CN102877121B - The adulterating method of Ge mono crystal growth used for solar batteries - Google Patents
The adulterating method of Ge mono crystal growth used for solar batteries Download PDFInfo
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- CN102877121B CN102877121B CN201210407264.XA CN201210407264A CN102877121B CN 102877121 B CN102877121 B CN 102877121B CN 201210407264 A CN201210407264 A CN 201210407264A CN 102877121 B CN102877121 B CN 102877121B
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Abstract
The adulterating method of Ge mono crystal growth used for solar batteries, it is characterized in that step is as follows: 1. cleaning-drying HpGe, 2. HpGe and doping agent are loaded in the crucible in single crystal growing furnace, 3. vacuumize, 4. heat, 5. after the raw material in crucible all melts, doped element is tentatively mixed in germanium, 6. lower the temperature, 7. make doped element Homogeneous phase mixing in germanium.Doping agent used in the present invention can be one or more of Ga, In, As, Sb etc.The method is simple to operate, only once need adulterate, doping agent just can be made to be uniformly distributed in germanium single crystal used for solar batteries, the uniform resistivity distribution of germanium single crystal, and axial change in resistance is little, is beneficial to suitability for industrialized production; By test, germanium single crystal resistivity, at 0.001 ~ 0.003 Ω cm, can reach the requirement of germanium single crystal uniform resistivity used for solar batteries distribution.
Description
Technical field
The invention belongs to the technical field of single crystal growth of adding dopant material, particularly a kind of adulterating method of Ge mono crystal growth.
Background technology
Solar cell germanium single crystal mainly adulterates 3 valencys or 5 valency elements in HpGe, and the resistivity controlling germanium single crystal is less than 0.05 Ω .cm, doping agent mainly gallium and the indium of germanium single crystal used for solar batteries.But because gallium and the indium segregation coefficient in germanium is less, the germanium single crystal resistivity distribution obtained in crystal pulling process is uneven, makes the axial change in resistance of germanium single crystal too large, be unfavorable for suitability for industrialized production.Current adulterating method mainly adds doping agent with doping spoon, this makes doping agent after germanium thawing is melted in district, can not reach Homogeneous phase mixing, the homogeneity of concentration of dopant is affected, cause doping agent and district to melt germanium ingot can not be mixed in proportion, do not reach the requirement of target resistivity.This adulterating method does not fundamentally solve doping agent equally distributed difficult problem in germanium, and existence need repeatedly be adulterated, complicated operation, easily causes the drawbacks such as body of heater gas leakage.
Summary of the invention
For the deficiency that existing adulterating method exists, the invention provides a kind of adulterating method of Ge mono crystal growth used for solar batteries, overcome and add doping agent with doping spoon, exist and repeatedly adulterate, complicated operation, the drawback of body of heater gas leakage, once doping just can make doping agent can be uniformly distributed in monocrystalline.
The adulterating method of Ge mono crystal growth used for solar batteries of the present invention, is characterized in that step is as follows:
Step one, cleaning-drying: the HpGe weighed up is placed in cleaning machine hot water tank, be warming up to 40 DEG C ~ 65 DEG C, then it is put into successively hot water acid bubble groove, ultrasonic overflow groove, cleaning, to without residual acid, is taken out and is put into Stainless Steel Disc, washed germanium is put into loft drier, setting Heating temperature is 100 DEG C ~ 120 DEG C, and constant temperature 2 ~ 3 hours takes out after cooling;
Step 2, charging: the HpGe after cleaning-drying is loaded in the crucible in single crystal growing furnace, then doping agent is placed between HpGe;
Step 3, vacuumizes: start Controlling System and start to vacuumize, treat that leak rate is up to the standards, arranging argon flow amount is 5 ~ 60slpm;
Step 4, heating: open well heater, temperature increasing for melting materials;
Step 5, preliminary mixing: control crucible rotation is 3 ~ 10 revs/min after the raw material in crucible all melts, rotating speed is improved with the speed of 0.2 ~ 0.8 rev/min, after 20 ~ 60 minutes, rotating speed is reduced, 3 times and namely reach the preliminary mixing of doped element in germanium above so repeatedly with the speed of 0.5 ~ 2 rev/min;
Step 6, cooling: reduce furnace temperature to 939 ~ 948 DEG C;
Step 7, Homogeneous phase mixing: seed crystal is put down contact germanium melt, seed crystal rotating speed is controlled at 5 ~ 20 revs/min, sense of rotation is contrary with crucible rotation direction, control crucible rotation 3 ~ 10 revs/min, improve rotating speed, after 20 ~ 60 minutes with the speed of 0.2 ~ 0.8 rev/min, rotating speed is reduced, 3 times and namely reach the Homogeneous phase mixing of doped element in germanium above so repeatedly with the speed of 0.5 ~ 2 rev/min.
Doping agent used in the present invention: can be one or more of Ga, In, As, Sb etc.
Beneficial effect of the present invention is: the method is simple to operate, only once need adulterate, doping agent just can be made to be uniformly distributed in germanium single crystal used for solar batteries, the uniform resistivity distribution of germanium single crystal, and axial change in resistance is little, is beneficial to suitability for industrialized production; By test, germanium single crystal resistivity, at 0.001 ~ 0.003 Ω × cm, can reach the requirement of germanium single crystal uniform resistivity used for solar batteries distribution.
Accompanying drawing explanation
Fig. 1 germanium single crystal doping process used for solar batteries FB(flow block);
Fig. 2 does not use the germanium single crystal resistivity genesis analysis schematic diagram of present invention process;
Fig. 3 uses germanium single crystal resistivity genesis analysis schematic diagram after present invention process;
Fig. 4 uses image during method growth for solar germanium single crystal of the present invention;
The pictorial diagram of the sun power germanium single crystal that Fig. 5 uses method of the present invention to obtain.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention is described in further details.
Embodiment one:
This example uses the inventive method to adulterate in germanium single crystal the embodiment of Ga, and its step is as follows:
Step one, is placed on the HpGe ingot weighed up in cleaning machine hot water tank, is warming up to 50 DEG C, and then it is put into successively hot water acid bubble groove, ultrasonic overflow groove, cleaning, to without residual acid, is taken out and put into Stainless Steel Disc.Washed germanium ingot is put into loft drier, and setting Heating temperature is 100 DEG C, and constant temperature 2 hours takes out after cooling;
Step 2, loads the HpGe after cleaning-drying in the crucible in single crystal growing furnace, is then placed between HpGe by doping agent Ga;
Step 3, start Controlling System and start to vacuumize, treat that leak rate is up to the standards, arranging argon flow amount is 30slpm;
Step 4, opens well heater, temperature increasing for melting materials;
Step 5, after the raw material in crucible all melts, control crucible rotation is 3 revs/min, improves rotating speed with the speed of 0.2 rev/min, after 20 minutes, reduces rotating speed, so repeatedly namely reach the preliminary mixing of Ga in germanium for 3 times with the speed of 0.5 rev/min;
Step 6, reduces furnace temperature to 940 DEG C;
Step 7, seed crystal is put down contact germanium melt, seed crystal rotating speed is controlled at 5 revs/min, sense of rotation is contrary with crucible rotation direction, control crucible rotation 3 revs/min, improve rotating speed, after 20 minutes with the speed of 0.2 rev/min, reduce rotating speed with the speed of 0.5 rev/min, so repeatedly namely reach the Homogeneous phase mixing of Ga in germanium for 3 times.
Embodiment two:
This example uses the inventive method to adulterate in germanium single crystal the embodiment of In, and its step is as follows:
Step one, is placed on the HpGe ingot weighed up in cleaning machine hot water tank, is warming up to 60 DEG C, and then it is put into successively hot water acid bubble groove, ultrasonic overflow groove, cleaning, to without residual acid, is taken out and put into Stainless Steel Disc.Washed germanium ingot is put into loft drier, and setting Heating temperature is 120 DEG C, and constant temperature 3 hours takes out after cooling;
Step 2, loads the HpGe after cleaning-drying in the crucible in single crystal growing furnace, is then placed between HpGe by doping agent In;
Step 3, start Controlling System and start to vacuumize, treat that leak rate is up to the standards, arranging argon flow amount is 40slpm;
Step 4, opens well heater, temperature increasing for melting materials;
Step 5, after the raw material in crucible all melts, control crucible rotation is 10 revs/min, improves rotating speed with the speed of 0.8 rev/min, after 60 minutes, reduces rotating speed, so repeatedly namely reach the preliminary mixing of In in germanium for 4 times with the speed of 2 revs/min;
Step 6, reduces furnace temperature to 947 DEG C;
Step 7, seed crystal is put down contact germanium melt, seed crystal rotating speed is controlled at 20 revs/min, sense of rotation is contrary with crucible rotation direction, control crucible rotation 10 revs/min, improve rotating speed, after 60 minutes with the speed of 0.8 rev/min, reduce rotating speed with the speed of 2 revs/min, so repeatedly namely reach the Homogeneous phase mixing of In in germanium for 4 times.
Embodiment three:
This example uses the inventive method to adulterate in germanium single crystal the embodiment of As, and its step is as follows:
Step one, is placed on the HpGe ingot weighed up in cleaning machine hot water tank, is warming up to 40 DEG C, and then it is put into successively hot water acid bubble groove, ultrasonic overflow groove, cleaning, to without residual acid, is taken out and put into Stainless Steel Disc.Washed germanium ingot is put into loft drier, and setting Heating temperature is 110 DEG C, and constant temperature 2.5 hours takes out after cooling;
Step 2, loads the HpGe after cleaning-drying in the crucible in single crystal growing furnace, is then placed between HpGe by doping agent As;
Step 3, start Controlling System and start to vacuumize, treat that leak rate is up to the standards, arranging argon flow amount is 50slpm;
Step 4, opens well heater, temperature increasing for melting materials;
Step 5, after the raw material in crucible all melts, control crucible rotation is 8 revs/min, improves rotating speed with the speed of 0.6 rev/min, after 40 minutes, reduces rotating speed, so repeatedly namely reach the preliminary mixing of As in germanium for 5 times with the speed of 1 rev/min;
Step 6, reduces furnace temperature to 939 DEG C;
Step 7, seed crystal is put down contact germanium melt, seed crystal rotating speed is controlled at 15 revs/min, sense of rotation is contrary with crucible rotation direction, control crucible rotation 8 revs/min, improve rotating speed, after 40 minutes with the speed of 0.6 rev/min, reduce rotating speed with the speed of 1 rev/min, so repeatedly namely reach the Homogeneous phase mixing of As in germanium for 5 times.
Embodiment four:
This example uses the inventive method to adulterate in germanium single crystal the embodiment of Sb, and its step is as follows:
Step one, is placed on the HpGe ingot weighed up in cleaning machine hot water tank, is warming up to 50 DEG C, and then it is put into successively hot water acid bubble groove, ultrasonic overflow groove, cleaning, to without residual acid, is taken out and put into Stainless Steel Disc.Washed germanium ingot is put into loft drier, and setting Heating temperature is 115 DEG C, and constant temperature 2.8 hours takes out after cooling.
Step 2, loads the HpGe after cleaning-drying in the crucible in single crystal growing furnace, is then placed between HpGe by doping agent Sb;
Step 3, start Controlling System and start to vacuumize, treat that leak rate is up to the standards, arranging argon flow amount is 30slpm;
Step 4, opens well heater, temperature increasing for melting materials;
Step 5, after the raw material in crucible all melts, control crucible rotation is 4 revs/min, improves rotating speed with the speed of 0.4 rev/min, after 45 minutes, reduces rotating speed, so repeatedly namely reach the preliminary mixing of As in germanium for 6 times with the speed of 1.5 revs/min;
Step 6, reduces furnace temperature to 942 DEG C;
Step 7, seed crystal is put down contact germanium melt, seed crystal rotating speed is controlled at 12 revs/min, sense of rotation is contrary with crucible rotation direction, control crucible rotation 5 revs/min, improve rotating speed, after 45 minutes with the speed of 0.4 rev/min, reduce rotating speed with the speed of 1.5 revs/min, so repeatedly namely reach the Homogeneous phase mixing of Sb in germanium for 6 times.
According to the relation of doping agent and resistivity, determine that the ratio of germanium is melted in doping agent and district, method of calculation are as follows:
Concentration of dopant is according to calculating, and calculating according to ratio of germanium is melted in doping agent and district:
。
(1) doping when only considering impurity segregation calculates: the w gram of Ge such as drawing electricalresistivityρ, and the amount that need add impurity is:
;
C
0for impurity concentration in melt (4 × 10
17cm
-3< C
s<1.0 × 10
19cm
-3), N
0for Avogadro constant (6.02 × 10
23), d is density (5.32 g/cm of Ge
3), A is the molar mass of impurity; Simultaneously when normal freezing-vertical pulling method,
,
G is drawing place ratio; K is that segregation coefficient is in table 1; Electricalresistivityρ and impurity concentration C
s, relation is as follows:
, μ is minority carrier transport factor,
。
The segregation coefficient K of major impurity in table 1 germanium
(2) approximate estimation in actual production, the ratio melting germanium according to doping agent and district is that about 1:3000 weighs suitable doping agent and is placed on district and melts between germanium.
Claims (3)
1. the adulterating method of Ge mono crystal growth used for solar batteries, is characterized in that step is as follows:
Step one, cleaning-drying: the HpGe weighed up is placed in cleaning machine hot water tank, be warming up to 40 DEG C ~ 65 DEG C, then it is put into successively hot water acid bubble groove, ultrasonic overflow groove, cleaning, to without residual acid, is taken out and is put into Stainless Steel Disc, washed germanium is put into loft drier, setting Heating temperature is 100 DEG C ~ 120 DEG C, and constant temperature 2 ~ 3 hours takes out after cooling;
Step 2, charging: the HpGe after cleaning-drying is loaded in the crucible in single crystal growing furnace, then doping agent is placed between HpGe;
Step 3, vacuumizes: start Controlling System and start to vacuumize, treat that leak rate is up to the standards, arranging argon flow amount is 5 ~ 60slpm;
Step 4, heating: open well heater, temperature increasing for melting materials;
Step 5, preliminary mixing: control crucible rotation is 3 ~ 10 revs/min after the raw material in crucible all melts, rotating speed is improved with the speed of 0.2 ~ 0.8 rev/min, after 20 ~ 60 minutes, rotating speed is reduced, 3 times and namely reach the preliminary mixing of doped element in germanium above so repeatedly with the speed of 0.5 ~ 2 rev/min;
Step 6, cooling: reduce furnace temperature to 939 ~ 948 DEG C;
Step 7, Homogeneous phase mixing: seed crystal is put down contact germanium melt, seed crystal rotating speed is controlled at 5 ~ 20 revs/min, sense of rotation is contrary with crucible rotation direction, control crucible rotation 3 ~ 10 revs/min, improve rotating speed, after 20 ~ 60 minutes with the speed of 0.2 ~ 0.8 rev/min, rotating speed is reduced, 3 times and namely reach the Homogeneous phase mixing of doped element in germanium above so repeatedly with the speed of 0.5 ~ 2 rev/min.
2., according to the adulterating method of Ge mono crystal growth used for solar batteries according to claim 1, it is characterized in that doping agent can be one or more of Ga, In, As, Sb.
3. according to the adulterating method of Ge mono crystal growth used for solar batteries according to claim 1, it is characterized in that the relation according to doping agent and resistivity, determine that the ratio that germanium is melted in doping agent and district is 1:3000.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2626359C1 (en) * | 2016-12-02 | 2017-07-26 | Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" | Method for growing germanium monocrystals |
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| CN103938270B (en) * | 2014-04-09 | 2017-02-15 | 云南北方驰宏光电有限公司 | Growth method of gallium heavily doped low-dislocation germanium single crystal |
| RU2563484C1 (en) * | 2014-11-24 | 2015-09-20 | Акционерное общество "ГЕРМАНИЙ" (АО "ГЕРМАНИЙ") | Growing of germanium crystals |
| CN108091708B (en) | 2017-12-08 | 2020-08-14 | 北京通美晶体技术有限公司 | Germanium single crystal wafer, method for producing the same, method for producing crystal bar, and use of single crystal wafer |
| CN108277528A (en) * | 2018-02-28 | 2018-07-13 | 昆明凯航光电科技有限公司 | A kind of method of germanium single crystal annealing process resistance control |
| CN110202419B (en) * | 2019-05-31 | 2021-10-19 | 北京通美晶体技术股份有限公司 | Germanium single crystal wafer, method for producing the same, method for producing crystal bar, and use of single crystal wafer |
| CN115279954A (en) * | 2020-03-12 | 2022-11-01 | 尤米科尔公司 | Heavily doped n-type germanium |
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| JP2001338988A (en) * | 2000-05-25 | 2001-12-07 | Hitachi Ltd | Semiconductor device and its manufacturing method |
| US6864517B2 (en) * | 2003-01-14 | 2005-03-08 | International Business Machines Corporation | Bipolar structure with two base-emitter junctions in the same circuit |
| CN100510205C (en) * | 2007-06-06 | 2009-07-08 | 中国科学院安徽光学精密机械研究所 | Yb-doped gadolinium germanate, lanthanum germanate and melt-method growth process thereof |
| CN101591808A (en) * | 2009-06-24 | 2009-12-02 | 浙江大学 | Mix directionally solidified casting monocrystalline silicon of germanium and preparation method thereof |
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