CN102254953B - Manufacturing method of N-type solar energy silicon wafer with minority carrier lifetime of more than 1000 microseconds - Google Patents
Manufacturing method of N-type solar energy silicon wafer with minority carrier lifetime of more than 1000 microseconds Download PDFInfo
- Publication number
- CN102254953B CN102254953B CN201110227678XA CN201110227678A CN102254953B CN 102254953 B CN102254953 B CN 102254953B CN 201110227678X A CN201110227678X A CN 201110227678XA CN 201110227678 A CN201110227678 A CN 201110227678A CN 102254953 B CN102254953 B CN 102254953B
- Authority
- CN
- China
- Prior art keywords
- minority carrier
- silicon wafer
- single crystal
- polishing
- solar energy
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a manufacturing method of an N-type solar energy silicon wafer with minority carrier lifetime of more than 1000 microseconds. With an N-type solar energy silicon single crystal rod with minority carrier lifetime of more than 1000 microseconds as a raw material, the manufacturing method comprises the specific processing steps of: mechanically polishing a square rod with a polishing current of 6-10A and a workpiece moving speed of 10-25mm/min, chemically polishing with an HF (Hydrofluoric) acid and HNO3, carrying out wire-electrode cutting, degumming a silicon wafer, cleaning the silicon wafer, drying the silicon wafer; and reducing stains in processes of silicon single crystal cutting, degumming and cleaning to keep the service life of the N-type single crystal silicon wafer. The manufacturing method has the advantages of practicability, high efficiency and low cost, can be used for manufacturing the N-type solar energy single crystal silicon wafer with (100) crystal orientation, electrical resistivity range of 1-20 omega.cm, IRON (Fe) of less than 5E+13atoms/cm<2>, COPPER (Cu) of less than 20E+13atoms/cm<2> and minority carrier lifetime of more than 1000 microseconds, ensures that the N-type solar energy single crystal silicon wafer is superior to the N-type single crystal wafer manufactured by adopting common methods, and can meet the requirement of high-efficiency solar cells.
Description
Technical field
The present invention relates to the monocrystalline silicon piece manufacturing process, particularly a kind of N-type minority carrier life time is greater than 1000 microsecond solar power silicon piece making methods.Be specially a kind of manufacturing process of the high minority carrier life time of solar level N-type (hereinafter to be referred as the life-span) monocrystalline silicon piece take the high life n type single crystal silicon as raw material, in the life-span of cutting at silicon single crystal, come unstuck, reducing to stain to keep the n type single crystal silicon sheet in cleaning, make it be much better than the n type single crystal silicon sheet that commonsense method makes.
Technical background
Monocrystalline silicon piece life-span and clean-up performance are strong corresponding proportional relations with solar cell (hereinafter to be referred as battery) conversion efficiency.Solar industry N-type high life silicon single crystal used is with the growth of CZ method (the monocrystalline bulk life time is higher than 1000 μ s, with BCT～300 type Sinton consulting lifetime tester tests).In the solar cell industry, the silicon single crystal pole need to be passed through following steps at present: square rod manufacturing, silicon chip cutting, come unstuck (silicon chip of namely cutting being completed that comes unstuck separates from frock), cleaning (cleaning silicon wafer surface) etc.In the square rod manufacture process, high-intensity machine cuts, grinding meeting produce larger mechanical stress and heavy metal at plane of crystal and stain that (the high-efficiency N-type battery request is as follows: Fe＜5E+13atoms/cm
2, Cu＜20E+13atoms/cm
2, measuring instrument Graphite Furnace AAS); In the cutting process of silicon chip, owing to adopting the multi-wire saw mode, the part that in cutting process, steel wire wears away can be mingled in the micro mist form of iron, copper the mortar (material that cutting process is used, whole cutting process silicon chip all is in contact with it) in, cause heavy metal iron, copper to the contamination of silicon chip surface.The contamination meeting of these heavy metals produces the complex centre on the silicon chip top layer, thereby obviously reduces minority carrier life time, then reduces the conversion efficiency of battery.Therefore, the manufacturing treatment process of square rod, coming unstuck after multi-wire saw, the minority carrier life time that the scavenger artistic skill effectively guarantees silicon single crystal do not lower the conversion efficiency that then guarantees stable solar cell in the course of processing.
Both at home and abroad there are no the report about solar level N-type high life monocrystalline silicon piece manufacturing process (wherein, raw materials used is that the life-span is higher than the n type single crystal silicon of 1000 μ s).
Summary of the invention
The purpose of this invention is to provide a kind of new N-type minority carrier life time greater than 1000 microsecond solar silicon wafers and manufacture methods.It is the manufacturing process for the N-type solar monocrystalline silicon slice of minority carrier life time＞1000 microseconds, adopt chemical mechanical polishing to remove silicon rod damage layer, adopt the soda acid cleaning to remove the top layer metal impurities, can solve the life-span reduction difficult problem of high life n type single crystal silicon in the silicon chip manufacture process.Growing method of the present invention is practical, efficient is high, cost is low, can avoid the life-span in the solar level monocrystalline silicon piece manufacture process of high life N-type to reduce, and can satisfy the requirement of N-type high performance solar batteries.
N-type minority carrier life time provided by the invention greater than 1000 microsecond solar silicon wafers is:＜100〉crystal orientation, and electrical resistivity range is 1～20 Ω cm, minority carrier lifetime＞1000 μ s, IRON (Fe)＜5E+13atoms/cm
2, COPPER (Cu)＜20E+13atoms/cm
2, interstitial oxygen content is [Oi]≤17.5ppma, the displacement carbon content is [Cs]≤0.5ppma; External form＞6 inch.
The step that N-type minority carrier life time provided by the invention comprises greater than the manufacture method of 1000 microsecond solar silicon wafers: it be take minority carrier life time greater than the N-type solar energy silicon single crystal rod of 1000 microseconds as raw material, press following concrete technology step: square rod mechanical polishing, the square rod chemical polishing, multi-wire saw, silicon wafer stripping, Wafer Cleaning, silicon chip drying.The concrete technology parameter:
Mechanical polishing electric current 6-10A, workpiece movable speed 10-25mm/min, chemical polishing HF acid HNO
3Mass ratio 1: 6, soak time 3-6min; Come unstuck with lactic acid solution concentration 30%-60%, 50 ± 5 ℃ of solution temperatures, reaction time 20-40min.
N-type minority carrier life time provided by the invention greater than the manufacture method of 1000 microsecond solar silicon wafers be take minority carrier life time greater than the N-type solar energy silicon single crystal rod of 1000 microseconds as raw material, concrete steps comprise:
1) mechanical polishing is adjusted the polishing principal current to 8-10A, polishing velocity 20mm/min; Adjust electric current to 7-8A polishing velocity 20mm/min; Adjust electric current to 6-7A speed 20mm/min.
2) positive and negative 3 degrees centigrade of room temperature to 25 is adjusted in chemical polishing, and proportioning hydrofluoric acid (analyzing pure) is 1: 6 with the mass ratio of nitric acid (analyzing pure), silicon rod is soaked 3-6 minute after mixing;
3) sticky stick and use multi-line cutting machine cutting;
4) silicon wafer stripping, the lactic acid solution of compound concentration 30%-60% is adjusted solution temperature to 50 ± 5 ℃, is soaked in lactic acid solution 30 minutes and comes unstuck;
5) adopt 9 groove cleaning machines in cleaning process, every groove time is 4 minutes, uses the pure water of resistivity 15 megohms centimetre.
The invention provides a kind of N-type minority carrier life time greater than 1000 microsecond solar power silicon piece making methods, can solve high life N-type silicon single crystal stress and a difficult problem of staiing the actual silicon chip life-span reduction that causes in the following process process.Manufacturing process of the present invention is practical, efficient is high, cost is low, can make N-type,＜100〉crystal orientation, electrical resistivity range is the solar level monocrystalline silicon piece of 1～20 Ω cm, IRON (Fe)＜5E+13atoms/cm2, COPPER (Cu)＜20E+13atoms/cm2, minority carrier lifetime＞1000 μ s, can satisfy the requirement of high performance solar batteries.
Description of drawings
Fig. 1 a is Φ 160mm monocrystalline silicon piece minority carrier lifetime result; Fig. 1 b is Φ 160mm monocrystalline silicon piece tenor test result.
Fig. 2 a is Φ 200mm monocrystalline silicon piece minority carrier lifetime result; Fig. 2 b is Φ 200mm monocrystalline silicon piece tenor test result.
Embodiment
The present invention is described in detail as follows with reference to embodiment:
The present invention uses solar energy to use minority carrier life time greater than the N-type solar energy single crystal silicon rod (commercially available) of 1000 microseconds.The minority carrier life time checkout equipment is the Sinton consulting lifetime tester BCT-300 type that U.S. Sinton company produces, and the tenor checkout equipment is that the U.S. produces Graphite Furnace AAS.Mechanical polisher is Japanese Sinto EM-ML229, and multi-line cutting machine is that Japanese NTC produces 442D.Cleaning machine is the SGR-10L that Zhangjiagang ultrasonic electrical equipment company produces.
Make 6 inches monocrystalline silicon pieces according to the present invention
N-type minority carrier life time provided by the invention mainly comprises mechanical polishing (Japanese Sinto EM-ML229), chemical polishing, multi-wire saw (Japanese NTC produces 442D), comes unstuck, cleans steps such as (SGR-10L) greater than 1000 microsecond solar power silicon piece making methods (the plane of crystal minority carrier life time is 1050 microseconds):
The first step: the square rod of roller milled is put on mechanical polisher (Japanese Sinto EM-ML229), adjusts the polishing machine electric current to 8-10A, adjust polishing velocity to 20mm/s, begin polishing for the first time.
Second step: adjust the polishing machine electric current to 7-8A, adjust polishing velocity to 20mm/s, begin polishing for the second time.
The 3rd step: adjust the polishing machine electric current to 6-7A, adjust polishing velocity to 20mm/s, begin polishing for the third time.
The 4th step: adjust and confirm that room temperature is 25 ± 3 ℃, it is 1: 6 with the mass ratio of analyzing pure level nitric acid that proportioning is analyzed pure stage hydrofluoric acid, silicon rod is soaked 3-6 minute after mixing, clean with pure water rinsing.
The 5th step: line cutting according to a conventional method, the lactic acid solution of compound concentration 30%-60% is adjusted solution temperature to 50 ± 5 ℃, and in the silicon rod after cut (eka-silicon sheet) 2 minutes in the immersion lactic acid solution, soaks 30 minutes.
The 6th step: configuration is cleaned and to be used solution, alkali lye proportioning (mol ratio) to be, ammoniacal liquor: potassium hydroxide: water=2: 1: 3, acid solution proportioning (mol ratio) is, citric acid: acetic acid: water=1: 1: 3.
The 7th step: following configuration cleaning equipment (the ultrasonic electrical equipment SGR-10L of company in Zhangjiagang).
The pure water of confirming resistivity 15 megohms centimetre connects normal, will install to piecewise water from the silicon chip that degumming tank takes out and clean with in frock, takes out silicon chip and it is passed through 8 rinse baths in upper table successively, and every groove 4 minutes dries in drier at last.Ultrasound condition is 1.8kw, 40kHz.
The silicon single crystal that embodiment obtains is tested minority carrier lifetimes with BCT～300 type Sinton consulting lifetime tester; With Graphite Furnace AAS test tenor.
Representative measuring is one of example as a result:
Φ 160mm monocrystalline silicon piece, N-type, non-equilibrium minority carrier life time τ＞1000 μ s, tenor IRON (Fe)＜5E+13atoms/cm
2, COPPER (Cu)＜20E+13atoms/cm
2
The minority carrier lifetime result as shown in Figure 1, a is Φ 160mm monocrystalline silicon piece minority carrier lifetime result; The present invention and common process (solar cell industry conventional process) make the contrast of monocrystalline silicon piece life-span, and b is that (Fig. 1 b annotates: the order of magnitude is 10 to Φ 160mm monocrystalline silicon piece tenor test result
13); The present invention and common process (solar cell industry conventional process) make the contrast of monocrystalline silicon piece tenor.Result shows, the minority carrier life time of the Φ 160mm monocrystalline silicon piece that technique of the present invention makes is far above the general technology gained, and the tenor of gained monocrystalline silicon sheet surface of the present invention (copper iron content) is far below the common process gained.
Representative measuring as a result example two: make Φ 200mm monocrystalline silicon piece with the process conditions identical with embodiment 1.
Φ 200mm monocrystalline silicon piece, N-type, non-equilibrium minority carrier life time τ＞1000 μ s, tenor IRON (Fe)＜5E+13atoms/cm
2, COPPER (Cu)＜20E+13atoms/cm
2
The minority carrier lifetime result as shown in Figure 2, a is Φ 200mm monocrystalline silicon piece minority carrier lifetime result; The present invention and common process (solar cell industry conventional process) make the contrast of monocrystalline silicon piece life-span, and b is that (Fig. 2 b annotates: the order of magnitude is 10 to Φ 200mm monocrystalline silicon piece tenor test result
13); The present invention and common process (solar cell industry conventional process) make the contrast of monocrystalline silicon piece tenor.Result shows, the minority carrier life time of the Φ 200mm monocrystalline silicon piece that technique of the present invention makes is far above the general technology gained, and the tenor of gained monocrystalline silicon sheet surface of the present invention (copper iron content) is far below the common process gained.
Claims (1)
1. a N-type minority carrier life time is greater than the manufacture method of 1000 microsecond solar monocrystalline silicon slices, and this monocrystalline silicon piece is:＜100〉crystal orientation, electrical resistivity range is 1～20 Ω cm, minority carrier lifetime＞1000 μ s, Fe＜5E+13atoms/cm
2, Cu＜20E+13atoms/cm2, interstitial oxygen content are [Oi]≤17.5ppma, the displacement carbon content is [Cs]≤0.5ppma; It is characterized in that it be take minority carrier life time greater than the N-type solar energy silicon single crystal rod of 1000 microseconds as raw material, concrete steps comprise:
1) mechanical polishing is adjusted the polishing principal current to 8-10A, polishing velocity 20mm/min; Adjust electric current to 7-8A polishing velocity 20mm/min; Adjust electric current to 6-7A, speed 20mm/min;
2) room temperature to 25 ± 3 ℃ are adjusted in chemical polishing, and the mass ratio of proportioning hydrofluoric acid and nitric acid is 1: 6, silicon rod is soaked 3-6 minute after mixing;
3) sticky stick and use multi-line cutting machine cutting;
4) lactic acid solution of compound concentration 30%-60% is adjusted solution temperature to 50 ± 5 ℃, soaks 30 minutes;
5) adopt 9 groove cleaning machines in cleaning process, every groove time is 4 minutes, uses the pure water of resistivity 15 megohms centimetre.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110227678XA CN102254953B (en) | 2011-08-10 | 2011-08-10 | Manufacturing method of N-type solar energy silicon wafer with minority carrier lifetime of more than 1000 microseconds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110227678XA CN102254953B (en) | 2011-08-10 | 2011-08-10 | Manufacturing method of N-type solar energy silicon wafer with minority carrier lifetime of more than 1000 microseconds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102254953A CN102254953A (en) | 2011-11-23 |
| CN102254953B true CN102254953B (en) | 2013-06-19 |
Family
ID=44982074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110227678XA Expired - Fee Related CN102254953B (en) | 2011-08-10 | 2011-08-10 | Manufacturing method of N-type solar energy silicon wafer with minority carrier lifetime of more than 1000 microseconds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102254953B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102818980A (en) * | 2012-08-13 | 2012-12-12 | 安阳市凤凰光伏科技有限公司 | Method for testing quality of silicon substrate in solar battery |
| CN103331831B (en) * | 2013-07-18 | 2015-09-02 | 天津荣辉电子有限公司 | The large workpiece multi-line cutting method of neodymium iron boron |
| CN106816497A (en) * | 2017-02-22 | 2017-06-09 | 邢台晶龙电子材料有限公司 | A kind of silicon wafer stripping cleaning method and device |
| CN108549003A (en) * | 2018-04-20 | 2018-09-18 | 江苏鑫华半导体材料科技有限公司 | A kind of preprocess method measuring semiconductor grade monocrystalline silicon minority carrier life time suitable for the high frequency method of photoconductivity decay measurement |
| CN112713103B (en) * | 2021-03-29 | 2021-06-25 | 西安奕斯伟硅片技术有限公司 | Method for measuring metal content in silicon wafer |
| CN115467017A (en) * | 2022-08-24 | 2022-12-13 | 杭州中欣晶圆半导体股份有限公司 | Preparation method of epitaxial wafer with high minority carrier lifetime |
| CN115832101A (en) * | 2022-11-04 | 2023-03-21 | 隆基绿能科技股份有限公司 | Pretreatment method of solar cell and silicon wafer abnormity detection method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101637947A (en) * | 2008-07-31 | 2010-02-03 | 江西晶科能源有限公司 | Technological method for slicing silicon |
| CN101710603A (en) * | 2009-12-04 | 2010-05-19 | 洛阳鸿泰半导体有限公司 | Multi-line cutting process combination for processing solar cell silicon wafer |
| CN101724899A (en) * | 2009-09-08 | 2010-06-09 | 任丙彦 | Growth process for N-type solar energy silicon single crystal with minority carrier service life of larger than or equal to 1,000 microseconds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6333377B1 (en) * | 1999-03-08 | 2001-12-25 | A&A Material Corporation | Ingot support device for slicing silicon |
-
2011
- 2011-08-10 CN CN201110227678XA patent/CN102254953B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101637947A (en) * | 2008-07-31 | 2010-02-03 | 江西晶科能源有限公司 | Technological method for slicing silicon |
| CN101724899A (en) * | 2009-09-08 | 2010-06-09 | 任丙彦 | Growth process for N-type solar energy silicon single crystal with minority carrier service life of larger than or equal to 1,000 microseconds |
| CN101710603A (en) * | 2009-12-04 | 2010-05-19 | 洛阳鸿泰半导体有限公司 | Multi-line cutting process combination for processing solar cell silicon wafer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102254953A (en) | 2011-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102254953B (en) | Manufacturing method of N-type solar energy silicon wafer with minority carrier lifetime of more than 1000 microseconds | |
| CN104576830B (en) | Texturing pretreatment liquid and texturing pretreatment method for diamond wire cutting polycrystalline silicon sheet, texturing pretreatment silicon sheet and application of texturing pretreatment silicon sheet | |
| CN104900509B (en) | The surface treatment method and etching method of diamond wire saw silicon chip | |
| CN102181935B (en) | Method and corrosive liquid for making texture surface of monocrystalline silicon | |
| CN102709401B (en) | Manufacturing method of N-type solar battery | |
| CN107039241B (en) | A kind of chemical cleavage method of ultra-thin silicon | |
| CN103464415A (en) | Solar monocrystalline silicon cleaning solution and cleaning method | |
| JP2014096459A (en) | Surface processing method of semiconductor substrate for solar cell, process of manufacturing semiconductor substrate for solar cell, process of manufacturing solar cell, and manufacturing apparatus of solar cell | |
| CN105154268A (en) | Cleaning fluid capable of reducing thickness of damaged layer of surface of silicon wafer and cleaning method | |
| CN105951184A (en) | Texturing method of diamond wire-cut polycrystalline silicon wafer | |
| CN102153090B (en) | Boron gettering method for metallurgical N-type polycrystalline silicon chip | |
| CN108649098A (en) | A kind of method of silicon chip single side etching polishing | |
| CN106733876B (en) | A kind of cleaning method of the crystal silicon chip of Buddha's warrior attendant wire cutting | |
| Liu et al. | Analysis of sawing characteristics of fine diamond wire slicing multicrystalline silicon | |
| CN102062733B (en) | Method for detecting surface residues of cleaned solar silicon wafer | |
| CN102153089B (en) | Method for gettering phosphorus in N-type polysilicon slice by metallurgical method | |
| CN108407118A (en) | A kind of diamond cutting line slicing machine | |
| CN105826410B (en) | A kind of polysilicon etching method for eliminating Buddha's warrior attendant wire cutting trace | |
| CN103806108A (en) | Improved crystalline silicon battery slice cleaning process | |
| CN102509707A (en) | Process of carrying out passivation protection on rectification chip by use of polyimide | |
| CN116536116A (en) | Microbubble cleaning solution and method for using same | |
| CN104299890A (en) | Method for cleaning ferrotungsten metal ions on surface of silicon wafer | |
| CN103236406B (en) | A kind of method detecting polycrystalline silicon wafer dislocation density | |
| CN103436387A (en) | Rough polishing cleaning fluid used before etching of monocrystal silicon chip | |
| CN208263217U (en) | A kind of diamond cutting line slicing machine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130619 Termination date: 20170810 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |