CN107974710A - The growing method of high-performance polycrystal silicon based on quartzy seed crystal - Google Patents
The growing method of high-performance polycrystal silicon based on quartzy seed crystal Download PDFInfo
- Publication number
- CN107974710A CN107974710A CN201711164477.3A CN201711164477A CN107974710A CN 107974710 A CN107974710 A CN 107974710A CN 201711164477 A CN201711164477 A CN 201711164477A CN 107974710 A CN107974710 A CN 107974710A
- Authority
- CN
- China
- Prior art keywords
- quartzy
- silicon
- seed crystal
- crucible
- silicon nitride
- 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
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
- 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
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
Abstract
The invention discloses a kind of growing method of the high-performance polycrystal silicon based on quartzy seed crystal, some V-shaped grooves are opened up in the crucible bottom for polycrystalline silicon oriented growth；In crucible internal walls coating silicon nitride coating；Quartzy subparticle is inserted in the groove of crucible bottom, to filling up the 30 60% of groove height；The coating silicon nitride layer again on the quartzy subparticle of crucible bottom；Growing polycrystalline silicon according to a conventional method.The polycrystalline silicon material grown using the present invention, has following features：Dislocation aggregation is effectively inhibited with diffusion；The crystal boundary ratio of angle random distribution is significantly increased, and the ratio of twin is significantly less；Average minority carrier lifetime is 10 ~ 13 μ s.
Description
Technical field
The invention belongs to field of polysilicon technology, more particularly to a kind of life of the high-performance polycrystal silicon based on quartzy seed crystal
Long method.
Background technology
Crystal silicon solar energy battery occupies global photovoltaic market close to the city of 90% share, wherein polycrystal silicon cell at present
Field occupancy volume has exceeded monocrystalline silicon battery, this is because polycrystalline silicon material has low volume production cost, relatively easy production work
Skill flow and scalability.In the growth course of polycrystal silicon ingot, raw material, crucible, growth technique etc. can introduce defect and impurity,
This is the key factor for restricting polycrystal silicon cell improved efficiency.The defects of crystal boundary, dislocation due to playing the role of complex centre and
The presence of impurity reduces the efficiency of battery, therefore, the presence of the defects of how reducing polysilicon and impurity and to reduce them right
The adverse effect of battery efficiency, is current photovoltaic industry circle urgent problem to be solved.
Compared with monocrystalline silicon, the defects of polysilicon, mostlys come from crystal boundary and dislocation.It is, in general, that as long as crystallite dimension surpasses
Cross certain scope, crystal boundary does not in itself influence solar cell properties particularly, but the dislocation that is derived of crystal boundary and
Sub- crystal boundary（Defect）Bigger is influenced on the performance of battery.Therefore, for this angle, the bigger crystal grain of size（Such as monocrystalline
Silicon）The defects of being derived is smaller, so as to be influenced on battery performance smaller.Quasi- monocrystalline is the technique based on polycrystalline cast ingot, in length
Casting ingot process when brilliant by using single crystal seed or without seed crystal guiding, obtains the polysilicon of appearance and the equal single crystal-like of electrical property
Piece.Compared to polycrystalline, the crystal boundary of quasi-monocrystalline silicon is few, dislocation density is low.It is difficult from technology although quasi- monocrystalline has certain advantage
From the point of view of point, it develops also restricts, it is necessary to which more technological break-through is to realize long term growth there are many.
The crystal grain of smaller is obtained by regulating and controlling crystal nucleation, rather than the crystal grain of growth bigger, be academia in recent years
With the hot issue of industrial circle discussion.By regulating and controlling nucleation of the crystalline silicon in early growth period, occur in crystal growing process
Dislocation aggregation is effectively inhibited with being diffused with to be likely to be obtained, and can so obtain the macro-uniformity with higher and different defects
The crystalline material of structure so that significantly reduce the gathering to have with subgrain boundary of dislocation, and the microscopic property of dislocation is also sent out
Change is given birth to.
The content of the invention
The object of the present invention is to provide a kind of growing method of the high-performance polycrystal silicon based on quartzy seed crystal, can reduce more
The defects of crystal silicon, improve the efficiency of polysilicon solar cell.
To realize goal of the invention, used technical solution is such：
The growing method of high-performance polycrystal silicon based on quartzy seed crystal, it is characterised in that：Include the following steps：
1）Some V-shaped grooves are opened up in the crucible bottom for polycrystalline silicon oriented growth；
2）In crucible internal walls coating silicon nitride coating；
3）Quartzy subparticle is inserted in the groove of crucible bottom, to the 30-60% for filling up groove height；
4）The coating silicon nitride layer again on the quartzy subparticle of crucible bottom；
5）Growing polycrystalline silicon according to a conventional method.
As preferable technical solution, the depth of the V-shaped groove is the 30 ~ 50% of crucible bottom thickness, the angle on its both sides
For 60 degree ~ 120 degree.
Step 2）In silicon nitride coating in, added with a certain amount of nanometer grade silica as adhesive.
Step 3）In quartzy subparticle in, added with a certain amount of polyvinyl alcohol（PVA）Organic bond.
Step 2）In silicon nitride coating thickness be 150 ~ 250 μm, step 4）In silicon nitride coating thickness be 40-70
μm。
In the method, since the specific surface area of spherical quartz subparticle is bigger, contact of the silicon melt with silicon nitride
Area can be significantly increased, and therefore, crystalline silicon nucleation site becomes more and more tiny crystal grain can be formed.Work as silicon material
During in molten condition, silicon melt penetrates into the hole of following cell quartz layer by thin layer of sin.In the first of crystalline silicon
Beginning growth phase, when the lifting of heat insulation layer forms certain temperature gradient, the nucleation of polysilicon first occurs at more
In the hole of hole quartz layer.
On the one hand, the separation due to quartz particles or barrier effect, the initial grain formed in hole is towards silicon melt
Direction rather than the continued growth of crucible bottom direction, the radial growth of crystal grain suppressed be subject to very big, and in different aperture
Grain growth be mutually independent, this situation persistently remains to the growth of silicon crystal grain beyond the nitridation above quartz particles
Silicon thin film.Therefore, substantial amounts of uniform and tiny silicon crystal grain can obtain, and the dislocation in crystalline silicon gathers and subgrain boundary
Obtain very big reduction.On the other hand, since the speed of growth of crystal difference crystal face has very big difference, on quartz layer
Silicon crystal grain in groove can realize the competitive growth of different crystal faces, be eliminated by crystal growth geometry, and final acquisition dislocation is close
Spend polysilicon low, that minority carrier life time is high.
The polycrystalline silicon material grown using this method, has following features：Dislocation aggregation is effectively inhibited with diffusion；
The crystal boundary ratio of angle random distribution is significantly increased, and the ratio of twin is significantly less；Average minority carrier lifetime is 10 ~ 13 μ s.
Brief description of the drawings
It is described in further detail below in conjunction with attached drawing and embodiments of the present invention
Fig. 1 is crucible bottom fluting schematic diagram；
Fig. 2 is crucible internal walls（Including groove）Silicon nitride coating schematic diagram；
Fig. 3 is filling quartz particles schematic diagram in crucible groove；
Fig. 4 is the silicon nitride coating schematic diagram above quartz particles.
In figure mark for：Crucible 1, groove 11, silicon nitride coating 2, quartz particles 3.
Embodiment
Referring to attached drawing.The square quartz ceramic crucible 1 that the present embodiment includes a kind of open top, the length of side is 200 mm（It is soft
Change temperature and be more than 1700 DEG C）, the thickness of 1 three walls of crucible is 15 mm, and the thickness H of bottom is 25 mm.Opened in 1 bottom of crucible
Groove, the shape of groove is " V " type, and crucible bottom is all booked groove 11, and the depth h of groove is 8 mm, and slot opening width w is 10
Mm, the number of groove 17, the angle on two sides of groove is 64 degree.
Firstth, the alpha-silicon nitride powders of 40 ~ 50 g are added in the deionized water of 300 g（Particle diameter is 0.5 ~ 1.5 μm）2
The SiO 2 powder of ~ 3 g（Particle diameter is 20 ~ 50 nm）, stir evenly, be configured to silicon nitride aqueous solution.Through over cleaning
Crucible is heated to 50 ~ 70 DEG C afterwards, and silicon nitride aqueous solution is sprayed into crucible internal walls using spray gun, and spray gun pressure is 30 ~ 40 psi,
Spraying needs to carry out several times, and total 2 thickness of silicon nitride coating is 150 ~ 250 μm.Need to use compressed air after often having sprayed one time
The silicon nitride particle to descend slowly and lightly in crucible is removed, crucible bottom, base angle, basal edge, suitably increase coating layer thickness at vertical rib.Spray
Finish after, crucible carried out at a temperature of 1050 DEG C heat treatment 4 ~ 6 it is small when.
Secondth, the quartz particles 3 of high-purity are filled up in the groove 11 of 1 bottom of crucible, purity is greater than 99.9995%,
A diameter of 60 ~ 120 μm of grain.The polyvinyl alcohol for being 0.1% ~ 0.5% in quartz particles addition content（PVA）Organic bond, quartz
Filling to the height of " V " type groove is 2.5 ~ 3.0 mm.
3rd, coat the silicon nitride layer 2 that thickness is 40-70 μm again on the quartz particles 3 of 1 bottom of crucible, spray work
Skill is identical with the first step.
4th, by 5.0kg, purity be 6N p-type raw material place crucible in, charging when, it should compared with
Bulk raw places crucible bottom and surrounding inner wall, and raw material in small, broken bits is placed on middle and above.The crucible for installing raw material is moved into
In polycrystalline silicon ingot or purifying furnace, furnace body is vacuumized, until the vacuum of furnace body is 20 Pa, is begun to warm up, and be passed through argon gas conduct
Protective gas.Heating-up temperature rises to 1540 DEG C, and keep the temperature 2 ~ 3 it is small when raw material is fully melted, then reduce temperature.Work as crucible
The temperature of melt silicon in the groove of bottom is down to 1400 ~ 1410 DEG C, and the nucleation of polysilicon initially forms, into crystal growing stage.
Insulation barrel is up lifted with the speed of 1 ~ 1.5 mm/h, makes the initial grain that is formed in quartzy hole towards the direction of silicon melt
Rather than crucible bottom direction continued growth.1 ~ 2 it is small when after, the lifting speed of insulation barrel increases to 3 ~ 5 mm/h, makes in groove
Crystal grain competitive growth, 3 ~ 4 it is small when after, pull rate is gradually increased to 8 ~ 12 mm/h, until long brilliant complete, starts to cool down.Work as temperature
Degree is when being reduced to 1300 DEG C, 1100 DEG C, 800 DEG C, keep the temperature respectively 3 it is small when, then natural cooling.
The polycrystal silicon ingot grown using this embodiment, highest minority carrier life time reach 22 μ s, and minimum minority carrier life time reaches 4 μ s,
Average minority carrier lifetime is 12 μ s.
Claims (5)
1. the growing method of the high-performance polycrystal silicon based on quartzy seed crystal, it is characterised in that：Include the following steps：
1）Some V-shaped grooves are opened up in the crucible bottom for polycrystalline silicon oriented growth；
2）In crucible internal walls coating silicon nitride coating；
3）Quartzy subparticle is inserted in the groove of crucible bottom, to the 30-60% for filling up groove height；
4）The coating silicon nitride layer again on the quartzy subparticle of crucible bottom；
5）Growing polycrystalline silicon according to a conventional method.
2. the growing method of the high-performance polycrystal silicon based on quartzy seed crystal as claimed in claim 1, it is characterised in that：The V
The depth of shape groove is the 30 ~ 50% of crucible bottom thickness, and the angle on its both sides is 60 degree ~ 120 degree.
3. the growing method of the high-performance polycrystal silicon based on quartzy seed crystal as claimed in claim 1, it is characterised in that：Step 2）
In silicon nitride coating in, added with a certain amount of nanometer grade silica as adhesive.
4. the growing method of the high-performance polycrystal silicon based on quartzy seed crystal as claimed in claim 1, it is characterised in that：Step 3）
In quartzy subparticle in, added with a certain amount of polyvinyl alcohol（PVA）Organic bond.
5. the growing method of the high-performance polycrystal silicon based on quartzy seed crystal as claimed in claim 1, it is characterised in that：Step 2）
In silicon nitride coating thickness be 150 ~ 250 μm, step 4）In silicon nitride coating thickness be 40-70 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711164477.3A CN107974710A (en) | 2017-11-21 | 2017-11-21 | The growing method of high-performance polycrystal silicon based on quartzy seed crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711164477.3A CN107974710A (en) | 2017-11-21 | 2017-11-21 | The growing method of high-performance polycrystal silicon based on quartzy seed crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107974710A true CN107974710A (en) | 2018-05-01 |
Family
ID=62010675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711164477.3A Pending CN107974710A (en) | 2017-11-21 | 2017-11-21 | The growing method of high-performance polycrystal silicon based on quartzy seed crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107974710A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108560048A (en) * | 2018-06-12 | 2018-09-21 | 山东大海新能源发展有限公司 | Polysilicon fine melt crucible for casting ingots and its preparation method and application |
| CN109704811A (en) * | 2018-12-29 | 2019-05-03 | 赛维Ldk太阳能高科技(新余)有限公司 | A kind of preparation method of fine melt high efficient crucible, fine melt high efficient crucible and application |
| CN110408992A (en) * | 2019-09-11 | 2019-11-05 | 江苏美科硅能源有限公司 | A kind of dislocation density is low, high-quality crystal grain accounting is high melts efficient polycrystalline silicon ingot preparation method entirely |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979718A (en) * | 2010-11-30 | 2011-02-23 | 奥特斯维能源（太仓）有限公司 | Quartz crucible and method for casting quasi-single crystal |
| CN201942782U (en) * | 2010-11-30 | 2011-08-24 | 奥特斯维能源（太仓）有限公司 | Quartz crucible |
| CN202144522U (en) * | 2011-07-19 | 2012-02-15 | 天威新能源控股有限公司 | Crucible |
| CN102776554A (en) * | 2012-04-01 | 2012-11-14 | 江西赛维Ldk太阳能高科技有限公司 | Polycrystalline silicon ingot, preparation method of polycrystalline silicon ingot and polycrystalline silicon slice |
| CN104018219A (en) * | 2014-06-17 | 2014-09-03 | 镇江环太硅科技有限公司 | Preparation method of high-efficiency polycrystalline silicon chip with narrow black edge |
| CN104018222A (en) * | 2014-06-20 | 2014-09-03 | 浙江师范大学 | Crucible for preparing polycrystalline silicon ingot and growth method of polycrystalline silicon ingot |
| CN204417645U (en) * | 2015-01-23 | 2015-06-24 | 晶科能源有限公司 | A kind of seed crystal distribution optimization device and a kind of ingot furnace |
| CN104831350A (en) * | 2015-05-26 | 2015-08-12 | 江西旭阳雷迪高科技股份有限公司 | Method of distributing seeding material to bottom of quartz ceramic crucible for ingot casting |
-
2017
- 2017-11-21 CN CN201711164477.3A patent/CN107974710A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979718A (en) * | 2010-11-30 | 2011-02-23 | 奥特斯维能源（太仓）有限公司 | Quartz crucible and method for casting quasi-single crystal |
| CN201942782U (en) * | 2010-11-30 | 2011-08-24 | 奥特斯维能源（太仓）有限公司 | Quartz crucible |
| CN202144522U (en) * | 2011-07-19 | 2012-02-15 | 天威新能源控股有限公司 | Crucible |
| CN102776554A (en) * | 2012-04-01 | 2012-11-14 | 江西赛维Ldk太阳能高科技有限公司 | Polycrystalline silicon ingot, preparation method of polycrystalline silicon ingot and polycrystalline silicon slice |
| CN104018219A (en) * | 2014-06-17 | 2014-09-03 | 镇江环太硅科技有限公司 | Preparation method of high-efficiency polycrystalline silicon chip with narrow black edge |
| CN104018222A (en) * | 2014-06-20 | 2014-09-03 | 浙江师范大学 | Crucible for preparing polycrystalline silicon ingot and growth method of polycrystalline silicon ingot |
| CN204417645U (en) * | 2015-01-23 | 2015-06-24 | 晶科能源有限公司 | A kind of seed crystal distribution optimization device and a kind of ingot furnace |
| CN104831350A (en) * | 2015-05-26 | 2015-08-12 | 江西旭阳雷迪高科技股份有限公司 | Method of distributing seeding material to bottom of quartz ceramic crucible for ingot casting |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108560048A (en) * | 2018-06-12 | 2018-09-21 | 山东大海新能源发展有限公司 | Polysilicon fine melt crucible for casting ingots and its preparation method and application |
| CN109704811A (en) * | 2018-12-29 | 2019-05-03 | 赛维Ldk太阳能高科技(新余)有限公司 | A kind of preparation method of fine melt high efficient crucible, fine melt high efficient crucible and application |
| CN110408992A (en) * | 2019-09-11 | 2019-11-05 | 江苏美科硅能源有限公司 | A kind of dislocation density is low, high-quality crystal grain accounting is high melts efficient polycrystalline silicon ingot preparation method entirely |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107573101B (en) | Crucible and preparation method thereof | |
| CN107974710A (en) | The growing method of high-performance polycrystal silicon based on quartzy seed crystal | |
| KR101594474B1 (en) | Poly-crystalline silicon ingot, silicon wafer therefrom and method of fabricating poly-crystalline silicon ingot | |
| TWI620838B (en) | Crystalline silicon ingot including nucleation promotion particles and method of fabricating the same | |
| EP2650405A2 (en) | Methods for preparing a melt of silicon powder for silicon crystal growth | |
| CN103911654B (en) | The method preparing the monocrystal silicon of a diameter of more than 400mm | |
| CN103469293A (en) | Preparation method of polycrystalline silicon | |
| WO2018130078A1 (en) | Process for ingot casting, melting, and crystallization of mono-like seed crystal in concave fashion | |
| CN104088014B (en) | A kind of bar-shaped sapphire crystal growth equipment and growing method thereof | |
| WO2014056157A1 (en) | Polycrystalline silicon ingot, method for producing the same, and crucible | |
| TW201315847A (en) | Crystalline silicon ingot and method of fabricating the same | |
| CN105063744A (en) | Silicon single crystal drawing method | |
| TW202113168A (en) | Process for growing silicon single crystal | |
| CN102776556B (en) | Polycrystalline silicon ingot and preparation method thereof as well as polycrystalline silicon wafer | |
| CN104451872A (en) | Production method of solar-grade czochralski silicon | |
| CN108315813A (en) | A kind of preparation method of polycrystalline silicon ingot casting | |
| CN203474952U (en) | Quartz crucible for ingot casting | |
| CN104203845A (en) | Method of preparing cast silicon by directional solidification | |
| CN1332072C (en) | Low oxygen control method in czochralski silicon monocrystal | |
| CN201634795U (en) | Czochralski crystal furnace graphite crucible | |
| CN114540951B (en) | Method for preparing polycrystalline silicon ingot by recycling silicon mud | |
| CN203159742U (en) | Efficient crucible for casting polycrystal ingot | |
| CN201990762U (en) | Heating device of czochralski single crystal furnace | |
| CN209144025U (en) | A kind of semiconductor grade silica crucible | |
| CN105401211B (en) | Draw C axles sapphire single crystal growth furnace and method |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180501 |