CN101597794A - The czochralski silicon monocrystal that a kind of gallium and germanium are mixed altogether - Google Patents
The czochralski silicon monocrystal that a kind of gallium and germanium are mixed altogether Download PDFInfo
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- CN101597794A CN101597794A CNA2009100999931A CN200910099993A CN101597794A CN 101597794 A CN101597794 A CN 101597794A CN A2009100999931 A CNA2009100999931 A CN A2009100999931A CN 200910099993 A CN200910099993 A CN 200910099993A CN 101597794 A CN101597794 A CN 101597794A
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- germanium
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Abstract
The invention discloses the czochralski silicon monocrystal that a kind of gallium and germanium are mixed altogether, containing concentration is 1 * 10
15～1 * 10
17/ cm
3Gallium, also containing concentration is 1 * 10
16～5 * 10
20/ cm
3Germanium.Avoid on the basis of optical attenuation as electroactive adulterant utilizing gallium, suppress the formation of primary microdefect in the silicon single-crystal by germanium, obtain minority carrier life time than the high silicon single-crystal more than 1 times of silicon single-crystal of mixing gallium separately, minority carrier life time is up to 100 μ s, can be used for the preparation of high-level efficiency solar cell.Simultaneously, its physical strength is higher more than 20% than the silicon single-crystal of mixing gallium separately, and room temperature fracture physical strength reaches as high as 300N/mm
2, when being applied in the solar cell, silicon chip can be cut thinlyyer, has reduced the manufacturing cost of solar cell.
Description
Technical field
The invention belongs to the semiconductor silicon material field, relate in particular to the czochralski silicon monocrystal that used for solar batteries gallium and germanium are mixed altogether.
Background technology
Sun power is inexhaustible clean energy, utilizes the light transfer characteristic of semiconductor material, is prepared into solar cell, sun power can be transformed into electric energy.
Czochralski silicon monocrystal is one of main raw of producing by solar cell.In the tradition heliotechnics, the boron-doped Czochralski silicon single-crystal is widely used in the preparation of solar cell.But, because the displacement boron atom in the boron-doped Czochralski silicon single-crystal and the Sauerstoffatom of silicon single crystal mid gap state can form boron oxygen complex body under illumination or under the current carrier injection, and boron oxygen complex body is the deep energy level deathnium, can reduce the life-span of minority carrier, thereby reduce the diffusion length of minority carrier, cause photoelectric transformation efficiency decay (this phenomenon is called photo attenuation), the efficient of solar cell reduces.At this problem, mix the gallium czochralski silicon monocrystal and extensively be used at present in the solar cell preparation, effectively avoided the generation of boron oxygen complex body.
During the Grown by CZ Method gallium doped monocrystaline silicon, inevitably introduce point defect (from gap Siliciumatom, hole), these point defects can combine with other impurity in the silicon and form formation or self the gathering formation defective that complex body promotes defective, thereby become the deathnium of few son, reduce the minority carrier life time of gallium doped monocrystaline silicon sheet, this raising for the photoelectric transformation efficiency of mixing the gallium solar cell is very disadvantageous.
In addition, influencing one of widely used major obstacle of solar cell at present is that cost is higher, and the prime cost of battery is silicon chip.In order to reduce cost, one of measure of adopting now is the thickness that reduces silicon chip, makes the material usage of each sheet silicon chip reduce.But because itself there is the lower shortcoming of physical strength in the present gallium czochralski silicon monocrystal of mixing, if the reduction silicon wafer thickness will make silicon chip dress up in processing, cell preparation and series of cells in the process such as assembly, damage, fragmentation easily, the percentage of damage of silicon chip increases, and certainly will cause the increase of cost.
Improving the minority carrier life time of mixing the gallium silicon chip and improving the physical strength of mixing the gallium silicon chip is to reduce the solar cell cost at present and improve the problem that solar battery efficiency presses for solution.
Summary of the invention
The invention provides the czochralski silicon monocrystal that a kind of gallium and germanium are mixed altogether, containing concentration is 1 * 10
15～1 * 10
17/ cm
3Gallium, also containing concentration is 1 * 10
16～5 * 10
20/ cm
3Germanium.Along with the increase of germanium concentration, the minority carrier life time of the czochralski silicon monocrystal that gallium and germanium are mixed altogether increases, and the photoelectric transformation efficiency that improves battery is had very important significance.
In the optimized technical scheme, the czochralski silicon monocrystal that above-mentioned gallium and germanium are mixed altogether, containing concentration is 5 * 10
15～5 * 10
16/ cm
3Gallium, also containing concentration is 1 * 10
18～2 * 10
20/ cm
3Germanium.Because the segregation coefficient of gallium in silicon is 0.008, much smaller than 1, so mix gallium 5 * 10 in vertical pulling silicon
15～5 * 10
16/ cm
3Scope, can improve the utilization ratio of whole single crystal preparation battery.And mix the germanium amount in the vertical pulling silicon 1 * 10
18/ cm
3When above, the silicon fragment minority carrier life time is greatly improved, and its physical strength also is enhanced on this threshold value; In silicon, mix the germanium amount greater than 2 * 10
20/ cm
3The time, form the segregation of germanium in the crystal growing process easily, cause dislocation and polycrystalline, be difficult to the growth of bonding crystal silicon, so preferred 1 * 10
18～2 * 10
20/ cm
3Mix germanium concentration.
The czochralski silicon monocrystal that gallium of the present invention and germanium are mixed altogether is that a certain amount of germanium that mixes in the existing silicon single-crystal that contains the gallium electrically active impurity constitutes.It is prepared from by following method; polysilicon is put into quartz crucible; the charging capacity of doping content calculating is according to target mixed germanium and gallium simultaneously; under vacuum, argon gas or nitrogen protection; the melting polysilicon; germanium and gallium are fused in the polysilicon liquation simultaneously, adjust the crystal growth parameter routinely, grow czochralski silicon monocrystal of the present invention.Usually be heated to the above melting polysilicon that gets final product of silicon fusing point, the present invention is preferably at 1410 ℃ of melting polysilicons.
Wherein, the concentration of germanium and gallium in the target doping content target product silicon single crystal that will prepare for the present invention.Among the present invention, the concentration of gallium is 1 * 10
15～1 * 10
17/ cm
3, the concentration of germanium is 1 * 10
16～5 * 10
20/ cm
3
The czochralski silicon monocrystal minority carrier life time that gallium of the present invention and germanium are mixed altogether is higher more than 1 times than the czochralski silicon monocrystal of mixing gallium separately, and physical strength is higher more than 20% than the czochralski silicon monocrystal of mixing gallium separately.
The beneficial effect of the czochralski silicon monocrystal that gallium of the present invention and germanium are mixed altogether is:
1, mixed simultaneously in the silicon single-crystal gallium and germanium, avoid on the basis of optical attenuation as electroactive adulterant utilizing gallium, by the formation that is used for suppress in silicon single-crystal primary microdefect of the realization of the germanium in the monocrystalline to point defect (from gap Siliciumatom, hole), thereby its minority carrier life time is higher more than 1 times than the silicon single-crystal of mixing gallium separately.The minority carrier life time of silicon single-crystal of the present invention reaches as high as 100 μ s, and high like this minority carrier life time is that the silicon single-crystal of mixing gallium separately can not reach.
2, in the silicon single-crystal that gallium and germanium are mixed altogether, germanium can pinning silicon in dislocation, stop dislocation glide, thereby improve the physical strength of silicon single-crystal, its physical strength is higher more than 20% than the silicon single-crystal of mixing gallium separately.The room temperature fracture physical strength of silicon single-crystal of the present invention reaches as high as 300N/mm
2More than, when being applied in the solar cell, silicon chip can be cut thinlyyer, has reduced the manufacturing cost of solar cell.
Embodiment
Embodiment 1
The polysilicon of 50kg is put into quartz crucible, mix the germanium of 0.078g and the gallium of 0.3g simultaneously.Under argon shield, at 1410 ℃ of melting polysilicons, germanium and gallium are fused in the polysilicon solution simultaneously, adjust the crystal growth parameter routinely, with 1.2mm/min growth czochralski silicon monocrystal.Wherein, gallium concentration is 1 * 10
15/ cm
3, germanium concentration is 1 * 10
16/ cm
3
Embodiment 2
The polysilicon of 50kg is put into quartz crucible, mix the germanium of 0.78g and the gallium of 3g simultaneously.Under argon shield, at 1410 ℃ of melting polysilicons, germanium and gallium are fused in the polysilicon solution simultaneously, adjust the crystal growth parameter routinely, with 1.2mm/min growth czochralski silicon monocrystal.Wherein, gallium concentration is 1 * 10
16/ cm
3, germanium concentration is 1 * 10
17/ cm
3
Embodiment 3
The polysilicon of 50kg is put into quartz crucible, mix the germanium of 7.8g and the gallium of 3g simultaneously.Under argon shield, at 1410 ℃ of melting polysilicons, germanium and gallium are fused in the polysilicon solution simultaneously, adjust the crystal growth parameter routinely, with 1.2mm/min growth czochralski silicon monocrystal.Wherein, gallium concentration is 1 * 10
16/ cm
3, germanium concentration is 1 * 10
18/ cm
3
Embodiment 4
The polysilicon of 50kg is put into quartz crucible, mix the germanium of 78g and the gallium of 0.3g simultaneously.Under argon shield, at 1410 ℃ of melting polysilicons, germanium and gallium are fused in the polysilicon solution simultaneously, adjust the crystal growth parameter routinely, with 1.2mm/min growth czochralski silicon monocrystal.Wherein, gallium concentration is 1 * 10
15/ cm
3, germanium concentration is 1 * 10
19/ cm
3
Embodiment 5
The polysilicon of 50kg is put into quartz crucible, mix the germanium of 780g and the gallium of 0.3g simultaneously.Under argon shield, at 1410 ℃ of melting polysilicons, germanium and gallium are fused in the polysilicon solution simultaneously, adjust the crystal growth parameter routinely, with 1.2mm/min growth czochralski silicon monocrystal.Wherein, gallium concentration is 1 * 10
15/ cm
3, germanium concentration is 1 * 10
20/ cm
3
Embodiment 6
The polysilicon of 50kg is put into quartz crucible, mix the germanium of 1.56kg and the gallium of 30g simultaneously.Under argon shield, at 1410 ℃ of melting polysilicons, germanium and gallium are fused in the polysilicon solution simultaneously, adjust the crystal growth parameter routinely, with 1.2mm/min growth czochralski silicon monocrystal.Wherein, gallium concentration is 1 * 10
17/ cm
3, germanium concentration is 2 * 10
20/ cm
3
Comparative Examples 1
Adopt the method identical with embodiment 1 to make the czochralski silicon monocrystal of mixing gallium, difference only is that the pure germanium that mixes is 0g.Wherein, gallium concentration is 1 * 10
15/ cm
3
Comparative Examples 2
Adopt the method identical with embodiment 2 to make the czochralski silicon monocrystal of mixing gallium, difference only is that the pure germanium that mixes is 0g.Wherein, gallium concentration is 1 * 10
16/ cm
3
The head sampling of the czochralski silicon monocrystal mixed altogether of germanium that obtains in embodiment 1～6 and Comparative Examples 1～2 and gallium respectively, test room temperature fracture physical strength and minority carrier life time.Room temperature fracture physical strength obtains by 3 curved method tests, and minority carrier life time is led the damped method test by RF-MW Photonics and obtained after surfaces nitrided silicon passivation.Test result sees Table 1.
Table 1
| Gallium concentration (/cm 3) | Germanium concentration (/cm 3) | Room temperature fracture physical strength (N/mm 2) | Minority carrier life time (μ s) | |
| Comparative Examples 1 | 1×10 15 | 0 | 180 | 10 |
| Comparative Examples 2 | 1×10 16 | 0 | 170 | 11 |
| Embodiment 1 | 1×10 15 | 1×10 16 | 220 | 15 |
| Embodiment 2 | 1×10 16 | 1×10 17 | 235 | 20 |
| Embodiment 3 | 1×10 16 | 1×10 18 | 250 | 35 |
| Embodiment 4 | 1×10 15 | 1×10 19 | 260 | 65 |
| Embodiment 5 | 1×10 15 | 1×10 20 | 290 | 80 |
| Embodiment 6 | 1×10 17 | 2×10 20 | 310 | 100 |
Claims (2)
1, the czochralski silicon monocrystal mixed altogether of a kind of gallium and germanium is characterized in that containing concentration is 1 * 10
15～1 * 10
17/ cm
3Gallium, and to contain concentration be 1 * 10
16～5 * 10
20/ cm
3Germanium.
2, the czochralski silicon monocrystal mixed altogether of gallium as claimed in claim 1 and germanium is characterized in that containing concentration is 5 * 10
15～5 * 10
16/ cm
3Gallium, and to contain concentration be 1 * 10
18～2 * 10
20/ cm
3Germanium.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011100879A1 (en) * | 2010-02-20 | 2011-08-25 | 西安隆基硅材料股份有限公司 | Monocrystalline silicon material co-doped with gallium and indium or co-doped with gallium, indium and germanium for solar batteries and manufacturing method thereof |
| WO2012071531A1 (en) * | 2010-11-24 | 2012-05-31 | Calisolar, Inc. | Germanium enriched silicon for solar cells |
| CN104711675A (en) * | 2015-02-16 | 2015-06-17 | 浙江金瑞泓科技股份有限公司 | Phosphorus, arsenic and antimony co-doped N-type heavily-doped Czochralski silicon single crystal and silicon epitaxial wafer thereof |
| CN105002557A (en) * | 2015-08-12 | 2015-10-28 | 常州天合光能有限公司 | Gallium, germanium and boron co-doped polycrystalline silicon and preparation method thereof |
| CN105063750A (en) * | 2015-08-12 | 2015-11-18 | 常州天合光能有限公司 | Ga-Ge-B co-doped monocrystalline silicon and preparation method thereof |
-
2009
- 2009-06-24 CN CNA2009100999931A patent/CN101597794A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8758507B2 (en) | 2008-06-16 | 2014-06-24 | Silicor Materials Inc. | Germanium enriched silicon material for making solar cells |
| WO2011100879A1 (en) * | 2010-02-20 | 2011-08-25 | 西安隆基硅材料股份有限公司 | Monocrystalline silicon material co-doped with gallium and indium or co-doped with gallium, indium and germanium for solar batteries and manufacturing method thereof |
| WO2012071531A1 (en) * | 2010-11-24 | 2012-05-31 | Calisolar, Inc. | Germanium enriched silicon for solar cells |
| CN103237928A (en) * | 2010-11-24 | 2013-08-07 | 思利科材料有限公司 | Germanium enriched silicon for solar cells |
| JP2013545706A (en) * | 2010-11-24 | 2013-12-26 | シリコー マテリアルズ インコーポレイテッド | Germanium-enriched silicon for solar cells |
| CN104711675A (en) * | 2015-02-16 | 2015-06-17 | 浙江金瑞泓科技股份有限公司 | Phosphorus, arsenic and antimony co-doped N-type heavily-doped Czochralski silicon single crystal and silicon epitaxial wafer thereof |
| CN104711675B (en) * | 2015-02-16 | 2017-11-10 | 浙江金瑞泓科技股份有限公司 | The N-type adulterating vertical pulling silicon monocrystalline and its silicon epitaxial wafer of phosphorus arsenic antimony codope |
| CN105002557A (en) * | 2015-08-12 | 2015-10-28 | 常州天合光能有限公司 | Gallium, germanium and boron co-doped polycrystalline silicon and preparation method thereof |
| CN105063750A (en) * | 2015-08-12 | 2015-11-18 | 常州天合光能有限公司 | Ga-Ge-B co-doped monocrystalline silicon and preparation method thereof |
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Open date: 20091209 |