CN102728573A - Process for cleaning damage layer of reactive ion etching (RIE) flocking surface of crystalline silicon - Google Patents
Process for cleaning damage layer of reactive ion etching (RIE) flocking surface of crystalline silicon Download PDFInfo
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- CN102728573A CN102728573A CN2012102029132A CN201210202913A CN102728573A CN 102728573 A CN102728573 A CN 102728573A CN 2012102029132 A CN2012102029132 A CN 2012102029132A CN 201210202913 A CN201210202913 A CN 201210202913A CN 102728573 A CN102728573 A CN 102728573A
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Abstract
The invention discloses a process for cleaning a damage layer of the reactive ion etching (RIE) flocking surface of crystalline silicon. The process comprises the following steps of: (1) precleaning the damage layer of the surface, which is etched by RIE, of a silicon wafer by using deionized water; (2) preparing a cleaning solution, wherein the cleaning solution is a mixed solution of HF, HCl and H2O2, and a volume ratio of the HF to the HCl to the H2O2 is (3-15):(3-15):(1-5); and (3) cleaning the damage layer of the silicon wafer for 4 to 15 minutes by using the cleaning solution so as to remove the damage layer. According to the cleaning process, the speed of etching the damage layer is low, and a flock structure on the surface of the silicon wafer is not influenced in the etching process, so the process is suitable for the damage removal process of a refined surface structure which is subjected to the RIE flocking of the crystalline silicon; the process is simple, alkaline washing and secondary acid washing are avoided, the process flow is reduced greatly, raw materials are saved, the production cost is reduced, and the process is suitable for industrial production; and the discharge of effluent is reduced substantially, and the burden of subsequent treatment is relieved.
Description
Technical field
The present invention relates to the silicon crystal cleaning, particularly be set to a kind of cleaning of crystalline silicon RIE making herbs into wool surface damage layer.
Background technology
In order to improve the efficient of photovoltaic generation, reduce the cost of photovoltaic generation, be making herbs into wool so introduced surperficial texture technology.It reduces surface reflectivity through increasing the absorption of battery to light, and the short circuit current that increases solar cell is to reach the purpose that improves efficiency of solar cell.People have attempted many new process for etching, like mechanical carving groove, reactive ion etching, honeycomb suede structure technology, electrochemical corrosion etc.At present, reactive ion etching method (RIE) is used more in industrialization is produced, and it can form more meticulous suede structure on the coarse matte that obtains after the common process making herbs into wool, reduce reflectivity greatly, improves battery efficiency.
But RIE making herbs into wool also has its weak point, wherein, after topmost problem is making herbs into wool, forms the damage layer at silicon chip surface, and thickness is at 0.1-0.4 μ m., the crystal silicon solar energy battery industrialization generally can adopt strong basicity (NaOH, KOH) in producing at present; Or the aqueous solution of highly acid (HF+HNO3) chemicals cleans the damage layer of silicon chip surface; Basic step is: (remove surface damage layer with HF+HNO3+H2O pickling earlier; Generate SiO2) → NaOH or KOH alkali cleaning (remove the porous silicon that generates after the pickling, in remained on surface acid solution) → HF pickling (remove SiO2, in remained on surface alkali lye).Overetch can occur but these routines remove to damage layer process, influence the sunken light effect of silicon chip surface.
Summary of the invention
The object of the invention promptly is to overcome the deficiency of present technology; A kind of cleaning of crystalline silicon RIE making herbs into wool surface damage layer is provided; Solve prior art and when cleaning silicon chip damage layer, excessive etching occurs, thereby have influence on the shortcoming of the sunken light effect of silicon chip surface because of easy.
The present invention realizes through following technical scheme: a kind of cleaning of crystalline silicon RIE making herbs into wool surface damage layer may further comprise the steps:
(1) damage of the silicon chip surface after RIE etching layer is carried out deionized water surface prerinse;
(2) preparation cleaning solution, this cleaning solution is HF, HCl and H
2O
2Mixed solution, and HF, HCl and H
2O
2Be 3～15:3～15:1～5 by volume;
(3) use the middle cleaning solution for preparing of step (2) that silicon chip is removed to damage layer and clean 4～15min, surperficial damage layer after the removal RIE etching, the recombination rate of reduction photo-generated carrier;
(4) with deionized water silicon chip is cleaned, it is subsequent use to dry the back again.
Further, in the cleaning solution described in the above-mentioned steps (2), adopt HF, HCl and H
2O
2Volume ratio is 3: 7:2, scavenging period 5～6min, the best results of cleaning like this.
The invention has the beneficial effects as follows:
(1) cleaning of the present invention is slower to the etch rate of damage layer, guarantees the silicon chip surface suede structure not to be exerted an influence in etching process, be applicable to crystalline silicon RIE making herbs into wool the surface texture that becomes more meticulous go damage process;
(2) technical process is simple, need not to have significantly reduced technological process through alkali cleaning and white picking, has saved raw material, lowers production cost, is fit to industrialization production;
(3) the discharging of waste liquid amount significantly reduces, and has alleviated the burden of subsequent treatment, helps the optimization of industry industry, and extraordinary development prospect is arranged.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment:
[embodiment 1]
A kind of cleaning of crystalline silicon RIE making herbs into wool surface damage layer may further comprise the steps:
(1) damage of the silicon chip surface after RIE etching layer is carried out deionized water surface prerinse;
(2) preparation cleaning solution, this cleaning solution is HF, HCl and H
2O
2Mixed solution, and HF, HCl and H
2O
2Be 3:3:1 by volume;
(3) use the middle cleaning solution for preparing of step (2) that silicon chip is removed to damage layer and clean 15min, surperficial damage layer after the removal RIE etching, the recombination rate of reduction photo-generated carrier;
(4) with deionized water silicon chip is cleaned, it is subsequent use to dry the back again.
The minority carrier life time that cleans the silicon chip after accomplishing through present embodiment is 4.53 μ s
[embodiment 2]
A kind of cleaning of crystalline silicon RIE making herbs into wool surface damage layer may further comprise the steps:
(1) damage of the silicon chip surface after RIE etching layer is carried out deionized water surface prerinse;
(2) preparation cleaning solution, this cleaning solution is HF, HCl and H
2O
2Mixed solution, and HF, HCl and H
2O
2Be 3:7:2 by volume;
(3) use the middle cleaning solution for preparing of step (2) that silicon chip is removed to damage layer and clean 6min, surperficial damage layer after the removal RIE etching, the recombination rate of reduction photo-generated carrier;
(4) with deionized water silicon chip is cleaned, it is subsequent use to dry the back again.
The minority carrier life time that cleans the silicon chip after accomplishing through present embodiment is 8.2 μ s.
[embodiment 3]
A kind of cleaning of crystalline silicon RIE making herbs into wool surface damage layer may further comprise the steps:
(1) damage of the silicon chip surface after RIE etching layer is carried out deionized water surface prerinse;
(2) preparation cleaning solution, this cleaning solution is HF, HCl and H
2O
2Mixed solution, and HF, HCl and H
2O
2Be 15:15:1 by volume;
(3) use the middle cleaning solution for preparing of step (2) that silicon chip is removed to damage layer and clean 4min, surperficial damage layer after the removal RIE etching, the recombination rate of reduction photo-generated carrier;
(4) with deionized water silicon chip is cleaned, it is subsequent use to dry the back again.
The minority carrier life time that cleans the silicon chip after accomplishing through present embodiment is 5.97 μ s.
This cleaning does not have influence basically to the reflectivity of silicon chip, and the minority carrier life time of silicon chip can reach 4～9 μ s, and compared with having minority carrier life time 3～5 μ s that cleaning technique obtains silicon chip now, effect has greatly improved.
Claims (3)
1. the cleaning of a crystalline silicon RIE making herbs into wool surface damage layer is characterized in that: may further comprise the steps:
(1) damage of the silicon chip surface after RIE etching layer is carried out deionized water surface prerinse;
(2) preparation cleaning solution, this cleaning solution is HF, HCl and H
2O
2Mixed solution, and HF, HCl and H
2O
2Be 3～15:3～15:1～5 by volume;
(3) use the middle cleaning solution for preparing of step (2) that silicon chip is removed to damage layer and clean 4～15min, surperficial damage layer after the removal RIE etching, the recombination rate of reduction photo-generated carrier;
(4) with deionized water silicon chip is cleaned, it is subsequent use to dry the back again.
2. the cleaning of a kind of crystalline silicon RIE making herbs into wool surface damage layer according to claim 1 is characterized in that: in the cleaning solution described in the step (2), and HF, HCl and H
2O
2Optimum volume ratio be 3:7:2.
3. the cleaning of a kind of crystalline silicon RIE making herbs into wool surface damage layer according to claim 1 is characterized in that: the optimum range of the scavenging period described in the step (3) is 5～6min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210202913.2A CN102728573B (en) | 2012-06-19 | 2012-06-19 | Process for cleaning damage layer of reactive ion etching (RIE) flocking surface of crystalline silicon |
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| CN201210202913.2A CN102728573B (en) | 2012-06-19 | 2012-06-19 | Process for cleaning damage layer of reactive ion etching (RIE) flocking surface of crystalline silicon |
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| CN102728573A true CN102728573A (en) | 2012-10-17 |
| CN102728573B CN102728573B (en) | 2014-12-03 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985787A (en) * | 2014-05-20 | 2014-08-13 | 新奥光伏能源有限公司 | Texturing method of transparent conductive oxide thin film |
| CN105154268A (en) * | 2015-08-29 | 2015-12-16 | 江西赛维Ldk太阳能高科技有限公司 | Cleaning fluid capable of reducing thickness of damaged layer of surface of silicon wafer and cleaning method |
| CN105655445A (en) * | 2016-03-25 | 2016-06-08 | 中节能太阳能科技（镇江）有限公司 | Surface finish cleaning method for RIE silicon wafer |
| CN106409977A (en) * | 2016-11-21 | 2017-02-15 | 新奥光伏能源有限公司 | Solar cell silicon wafer cleaning method and solar cell preparation method |
| CN109994558A (en) * | 2019-03-27 | 2019-07-09 | 通威太阳能（成都）有限公司 | A kind of preparation method of reverse pyramid monocrystalline flannelette |
| CN111668096A (en) * | 2020-06-22 | 2020-09-15 | 徐文凯 | Etching method and device for third-generation semiconductor |
| CN111696852A (en) * | 2020-06-22 | 2020-09-22 | 徐文凯 | Method for cleaning third generation semiconductor |
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| CN102364697A (en) * | 2011-06-30 | 2012-02-29 | 常州天合光能有限公司 | Method for removing micro-damage layer from crystalline silicon surface after RIE (Reactive Ion Etching) flocking |
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Patent Citations (7)
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| JPH03228327A (en) * | 1990-02-02 | 1991-10-09 | Nec Corp | Cleaning method of semiconductor wafer |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985787A (en) * | 2014-05-20 | 2014-08-13 | 新奥光伏能源有限公司 | Texturing method of transparent conductive oxide thin film |
| CN105154268A (en) * | 2015-08-29 | 2015-12-16 | 江西赛维Ldk太阳能高科技有限公司 | Cleaning fluid capable of reducing thickness of damaged layer of surface of silicon wafer and cleaning method |
| CN105655445A (en) * | 2016-03-25 | 2016-06-08 | 中节能太阳能科技（镇江）有限公司 | Surface finish cleaning method for RIE silicon wafer |
| CN106409977A (en) * | 2016-11-21 | 2017-02-15 | 新奥光伏能源有限公司 | Solar cell silicon wafer cleaning method and solar cell preparation method |
| CN106409977B (en) * | 2016-11-21 | 2018-02-16 | 新奥光伏能源有限公司 | A kind of cleaning method of silicon chip of solar cell, the preparation method of solar cell |
| CN109994558A (en) * | 2019-03-27 | 2019-07-09 | 通威太阳能（成都）有限公司 | A kind of preparation method of reverse pyramid monocrystalline flannelette |
| CN109994558B (en) * | 2019-03-27 | 2021-03-09 | 通威太阳能（成都）有限公司 | Preparation method of inverted pyramid-shaped single crystal suede |
| CN111668096A (en) * | 2020-06-22 | 2020-09-15 | 徐文凯 | Etching method and device for third-generation semiconductor |
| CN111696852A (en) * | 2020-06-22 | 2020-09-22 | 徐文凯 | Method for cleaning third generation semiconductor |
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| CN102728573B (en) | 2014-12-03 |
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Granted publication date: 20141203 Termination date: 20170619 |