CN102051618A - Method for preparing black silicon based on liquid-phase chemical reaction - Google Patents
Method for preparing black silicon based on liquid-phase chemical reaction Download PDFInfo
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- CN102051618A CN102051618A CN 201010532330 CN201010532330A CN102051618A CN 102051618 A CN102051618 A CN 102051618A CN 201010532330 CN201010532330 CN 201010532330 CN 201010532330 A CN201010532330 A CN 201010532330A CN 102051618 A CN102051618 A CN 102051618A
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Abstract
The invention relates to a method for preparing black silicon based on liquid-phase chemical reaction, comprising the following steps of: placing a silicon slice in a corrosive solution; then adding a metal compound to the corrosive solution; and carrying out texturing treatment on the surface of the silicon slice through ion etching reaction under catalysis to form a black silicon material with a microstructural surface. By carrying out surface texturing of a nano scale on the silicon surface, the band absorption and reflectivity of the product can be effectively controlled so that the conversion efficiency of a silicon-based solar battery can be improved. The method can be applied to preparing large-area black silicon material, and the surface of the prepared black silicon material contains microstructures, such as a silicon microcolumn, a silicon particle, silicon microholes and the like. The light absorption of the black silicon material in the wavelength range of 300-2000nm can be up to over 90%, and the light absorption in the wavelength range of 300-800nm can be up to over 95%.
Description
Technical field
The present invention relates to a kind of black silicon preparation method, particularly utilize reactive ion etching in the liquid phase to carry out the method for silicon single crystal, polysilicon and amorphous silicon surfaces texture based on liquid-phase chemical reaction.Belong to the Semiconductor Optoeletronic Materials preparing technical field,
Background technology
At present in the product of commercialization solar cell, the market share maximum of silica-based solar cell, yet one of bottleneck technology of restriction silica-based solar cell is exactly a solar conversion efficiency to be difficult to further promote again, so the finishing of silica-base material and micro-nano texturing just become a focus of recent silica-based solar cell research.This wherein forms black silicon on the surface of silicon, and then effectively reduces solar cell to sun reflection of light, is an effectively technology and method.
The special microstructure on black silicon material surface, make it have peculiar photoelectric property, and have important use in fields such as the energy and military affairs and be worth, therefore black silicon has become worldwide research focus, and its technology of preparing and correlative study also have been subjected to paying close attention to widely.Up to the present, laser irradiation in the specific gas environment of starting based on professor E.Mazur more than the technology of preparing of relevant black silicon, though this method is a successful method the most at present, but its high equipment input makes us feeling frustrated, be difficult to obtain to promote on a large scale, limited the application of this method greatly.Therefore, need to seek efficiently a kind of and black cheaply silicon preparation method.Chemical process is to create the most effectual way of novel substance, wherein also comprise original material is carried out modification and optimization, particularly, utilize the molecule self-assembly that the synthetic and study on the modification that material carries out nanoscale has been obtained unprecedented development especially along with the rapid emergence of nano science.Various countries' scientists also begins attempt to adopt chemical process to prepare black silicon: silicon face is carried out the surface-texturing of nanoscale, in the hope of can effectively controlling its absorption bands and reflectivity, thereby can improve the transformation efficiency of silica-based solar cell.
At present, in disclosed black silicon material manufacturing technology, use be the method for making black silicon material with laser light source scanning, as patent CN 101824654 A and CN 101824653 A, or the method for the black silicon of gas reaction ion etching preparation, as patent CN 101734611 A.
Summary of the invention
The object of the present invention is to provide a kind of black silicon preparation method based on liquid-phase chemical reaction.This method is that silicon chip is placed etchant solution, to wherein adding metallic compound, is reflected at silicon chip surface by the ion etching under the katalysis and carries out the texturing processing then, forms the black silicon material with micro-structure surface.Silicon face is carried out the surface-texturing of nanoscale, and product can effectively be controlled its absorption bands and reflectivity, thereby can improve the transformation efficiency of silica-based solar cell.
The present invention implements according to the following steps,
This method is that silicon chip is placed etchant solution, to wherein adding the metal ion compound with catalytic activity, is reflected at silicon chip surface by the ion etching under the katalysis and carries out the texturing processing then, forms the black silicon material with micro-structure surface.
Described etchant solution is the mixing solutions that hydrofluoric acid and hydrogen peroxide are formed, and wherein the concentration expressed in percentage by weight of hydrofluoric acid is 1%～20%, and the concentration expressed in percentage by weight of hydrogen peroxide is 0.1%～30%; The mixed weight ratio of hydrofluoric acid and hydrogen peroxide is 1: 3～6;
The metal ion compound that adds in the described etchant solution comprises the compound of gold and silver, iron, copper, nickel, zinc and/or tin for etching reaction provides the metal ion with catalytic activity;
The temperature of described ion etching reaction is 5-85 ℃, and the ion etching reaction times is 1-120 minute;
Described catalytic metal ion can use separately, also can two kinds or above metal ion mix composite use.
Photoabsorption in the 300-2000nm scope can reach more than 90% the black silicon material for preparing to wavelength, and the photoabsorption in the 300-800nm scope can reach more than 95% to wavelength.
Beneficial effect of the present invention: the wet chemical etching process all is from being begun to take place by the surface of erosion thing, and then be deep into inside, therefore be particularly suitable for the surface topography modification of solid material, especially make the material that black silicon has peculiar micro-nano light trapping structure like this.The present invention adopts the wet chemical etching to prepare black silicon material, can be applicable to large-area black silicon material preparation, and preparation-obtained black silicon material surface comprises microstructures such as silicon microtrabeculae, silicon particle and the little hole of silicon.Photoabsorption in the 300-2000nm scope can reach more than 90% this black silicon material to wavelength, to the photoabsorption of wavelength in the 300-800nm scope especially up to more than 95%.
Description of drawings
Fig. 1 is after embodiment 1 adds hydrochloro-auric acid, the SEM figure of the black silicon material that formed in 4.5 minutes without the silicon chip erosion of polishing; Fig. 2 is the reflectance curve figure of the black silicon material of embodiment 1.
Embodiment
Embodiment 1: the weight ratio by hydrofluoric acid and hydrogen peroxide is 100 milliliters of mixing solutionss of configuration in 1: 4, and wherein the concentration expressed in percentage by weight of hydrofluoric acid is 8%, and the concentration expressed in percentage by weight of hydrogen peroxide is 24%.To put into the solution that is heated to 15 ℃ without the monocrystalline silicon piece of polishing, add the hydrochloro-auric acid of 0.2 mmole immediately, take out silicon chip after 4.5 minutes, rinse well, dry naturally.The black silicon material for preparing to the photoabsorption of wavelength in the 300-800nm scope up to more than 95%.The SEM vertical view of black silicon material as shown in Figure 1, this black silicon material surface of Fig. 1 has formed the structure in the little hole of a large amount of silicon.Fig. 2 shows that the photoabsorption of this black silicon material in the 300-800nm wavelength region is up to more than 95%.
Embodiment 2: the weight ratio by hydrofluoric acid and hydrogen peroxide is 100 milliliters of mixing solutionss of configuration in 1: 3, and wherein the concentration expressed in percentage by weight of hydrofluoric acid is 5%, and the concentration expressed in percentage by weight of hydrogen peroxide is 10%.Heated solution to 50 ℃ is put into the mixing solutions that is heated to 25 ℃ with monocrystalline silicon piece, adds the Silver Nitrate of 1 mmole immediately, takes out silicon chip after 60 minutes, rinses well, dries naturally, prepares black silicon material.
Embodiment 3: by the hydrofluoric acid and the weight ratio of hydrogen peroxide is two parts of 100 milliliters of identical mixing solutionss of configuration in 1: 6, and wherein the concentration expressed in percentage by weight of hydrofluoric acid is 20%, and the concentration expressed in percentage by weight of hydrogen peroxide is 0.5%.Monocrystalline silicon piece is put into the first part of solution that is heated to 25 ℃, add the Silver Nitrate of 1 mmole immediately, take out silicon chip after 1 minute; Another part of reheat solution to 50 ℃ is put into solution with this silicon chip, adds the iron nitrate of 2 mmoles immediately, takes out silicon chip after 50 minutes, rinses well, dries naturally, prepares black silicon material.
Claims (3)
1. black silicon preparation method based on liquid-phase chemical reaction, it is characterized in that: it is implemented according to the following steps,
Silicon chip is placed etchant solution, to wherein adding metal ion compound, be reflected at silicon chip surface by the ion etching under the katalysis and carry out the texturing processing then, form black silicon material with micro-structure surface with catalytic activity;
Described etchant solution is the mixing solutions that hydrofluoric acid and hydrogen peroxide are formed, and wherein the concentration expressed in percentage by weight of hydrofluoric acid is 1%～20%, and the concentration expressed in percentage by weight of hydrogen peroxide is 0.1%～30%; The mixed weight ratio of hydrofluoric acid and hydrogen peroxide is 1: 3～6;
That adds in the described etchant solution comprises the compound of gold and silver, iron, copper, nickel, zinc and/or tin for etching reaction provides the metal ion compound with catalytic activity effect;
The temperature of described ion etching reaction is 5-85 ℃, and the ion etching reaction times is 1-60 minute;
Described catalytic metal ion can use separately, also can two kinds or above metal ion mix composite use.
2. the black silicon preparation method based on liquid-phase chemical reaction according to claim 1, it is characterized in that: the weight ratio by hydrofluoric acid and hydrogen peroxide is 100 milliliters of mixing solutionss of being made up of hydrofluoric acid and hydrogen peroxide of configuration in 1: 4, wherein the concentration expressed in percentage by weight of hydrofluoric acid is 8%, the concentration expressed in percentage by weight of hydrogen peroxide is 24%, to put into the mixing solutions that is heated to 15 ℃ without the monocrystalline silicon piece of polishing, the hydrochloro-auric acid that adds 0.2 mmole immediately, 4.5 take out silicon chip after minute, rinse well, naturally dry, make black silicon material.
3. the black silicon preparation method based on liquid-phase chemical reaction according to claim 1, it is characterized in that: by the hydrofluoric acid and the weight ratio of hydrogen peroxide is two parts of 100 milliliters of identical mixing solutionss of being made up of hydrofluoric acid and hydrogen peroxide of configuration in 1: 6, wherein the concentration expressed in percentage by weight of hydrofluoric acid is 20%, the concentration expressed in percentage by weight of hydrogen peroxide is 0.5%, monocrystalline silicon piece is put into the first part of solution that is heated to 25 ℃, the Silver Nitrate that adds 1 mmole immediately took out silicon chip after 1 minute; Heat another part solution to 50 ℃, this silicon chip is put into solution, add the iron nitrate of 2 mmoles immediately, take out silicon chip after 50 minutes, rinse well, dry naturally, prepare black silicon material.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286785A (en) * | 2011-08-16 | 2011-12-21 | 苏州阿特斯阳光电力科技有限公司 | Etching liquid for preparing texture surface of monocrystalline silicon solar cell |
| CN102768951A (en) * | 2012-07-06 | 2012-11-07 | 南京大学 | Method for preparing black silicon by metallic copper ion auxiliary etching |
| CN102931277A (en) * | 2012-10-29 | 2013-02-13 | 沈鸿烈 | Method for preparing black silicon by Ni assisted chemical etching method |
| CN102938435A (en) * | 2012-11-23 | 2013-02-20 | 中国科学院半导体研究所 | Method for preparing over-saturation sulphur element doped silicon |
| CN103413865A (en) * | 2013-08-19 | 2013-11-27 | 电子科技大学 | Black silicon super-hydrophobic material and manufacturing method thereof |
| CN104584231A (en) * | 2012-03-19 | 2015-04-29 | 可持续能源联合有限责任公司(美国) | Copper-assisted, anti-reflection etching of silicon surfaces |
| CN106299026A (en) * | 2016-08-29 | 2017-01-04 | 浙江启鑫新能源科技股份有限公司 | A kind of preparation method of the black silion cell of wet method |
| CN107742660A (en) * | 2017-09-25 | 2018-02-27 | 江西展宇新能源股份有限公司 | The process of difference between a kind of improvement black silicon solar cell crystal orientation of polycrystalline |
| CN109980043A (en) * | 2019-02-27 | 2019-07-05 | 镇江仁德新能源科技有限公司 | A kind of efficient volume production preparation method of the black silicon wafer of wet process |
| CN110528005A (en) * | 2019-08-28 | 2019-12-03 | 贵州大学 | The preparation method of one metal ion species auxiliary etch porous silicon |
| CN112577612A (en) * | 2020-12-09 | 2021-03-30 | 中国电子科技集团公司第四十四研究所 | Black silicon plasmon auxiliary absorption thermopile chip and manufacturing method thereof |
| CN114686806A (en) * | 2022-03-30 | 2022-07-01 | 电子科技大学 | High-absorption and wide-spectrum black silicon composite material and preparation method thereof |
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| US20090236317A1 (en) * | 2008-03-21 | 2009-09-24 | Midwest Research Institute | Anti-reflection etching of silicon surfaces catalyzed with ionic metal solutions |
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2010
- 2010-11-05 CN CN 201010532330 patent/CN102051618A/en active Pending
Patent Citations (1)
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| US20090236317A1 (en) * | 2008-03-21 | 2009-09-24 | Midwest Research Institute | Anti-reflection etching of silicon surfaces catalyzed with ionic metal solutions |
Non-Patent Citations (1)
| Title |
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| 《IEEE》 20091230 Hao-Chih Yuan et al. EFFICIENT BLACK SILICON SOLAR CELLS WITH NANOPOROUS ANTI-REFLECTION MADE IN A SINGLE-STEP LIQUID ETCH 第141-145页 , 2 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286785A (en) * | 2011-08-16 | 2011-12-21 | 苏州阿特斯阳光电力科技有限公司 | Etching liquid for preparing texture surface of monocrystalline silicon solar cell |
| CN104584231A (en) * | 2012-03-19 | 2015-04-29 | 可持续能源联合有限责任公司(美国) | Copper-assisted, anti-reflection etching of silicon surfaces |
| CN102768951A (en) * | 2012-07-06 | 2012-11-07 | 南京大学 | Method for preparing black silicon by metallic copper ion auxiliary etching |
| CN102931277A (en) * | 2012-10-29 | 2013-02-13 | 沈鸿烈 | Method for preparing black silicon by Ni assisted chemical etching method |
| CN102931277B (en) * | 2012-10-29 | 2015-09-30 | 沈鸿烈 | A kind of Ni assistant chemical etch prepares the method for black silicon |
| CN102938435B (en) * | 2012-11-23 | 2015-05-06 | 中国科学院半导体研究所 | Method for preparing over-saturation sulphur element doped silicon |
| CN102938435A (en) * | 2012-11-23 | 2013-02-20 | 中国科学院半导体研究所 | Method for preparing over-saturation sulphur element doped silicon |
| CN103413865A (en) * | 2013-08-19 | 2013-11-27 | 电子科技大学 | Black silicon super-hydrophobic material and manufacturing method thereof |
| CN106299026A (en) * | 2016-08-29 | 2017-01-04 | 浙江启鑫新能源科技股份有限公司 | A kind of preparation method of the black silion cell of wet method |
| CN106299026B (en) * | 2016-08-29 | 2017-07-18 | 浙江启鑫新能源科技股份有限公司 | A kind of preparation method of the black silion cell of wet method |
| CN107742660A (en) * | 2017-09-25 | 2018-02-27 | 江西展宇新能源股份有限公司 | The process of difference between a kind of improvement black silicon solar cell crystal orientation of polycrystalline |
| CN109980043A (en) * | 2019-02-27 | 2019-07-05 | 镇江仁德新能源科技有限公司 | A kind of efficient volume production preparation method of the black silicon wafer of wet process |
| CN110528005A (en) * | 2019-08-28 | 2019-12-03 | 贵州大学 | The preparation method of one metal ion species auxiliary etch porous silicon |
| CN112577612A (en) * | 2020-12-09 | 2021-03-30 | 中国电子科技集团公司第四十四研究所 | Black silicon plasmon auxiliary absorption thermopile chip and manufacturing method thereof |
| CN114686806A (en) * | 2022-03-30 | 2022-07-01 | 电子科技大学 | High-absorption and wide-spectrum black silicon composite material and preparation method thereof |
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Application publication date: 20110511 |