CN114059152A - Gallium element doping method for producing silicon single crystal rod by Czochralski method - Google Patents
Gallium element doping method for producing silicon single crystal rod by Czochralski method Download PDFInfo
- Publication number
- CN114059152A CN114059152A CN202111373534.5A CN202111373534A CN114059152A CN 114059152 A CN114059152 A CN 114059152A CN 202111373534 A CN202111373534 A CN 202111373534A CN 114059152 A CN114059152 A CN 114059152A
- Authority
- CN
- China
- Prior art keywords
- gallium
- silicon
- single crystal
- melting
- czochralski method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
- C30B15/04—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
Abstract
The invention discloses a gallium element doping method for producing a silicon single crystal rod by a Czochralski method, which specifically comprises the following steps: (1) weighing the frozen pure gallium and the silicon material, mixing and placing in a small crucible; (2) a plurality of small crucibles are put together in the same thermal field and melted simultaneously; (3) after the melting is finished, quickly cooling and crystallizing to produce the gallium-silicon master alloy; (4) putting the produced gallium-silicon master alloy and the silicon material into a crucible to be melted simultaneously, and diluting the gallium element concentration in the gallium-silicon master alloy by the melted silicon liquid; (5) after melting, carrying out Czochralski method single crystal growth; the method is simple and easy to implement, and effectively solves the problems that the crystal growth is difficult and the dislocation is easy to generate after the gallium-doped single crystal silicon rod is fed for the first time.
Description
Technical Field
The invention relates to a doping method for producing a silicon single crystal rod by a czochralski method, in particular to a gallium element doping method for producing the silicon single crystal rod by the czochralski method, belonging to the technical field of solar photovoltaics.
Background
The P-type monocrystalline silicon rod material for producing the solar cell is mainly divided into two types of boron doping and gallium doping. For a boron-doped Cz cell, when the cell is exposed to light, the cell performance is attenuated, namely, the phenomenon of light-induced attenuation; and the light-induced degradation of the gallium-doped cell slice is much smaller. The test data reported at home and abroad show that the attenuation efficiency of the gallium-doped CZ battery piece is generally less than 1%, and the attenuation efficiency of the boron-doped CZ battery piece is generally more than 3%.
At present, when a doping element in a silicon single crystal rod produced by a czochralski method is gallium, a doping mode flow is pure element doping as shown in figure 1, but the gallium has a low melting point and can be melted into a liquid state at normal temperature, and is easy to adhere to the surface of a container during doping to cause loss, so that the doping concentration is influenced, and the resistivity characteristic of the crystal is influenced; the segregation coefficient of the gallium element in the growth of the silicon crystal is low, and most of the gallium element is enriched in the melt in the growth process of the crystal; pure gallium is doped into silicon melt, when the materials are initially melted, due to the fact that the silicon melt and gallium are mixed and stirred unevenly, the gallium is not dissolved sufficiently in the silicon melt, atomic arrangement is prone to being abnormal in the process that gallium atoms and silicon atoms form covalent bonds, dislocation is caused in crystals, and product quality is affected.
According to the rule summarized from the growth of the boron-doped silicon single crystal rod, the problem of dislocation of the crystal after initial feeding can be effectively solved by using a high-concentration alloy doping mode.
The process of dissolving gallium into silicon melt is the process of forming covalent bond between gallium atom and silicon atom, because the radius (1.40) of gallium atom is relatively close to the radius (1.34) of silicon atom, the binding force of atomic nucleus to outermost layer electron is close; and the valence radius (+ 3) of the gallium atom is 0.47, and the valence radius (+ 4) of the silicon atom is 0.24, further proving that the two atoms are relatively slow in the process of forming the covalent bond, so that the gallium element is slowly dissolved in the silicon melt, and the insufficiently dissolved gallium element enters the silicon crystal, and the crystal generates dislocation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a gallium element doping method for producing a monocrystalline silicon rod by a Czochralski method, the method is simple and easy to implement, and the problems that the crystal growth is difficult and dislocation is easy to generate after the monocrystalline silicon rod doped with gallium is fed for the first time are effectively solved.
In order to solve the technical problems, the invention provides a gallium element doping method for producing a silicon single crystal rod by a czochralski method, which comprises the following steps:
(1) weighing the frozen pure gallium and the silicon material, mixing and placing in a small crucible;
(2) a plurality of small crucibles are put together in the same thermal field and melted simultaneously;
(3) after the melting is finished, quickly cooling and crystallizing to produce the gallium-silicon master alloy;
(4) putting the produced gallium-silicon master alloy and the silicon material into a crucible to be melted simultaneously, and diluting the gallium element concentration in the gallium-silicon master alloy by the melted silicon liquid;
(5) after melting, the single crystal is grown by the Czochralski method.
The technical scheme of the invention is further defined as follows:
further, in the gallium element doping method for producing the silicon single crystal rod by the czochralski method, in the step (1), pure gallium and silicon materials are calculated according to the weight ratio: the silicon material =1:1000-1: 20.
In the gallium element doping method for producing the silicon single crystal rod by the Czochralski method, argon is continuously introduced in the melting process in the step (2), and the flow of the argon is 30-200 slpm.
In the gallium element doping method for producing the silicon single crystal rod by the czochralski method, in the step (4), the gallium-silicon mother alloy and the silicon material are calculated according to the weight ratio: the silicon material =1:50-1: 500.
In the gallium element doping method for producing the silicon single crystal rod by the Czochralski method, the melting temperature in the step (4) is 1500-1800 ℃, and the melting time is 3-20 hours.
According to the gallium element doping method for producing the silicon single crystal rod by the Czochralski method, gallium concentration before melting and diluting in the step (4) is carried out in a manner of 1 x 1018-9 x 1018/cm, and gallium concentration after melting and diluting is carried out in a manner of 1 x 1016-8 x 1016/cm.
The invention has the beneficial effects that:
the impurity elements are directly mixed into the silicon melt, and because the dissolution process is relatively slow and the duration is long, the silicon single crystal rod grows when the silicon single crystal rod is not completely dissolved, and the dislocation is easily generated.
Because the condensation coefficient of gallium in a silicon crystal is very low, the alloy can not be produced by a crystal growth mode, the gallium-silicon master alloy is produced by quantitatively proportioning the gallium and the silicon (gallium: silicon material =1:1000-1: 20), mixing the gallium and the silicon in a small quartz crucible, melting the silicon, fully mixing the silicon with the gallium, rapidly cooling and crystallizing, and then adding a fixed amount (the weight ratio of the alloy: silicon material =1:50-1: 500), the gallium-silicon master alloy is put in the silicon material, the molten silicon liquid dilutes the concentration of gallium in the gallium-silicon master alloy (the concentration of gallium before the dilution is melted is 1 x 1018-9 x 1018/cm, the concentration of gallium after the dilution is melted is 1 x 1016-8 x 1016/cm for carrying out the process), the gallium is fully dissolved in the silicon melt, the single crystal growth by the czochralski method is carried out, the gallium is fully dissolved, the gallium atoms and the silicon atoms form covalent bonds, the lattice structure cannot be damaged, the probability of dislocation generation is reduced, and the electrical performance requirement of the gallium-doped silicon single crystal rod is met.
The alloy used in the invention can effectively accelerate the formation of covalent bonds between gallium and silicon atoms, reduce the probability of dislocation and wire breakage of the crystal caused by condensation and nucleation of gallium atoms, and reduce the introduction and release times of the first crystal from 3 times to less than 1.5 times.
The alloy doping of the invention can effectively control the doping weight and improve the crystal resistivity hit degree, the deviation of the resistivity of the head of the directly element-doped crystal is +/-0.2 omega cm, the deviation of the resistivity of the head of the alloy-doped crystal can be controlled +/-0.05 omega cm, and the qualified finished product proportion of the crystal is effectively improved by 3 percent.
Drawings
FIG. 1 is a flow chart of a prior art gallium doping process for producing single crystal silicon rods by the Czochralski method;
FIG. 2 is a flow chart of the gallium doping method for producing the silicon single crystal rod by the Czochralski method.
Detailed Description
Example 1
The process of the gallium doping method for producing the silicon single crystal rod by the czochralski method provided by the embodiment is shown in fig. 2, and specifically comprises the following steps:
(1) weighing the frozen pure gallium and the silicon material, mixing and placing in a small crucible;
pure gallium and silicon materials are calculated according to the weight ratio, pure gallium: silicon material =1:1000-1:20, the amount of silicon material placed in each crucible is 100-2000 g, and pure gallium is 5-20 g;
(2) a plurality of small crucibles are put together in the same thermal field and melted simultaneously;
in order to maximize the yield, a plurality of crucibles can be placed in the same thermal field and melted simultaneously;
continuously introducing argon with a certain flow from the beginning of material melting, wherein the specific argon flow is 30-200 SLPM;
(3) after the melting is finished, quickly cooling and crystallizing to produce the gallium-silicon master alloy;
(4) putting the produced gallium-silicon master alloy and the silicon material into a crucible to be melted simultaneously, and diluting the gallium element concentration in the gallium-silicon master alloy by the melted silicon liquid;
the gallium-silicon master alloy and the silicon material are calculated according to the weight ratio: silicon material =1:50-1: 500;
according to the existing material melting process conditions for normal single crystal production, the melting temperature is 1500-1800 ℃, and the material melting time is 3-20 hours;
carrying out thin film transformation on the gallium and the aluminum alloy, wherein the gallium concentration before melting and diluting is 1 x 1018-9 x 1018/cm, and carrying out thin film transformation on the gallium and the aluminum alloy after melting and diluting is 1 x 1016-8 x 1016/cm;
(5) after melting, the single crystal is grown by the Czochralski method.
The impurity elements are directly mixed into the silicon melt, and because the dissolution process is relatively slow and the duration is long, the silicon single crystal rod grows when the silicon single crystal rod is not completely dissolved, and the dislocation is easily generated.
The alloy doping of the invention can effectively control the doping weight and improve the crystal resistivity hit degree, the deviation of the resistivity of the head of the directly element-doped crystal is +/-0.2 omega cm, the deviation of the resistivity of the head of the alloy-doped crystal can be controlled +/-0.05 omega cm, and the qualified finished product proportion of the crystal is effectively improved by 3 percent.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (6)
1. A gallium element doping method for producing a silicon single crystal rod by a Czochralski method is characterized by comprising the following steps:
(1) weighing the frozen pure gallium and the silicon material, mixing and placing in a small crucible;
(2) a plurality of small crucibles are put together in the same thermal field and melted simultaneously;
(3) after the melting is finished, quickly cooling and crystallizing to produce the gallium-silicon master alloy;
(4) putting the produced gallium-silicon master alloy and the silicon material into a crucible to be melted simultaneously, and diluting the gallium element concentration in the gallium-silicon master alloy by the melted silicon liquid;
(5) after melting, the single crystal is grown by the Czochralski method.
2. The method for doping gallium produced from the silicon single crystal rod by the czochralski method according to claim 1, wherein: in the step (1), pure gallium and silicon materials are calculated according to the weight ratio: the silicon material =1:1000-1: 20.
3. The method for doping gallium produced from the silicon single crystal rod by the czochralski method according to claim 1, wherein: and (3) continuously introducing argon when melting in the step (2), wherein the flow of the argon is 30-200 slpm.
4. The method for doping gallium produced from the silicon single crystal rod by the czochralski method according to claim 1, wherein: in the step (4), the gallium-silicon master alloy and the silicon material are calculated according to the weight ratio: the silicon material =1:50-1: 500.
5. The method for doping gallium produced from the silicon single crystal rod by the czochralski method according to claim 1, wherein: in the step (4), the melting temperature is 1500-1800 ℃, and the melting time is 3-20 hours.
6. The method for doping gallium produced from the silicon single crystal rod by the czochralski method according to claim 1, wherein: and (4) carrying out thin film seed cultivation on the gallium concentration before melting and diluting at 1 x 1018-9 x 1018/cm, and carrying out thin film seed cultivation on the gallium concentration after melting and diluting at 1 x 1016-8 x 1016/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111373534.5A CN114059152A (en) | 2021-11-19 | 2021-11-19 | Gallium element doping method for producing silicon single crystal rod by Czochralski method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111373534.5A CN114059152A (en) | 2021-11-19 | 2021-11-19 | Gallium element doping method for producing silicon single crystal rod by Czochralski method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114059152A true CN114059152A (en) | 2022-02-18 |
Family
ID=80278210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111373534.5A Pending CN114059152A (en) | 2021-11-19 | 2021-11-19 | Gallium element doping method for producing silicon single crystal rod by Czochralski method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114059152A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115044975A (en) * | 2022-07-21 | 2022-09-13 | 天合光能股份有限公司 | Method for preparing czochralski silicon |
| CN115558999A (en) * | 2022-10-09 | 2023-01-03 | 包头美科硅能源有限公司 | Method for improving resistivity hit degree of large-size N-type single crystal |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381888A (en) * | 2008-09-25 | 2009-03-11 | 苏州市矽美仕半导体材料有限公司 | Method for producing silicon single crystal |
| CN102220633A (en) * | 2011-07-15 | 2011-10-19 | 西安华晶电子技术股份有限公司 | Production technology of semiconductor grade silicon single crystal |
| CN105755532A (en) * | 2016-04-13 | 2016-07-13 | 江西赛维Ldk太阳能高科技有限公司 | Crystalline silicon preparation method and crystalline silicon |
| CN105821474A (en) * | 2016-04-13 | 2016-08-03 | 江西赛维Ldk太阳能高科技有限公司 | Preparation method of crystalline silicon and crystalline silicon |
| CN107488873A (en) * | 2017-09-19 | 2017-12-19 | 晶科能源有限公司 | A kind of method of silicon ingot casting |
| CN108531983A (en) * | 2018-05-22 | 2018-09-14 | 英利能源（中国）有限公司 | It mixes the preparation method of gallium polycrystal silicon ingot and mixes gallium polycrystal silicon ingot |
| CN109023509A (en) * | 2018-08-31 | 2018-12-18 | 包头美科硅能源有限公司 | A method of preparing solar level n type single crystal silicon |
| CN110438566A (en) * | 2019-08-09 | 2019-11-12 | 湖南红太阳光电科技有限公司 | Preparation method, more doping silicon ingots and the silicon wafer of more doping silicon ingots |
| CN112151628A (en) * | 2020-09-15 | 2020-12-29 | 四川晶科能源有限公司 | Solar cell and preparation method of gallium and hydrogen doped monocrystalline silicon |
| CN112831828A (en) * | 2021-01-07 | 2021-05-25 | 杭州晶宝新能源科技有限公司 | Growth method of gallium-doped Czochralski monocrystalline silicon, gallium-doped monocrystalline silicon and application |
-
2021
- 2021-11-19 CN CN202111373534.5A patent/CN114059152A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381888A (en) * | 2008-09-25 | 2009-03-11 | 苏州市矽美仕半导体材料有限公司 | Method for producing silicon single crystal |
| CN102220633A (en) * | 2011-07-15 | 2011-10-19 | 西安华晶电子技术股份有限公司 | Production technology of semiconductor grade silicon single crystal |
| CN105755532A (en) * | 2016-04-13 | 2016-07-13 | 江西赛维Ldk太阳能高科技有限公司 | Crystalline silicon preparation method and crystalline silicon |
| CN105821474A (en) * | 2016-04-13 | 2016-08-03 | 江西赛维Ldk太阳能高科技有限公司 | Preparation method of crystalline silicon and crystalline silicon |
| CN107488873A (en) * | 2017-09-19 | 2017-12-19 | 晶科能源有限公司 | A kind of method of silicon ingot casting |
| CN108531983A (en) * | 2018-05-22 | 2018-09-14 | 英利能源（中国）有限公司 | It mixes the preparation method of gallium polycrystal silicon ingot and mixes gallium polycrystal silicon ingot |
| CN109023509A (en) * | 2018-08-31 | 2018-12-18 | 包头美科硅能源有限公司 | A method of preparing solar level n type single crystal silicon |
| CN110438566A (en) * | 2019-08-09 | 2019-11-12 | 湖南红太阳光电科技有限公司 | Preparation method, more doping silicon ingots and the silicon wafer of more doping silicon ingots |
| CN112151628A (en) * | 2020-09-15 | 2020-12-29 | 四川晶科能源有限公司 | Solar cell and preparation method of gallium and hydrogen doped monocrystalline silicon |
| CN112831828A (en) * | 2021-01-07 | 2021-05-25 | 杭州晶宝新能源科技有限公司 | Growth method of gallium-doped Czochralski monocrystalline silicon, gallium-doped monocrystalline silicon and application |
Non-Patent Citations (1)
| Title |
|---|
| 周永溶: "半导体材料", vol. 1, 北京理工大学出版社, pages: 82 - 83 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115044975A (en) * | 2022-07-21 | 2022-09-13 | 天合光能股份有限公司 | Method for preparing czochralski silicon |
| CN115558999A (en) * | 2022-10-09 | 2023-01-03 | 包头美科硅能源有限公司 | Method for improving resistivity hit degree of large-size N-type single crystal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114059152A (en) | Gallium element doping method for producing silicon single crystal rod by Czochralski method | |
| JP4528995B2 (en) | Method for producing Si bulk polycrystalline ingot | |
| CN105821474B (en) | The preparation method and crystalline silicon of a kind of crystalline silicon | |
| CN108842179B (en) | Method for preparing double-crystal-orientation polycrystalline silicon ingot by setting sigma 3 twin crystal boundary | |
| EP4257734A1 (en) | Crystal pulling process for single-crystal silicon | |
| JP4723071B2 (en) | Silicon crystal, silicon crystal wafer, and manufacturing method thereof | |
| CN101694008A (en) | Gallium-doped metallic silicon and directional solidification casting method thereof | |
| CN101851779A (en) | Method for manufacturing monocrystalline silicon chip of solar cell | |
| CN105019022A (en) | Quasi mono-crystalline silicon co-doped with gallium, germanium and boron and preparing method thereof | |
| US20090098715A1 (en) | Process for manufacturing silicon wafers for solar cell | |
| US20230250549A1 (en) | Method for preparing monocrystalline silicon and solar cell and photovoltaic module with monocrystalline silicon | |
| CN114540950B (en) | Method for growing n-type Czochralski silicon by reducing furnace pressure | |
| CN114592236B (en) | Growth method of P-type gallium-doped silicon single crystal | |
| CN111910248B (en) | Ingot casting single crystal seed crystal, cast single crystal silicon ingot and preparation method thereof, cast single crystal silicon slice and preparation method thereof | |
| CN101555621A (en) | Method for growing silicon single crystal by nitrogen-doped inoculating crystal | |
| CN1233883C (en) | Method for growing low-imperfection-density direct-drawing silicon monocrystal in magnetic field | |
| JP4383639B2 (en) | Method for producing Ga-doped silicon single crystal, Ga-doped silicon single crystal, and silicon single-crystal solar cell produced therefrom | |
| CN101363131B (en) | Top seed solution growth reentrance technology in fluxing agent growth method | |
| JP4534022B2 (en) | Ga-doped crystalline silicon, method for producing the same, device for producing Ga-doped crystalline silicon used in the method for producing the same, solar cell using Ga-doped crystalline silicon substrate, and method for producing the same | |
| Lei et al. | Growth of high-quality multi-crystalline silicon ingot by using Si particles embedded in the Si3N4 layer | |
| JP2001192289A (en) | Method of producing compound semiconductor single crystal | |
| US20190006190A1 (en) | Fz silicon and method to prepare fz silicon | |
| JP4002721B2 (en) | Silicon single crystal wafer for Ga-doped solar cell and method for producing the same | |
| CN103305905A (en) | Variable crucible ratio monocrystal silicon growth method | |
| JP2002104898A (en) | Silicon crystal and silicon crystal wafer and method of manufacturing them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |