CN101021480A - Coloration method for detecting sorting waste silicon material - Google Patents

Coloration method for detecting sorting waste silicon material Download PDF

Info

Publication number
CN101021480A
CN101021480A CN 200610155647 CN200610155647A CN101021480A CN 101021480 A CN101021480 A CN 101021480A CN 200610155647 CN200610155647 CN 200610155647 CN 200610155647 A CN200610155647 A CN 200610155647A CN 101021480 A CN101021480 A CN 101021480A
Authority
CN
China
Prior art keywords
silicon material
silicon
solution
coloration
acid
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
Application number
CN 200610155647
Other languages
Chinese (zh)
Inventor
吴云才
刘磊磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Yuhui Yangguang Energy Resources Co Ltd
Original Assignee
Zhejiang Yuhui Yangguang Energy Resources Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Yuhui Yangguang Energy Resources Co Ltd filed Critical Zhejiang Yuhui Yangguang Energy Resources Co Ltd
Priority to CN 200610155647 priority Critical patent/CN101021480A/en
Publication of CN101021480A publication Critical patent/CN101021480A/en
Pending legal-status Critical Current

Links

Landscapes

  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention belongs to testing technology of silicon, especially relates to a coloration method for testing grade abandoned silicon. (1) Prepare coloration solvent: mix hydrogen fluoride, nitric acid, acetum and pure water with a volume ratio of 1:3:6-9:4-6 into an acid-proof gutter. (2) Weigh clean abandoned silicon and put it into acid-proof basket. (3) Put basket into acid-proof gutter containing coloration solvent and stir silicon. (4) Immerse for 3-8 minutes for silicon coloring and move away basket. (5) Wash silicon in basket (PH of washed solution is 7) and dry silicon. Coloration solvent prepared using this method can separate low-density impure qualified materials from high-density impure heavy doped materials quickly without testing silicon one by one manually, which improves grading efficiency and accuracy, saves costly investment in testing apparatuses and reduces production cost.

Description

A kind of coloration method that is used to detect sorting waste silicon material
Technical field
The invention belongs to silicon material detection technique field, particularly a kind of coloration method that is used to detect sorting waste silicon material.
Background technology
At present, sun power changes the widespread use of electrical energy devices, the raw material supply day of solar level silicon materials is becoming tight, and the recycling of useless silicon materials becomes an important source of solar power silicon raw material, reclaims useless silicon material for alleviating the short significant of silicon raw material.
Because the useless silicon material that reclaims contains the heavily doped material and the rich buildup of impurity of low-resistivity high-concentration dopant, so need carry out to use after resistivity and the conductivity model detection to it.Detection resistivity and conductivity model mainly rely on manually and are undertaken piecewise or by grain ground at present, need a large amount of conductivity model instrument and four point probe resistivity detector, and labour that need be a large amount of, make solar power silicon material recovery industry become labour concentrated industry.And little to the particle diameter of silicon material in some reclaimed materials, its detection difficulty is bigger, efficient is lower.Moreover omission and workman detect main points and grasp deficiency, and the accuracy rate of detection is reduced greatly, and it is just secure to need process to recheck, and is again to cause the situation that efficient is low, accuracy rate is low.In addition, the silicon material of rich long-pending impurity in the crucible flavoring food only depended on to detect resistivity be not enough, and if every flavoring food is all made the ICP purity analysis, cost is very high, does not meet the production demand.Sub-elect qualified useless silicon material so need a kind of detection method for separating simple, accurate, that efficient is high of searching badly, to overcome the above-mentioned many shortcomings that exist.
Summary of the invention
The objective of the invention is to disclose the coloration method that is used to detect sorting waste silicon material of a kind of few labour, high-level efficiency, high-accuracy.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of coloration method that is used to detect sorting waste silicon material, and 1. allocate chromophoric solution: hydrogen fluoride, nitric acid, acetum and pure water 1: 3: 6 by volume～9: 4～6 places acidproof groove mixed;
2. take by weighing the useless silicon material of cleaning, contain in the acidproof hand basket;
3. will insert in the acidproof groove that fills chromophoric solution the stir silicon material with the hand basket of useless silicon material;
4. soaked 3-8 minute in chromophoric solution, the colour developing of silicon material is removed hand basket from acidproof groove;
5. the silicon material in the water flushing hand basket is treated washing lotion PH=7, oven dry silicon material.
The described coloration method that is used to detect sorting waste silicon material, each component concentrations is in the chromophoric solution: hydrogen fluoride solution 48-50%, salpeter solution 68-72%, acetum 98-99%.
The described coloration method that is used to detect sorting waste silicon material, each component concentrations is in the chromophoric solution: hydrogen fluoride solution 49%, salpeter solution 68%, acetum 98.5%.
The described coloration method that is used to detect sorting waste silicon material, chromophoric solution adds the hydrogen peroxide of liquor capacity 0.8-1.5% through repeatedly soaking the silicon material.
The described coloration method that is used to detect sorting waste silicon material, the volume of hydrogen peroxide be solution 1%, concentration 33%.
The principle of the invention is as follows: when semiconductor silicon contains impurity, its galvanochemistry potential energy and surfactivity also change thereupon, heavily doped material is bigger and fast with acid liquid reaction speed than the chemical potential of light spike, and the heavily doped material and the colour-developing solvent of the accept of low concentration doping and high-concentration dopant have had optionally corrosive effect; Because the P type is different with N type impurities kind in the heavily doped material, galvanochemistry potential energy is also different, therefore and the corrosive liquid reaction rate inequality, solution at first with heavily doped material reaction, make heavily doped material surface generation one deck SiO 2Film is along with SiO 2Film thickens, and Show Color also changes thereupon, and the heavily doped material of P type shows black-and-blue SiO 2Film, the heavily doped material of N type shows filemot SiO 2Film, take out the silicon material and clean and oven dry SiO this moment from solution 2The film color is clear, and not can because of the oven dry and mechanical friction fade.
Chemical reaction mechanism of the present invention:
Chromophoric solution is made up of hydrogen fluoride solution, salpeter solution, acetum and high purity water.
1, HNO 3Reaction generates SiO with Si 2, add HF reaction velocity is accelerated, make the SiO of generation 2The film colour developing is also visual.
Si+2HNO 3→SiO 2+2HNO 2
2HNO 2→NO+NO 2+H 2O
2, adjust CH within the specific limits 3COOH content, the effect of control selective reaction, CH 3COOH, H 2O slows down agent.Add CH 3COOH, H 2O makes reaction rate be controlled and make SiO in order to suppress subsidiary reaction 2Film is not interfered by following subsidiary reaction when chromogenic reaction and is faded:
SiO 2+6HF→H 2SiF+H 2O
Si+HNO 3+6HF→H 2SiF+HNO 2+H 2+H 2O
3, add the activating agent oxydol H 2O 2Reaction principle
Solution repeatedly uses HNO in the solution 3Loss is many, and resultant of reaction HNO 2Concentration increase, make solution to resistivity little silicon materials corrosion select than reducing, color developing effect is not obvious, adds H this moment 2O 2Make HNO 2Be converted into HNO 3, recover the solution activity.
HNO 2+H 2O 2→HNO 3+H 2O
Coloration method of the present invention is by allotment chromophoric solution and control temperature and reaction time, solution is selected than reaching maximum the corrosion of the little silicon materials of resistivity, promptly at the appointed time with the speed of heavily doped material reaction much larger than with the reaction velocity of light spike, and the speed of control subsidiary reaction, make subsidiary reaction not influence color developing effect, thereby the heavily doped silicon material surface selectivity oxidation that solution is little with resistivity, the thickness of oxide film is controlled by the ratio and the oxidization time of each component of solution.The SiO that reaction generates 2When the film Show Color reaches the easiest distinctive points, the silicon material is taken out and oven dry, the color of showing according to the silicon material sub-elects heavily doped material then, and accept cleans the back and drops into single crystal growing furnace crystal pulling or ingot casting, makes it satisfy the technical indicator of solar energy level silicon material.Adopt the present invention to come sorting silicon material, saved prior art by manually pursuing a grain ground testing process piecewise, apace the heavily doped material of the accept of low concentration doping and high-concentration dopant is distinguished, the efficiency of separation and accuracy rate have been improved, and the input of having saved expensive detecting instrument, reduced production cost.
If the particle diameter of silicon is 5～12mm, chromophoric solution can make the silicon material colour developing of about 10 times of own wts.After solution repeatedly used, the active and color developing effect reduction of solution added the oxydol H about one of liquor capacity percentage this moment 2O 2Prolong the serviceable life of chromophoric solution; Replenish about five times hydrogen peroxide, solution can make the silicon material colour developing that is equivalent to about 20 times of own wts at least.
Embodiment
Below the embodiment of the invention is elaborated.
Embodiment 1:
1. under 20 ℃ of conditions of room temperature, in the acidproof groove of fuming cupboard, press following proportional arrangement chromophoric solution: HF: HNO 3: CH 3COOH: H 2O=1: 3: 8: 5, wherein the concentration of each component solution was as follows: hydrogen fluoride HF48%, nitric acid HNO 372%, acetic acid CH 3COOH99%, high purity water amount to 17 liters;
2. through surface clean clean contain heavily doped P type integrated circuit broken silicon wafers, thickness is 220～800 microns, particle diameter is 5～80 millimeters, takes by weighing 1.7 kilograms and puts into acidproof hand basket;
3. drop in the solution of acid tank and soak, stir gently with acidproof sticking plaster;
4. through after 5 minutes, the heavily doped material of P type becomes mazarine, then hand basket is removed;
5. take out the residual acid that water behind the hand basket washes away silicon chip, and check with the PH test paper whether acid solution is rinsed well, when the PH=7 of washing fluid, stop flushing, silicon chip is put into baking oven oven dry back by the colour sorting that manually manifests according to the silicon material.After aforesaid operations finishes, since the 2. above step of step repetition.
When silicon chip is dipped into 170 kilograms, in solution, replenish 170 milliliters, concentration and be 33% H 2O 2Continue to use.40 kilograms of silicon chips of later every immersion replenish 170 milliliters of H 2O 2, when silicon material immersion total amount reaches 330 kilograms, solution is cancelled.
The oven dry of the silicon material of colour developing, through artificial separation, the heavily doped material of colour developing is selected, with each 60 kilograms of single crystal growing furnaces that drop into behind the qualified silicon material cleaning, drying, pull out the diameter 150mm monocrystalline of monocrystalline, about 1 meter of length.Detecting resistivity is 1～1.1 Ω .cm, and conductivity model is the P type, has reached the technical indicator of solar energy level silicon material requirement.
Do the rust cleaning of mordant or metal surface when lean solution can be used for reclaiming other silicon chip, spent acid solution is handled by national spent acid emission standard.
Embodiment 2:
1. under 20 ℃ of conditions, in the acidproof groove of fuming cupboard, by following proportional arrangement chromophoric solution: HF: HNO 3: CH 3COOH: H 2O=1: 3: 7: 6, wherein each component solution concentration was as follows: hydrogen fluoride HF49%, nitric acid HNO 369%, acetic acid CH 3COOH98.5%, pure water amount to 17 liters;
2. the surface is through the P type broken silicon wafers of cleaning, and thickness is 220～800 microns, and particle diameter is 5～20 millimeters, takes by weighing 1.7 kilograms and puts into acidproof hand basket;
3. drop into then in the solution of acid tank and soak, stir gently with acidproof sticking plaster;
4. through after 4 minutes, the variable color of heavily doped silicon material, P type resistivity becomes mazarine less than the heavily doped material of 0.5 Ω .cm, then hand basket is removed;
5. water washes away residual acid after taking out hand basket, and checks with the PH test paper whether acid solution is rinsed well, when the PH=7 of washing fluid, stops flushing, and silicon chip is put into baking oven oven dry back by the colour sorting that manually manifests according to the silicon material.After above-mentioned steps finishes, since the 2. above step of step repetition.
When being dipped into 160 kilograms, in solution, mend 170 milliliters of H 2O 2Continue to use.Later every immersion is mended 170 milliliters of H for 30 kilograms 2O 2, when immersion silicon material total amount reaches 280 kilograms solution is cancelled.
The oven dry of the silicon material of colour developing, through artificial separation, the heavily doped material of dyeing is selected, throw 60 kilograms with each behind the qualified silicon material cleaning, drying, pull out the diameter 150mm monocrystalline of monocrystalline, about 1 meter of length.Detecting resistivity is 2.8～3.0 Ω .cm, and conductivity model is the P type, has reached the technical indicator of solar energy level silicon material requirement.
Embodiment 3:
1. under 20 ℃ of conditions, in the acidproof groove of fuming cupboard, by following proportional arrangement chromophoric solution: HF: HNO 3: CH 3COOH: H 2O=1: 3: 9: 6, wherein the concentration of each component solution was as follows: hydrogen fluoride HF48.5%, nitric acid HNO 368.5%, acetic acid CH 3COOH98% amounts to 17 liters;
2. through surface clean clean contain heavily doped integrated circuit broken silicon wafers based on the P type, thickness is 220～800 microns, particle diameter is 5～12 millimeters, takes by weighing 1.7 kilograms and puts into acidproof hand basket;
3. drop into then in the solution of acid tank and soak, stir gently with acidproof sticking plaster;
4. through after 6 minutes, the variable color of heavily doped silicon material, P type resistivity becomes mazarine less than the heavily doped material of 0.5 Ω .cm, then hand basket is removed;
5. water washes away residual acid after taking out hand basket, and checks with the PH test paper whether acid solution is rinsed well, when the PH=7 of washing fluid, stops flushing, and silicon chip is put into baking oven oven dry back by the colour sorting that manually manifests according to the silicon material.After aforesaid operations finishes, since the 2. above step of step repetition.
When being dipped into 180 kilograms, in solution, mend 170 milliliters of H 2O 2Continue to use.Later every immersion is mended 170 milliliters of H for 60 kilograms 2O 2, when immersion silicon material total amount reaches 300 kilograms solution is cancelled.
The oven dry of the silicon material of colour developing,, the heavily doped material of dyeing is selected then, thrown 60 kilograms, pull out the diameter 150mm monocrystalline of monocrystalline, about 1 meter of length each behind the qualified silicon material cleaning, drying through artificial separation.Detecting resistivity is 2.0～2.1 Ω .cm, and conductivity model is the P type, has reached the technical indicator of solar energy level silicon material requirement.
Embodiment 4:
1. under 22 ℃ of conditions, in the acidproof groove of fuming cupboard, by following proportional arrangement chromophoric solution: HF: HNO 3: CH 3COOH: H 2O=1: 3: 7.5: 4, wherein the concentration of each component solution was as follows: hydrogen fluoride HF50%, nitric acid HNO 371%, acetic acid CH 3COOH99% amounts to 20 liters;
2. through surface clean clean contain heavily doped integrated circuit broken silicon wafers based on the N type, thickness is 220～800 microns, particle diameter is 5～12 millimeters, takes by weighing 2 kilograms and puts into acidproof hand basket;
3. drop into then in the solution of acid tank and soak, stir gently with acidproof sticking plaster;
4. through after 6 minutes, the variable color of heavily doped silicon material, N type resistivity becomes tawny less than the heavily doped material of 0.4 Ω .cm, then hand basket is removed;
5. water washes away residual acid after taking out hand basket, and checks with the PH test paper whether acid solution is rinsed well, when the PH=7 of washing fluid, stops flushing, and silicon chip is put into baking oven oven dry back by the colour sorting that manually manifests according to the silicon material.
After above-mentioned steps is finished, since the 2. above step of step repetition.When being dipped into 210 kilograms, in solution, mend 200 milliliters of H 2O 2Continue to use.
Embodiment 5:
1. under 18 ℃ of conditions, in the acidproof groove of fuming cupboard, by following proportional arrangement chromophoric solution: HF: HNO 3: CH 3COOH: H 2O=1: 3: 7.5: 4, wherein the concentration of each component solution was as follows: hydrogen fluoride HF49.5%, nitric acid HNO 370%, acetic acid CH 3COOH98.5% amounts to 15 liters;
2. through the heavily doped integrated circuit broken silicon wafers based on the N type that contains of surface clean, thickness is 220～800 microns, and particle diameter is 5～12 millimeters, takes by weighing 1.5 kilograms and puts into acidproof hand basket;
3. drop into then in the solution of acid tank and soak, stir gently with acidproof sticking plaster;
4. through after 6 minutes, the heavily doped material of N type becomes tawny, then hand basket is removed;
5. water washes away residual acid after taking out hand basket, and checks with the PH test paper whether acid solution is rinsed well, when the PH=7 of washing fluid, stops flushing, with silicon chip oven dry back by the colour sorting that manually manifests according to the silicon material.
After above-mentioned steps is finished, since the 2. above step of step repetition.When being dipped into 150 kilograms, in solution, mend 150 milliliters of H 2O 2Continue to use.
Embodiment 6:
1. under 19 ℃ of conditions, in the acidproof groove of fuming cupboard, by following proportional arrangement chromophoric solution: HF: HNO 3: CH 3COOH: H 2O=1: 3: 7.5: 4, wherein concentration was as follows: hydrogen fluoride HF49.5%, nitric acid HNO 371%, acetic acid CH 3COOH98% amounts to 18 liters;
2. pass through the N type broken silicon wafers of surface clean, thickness is 220～800 microns, and particle diameter is 5～12 millimeters, takes by weighing 1.8 kilograms and puts into acidproof hand basket;
3. drop into then in the solution of acid tank and soak, stir gently with acidproof sticking plaster;
4. through after 3 minutes, the variable color of heavily doped silicon material, N type resistivity becomes tawny less than the heavily doped material of 0.4 Ω .cm, then hand basket is removed;
5. water washes away residual acid after taking out hand basket, and checks with the PH test paper whether acid solution is rinsed well, when the PH=7 of washing fluid, stops flushing, and silicon chip is put into baking oven oven dry back by the colour sorting that manually manifests according to the silicon material.
After aforesaid operations finishes, since the 2. above step of step repetition.When being dipped into 180 kilograms, in solution, mend 180 milliliters of H 2O 2Continue to use.

Claims (5)

1, a kind of coloration method that is used to detect sorting waste silicon material is characterized in that:
1. allocate chromophoric solution: hydrogen fluoride, nitric acid, acetum and pure water 1: 3: 6 by volume～9: 4～6 places acidproof groove mixed;
2. take by weighing the useless silicon material of cleaning, contain in the acidproof hand basket;
3. will insert in the acidproof groove that fills chromophoric solution the stir silicon material with the hand basket of useless silicon material;
4. soaked 3-8 minute in chromophoric solution, the colour developing of silicon material is removed hand basket from acidproof groove;
5. the silicon material in the water flushing hand basket is treated washing lotion PH=7, oven dry silicon material.
2, the coloration method that is used to detect sorting waste silicon material according to claim 1, it is characterized in that: each component concentrations is in the chromophoric solution: hydrogen fluoride solution 48-50%, salpeter solution 68-72%, acetum 98-99%.
3, the coloration method that is used to detect sorting waste silicon material according to claim 2, it is characterized in that: each component concentrations is in the chromophoric solution: hydrogen fluoride solution 49%, salpeter solution 68%, acetum 98.5%.
4, the coloration method that is used to detect sorting waste silicon material according to claim 1 is characterized in that: the hydrogen peroxide that adds liquor capacity 0.8-1.5% in the chromophoric solution.
5, the coloration method that is used to detect sorting waste silicon material according to claim 4 is characterized in that: the volume of hydrogen peroxide be solution 1%, concentration 33%.
CN 200610155647 2006-12-30 2006-12-30 Coloration method for detecting sorting waste silicon material Pending CN101021480A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200610155647 CN101021480A (en) 2006-12-30 2006-12-30 Coloration method for detecting sorting waste silicon material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200610155647 CN101021480A (en) 2006-12-30 2006-12-30 Coloration method for detecting sorting waste silicon material

Publications (1)

Publication Number Publication Date
CN101021480A true CN101021480A (en) 2007-08-22

Family

ID=38709314

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200610155647 Pending CN101021480A (en) 2006-12-30 2006-12-30 Coloration method for detecting sorting waste silicon material

Country Status (1)

Country Link
CN (1) CN101021480A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102004101A (en) * 2010-09-20 2011-04-06 邢台晶龙电子材料有限公司 Chromogenic solution and method for distinguishing P/N-type silicone materials
CN104624512A (en) * 2015-01-21 2015-05-20 江西久顺科技有限公司 Method for sorting P-type heavy-doped silicon material and N-type heavy-doped silicon material in dyeing manner

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102004101A (en) * 2010-09-20 2011-04-06 邢台晶龙电子材料有限公司 Chromogenic solution and method for distinguishing P/N-type silicone materials
CN102004101B (en) * 2010-09-20 2012-10-10 邢台晶龙电子材料有限公司 Chromogenic solution and method for distinguishing P/N-type silicone materials
CN104624512A (en) * 2015-01-21 2015-05-20 江西久顺科技有限公司 Method for sorting P-type heavy-doped silicon material and N-type heavy-doped silicon material in dyeing manner

Similar Documents

Publication Publication Date Title
Robbins et al. Chemical etching of silicon: II. The system, and
CN100561683C (en) A kind of chemical passivation method of measuring crystalline silicon body minority carrier life time
CN104359737B (en) The method of testing of crystalline silicon body minority carrier life time
CN1947869A (en) Method for cleaning silicon material
CN105449045B (en) Surface micro corrosion cleaning method applicable for crystal silicon wafer after RIE (Reactive Ion Etching) texturing
CN102020280B (en) Method for inhibiting yellow smog during pickling of silicon materials
Lippold et al. HF-HNO3-H2SO4/H2O mixtures for etching multicrystalline silicon surfaces: formation of NO2+, reaction rates and surface morphologies
CN102515555B (en) Quartz crucible surface processing method
CN101021480A (en) Coloration method for detecting sorting waste silicon material
CN109309142B (en) Liquid source diffusion process before silicon wafer glass passivation
CN102040222B (en) Method for separating silicon material from heavily doped silicon material
JPS6056289B2 (en) Method and detection solution for detecting crystal defects in semiconductor silicon
CN102004101B (en) Chromogenic solution and method for distinguishing P/N-type silicone materials
CN101021481A (en) Colour-developing solvent for detecting sorting waste silicon material
CN109457292A (en) Utilize the method for gallium doped monocrystaline silicon reclaimed materials production low light attenuation pulling of crystals silicon rod
CN112447544B (en) Silicon wafer quality detection method and classification method
CN113188983A (en) Deviation<100>Crystal orientation 9oDislocation density measuring method for germanium single crystal wafer
CN103236406A (en) Method for detecting polycrystalline silicon wafer dislocation density
Syvertsen et al. Recycling of broken Si based structures and solar cells
Sopori et al. Wafer preparation and iodine-ethanol passivation procedure for reproducible minority-carrier lifetime measurement
CN113145553A (en) Classifying method for cast monocrystalline silicon wafers
CN112680229A (en) Silicon-based material etching solution for wet electron chemistry and preparation method thereof
CN103000544B (en) A kind of circulation utilization method of phosphorus boron prediffused technique test pieces
CN111040766A (en) Polycrystalline silicon wafer texturing solution, preparation method of black silicon material and application of black silicon material in accelerating PERC battery LeTID recovery
CN116791202A (en) OiSF defect corrosive liquid without heavy metal participation and defect testing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Open date: 20070822