CN104451872A - Production method of solar-grade czochralski silicon - Google Patents
Production method of solar-grade czochralski silicon Download PDFInfo
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- CN104451872A CN104451872A CN201410644271.0A CN201410644271A CN104451872A CN 104451872 A CN104451872 A CN 104451872A CN 201410644271 A CN201410644271 A CN 201410644271A CN 104451872 A CN104451872 A CN 104451872A
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- 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
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- 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
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Abstract
The invention discloses a production method of solar-grade czochralski silicon, and relates to the technical field of czochralski silicon. The production method comprises the following eight steps of charging, melting, stabilizing the temperature, seeding, shouldering, performing equal-diameter growth and ending. According to the production method disclosed by the invention, in the seeding process, the crystal rotation and the crucible rotation are set to be 8 revolutions per minute. The production method is simple and convenient to operate, easy to realize, capable of effectively reducing crystal defects which possibly appear in a crystallization process, lowering a problem of producing black chips and black angle plates in the czochralski silicon, remarkably improving the quality of the single crystal and prolonging the service life of the single crystal, avoiding returned goods due to product quality defects and saving unnecessary fund waste for the enterprises.
Description
Technical field
The present invention relates to pulling of silicon single crystal technical field.
Background technology
Sun power is one of following most important green energy resource, and as the core of high efficiency solar cell, colory silicon single crystal is the major products that people research and develop always.
The production method of silicon single crystal mainly contains vertical pulling method (CZ), zone melting method (FZ) and epitaxial method, and wherein vertical pulling method and zone melting method are for extending silicon single crystal bar, and epitaxial method is for extending monocrystalline silicon thin film.The silicon single crystal produced due to vertical pulling method is widely used in semiconductor integrated circuit, diode, epitaxial wafer substrate, and the essential domain such as solar cell, is thus subject to the special concern of people.
At present in the production field of pulling of silicon single crystal, oxygen is a kind of usual impurities in pulling of silicon single crystal, and this is mainly caused by the production technique of silicon single crystal.Practice shows, the oxygen in silicon single crystal mainly concentrates on its head, if the head oxygen level of silicon single crystal is too high, will causes so-called " black chip " and " black gusset plate " problem, thus affect quality product.
The harm of oxygen is, oxygen can form Thermal donor and new promoted university, and the resistivity evenness of silicon single crystal is deteriorated; In addition, oxygen also with the formation close relation of microdefect in pulling of silicon single crystal, and the microdefect of silicon chip surface also can have influence on the yield rate of device in device thermal oxidation technology.Therefore, in the detection of silicon single crystal, generally the black chip in silicon chip and black gusset plate phenomenon are taked to the attitude of zero tolerance at present.But, the current method but also lacking the black chip of a kind of simple, effective, easy minimizing and black gusset plate.
Summary of the invention
The technical problem to be solved in the present invention is for above-mentioned the deficiencies in the prior art, a kind of production method of solar level pulling of silicon single crystal is provided, it is for the defect of current pulling of silicon single crystal production technique, prior art is improved, by improving the way of contact of seed crystal and silicon liquid liquid level, reduce the oxygen level of monocrystalline, thus reach the object reducing black chip and black gusset plate in pulling of silicon single crystal.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of production method of solar level pulling of silicon single crystal, it comprises the steps:
(1) reinforced: silicon raw material and doping agent are put into quartz crucible by semiconductor type as required; The kind of doping agent determines according to the type N-type of semi-conductor or P type, and the doping agent of P type is generally boron or gallium, and N-type doping agent is generally phosphorus;
(2) melt: single crystal growing furnace cut out and vacuumizes, making the pressure in single crystal growing furnace maintain below 5Pa, then rising to disposable for heating power 95 ~ 100 kilowatts (about 1420 DEG C); Although use excessive power to carry out melted silicon raw material can shorten fusing time, the excessive damage of quartz crucible wall may be caused, reduce the life-span of quartz crucible, otherwise if power is too small, then whole melting process is consuming time too of a specified duration, causes production capacity to decline;
(3) surely warm: after silicon melting sources becomes liquid, heating power to be down to 45 kilowatts and to drop into temperature auto-programming, temperature auto-programming makes in-furnace temperature keep constant and lasting 1 hour;
(4) seeding: adjustment crucible position makes silicon liquid liquid level be 15 mm apart from the distance of guide shell, turns crystalline substance to turn with crucible and is all set to 8 circle per minutes, then seed crystal is down to silicon liquid liquid level place, and contacts more than 30 minutes with liquid level, then carry out seeding; During seeding, seed crystal immerses in melted silicon according to the crystal orientation of <100> or <111>, the total length of seeding is 130 ~ 150 mm, during seeding, average pull rate controls at 3 ~ 6 mm/min, initial stage casting speed control is at 1 ~ 3 mm/min, and seeding to reach casting speed control after 30 mm at 3 ~ 6 mm/min;
(5) shouldering: after seeding completes, is down to 0.7 mm/min by pulling rate, heating power reduces by 5 kilowatts, 3 ~ 4 hours shouldering time; In this step, most important parameter is the amplifying speed rate (that is angle of shouldering) of diameter, the shape of shouldering and angle will affect solid-liquid interface shape and the crystal bar quality of crystal bar head, if it is too fast to lower the temperature, liquid level presented cold situation, the shape of shoulder becomes square because diameter amplifies fast, easily causes the generation of dislocation and lose the structure of monocrystalline time serious;
(6) turn shoulder: when silicon rod diameter also has 5 ~ 10 mm apart from isometrical diameter, carried by pulling rate to 2.0 mm/min, carry out turning shoulder;
(7) isodiametric growth; When silicon rod diameter reaches isometrical diameter, the initial pulling rate of wire diameter automatic such as pulling rate to be down to, to be set to 1.15 mm/min etc. the initial pulling rate of wire diameter automatic, setting crucible lifting speed, then drops into isometrical auto-programming and carries out isodiametric growth;
Crucible lifting speed S ' calculates according to following formula 1:
；
In formula: Φ is crystal diameter, Φ ' is crucible internal diameter, and S is crystal pull rate;
The judging criterion that isodiametric growth completes is, when etc. electrical path length reach L time grown, the numerical value of L is calculated by following formula 2:
；
In formula: D is crystal diameter; ρ is the density of silicon, i.e. 2.33 g/cm
3; W is crystal weight, i.e. the difference of province's doses at the bottom of charge amount and crucible;
(8) finish up: after isodiametric growth completes, exit isometrical auto-programming, stop crucible liter, pulling rate is carried to 1.0 mm/min, drop into ending auto-programming, put off blowing out when length reaches diameter value; After isodiametric growth completes, if crystal bar and liquid level separated at once, so thermal stresses will make crystal bar occur dislocation and slip line, in order to avoid the generation of this problem, the diameter of crystal bar slowly must be reduced, until become a cusp and separate with liquid level, this process is called ending.
The parameter of ending auto-programming foundation is according to listed by following table 1:
Table 1.
As preferably, in step (4), the total length of seeding is 150 millimeters.
As preferably, in step (4), the total length of seeding is 140 millimeters.
The beneficial effect that produces of technique scheme is adopted to be: the inventive method effectively can reduce black chip in pulling of silicon single crystal and black gusset plate problem, and its principle is:
1, is shortened to the temperature fluctuation that 1 hour greatly can reduce seeding initial period steady time, reduce the void-type defect of the crystal bar head brought by thermal stresses, reduce black-film and black gusset plate phenomenon;
2, the oxygen of the monocrystalline overwhelming majority comes from quartz crucible, uses 8 switchings tactile 8 to quote in advance and can make to be rotated by high temperature silicon liquid to discharge in advance the produced oxygen element that washes away of quartz crucible, thus reduce the oxygen level of monocrystalline, reduce black-film and black gusset plate phenomenon.
After using present method, the oxygen level in silicon single crystal and lattice defect obviously reduce, and substantially increase quality and the life-span of product.
Embodiment
With embodiment form, the present invention is further detailed explanation below.
Embodiment 1:
A production method for solar level pulling of silicon single crystal, it comprises the steps:
(1) reinforced: in quartz crucible, to add the silicon raw material of 120 kilograms and the boron of 31.49 grams;
(2) melt: single crystal growing furnace cut out and vacuumizes, making the pressure in single crystal growing furnace maintain below 5Pa, then rising to disposable for heating power 95 ~ 100 kilowatts (about 1420 DEG C);
(3) surely warm: after silicon melting sources becomes liquid, heating power to be down to 45 kilowatts and to drop into temperature auto-programming, temperature auto-programming makes in-furnace temperature keep constant and lasting 1 hour;
(4) seeding: adjustment crucible position makes silicon liquid liquid level be 15 mm apart from the distance of guide shell, turns crystalline substance to turn with crucible and is all set to 8 circle per minutes, then seed crystal is down to silicon liquid liquid level place, and contacts more than 30 minutes with liquid level, then seeding one hour; During seeding, seed crystal immerses in melted silicon according to the crystal orientation of <100> or <111>, the total length of seeding is 150 mm, during seeding, average pull rate controls at 3 ~ 6 mm/min, initial stage casting speed control is at 1 ~ 3 mm/min, and seeding to reach casting speed control after 30 mm at 3 ~ 6 mm/min;
(5) shouldering: after seeding completes, is down to 0.7 mm/min by pulling rate, heating power reduces by 5 kilowatts, 3 ~ 4 hours shouldering time;
(6) turn shoulder: when silicon rod diameter reaches 200 mm, pulling rate is carried to 2.0 mm/min, carry out turning shoulder;
(7) isodiametric growth; When silicon rod diameter reaches 205 mm, the initial pulling rate of wire diameter automatic such as pulling rate to be down to, to be set to 1.15 mm/min etc. the initial pulling rate of wire diameter automatic, and crucible lifting speed to be set to 0.189 mm/min, then drop into isometrical auto-programming and carry out isodiametric growth;
(8) finish up: after isodiametric growth completes, exit isometrical auto-programming, stop crucible liter, carried by pulling rate to 1.0 mm/min, drop into ending auto-programming, put off blowing out when length reaches diameter value, the parameter of ending auto-programming is as shown in table 1.
Present method is simple, and it effectively reduces black chip in pulling of silicon single crystal and black gusset plate phenomenon, improves life-span and the quality of monocrystalline.The silicon single crystal that this method is made has fine qualities, and can be used for producing the products such as solar cell.
Claims (3)
1. a production method for solar level pulling of silicon single crystal, is characterized in that: comprise the steps:
(1) reinforced: silicon raw material and doping agent are put into quartz crucible by semiconductor type as required;
(2) melt: single crystal growing furnace cut out and vacuumizes, making the pressure in single crystal growing furnace maintain below 5Pa, then rising to 95 ~ 100 kilowatts by disposable for heating power;
(3) surely warm: after silicon melting sources becomes liquid, heating power to be down to 45 kilowatts and to drop into temperature auto-programming, temperature auto-programming makes in-furnace temperature keep constant and maintain constant temperature 1 hour;
(4) seeding: adjustment crucible position makes silicon liquid liquid level be 15 mm apart from the distance of guide shell, turns crystalline substance to turn with crucible and is all set to 8 circle per minutes, then seed crystal is down to silicon liquid liquid level place, and contacts more than 30 minutes with liquid level, then carry out seeding; The total length of seeding is 130 ~ 150 mm, and during seeding, average pull rate controls at 3 ~ 6 mm/min, and initial stage casting speed control is at 1 ~ 3 mm/min, and seeding to reach casting speed control after 30 mm at 3 ~ 6 mm/min;
(5) shouldering: after seeding completes, is down to 0.7 mm/min by pulling rate, heating power reduces by 5 kilowatts, 3 ~ 4 hours shouldering time;
(6) turn shoulder: when silicon rod diameter also has 5 ~ 10 mm apart from isometrical diameter, carried by pulling rate to 2.0 mm/min, carry out turning shoulder;
(7) isodiametric growth; When silicon rod diameter reaches isometrical diameter, the initial pulling rate of wire diameter automatic such as pulling rate to be down to, to be set to 1.15 mm/min etc. the initial pulling rate of wire diameter automatic, setting crucible lifting speed, then drops into isometrical auto-programming and carries out isodiametric growth;
(8) finish up: after isodiametric growth completes, exit isometrical auto-programming, stop crucible liter, pulling rate is carried to 1.0 mm/min, drop into ending auto-programming, put off blowing out when length reaches diameter value.
2. the production method of a kind of solar level pulling of silicon single crystal according to claim 1, is characterized in that, in described step (4), the total length of seeding is 150 millimeters.
3. the production method of a kind of solar level pulling of silicon single crystal according to claim 1, is characterized in that, in described step (4), the total length of seeding is 140 millimeters.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803519A (en) * | 2016-05-31 | 2016-07-27 | 邢台晶龙电子材料有限公司 | Rapid M2-type monocrystalline silicon ending method |
| CN105803520A (en) * | 2016-05-31 | 2016-07-27 | 邢台晶龙电子材料有限公司 | Automatic tailing method for CZ-80 single crystal furnace |
| CN107955965A (en) * | 2017-11-22 | 2018-04-24 | 邢台晶龙电子材料有限公司 | A kind of method that vertical pulling method prepares monocrystalline silicon |
| CN108977878A (en) * | 2017-06-01 | 2018-12-11 | 江苏拓正茂源新能源有限公司 | Method based on monocrystalline growth with czochralski silicon |
| CN109097825A (en) * | 2018-08-29 | 2018-12-28 | 内蒙古中环协鑫光伏材料有限公司 | A kind of process for preventing pulling of crystals growth from shaking |
| CN112359412A (en) * | 2020-11-03 | 2021-02-12 | 上海新昇半导体科技有限公司 | Seeding method for crystal growth |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803519A (en) * | 2016-05-31 | 2016-07-27 | 邢台晶龙电子材料有限公司 | Rapid M2-type monocrystalline silicon ending method |
| CN105803520A (en) * | 2016-05-31 | 2016-07-27 | 邢台晶龙电子材料有限公司 | Automatic tailing method for CZ-80 single crystal furnace |
| CN108977878A (en) * | 2017-06-01 | 2018-12-11 | 江苏拓正茂源新能源有限公司 | Method based on monocrystalline growth with czochralski silicon |
| CN107955965A (en) * | 2017-11-22 | 2018-04-24 | 邢台晶龙电子材料有限公司 | A kind of method that vertical pulling method prepares monocrystalline silicon |
| CN109097825A (en) * | 2018-08-29 | 2018-12-28 | 内蒙古中环协鑫光伏材料有限公司 | A kind of process for preventing pulling of crystals growth from shaking |
| CN112359412A (en) * | 2020-11-03 | 2021-02-12 | 上海新昇半导体科技有限公司 | Seeding method for crystal growth |
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Application publication date: 20150325 |