CN102653887A - Treatment method and etching method of crystalline silicon wafer with oil stains - Google Patents
Treatment method and etching method of crystalline silicon wafer with oil stains Download PDFInfo
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- CN102653887A CN102653887A CN2011100602286A CN201110060228A CN102653887A CN 102653887 A CN102653887 A CN 102653887A CN 2011100602286 A CN2011100602286 A CN 2011100602286A CN 201110060228 A CN201110060228 A CN 201110060228A CN 102653887 A CN102653887 A CN 102653887A
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- silicon chip
- crystal silicon
- greasy dirt
- etching method
- etching
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000005530 etching Methods 0.000 title claims abstract description 26
- 239000003921 oil Substances 0.000 title abstract description 9
- 229910021419 crystalline silicon Inorganic materials 0.000 title abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 65
- 239000010703 silicon Substances 0.000 claims description 65
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000013078 crystal Substances 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 235000008216 herbs Nutrition 0.000 claims description 27
- 210000002268 wool Anatomy 0.000 claims description 27
- 238000000137 annealing Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 11
- 238000007669 thermal treatment Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
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Abstract
The invention provides a treatment method and an etching method of a crystalline silicon wafer with oil stains, belonging to the technical field of solar cell manufacturing. In the oil stain treatment method, the crystalline silicon wafer is subjected to heat treatment in an oxygen-containing gas atmosphere to remove the oil stains by oxidation. The etching method comprises the following steps: removing the oil stains on the crystalline silicon wafer with oil stains by oxidation after the primary etching, and carrying out secondary etching. The treatment method can effectively remove oil stains on the crystalline silicon wafer surface; and in the etching method using the treatment method, after the crystalline silicon wafer subjected to oil stain removal by oxidation is subjected to secondary etching, the crystalline silicon wafer subjected to the secondary etching can not have the phenomenon of defective color spots, thereby enhancing the quality of the etching finished product.
Description
Technical field
The invention belongs to solar cell manufacturing technology field, the etching method that relates to the treatment process of greasy dirt crystal silicon chip and use this treatment process.
Background technology
Because the finiteness that conventional energy resources is supplied with and the increase of environmental protection pressure; Many in the world countries have started the upsurge of development and use sun power and renewable energy source at present; Solar utilization technique has obtained fast development, wherein utilizes utilization that semi-conductive photovoltaic effect changes sun power into electric energy more and more widely.And crystal-silicon solar cell is exactly that wherein the most generally to be used to solar energy converting be the device of electric energy.
In the preparation process of crystal-silicon solar cell, mainly may further comprise the steps: (one) goes affected layer, making herbs into wool and cleaning; (2) diffusion preparation PN junction; (3) etching trimming; (4) diffusion back cleaning process; (5) preparation antireflective coating; (6) screen printing electrode; (7) sintering; (8) battery testing.Crystal-silicon solar cell through above process monolithic will form, and form solar module through assembly production then.
In above step (), must remove the affected layer and the dirt on crystal silicon chip surface earlier.Usually, promptly surperficial through the method for chemical reaction with 20% sodium hydroxide solution corrosion crystal silicon chip, peel off one deck silicon on crystal silicon chip surface, thereby reach the purpose of removing affected layer.In the making herbs into wool process, employing contains NaOH (sodium hydroxide), Na to monocrystalline silicon piece then
2SiO
3The Woolen-making liquid of (water glass) and IPA (Virahol) is made matte; Its principle is that sodium hydroxide is different to the corrosion speed in each crystal orientation of monocrystalline silicon sheet surface; Thereby cause monocrystalline silicon sheet surface to form rough state (state of preferable formation pyramid-like shape), Here it is so-called matte.The effect of matte is to make light at silicon chip surface generation multiple reflection, thereby increases the probability that light is injected crystal silicon chip, and monocrystalline silicon piece correspondingly obtains more energy.Therefore, making herbs into wool helps improving the efficiency of conversion of solar cell.
But, before the making herbs into wool production process, can form greasy dirt on the surface of crystal silicon chip (for example monocrystalline silicon piece) inevitably, for example, residual greasy dirt in the silicon chip cutting process, workman's misoperation, the greasy dirts such as fingerprint that caused by its finger contact.These greasy dirts (greasy dirt that particularly fingerprint caused) are to be difficult to remove through the method for the cleaning of the routine before making herbs into wool decontamination.And,, have fingerprint smeary crystal silicon chip and before making herbs into wool, be difficult to picked out if only judge from the silicon chip surface outward appearance.Therefore; In the prior art, have the sector-meeting of smeary crystalline silicon by unified making herbs into wool, the matte (for example pyramid structure) that on crystal silicon chip, has a zone at greasy dirt place and other normal region be difference to some extent; Can form shade deviation in appearance, it is bad that it is collectively referred to as color spot.And then this color spot bad phenomenon can reduce the quality grade of solar cell greatly.
In view of this, be necessary to propose a kind of smeary method that can effectively remove the crystal silicon chip surface.
Summary of the invention
The technical problem that the present invention will solve is to avoid because the crystal silicon chip surface after the making herbs into wool that greasy dirt caused forms bad phenomenon such as color spot.
For solving above technical problem, according to one side of the present invention, the treatment process of greasy dirt crystal silicon chip is provided, said crystal silicon chip is used to prepare solar cell, and wherein, said crystal silicon chip is heat-treated in the oxygen-containing gas atmosphere with the said greasy dirt of oxidation removal.
Preferably, said thermal treatment is accomplished in the annealing boiler tube.
Preferably; Said oxidation removal smeary processing condition comprise: the scope of the oxygen flow of feeding is 2000sccm (Standard-State Cubic Centimeter per Minute; Mark condition cubic centimetre PM) to 9000sccm; TR is 600 ℃ to 900 ℃, and the scope of holding time is 3-8 minute.
Preferably; Before the aerating oxygen oxidation removal greasy dirt and/or afterwards; Said thermal treatment also is included in the step that feeds nitrogen in 600 ℃ to the 900 ℃ TRs, and the flow range of said nitrogen is 10000sccm to 20000sccm, and the time range that feeds nitrogen is 3-10 minute.
According to another aspect of the present invention, a kind of etching method is provided, be used to prepare solar cell, it is characterized in that, may further comprise the steps:
(1) is provided for preparing the crystal silicon chip of solar cell;
(2) said crystal silicon chip being carried out the making herbs into wool first time handles;
(3) pick out the greasy dirt crystal silicon chip the said crystal silicon chip after the making herbs into wool first time is handled;
(4) said greasy dirt crystal silicon chip is heat-treated in the oxygen-containing gas atmosphere with the said greasy dirt of oxidation removal; And
(5) said greasy dirt crystal silicon chip being carried out the making herbs into wool second time handles.
Particularly, in said step (3), pick out the bad crystal silicon chip of color spot as said greasy dirt crystal silicon chip.
Preferably, said step (4) is accomplished in the annealing boiler tube.
Preferably, also comprise step between said step (4) and the step (5):
(4a) take out said greasy dirt crystal silicon chip and cool off from said annealing boiler tube.
Preferably, oxidation removal smeary processing condition comprise described in the said step (4): the scope of the oxygen flow of feeding is 2000sccm to 9000sccm, and TR is 600 ℃ to 900 ℃, and the scope of holding time is 3-8 minute.
Preferably; Before the aerating oxygen oxidation removal greasy dirt and/or afterwards; Said thermal treatment also is included in the step that feeds nitrogen in 600 ℃ to the 900 ℃ TRs, and the flow range of said nitrogen is 10000sccm to 20000sccm, and the time range that feeds nitrogen is 3-10 minute.
Technique effect of the present invention is; Can remove the greasy dirt on crystal silicon chip surface effectively through the greasy dirt treatment process; Use in the etching method of this treatment process; Handle through the greasy dirt crystal silicon chip is carried out the making herbs into wool second time behind the oxidation removal greasy dirt, the crystal silicon chip after making herbs into wool is for the second time handled the color spot bad phenomenon can not occur, has improved the final product quality of making herbs into wool greatly.
Description of drawings
Fig. 1 is the schematic flow sheet of the etching method of the solar cell that provides according to the embodiment of the invention.
Embodiment
What introduce below is some among a plurality of possibility embodiment of the present invention, aims to provide basic understanding of the present invention, is not intended to confirm key of the present invention or conclusive key element or limits claimed scope.Understand easily, according to technical scheme of the present invention, do not changing under the connotation of the present invention, but one of ordinary skill in the art can propose other implementation of mutual alternative.Therefore, following embodiment and accompanying drawing only are the exemplary illustrations to technical scheme of the present invention, and should not be regarded as qualification or the restriction to technical scheme of the present invention that all perhaps be regarded as of the present invention.
The schematic flow sheet of the etching method for the solar cell that provides according to the embodiment of the invention shown in Figure 1.In this embodiment, use the treatment process of greasy dirt crystal silicon chip provided by the invention simultaneously, thereby removed the greasy dirt on crystal silicon chip surface.In conjunction with shown in Figure 1, the etching method of this embodiment is elaborated.
At first, step S110 provides the crystal silicon chip that is used to prepare solar cell after routine is cleaned.
In this step, conventional purging method is the known technology of the technical field of solar cell preparing technical field, gives unnecessary details no longer one by one at this.The concrete quantity of crystal silicon chip is not restrictive, and crystal silicon chip can be monocrystalline silicon piece, and in other embodiments, it also can be polysilicon chip.In the present embodiment, be that monocrystalline silicon piece is that example describes with the crystal silicon chip.
Step S120 carries out the making herbs into wool first time with crystal silicon chip and handles.
In this step, the concrete grammar that making herbs into wool is for the first time handled is that those skilled in the art are known, gives unnecessary details no longer one by one at this.After step S120 accomplished, the crystal silicon chip surface formed the pattern of similar pyramid structure.Described in background technology, from the silicon chip external inspection, some have smeary greasy dirt crystal silicon chip before making herbs into wool be difficult to be not with smeary crystal silicon chip phase region other, therefore, in this step, unified carry out making herbs into wool and handle.
Step S130 picks out the bad crystal silicon chip of color spot as the greasy dirt crystal silicon chip the crystal silicon chip after the making herbs into wool first time is handled, and inserts then in the annealing boiler tube.
In this step; Because wherein some crystal silicon chip surface has greasy dirt (for example fingerprint pollutes the greasy dirt cause), after having the smeary crystal silicon chip and being handled by making herbs into wool, it is bad to show as color spot in appearance; Therefore; Can pick out the bad sample of color spot through the outward appearance performance, carry out next step greasy dirt treating processes so that insert the annealing boiler tube.In this embodiment, select to use the process of annealing boiler tube performing step S140, still, concrete employed equipment is not limited by the embodiment of the invention.
Step S140 heat-treats in the oxygen-containing gas atmosphere, with the greasy dirt on oxidation removal crystal silicon chip surface.
In this step, through sequencing be provided with annealing boiler tube processing condition, thereby the heat treatment process of automatically performing.Table 1 is depicted as the processing condition in the concrete preferred embodiment, and when using these processing condition, step S140 can be divided into four step S141, S142, S143, S144.
Table 1 thermal treatment process condition
Wherein, among the step S141, feed the nitrogen of 15000sccm in the annealing boiler tube, and the furnace tube temperature of will anneal is set at 800 ℃ basically, keeps about 8 minutes (as shown in table 1), thereby realize preheating and remove the original air atmosphere of boiler tube of annealing;
Among the step S142, feed the nitrogen of 15000sccm in the annealing boiler tube, and the furnace tube temperature of will anneal is set at 820 ℃ basically, keeps about 3 minutes (as shown in table 1), thereby realize oxidizing thermal treatment preparation before;
Among the step S143, change the oxygen that feeds 6000sccm in the annealing boiler tube into, and the furnace tube temperature of will anneal is set at 820 ℃ basically, keeps about 3 minutes (as shown in table 1), thereby realize the greasy dirt that the oxidation removal crystal silicon chip is surperficial; Wherein, preferably, the gas purity of oxygen requires more than or equal to 95% (concentration of volume percent); Being provided with of concrete processing condition can be provided with according to smeary weight situation, and in another interchangeable embodiment, heat treated TR can be 600 ℃ to 900 ℃, and the time of oxidizing thermal treatment process can be 3-8 minute; In an interchangeable embodiment again, the flow range of oxygen is 2000sccm to 9000sccm; Through this step S143, greasy dirt can oxidized and at high temperature volatilize and be removed;
Among the step S144, change the nitrogen that feeds 15000sccm in the annealing boiler tube into, and the furnace tube temperature of will anneal is set at 800 ℃ basically, keeps about 6 minutes (as shown in table 1), thereby realize the preparation before of coming out of the stove.
Need to prove that the heat treatment process of step S140 and processing condition are not limited by above embodiment, those skilled in the art can use other heat treatment process to realize the processing of surface and oil contaminant according to the enlightenment of last concrete technological process.
It will be appreciated by those skilled in the art that smeary particular type of the present invention is not restrictive, just in actual production process, more greasy dirt is the misoperation from the employee, and for example fingerprint pollutes the fingerprint greasy dirt that is caused.
Step S150 takes out crystal silicon chip and cools off from the annealing boiler tube.
Step S160 carries out the making herbs into wool second time and handles.
In this step, the process of making herbs into wool for the second time can adopt with the process of making herbs into wool for the first time and adopt identical processing condition and/or equipment, and concrete etching method process is not limited by the present invention.
So far, etching method process of the present invention is accomplished, thereby can remove the greasy dirt on crystal silicon chip surface fully, the color spot bad phenomenon can not occur, has improved the final product quality of making herbs into wool greatly.
In above procedure, step S140 has explained one of them specific embodiment of the greasy dirt treatment process that another aspect of the invention provides simultaneously.
Above example has mainly been explained greasy dirt treatment process of the present invention and etching method.Although only some of them embodiment of the present invention is described, those of ordinary skills should understand, and the present invention can be in not departing from its purport and scope implements with many other forms.Therefore, example of being showed and embodiment are regarded as schematic and nonrestrictive, are not breaking away under the situation of liking defined spirit of the present invention of each claim and scope enclosed, and the present invention possibly contained various modifications and replacement.
Claims (10)
1. the treatment process of a greasy dirt crystal silicon chip, said crystal silicon chip is used to prepare solar cell, it is characterized in that, and said crystal silicon chip is heat-treated in the oxygen-containing gas atmosphere with the said greasy dirt of oxidation removal.
2. treatment process as claimed in claim 1 is characterized in that, said thermal treatment is accomplished in the annealing boiler tube.
3. according to claim 1 or claim 2 treatment process is characterized in that said oxidation removal smeary processing condition comprise: the oxygen flow scope of feeding is 2000sccm to 9000sccm, and TR is 600 ℃ to 900 ℃, and the scope of holding time is 3-8 minute.
4. treatment process as claimed in claim 3; It is characterized in that; Before the aerating oxygen oxidation removal greasy dirt and/or afterwards; Said thermal treatment also is included in the step that feeds nitrogen in 600 ℃ to the 900 ℃ TRs, and the flow range of said nitrogen is 10000sccm to 20000sccm, and the time range that feeds nitrogen is 3-10 minute.
5. an etching method is used to prepare solar cell, it is characterized in that, may further comprise the steps:
(1) is provided for preparing the crystal silicon chip of solar cell;
(2) said crystal silicon chip being carried out the making herbs into wool first time handles;
(3) pick out the greasy dirt crystal silicon chip the said crystal silicon chip after the making herbs into wool first time is handled;
(4) said greasy dirt crystal silicon chip is heat-treated in the oxygen-containing gas atmosphere with the said greasy dirt of oxidation removal; And
(5) said greasy dirt crystal silicon chip being carried out the making herbs into wool second time handles.
6. etching method as claimed in claim 5 is characterized in that, in said step (3), picks out the bad crystal silicon chip of color spot as said greasy dirt crystal silicon chip.
7. etching method as claimed in claim 5 is characterized in that, said step (4) is accomplished in the annealing boiler tube.
8. etching method as claimed in claim 7 is characterized in that, also comprises step between said step (4) and the step (5):
(4a) take out said greasy dirt crystal silicon chip and cool off from said annealing boiler tube.
9. etching method as claimed in claim 5; It is characterized in that; Oxidation removal smeary processing condition comprise described in the said step (4): the scope of the oxygen flow of feeding is 2000sccm to 9000sccm, and TR is 600 ℃ to 900 ℃, and the scope of holding time is 3-8 minute.
10. etching method as claimed in claim 9; It is characterized in that; Before the aerating oxygen oxidation removal greasy dirt and/or afterwards; Said thermal treatment also is included in the step that feeds nitrogen in 600 ℃ to the 900 ℃ TRs, and the flow range of said nitrogen is 10000sccm to 20000sccm, and the time range that feeds nitrogen is 3-10 minute.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100602286A CN102653887A (en) | 2011-03-04 | 2011-03-04 | Treatment method and etching method of crystalline silicon wafer with oil stains |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269348A (en) * | 2014-09-26 | 2015-01-07 | 安庆美晶新材料有限公司 | Method for removing impurities attached to base material surface through annealing in low-pressure environment |
| CN105304756A (en) * | 2015-10-30 | 2016-02-03 | 湖南红太阳光电科技有限公司 | Reworked solar crystal silicon cell processing technology |
| CN107256907A (en) * | 2017-06-20 | 2017-10-17 | 常州亿晶光电科技有限公司 | Improve the annealing process of PERC high-efficiency battery piece outward appearance small particles |
| CN107394010A (en) * | 2017-08-14 | 2017-11-24 | 平煤隆基新能源科技有限公司 | A kind of method for annealing for reducing silicon chip film-coated hickie piece |
| CN113066903A (en) * | 2021-03-26 | 2021-07-02 | 常州时创能源股份有限公司 | Silicon wafer texturing process |
| CN113061991A (en) * | 2021-03-23 | 2021-07-02 | 韩华新能源（启东）有限公司 | Preparation method for improving pyramid texture surface uniformity of monocrystalline silicon wafer and solar cell |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269348A (en) * | 2014-09-26 | 2015-01-07 | 安庆美晶新材料有限公司 | Method for removing impurities attached to base material surface through annealing in low-pressure environment |
| CN105304756A (en) * | 2015-10-30 | 2016-02-03 | 湖南红太阳光电科技有限公司 | Reworked solar crystal silicon cell processing technology |
| CN105304756B (en) * | 2015-10-30 | 2017-05-17 | 湖南红太阳光电科技有限公司 | Reworked solar crystal silicon cell processing technology |
| CN107256907A (en) * | 2017-06-20 | 2017-10-17 | 常州亿晶光电科技有限公司 | Improve the annealing process of PERC high-efficiency battery piece outward appearance small particles |
| CN107394010A (en) * | 2017-08-14 | 2017-11-24 | 平煤隆基新能源科技有限公司 | A kind of method for annealing for reducing silicon chip film-coated hickie piece |
| CN113061991A (en) * | 2021-03-23 | 2021-07-02 | 韩华新能源（启东）有限公司 | Preparation method for improving pyramid texture surface uniformity of monocrystalline silicon wafer and solar cell |
| CN113066903A (en) * | 2021-03-26 | 2021-07-02 | 常州时创能源股份有限公司 | Silicon wafer texturing process |
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Application publication date: 20120905 |