps of: doping tin and boron in a polysilicon raw material, wherein the tin concentration is 1016-1021 cm<-3>, and the boron concentration is 1015-1017 cm<-3>; then, growing the tin-doped crystalline silicon under the shielding gas atmosphere; slicing the tin-doped crystalline silicon to prepare a solar cell, wherein the preparation process comprises the steps of: cleaning the sliced silicon chips and flocking; carrying out phosphorus dispersion after flocking; etching and depositing an anti-reflecting film; and finally preparing electrodes and sintering to obtain the tin-doped crystalline silicon solar cell. The invention has simple method and low cost, is compatible with the preparation of the whole solar cell and the conventional process, and the prepared tin-doped crystalline silicon solar cell is capable of effectively inhibiting the light attenuation.

Description

A kind of suppress optical attenuation mix tin crystal-silicon solar cell and preparation method thereof
Technical field
The present invention relates to the silicon solar cell technical field, relate in particular to a kind of suppress optical attenuation mix tin crystal-silicon solar cell and preparation method thereof.
Background technology
Utilizing the solar cell of photovoltaic effect preparation directly to be converted into electric energy to luminous energy, is a kind of mode of more effectively utilizing solar energy, also is important renewable clear energy sources.Since the nineties, photovoltaic industry every year, the speed with 30-40% increased fast; Especially over past ten years, under the policies of various countries promote, the growth of explosion type especially of annual solar cell output.Wherein crystal-silicon solar cell has accounted for the market share of 80-90%, and from now on will dominate in for a long time.The major obstacle of restriction crystal-silicon solar cell large-scale application remains its higher cost at present, is the target that industrial quarters and research circle constantly make great efforts so improve constantly the conversion efficiency of silicon solar cell and reduce cost always.
The crystal-silicon solar cell overwhelming majority is based on the p type substrate preparation of boron-doping, yet there are relatively distinct issues in the boron-doping battery: efficient photo attenuation phenomenon.As far back as 1973, Fischer etc. just found that efficient relaxation phenomenon (H.Fischer and W.Pschunder, Proceedings of the 10th IEEE PhotovoltaicSpecialists Conference can appear in the pulling of crystals silicon solar cell under solar light irradiation; Palo Alto; CA, IEEE, New York; 1973, p.404.).Up to 1997, J.schmidt just proposed the displacement boron in this decay and the silicon, complex relevant (J.Schmidt, the A.G.Aberle and R.Hezel that interstitial oxygen concentration forms; Proceedings of the 26th IEEEPhotovoltaic Specialists Conference, Anaheim, CA; IEEE; New York, 1997,13.).Subsequently, J.schmidt etc. discover that further this complex defect density is directly proportional with the concentration of boron, become quadratic power ratio (J.Schmidt and K.Bothe, Phys.Rev.B69,024107 (2004) .) basically with the concentration of oxygen.
Because boron is easy to mix in silicon, and the segregation coefficient of boron approaches 1, and the crystal resistivity after the boron-doping is evenly distributed.In addition, in crystal growing process,, inevitably can in crystal, introduce oxygen impurities owing to the use of silica crucible.Usually the content of oxygen is very high in the pulling of silicon single crystal (can reach 10 18Cm -3About), so that the optical attenuation problem seems is particularly outstanding.After the illumination, the efficient of pulling of crystals silicon solar cell decay absolute value is generally about 1%-3%.
The content of oxygen is lower than pulling of silicon single crystal in the casting polycrystalline silicon, so the attenuation ratio pulling of silicon single crystal of polycrystalline silicon solar cell efficient is smaller.It is 17-18% that the pulling of silicon single crystal efficiency of solar cell is made in industry at present, and the casting polycrystalline silicon efficiency of solar cell is 15-16%.In the laboratory, the single crystal silicon solar cell peak efficiency is 24.7%, and the polycrystalline silicon solar cell peak efficiency is 20.3%.Therefore, battery efficiency also has certain room for promotion on the industry.Along with silicon solar cell to the development of high efficiency more, it is extremely important that the solution of optical attenuation problem just seems.
The optical attenuation problem can solve through the method that reduces (or substituting) boron or reduction oxygen concentration.Mainly contain following several kinds of approach: replace boron to make dopant with gallium or other IIIA element, because the segregation coefficient of gallium in silicon is 0.008, the segregation coefficient of boron is 0.8, and the gallium concentration change is very big end to end so mix the gallium crystalline silicon, and resistivity is very inhomogeneous.Gallium is dense in the afterbody of crystal and the crucible material, forms heavily dopedly, is difficult to utilize again.Also to partly carry out sorting when producing battery to the crystal different resistivity.And replace boron growth N type crystalline silicon with N type dopants such as phosphorus, and to form the pn knot through diffused with boron during cell preparation, this is incompatible with conventional at present battery structure and technology.In addition, adopt the magnetic control pulling of silicon single crystal,, can cause cost obviously to increase though can significantly reduce the concentration of oxygen.
Summary of the invention
The invention provides a kind of suppress optical attenuation mix tin crystal-silicon solar cell and preparation method thereof, the efficient decay of tin crystal-silicon solar cell under illumination of mixing that makes effectively reduces, thereby improves the operating efficiency of battery.
A kind of preparation method who mixes the tin crystal-silicon solar cell who suppresses optical attenuation may further comprise the steps:
(1) in polycrystalline silicon raw material, mix tin and boron, the concentration of tin is 10 16～10 21Cm -3, the concentration of boron is 10 15～10 17Cm -3, under protective atmosphere, the crystalline silicon of tin is mixed in growth then;
(2) after the crystalline silicon of mixing tin that step (1) growth is obtained is cut into slices, carry out the preparation of solar cell, comprising: the silicon chip to obtaining after the section cleans and making herbs into wool; Carry out phosphorous diffusion after the making herbs into wool; Carry out the deposition of etching and antireflective coating; Prepare electrode and sintering at last, obtain mixing the tin crystal-silicon solar cell.
In the step (1), described protective atmosphere is inert gas or nitrogen, preferred argon gas or nitrogen.
In the step (1), described growth is mixed the process of the crystalline silicon of tin and can in single crystal growing furnace, be carried out, and also can in polycrystalline furnace, carry out.
The crystalline silicon of mixing tin when the growth described in the step (1) carries out under protective atmosphere in single crystal growing furnace; In silica crucible, put into polysilicon, and mix boron and tin, furnace temperature rises to 1400～1500 ℃; Polysilicon and tin, boron fusion; By conventional pulling of silicon single crystal growth technique adjustment growth parameter(s), obtain mixing the pulling of silicon single crystal of tin, the concentration of tin is 10 in the crystal 16～10 20Cm -3, the concentration of boron is 10 15～10 17Cm -3Described protective atmosphere is inert gas or nitrogen, preferred argon gas or nitrogen.
The crystalline silicon of mixing tin when the growth described in the step (1) carries out under protective atmosphere in polycrystalline furnace; In silica crucible, put into polysilicon, and mix boron and tin, furnace temperature rises to 1400～1500 ℃; Polysilicon and tin, boron fusion; By conventional polycrystalline silicon growth process adjustment growth parameter(s), growth obtains mixing the polysilicon of tin, and the concentration of tin is 10 in the crystal 16～10 20Cm -3, the concentration of boron is 10 15～10 17Cm -3Described protective atmosphere is inert gas or nitrogen, preferred argon gas or nitrogen.
When step (1) obtained mixing tin monocrystalline silicon, the technology through step (2) finally obtained mixing the tin single crystal silicon solar cell.
When step (1) obtained mixing the tin polysilicon, the technology through step (2) finally obtained mixing the tin polycrystalline silicon solar cell.
Among the present invention, described tin is high purity tin, and its purity is more than 99.999%, to avoid the introducing of impurity.
That adopts that described preparation method makes mixes the tin crystal-silicon solar cell, because trace doped tin and silicon is congeners, so tin can not influence the electric property of silicon materials basically; Simultaneously, utilize the atomic size of tin bigger, increase the potential barrier of oxygen diffusion and combine to form complex, suppress the formation of boron oxygen complex, thereby reduce the optical attenuation of crystal-silicon solar cell with boron.
The inventive method is simple, and is with low cost, realized crystal growth technique and conventional solar cell preparation technology's compatibility, and for preparing effective inhibition optical attenuation mixes tin crystalline silicon (monocrystalline silicon, polysilicon) solar cell.
Description of drawings
Fig. 1 for the efficient attenuation ratio of mixing tin pulling of crystals silicon solar cell and ordinary straight crystal-pulling silicon solar cell that obtains among the embodiment 3;
Fig. 2 for the efficient attenuation ratio of mixing tin pulling of crystals silicon solar cell and ordinary straight crystal-pulling silicon solar cell that obtains among the embodiment 4.
Embodiment
Embodiment 1
(1) in the 270Kg polycrystalline silicon raw material, mixes 11.4g tin and 5.3 * 10 -2G boron, the concentration of tin are 5 * 10 17Cm -3, the concentration of boron is 2.5 * 10 16Cm -3, (be every cm 3The atomicity of tin is 5 * 10 in the polycrystalline silicon raw material 17Individual, every cm 3The atomicity of boron is 2.5 * 10 in the polycrystalline silicon raw material 16Individual) then in the polycrystalline ingot furnace, under the argon shield atmosphere, pressure is 700torr, and furnace temperature rises to 1450 ℃, and tin, boron fuse in the polysilicon solution, and the casting polycrystalline silicon of tin is mixed in growth.
Identical polycrystalline silicon raw material and boron doping amount are adopted in (1 '), in same polycrystalline ingot furnace, and identical growth parameter(s), the conventional cast polysilicon that tin is not mixed in growth is as contrast.
(2) behind the conventional cast polycrystalline silicon ingot evolution that the casting polycrystalline silicon of mixing tin that step (1) is obtained and step (1 ') obtain, utilize line to be cut into 220 microns silicon chips, after the cleaning, the casting polycrystalline silicon silicon chip of mixing tin separates packing with conventional cast polysilicon silicon chip.
(3) the casting polycrystalline silicon silicon chip, the conventional cast polysilicon silicon chip that adopt step (2) to obtain mixing tin respectively prepare solar cell, comprising: silicon chip is cleaned and sour making herbs into wool; At 850 ℃ of following phosphorous diffusion 30min; The deposition of etching and SiNx; Screen printing electrode, at 775 ℃ of following sintering, the time is 6min at last.Obtain mixing the casting polycrystalline silicon solar cell piece and the conventional cast polycrystalline silicon solar cell sheet of tin respectively.
After cell preparation is accomplished, according to the automatic stepping of efficiency test.With the above-mentioned casting polycrystalline silicon battery sheet of mixing tin that obtains and conventional cast polycrystal silicon cell sheet according to efficient stepping 15.2-15.4%; 15.4-15.6%; Mix the casting polycrystalline silicon battery sheet and the conventional cast polycrystal silicon cell sheet of tin in each efficient stepping and respectively get 15, test light is according to preceding efficient.Under 1 sunlight light intensity, shone 24 hours subsequently, again the battery efficiency after the test decay.
Table 1 is for mixing the casting polycrystalline silicon battery sheet and the conventional cast polycrystal silicon cell sheet efficient pad value of tin before and after the illumination.
Table 1
The efficient shelves Common polycrystal silicon cell Mix the tin polycrystal silicon cell
15.4-15.6％ 0.62％ 0.44％
15.2-15.4％ 0.48％ 0.36％
On average 0.55％ 0.40％
Can find out that from table 1 it is obviously littler than the efficient decay of conventional cast polycrystal silicon cell sheet that each efficient shelves is mixed tin polycrystal silicon cell sheet, mix tin polycrystal silicon cell sheet efficient decay average out to 0.40%, common polycrystal silicon cell sheet efficient decays to 0.55%.
Embodiment 2
(1) in the 450Kg polycrystalline silicon raw material, mixes 3.8Kg tin and 2.0 * 10 -2G boron, the concentration of tin are 1 * 10 20Cm -3, the concentration of boron is 6 * 10 15Cm -3, in the polycrystalline ingot furnace, under the argon shield atmosphere, pressure is 550torr then, and furnace temperature rises to 1480 ℃, and tin, boron fuse in the polysilicon solution, and the casting polycrystalline silicon of tin is mixed in growth.
Identical polycrystalline silicon raw material and boron doping amount are adopted in (1 '), in same polycrystalline ingot furnace, and identical growth parameter(s), the conventional cast polysilicon that tin is not mixed in growth is as contrast.
(2) behind the conventional cast polycrystalline silicon ingot evolution that the casting polycrystalline silicon of mixing tin that step (1) is obtained and step (1 ') obtain, utilize line to be cut into 180 microns silicon chips, after the cleaning, the casting polycrystalline silicon silicon chip of mixing tin separates packing with conventional cast polysilicon silicon chip.
(3) the casting polycrystalline silicon silicon chip, the conventional cast polysilicon silicon chip that adopt step (2) to obtain mixing tin respectively prepare solar cell, comprising: silicon chip is cleaned and sour making herbs into wool; At 880 ℃ of following phosphorous diffusion 25min; The deposition of etching and SiNx; Screen printing electrode, at 820 ℃ of following sintering, the time is 3min at last.Obtain mixing the casting polycrystalline silicon solar cell piece and the conventional cast polycrystalline silicon solar cell sheet of tin respectively.
After cell preparation is accomplished, according to the automatic stepping of efficiency test.With the above-mentioned casting polycrystalline silicon battery sheet of mixing tin that obtains and conventional cast polycrystal silicon cell sheet according to efficient stepping 15.4-15.6%; 15.6-15.8%; Mix the casting polycrystalline silicon battery sheet and the conventional cast polycrystal silicon cell sheet of tin in each efficient stepping and respectively get 20, test light is according to preceding efficient.Under 1 sunlight light intensity, shone 24 hours subsequently, again the battery efficiency after the test decay.
Table 2 is for mixing the casting polycrystalline silicon battery sheet and the conventional cast polycrystal silicon cell sheet efficient pad value of tin before and after the illumination.
Table 2
The efficient shelves Common polycrystal silicon cell Mix the tin polycrystal silicon cell
15.6-15.8％ 0.48％ 0.22％
15.4-15.6％ 0.40％ 0.18％
On average 0.44％ 0.20％
Can find out that from table 2 it is all obviously little than the efficient decay of conventional cast polycrystal silicon cell that each efficient shelves is mixed tin polycrystal silicon cell sheet, mixes tin polycrystal silicon cell sheet efficient decay average out to 0.20%, common polycrystal silicon cell sheet efficient decays to 0.44%.
Embodiment 3
(1) in the 55Kg polycrystalline silicon raw material, mixes 4.6g tin and 2.1 * 10 -3G boron, the concentration of tin are 1 * 10 18Cm -3, the concentration of boron is 5 * 10 15Cm -3, in single crystal growing furnace, under the argon shield atmosphere, pressure is 12torr then, and furnace temperature rises to 1430 ℃, and tin, boron fuse in the polysilicon solution, and the pulling of silicon single crystal of tin is mixed in growth.
Identical polycrystalline silicon raw material and boron doping amount are adopted in (1 '), in same single crystal growing furnace, and identical growth parameter(s), the common pulling of silicon single crystal that tin is not mixed in growth is as contrast.
(2) behind the ordinary straight crystal-pulling silicon wafer ingot butt that the pulling of silicon single crystal of mixing tin that step (1) is obtained and step (1 ') obtain, utilize line to be cut into 200 microns silicon chips, after the cleaning, the pulling of silicon single crystal silicon chip of mixing tin separates packing with common pulling of silicon single crystal silicon chip.
(3) adopt step (2) to obtain mixing the pulling of silicon single crystal silicon chip of tin respectively, common pulling of silicon single crystal silicon chip prepares solar cell, comprising: silicon chip is cleaned and alkali making herbs into wool; At 875 ℃ of following phosphorous diffusion 30min; The deposition of etching and SiNx; Screen printing electrode, at 800 ℃ of following sintering, the time is 5min at last.Obtain mixing the pulling of silicon single crystal solar cell piece and the ordinary straight crystal-pulling silicon solar cell sheet of tin respectively.
After cell preparation is accomplished, according to the automatic stepping of efficiency test.With the above-mentioned pulling of crystals silion cell sheet of mixing tin that obtains and ordinary straight crystal-pulling silicon cell according to efficient stepping 17.4-17.6%; 17.6-17.8%; Mix the pulling of crystals silion cell sheet and the ordinary straight crystal-pulling silicon cell of tin in each efficient stepping and respectively get 20, test light is according to preceding efficient.Under 1 sunlight light intensity, shone 24 hours subsequently, again the battery efficiency after the test decay.
Fig. 1 is the variation of ordinary straight crystal-pulling silicon cell with the pulling of crystals silion cell sheet illumination front and back average efficiency value of mixing tin.Fig. 1 can find out that to mix tin monocrystalline silicon battery sheet littler than the decay of the efficient of ordinary straight crystal-pulling silicon cell, mixes tin monocrystalline silicon battery sheet efficient and decays to 2.3%, and common monocrystalline silicon battery sheet efficient decays to 3.4%.
Embodiment 4
(1) in the 55Kg polycrystalline silicon raw material, mixes 464.7g tin and 8.4 * 10 -3G boron, the concentration of tin are 1 * 10 20Cm -3, the concentration of boron is 2 * 10 16Cm -3, in single crystal growing furnace, under the argon shield atmosphere, pressure is 10torr then, and furnace temperature rises to 1450 ℃, and tin, boron fuse in the polysilicon solution, and the pulling of silicon single crystal of tin is mixed in growth.
Identical polycrystalline silicon raw material and boron doping amount are adopted in (1 '), in same single crystal growing furnace, and identical growth parameter(s), the common pulling of silicon single crystal that tin is not mixed in growth is as contrast.
(2) behind the ordinary straight crystal-pulling silicon wafer ingot butt that the pulling of silicon single crystal of mixing tin that step (1) is obtained and step (1 ') obtain, utilize line to be cut into 180 microns silicon chips, after the cleaning, mix tin and separate packing with common pulling of silicon single crystal silicon chip.
(3) adopt step (2) to obtain mixing the pulling of silicon single crystal silicon chip of tin respectively, common pulling of silicon single crystal silicon chip prepares solar cell, comprising: silicon chip is cleaned and sour making herbs into wool; At 860 ℃ of following phosphorous diffusion 35min; The deposition of etching and SiNx; Screen printing electrode, at 810 ℃ of following sintering, the time is 5min at last.Obtain mixing the pulling of silicon single crystal solar cell piece and the ordinary straight crystal-pulling silicon solar cell sheet of tin respectively.
After cell preparation is accomplished, according to the automatic stepping of efficiency test.With the above-mentioned pulling of crystals silion cell sheet of mixing tin that obtains and ordinary straight crystal-pulling silicon cell according to efficient stepping 17.2-17.4%; 17.4-17.6%; Mix the pulling of crystals silion cell sheet and the ordinary straight crystal-pulling silicon cell of tin in each efficient stepping and respectively get 20, test light is according to preceding efficient.Under 1 sunlight light intensity, shone 24 hours subsequently, again the battery efficiency after the test decay.
Fig. 2 is the variation of ordinary straight crystal-pulling silicon cell with the pulling of crystals silion cell sheet illumination front and back average efficiency value of mixing tin.Fig. 2 can find out that to mix tin monocrystalline silicon battery sheet obviously littler than the decay of the efficient of ordinary straight crystal-pulling silicon cell, mixes tin monocrystalline silicon battery sheet efficient and decays to 2.3%, and common monocrystalline silicon battery sheet efficient decays to 4.6%.

Claims (4)

1. a preparation method who mixes the tin crystal-silicon solar cell who suppresses optical attenuation is characterized in that, may further comprise the steps:
(1) in polycrystalline silicon raw material, mix tin and boron, the concentration of tin is 10 16～10 21Cm -3, the concentration of boron is 10 15～10 17Cm -3, under argon gas or nitrogen protection atmosphere, the crystalline silicon of tin is mixed in growth then;
(2) after the crystalline silicon of mixing tin that step (1) growth is obtained is cut into slices, carry out the preparation of solar cell, comprising: the silicon chip to obtaining after the section cleans and making herbs into wool; Carry out phosphorous diffusion after the making herbs into wool; Carry out the deposition of etching and antireflective coating; Prepare electrode and sintering at last, obtain mixing the tin crystal-silicon solar cell.
2. preparation method as claimed in claim 1 is characterized in that, in the step (1); The crystalline silicon that tin is mixed in described growth carries out in single crystal growing furnace, in silica crucible, puts into polysilicon, and mixes boron and tin; Furnace temperature rises to 1400～1500 ℃; Polysilicon and tin, boron fusion, growth obtains mixing the pulling of silicon single crystal of tin under protective atmosphere, and the concentration of tin is 10 in the crystal 16～10 20Cm -3, the concentration of boron is 10 15～10 17Cm -3
3. preparation method as claimed in claim 1 is characterized in that, in the step (1); The crystalline silicon that tin is mixed in described growth carries out in polycrystalline furnace, in silica crucible, puts into polysilicon, and mixes boron and tin; Furnace temperature rises to 1400-1500 ℃; Polysilicon and tin, boron fusion, growth obtains mixing the polysilicon of tin under protective atmosphere, and the concentration of tin is 10 in the crystal 16～10 20Cm -3, the concentration of boron is 10 15～10 17Cm -3
4. the inhibition optical attenuation that makes like the arbitrary described preparation method of claim 1～3 mix the tin crystal-silicon solar cell.
CN2010105099424A 2010-10-18 2010-10-18 Tin-doped crystalline silicon solar cell for inhibiting light attenuation and preparation method thereof Expired - Fee Related CN102005505B (en)

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