CN101673785A - Method for preparing reflection reduction film with surface embedded type porous silicon structure of silicon base solar battery - Google Patents
Method for preparing reflection reduction film with surface embedded type porous silicon structure of silicon base solar battery Download PDFInfo
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Abstract
The invention relates to a method for preparing a reflection reduction film with a surface embedded type porous silicon structure of a silicon base solar battery, which belongs to the technical fieldof electrochemical corrosion. The method is characterized in that a metal aluminum film anode electrode is prepared at the back face of a silicon wafer by a traditional silk screen printing method firstly, and Al and silicon have favorable ohmic contact; in addition, a platinum wafer or a platinum wire is used as a cathode electrode; afterwards, the front face of the silicon wafer is put into corrosive liquid with HF:H2O of 1:10 (volume ratio) and soaked for 1 minute; the temperature of the corrosive liquid is 26 DEG C; then, the front face of the silicon wafer is put into a container under anultrasonic condition of the ultrasonic frequency of 40-60Hz, and electrochemical corrosion processing is carried out in mixed liquid with HF:H2O:C2H5OH of 2:1:1 (volume ratio) of electrolyte; the temperature of the electrolyte is 40 DEG C; the surface density of electrolytic corrosion current is 5-10mA/cm<2>; the electrolytic corrosion time is 40-60s; and finally, the reflection reduction layer film with the surface embedded type porous silicon structure is formed at the front face of the silicon wafer, and the reflectivity of the reflection reduction layer film is 1.42% averagely.
Description
Technical field
The present invention relates to a kind of preparation method of reflection reduction film with surface embedded type porous silicon structure of silicon base solar battery, belong to the electrochemical corrosion technical field.
Background technology
At present for monocrystaline silicon solar cell, industrial normal employing TiO
2, MgF
2, ZnS and Si
3N
4Deng antireflective coating, higher, the complex process of its production cost.How cheap the antireflective coating for preparing silica-based solar cell reliably be that the photoelectric conversion efficiency of solar cell improves constantly, one of the key technology of extensive industrialization.And the micro-meter scale porous silicon has following advantage as the embedded antireflection layer of solar cell:
(1), the surface embedded type porous silicon has higher matte texture density, the orientation at random, good uniformity, can be used to the available light that directly " facing " all directions incident comes, strengthen the acquisition probability of light quantum greatly, improve the internal quantum efficiency of silicon-based semiconductor.Aspect preparation, traditional NaOH or KOH etchant solution can only be with＜100〉monocrystalline silicon surface of orientation corrodes into pyramid, as the matte that falls into light.Yet the preparation of surface embedded type porous silicon does not have the limitation in crystal orientation technically.The surface preparation of monocrystalline, polycrystalline or the microcrystal silicon of any orientation can be become embedded porous silicon.The surface embedded type porous silicon covers the top layer of silicon, and its anti-reflective effect can be comparable with other complicated membrane structure, even be better than double membrane structure.
(2), surface embedded type porous silicon solar cell has bright development prospect, adopt electrochemical erosion method, the cost degradation for preparing embedded porous silicon, and characteristics such as easy to operate, easy to control, than other method (as ion beam sputtering, the laser ablation pattern technology) more noticeable, be easy to realize suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of method by electrochemical corrosion prepares and forms surface embedded type porous silicon structure antireflection layer film
The preparation method of a kind of reflection reduction film with surface embedded type porous silicon structure of silicon base solar battery of the present invention is characterized in that having following process and step:
A. select the solar cell silicon substrate material for use, it is pulling of silicon single crystal, P type, crystal orientation＜100 〉, thickness is 200～240 μ m, not polishing; At first will in NaOH magnetic solution, tentatively corrode, to remove the mechanical damage layer of silicon chip surface as the silicon slice placed of solar cell silicon substrate material; The preparation of alkali lye is that the volume proportion of NaOH and water is 1: 5; The temperature of alkali lye is 80 ℃; Described silicon slice placed is placed described alkali lye, and under the ultrasonic wave effect, corrode 1～2 minute;
B. prepare metallic aluminium thin film positive pole electrode at the described silicon chip back side with traditional silk screen print method, and make Al film and silicon substrate have good Ohmic contact; Connect a cathode electrode platinized platinum or a platinum filament in the front of silicon chip opposite side by lead in addition;
C. the silicon chip front is positioned in the etching acid solution corrosion liquid and soaked 1～2 minute, to remove the natural oxidizing layer of silicon chip surface; The preparation of etching acid solution is HF and H
2The volume proportion of O is 1: 10; The temperature of corrosive liquid is 26～30 ℃;
D. then the silicon chip front is placed in the container that has under the ultrasound condition that ultrasonic frequency is 40～60Hz, and in the mixed liquor that electrolyte etching acid, water and ethanol are formed, carries out electrochemical corrosion and handle; Described electrolyte is the mixed liquor of etching acid, water and organic solvent ethanol, and its three's volume ratio is: HF: H
2O: C
2H
5OH=2: 1: 1; The temperature of electrolyte is 40～50 ℃; Connect DC power supply then, the surface density of electrolytic corrosion electric current is 5～10mA/cm
2The electrolytic corrosion time is 40～60s; Finally at the positive antireflection layer film that forms surface embedded type porous silicon structure of silicon chip, its reflectivity average out to 1.42%; The thickness of this antireflective tunic is 380～1100nm, has loose structure.
The characteristics and the principle of the inventive method are as described below:
Use electrochemical erosion method, prepare in the process of surface embedded type porous silicon of ultralow reflectivity, adopt platinized platinum as cathode electrode, silicon chip contacts as anode electrode with Al's, carries out electrochemical corrosion in the mixed solution that contains HF acid.In the anode oxidation process, think that big technological parameter comprises concentration, electric current surface density, etching time, the matrix doping type of acid in ambient temperature, the mixed solution, resistivity, polishing degree etc., they have very big influence to the structure and the optical property of surface embedded type porous silicon.
Electrolyte commonly used is the mixed solution that certain density HF and organic solvent are made into.Experiment showed, in the preparation of porous silicon, to add the wettability that organic solvent can increase silicon face, reduce the surface tension of electrolyte.In anode oxidation process, there is a large amount of hydrogen to produce, thereby produces a large amount of bubbles.Glassware for drinking water has very big surface tension, when hydrogen produces, because the capillary cause of water makes hydrogen be adsorbed on the surface of silicon firmly, can not overflow freely, stops next step electrochemical reaction.By organic solvent and hyperacoustic adding, can reduce the surface tension of corrosive liquid, the effect of organic solvent can be determined that important a bit is the solubility of organic solvent in water by several factors.Add ethanol and can make porous silicon on the degree of depth, keep uniformity and consistency, and can make the surface topography of porous silicon even.
In the inventive method, it is as described below that surface embedded type porous silicon electrochemistry forms mechanism:
Silicon is dissolving constantly in the HF aqueous solution, and the chemical corrosion speed of Si in HF is extremely slow generally speaking, and its surperficial silicon dangling bonds can be formed Si-H and Si-H by the hydrogen passivation
2Two kinds of keys.Be that anode constantly has the hole to provide in the silicon body in electrochemical process, the hydrogen atom of the outstanding key of passivation silicon will be repelled in the hole that is diffused near surface, and si-h bond is weakened.The F atom can be replaced a H atom, discharges an electronics simultaneously.After having lost a H atom, another H atom stability decreases on the silicon atom, other F atom can replace, and discharges an electronics to silicon.The H of two H atomic buildings that emits
2Molecule.The silicon atom that has lost the passivation of H atom is dissolved by HF, produces SiF
4And then combine with the F atom and to form SiF
6Group.Promptly move to silicon face when the hole in body, the Si-H bond fission forms the Si-F key.Thereby the Si-Si key is dissolved by HF.(seeing shown in Figure 2)
Electrochemical reaction process:
Si+2HF+2e
+→SiF
2+2H
+
SiF
2+4HF→H
2SiF
6+H
2↑
Description of drawings
Fig. 1 is for preparing the device schematic diagram of antireflective coating with electrochemical erosion method among the present invention.
Fig. 2 forms mechanism figure for surface embedded type porous electrochemical erosion method among the present invention.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment
The process and the step of present embodiment are as described below
Device used in the present embodiment is referring to the Fig. 1 in the accompanying drawing.Fig. 1 is for preparing the device schematic diagram of antireflective coating or antiradar reflectivity film with electrochemical erosion method.This device is the common laboratory installation of using.
(1), select the solar cell silicon substrate material for use, it is pulling of silicon single crystal, P type, crystal orientation＜100 〉, thickness is 220 μ m, the polishing; At first will in NaOH magnetic solution, tentatively corrode, to remove the mechanical damage layer of silicon chip surface as the silicon slice placed of solar cell silicon substrate material; The preparation of alkali lye is that the volume proportion of NaOH and water is 1: 5; The temperature of alkali lye is 80 ℃; Described silicon slice placed is placed described alkali lye, and under the ultrasonic wave effect, corroded 1 minute;
(2), at the described silicon chip back side, also be upper surface, prepare metallic aluminium thin film positive pole electrode with traditional silk screen print method, and make Al film and silicon substrate have good Ohmic contact; In the front of silicon chip opposite side, also be lower surface in addition, connect a cathode electrode platinized platinum or a platinum filament by lead;
(3), the silicon chip front is positioned in the etching acid solution corrosion liquid soaked 1 minute, to remove the natural oxidizing layer of silicon chip surface; The preparation of etching acid solution is HF and H
2The volume proportion of O is 1: 10; The temperature of corrosive liquid is 26 ℃;
(4), then the silicon chip front is placed in the container that has under the ultrasound condition that ultrasonic frequency is 40Hz, and in the mixed liquor that electrolyte etching acid, water and ethanol are formed, carry out electrochemical corrosion and handle; Described electrolyte is the mixed liquor of etching acid, water and organic solvent ethanol, and its three's volume ratio is: HF: H
2O: C
2H
5OH=2: 1: 1; The temperature of electrolyte is 40 ℃; Connect DC power supply then, the surface density of electrolytic corrosion electric current is 5mA/cm
2The electrolytic corrosion time is 40s; Finally at the positive antireflection layer film that forms surface embedded type porous silicon structure of silicon chip; This antireflection layer film has extremely low reflectivity; Its reflectivity average out to 1.42%; The thickness of this antireflective tunic is 700～900nm, has loose structure.
Claims (1)
1, a kind of preparation method of reflection reduction film with surface embedded type porous silicon structure of silicon base solar battery is characterized in that having following process and step:
A. select the solar cell silicon substrate material for use, it is pulling of silicon single crystal, P type, crystal orientation＜100 〉, thickness is 200～240 μ m, not polishing; At first will in NaOH magnetic solution, tentatively corrode, to remove the mechanical damage layer of silicon chip surface as the silicon slice placed of solar cell silicon substrate material; The preparation of alkali lye is that the volume proportion of NaOH and water is 1: 5; The temperature of alkali lye is 80 ℃; Described silicon slice placed is placed described alkali lye, and under the ultrasonic wave effect, corrode 1～2 minute;
B. prepare metallic aluminium thin film positive pole electrode at the described silicon chip back side with traditional silk screen print method, and make Al film and silicon substrate have good Ohmic contact; Connect a cathode electrode platinized platinum or a platinum filament in the front of silicon chip opposite side by lead in addition;
C. the silicon chip front is positioned in the etching acid solution corrosion liquid and soaked 1～2 minute, to remove the natural oxidizing layer of silicon chip surface; The preparation of etching acid solution is HF and H
2The volume proportion of O is 1: 10; The temperature of corrosive liquid is 26～30 ℃;
D. then the silicon chip front is placed in the container that has under the ultrasound condition that ultrasonic frequency is 40～60Hz, and in the mixed liquor that electrolyte etching acid, water and ethanol are formed, carries out electrochemical corrosion and handle; Described electrolyte is the mixed liquor of etching acid, water and organic solvent ethanol, and its three's volume ratio is: HF: H
2O: C
2H
5OH=2: 1: 1; The temperature of electrolyte is 40～50 ℃; Connect DC power supply then, the surface density of electrolytic corrosion electric current is 5～10mA/cm
2The electrolytic corrosion time is 40～60s; Finally at the positive antireflection layer film that forms surface embedded type porous silicon structure of silicon chip, its reflectivity average out to 1.42%; The thickness of this antireflective tunic is 380～1100nm, has loose structure.
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Cited By (14)
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| CN101975815A (en) * | 2010-09-21 | 2011-02-16 | 上海大学 | Measuring method of recombination center concentration and trap center concentration in solar-grade crystalline silicon |
| CN102005500A (en) * | 2010-09-09 | 2011-04-06 | 中国科学院电工研究所 | Method for preparing SiO2-containing metal oxide composite film |
| CN102020485A (en) * | 2010-10-26 | 2011-04-20 | 万平喜 | Method for preparing calcium silicate biofilm on surface of crystalline silicon in situ |
| CN102623324A (en) * | 2010-12-13 | 2012-08-01 | 罗门哈斯电子材料有限公司 | Electrochemical etching of semiconductors |
| CN103618026A (en) * | 2013-11-11 | 2014-03-05 | 杭州电子科技大学 | Micro-nanometer machining device and method of meshed polycrystalline silicon |
| CN103721972A (en) * | 2013-12-20 | 2014-04-16 | 天津力神电池股份有限公司 | Method for wetting polymer lithium ion batteries |
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| CN112928185A (en) * | 2021-02-10 | 2021-06-08 | 浙江工业大学 | Preparation method of silicon surface passivation layer |
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| CN102005500A (en) * | 2010-09-09 | 2011-04-06 | 中国科学院电工研究所 | Method for preparing SiO2-containing metal oxide composite film |
| CN101975815A (en) * | 2010-09-21 | 2011-02-16 | 上海大学 | Measuring method of recombination center concentration and trap center concentration in solar-grade crystalline silicon |
| CN102020485B (en) * | 2010-10-26 | 2012-08-29 | 万平喜 | Method for preparing calcium silicate biofilm on surface of crystalline silicon in situ |
| CN102020485A (en) * | 2010-10-26 | 2011-04-20 | 万平喜 | Method for preparing calcium silicate biofilm on surface of crystalline silicon in situ |
| CN102623324B (en) * | 2010-12-13 | 2014-12-10 | 罗门哈斯电子材料有限公司 | Electrochemical etching of semiconductors |
| CN102623324A (en) * | 2010-12-13 | 2012-08-01 | 罗门哈斯电子材料有限公司 | Electrochemical etching of semiconductors |
| CN103618026A (en) * | 2013-11-11 | 2014-03-05 | 杭州电子科技大学 | Micro-nanometer machining device and method of meshed polycrystalline silicon |
| CN103618026B (en) * | 2013-11-11 | 2016-05-04 | 杭州电子科技大学 | A kind of polysilicon micro-nano processing unit (plant) and method of gridding |
| CN103721972A (en) * | 2013-12-20 | 2014-04-16 | 天津力神电池股份有限公司 | Method for wetting polymer lithium ion batteries |
| CN103903960A (en) * | 2014-01-10 | 2014-07-02 | 浙江晶科能源有限公司 | HIT battery front-cleansing method |
| CN105047767A (en) * | 2015-09-10 | 2015-11-11 | 浙江晶科能源有限公司 | Texturizing method of silicon wafer |
| CN105755528A (en) * | 2016-04-07 | 2016-07-13 | 厦门大学 | Method for controlling corrosion depth of porous silicon |
| CN111267244A (en) * | 2018-12-05 | 2020-06-12 | 上海新昇半导体科技有限公司 | Crystal bar slicing device |
| CN111267247A (en) * | 2018-12-05 | 2020-06-12 | 上海新昇半导体科技有限公司 | Crystal bar slicing device |
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| CN112928185A (en) * | 2021-02-10 | 2021-06-08 | 浙江工业大学 | Preparation method of silicon surface passivation layer |
| CN112928185B (en) * | 2021-02-10 | 2023-10-20 | 浙江工业大学 | Preparation method of silicon surface passivation layer |
| CN115117207A (en) * | 2021-03-22 | 2022-09-27 | 浙江爱旭太阳能科技有限公司 | HJT battery passivation method, HJT battery and HJT battery component |
| CN115117207B (en) * | 2021-03-22 | 2023-12-22 | 浙江爱旭太阳能科技有限公司 | HJT battery passivation method, HJT battery and assembly thereof |
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