CN102234845B - Preparation method of single crystal silicon texture surface structure - Google Patents
Preparation method of single crystal silicon texture surface structure Download PDFInfo
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- CN102234845B CN102234845B CN201010154626XA CN201010154626A CN102234845B CN 102234845 B CN102234845 B CN 102234845B CN 201010154626X A CN201010154626X A CN 201010154626XA CN 201010154626 A CN201010154626 A CN 201010154626A CN 102234845 B CN102234845 B CN 102234845B
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- suede structure
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Abstract
The invention provides a preparation method of a single crystal silicon texture surface structure, relates to the technical field of solar energy application, and is invented to effectively reduce reflection loss of incident light of a texture surface and to increase forming speed of a texture surface. The preparation method of a single crystal silicon texture surface comprises the following steps: depositing discrete metal particles on a silicon wafer surface; performing corrosion of the silicon wafer deposited with metal particles by a mixed solution of hydrofluoric acid and hydrogen peroxide so as to form a texture surface structure on the silicon wafer surface. The invention is applicable to the preparation process of solar cells.
Description
Technical field
The present invention relates to application of solar, relate in particular to a kind of preparation method of monocrystalline silicon suede structure.
Background technology
The preparation of suede structure is the operation together commonly used in the crystal silicon solar energy battery production technique, and suede structure can effectively reduce the reflection loss of incident light at silicon chip surface, increases the utilization ratio of light, and then improves the efficiency of conversion of battery.As shown in Figure 1, the matte typical structure that adopts at present is the matte pyramid structure.For the silicon chip of light face, incide in the sunlight on surface and approximately have 33% light to be gone out by surface reflection, can't be absorbed by battery.And for the matte pyramid structure, due to the pyramid structure that surface exists, secondary incident can occur in reflected light after incident again, reduces reflection loss.
In prior art, prepare the method that suede structure mainly adopts chemical corrosion, utilize the anisotropy of monocrystalline silicon piece corrosion, the alkaline solution of lower concentration has the principle of different erosion rates on the different crystal orientation to crystalline silicon, directly immerse monocrystalline silicon piece in alkali lye, adopt certain processing parameter proportioning, erode away simultaneously the surface topography of densely covered Pyramid on the upper and lower surface of silicon chip.Fig. 2 is the contrast schematic diagram of the luminous reflectance factor of the suede structure that adopts the prior art preparation and light face structure, as shown in Figure 2, the suede structure of the method preparation by this chemical corrosion, incident light reflection loss between 300～1100 nanometers (nm) wavelength is less than the loss of light face, more light is incided in battery, increase the utilization ratio of light.
Yet, state in realization in the process of suede structure preparation, the contriver finds that in prior art, there are the following problems at least: although the suede structure of the method for chemical corrosion preparation with respect to light face structure decrease the reflection loss of sunlight, but due to the matte pyramid size of the method preparation usually between 3～15 microns (um) magnitudes, be much higher than lambda1-wavelength, as shown in Figure 2, still have and be not less than 15% reflectivity in the strongest 600nm wavelength period of absorption sunlight, battery efficiency is restricted.In addition, the formation speed of the method matte is slower, usually needs the approximately corrosion of 30 minutes (min) just can prepare suede structure, has restricted production capacity.
Summary of the invention
The invention provides a kind of preparation method of monocrystalline silicon suede structure, can effectively reduce the reflection loss of matte incident light, improved the formation speed of matte.
For achieving the above object, embodiments of the invention adopt following technical scheme:
A kind of preparation method of monocrystalline silicon suede structure comprises:
At the discrete metallic particles of silicon chip surface deposition;
Utilize hydrofluoric acid (HF) and hydrogen peroxide (H
2O
2) mixing solutions the described silicon chip that has deposited metallic particles is corroded, form suede structure at described silicon chip surface.
After adopting technique scheme, the preparation method of monocrystalline silicon suede structure provided by the invention, can access the suede structure of the finer silicon single crystal of size, effectively reduced the reflection loss of incident light; And, preparation method provided by the invention, the formation speed of matte is fast, has effectively saved the process time, has improved production capacity.
Description of drawings
Fig. 1 is the typical structure schematic diagram of the matte of prior art preparation;
Fig. 2 is the contrast schematic diagram of the reflectivity of the suede structure of preparation of prior art preparation and light face structure;
The preparation method's that Fig. 3 provides for the embodiment of the present invention schema;
The preparation method's that Fig. 4 (a) provides for the embodiment of the present invention principle schematic;
The preparation method's that Fig. 4 (b) provides for the embodiment of the present invention another principle schematic;
Another principle schematic of the preparation method that Fig. 4 (c) provides for the embodiment of the present invention;
Fig. 5 is the preparation method's of the embodiment of the present invention one schema;
Fig. 6 is that the embodiment of the present invention one is carried out the post-depositional silicon chip shape appearance figure of metallic particles;
Fig. 7 is the suede structure shape appearance figure of the embodiment of the present invention one preparation;
Fig. 8 is the suede structure of the embodiment of the present invention one preparation and the contrast schematic diagram of the suede structure emittance that prior art prepares.
Embodiment
Be described in further details below in conjunction with the embodiment of accompanying drawing to the preparation method of monocrystalline silicon suede structure of the present invention.Wherein described embodiment is only part embodiment of the present invention, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment that obtains, belong to the scope of protection of the invention.
The preparation method of the matte that embodiments of the invention provide, schema as shown in Figure 3 comprises:
S11, at the discrete metallic particles of silicon chip surface deposition;
S12, utilize the mixing solutions of hydrofluoric acid and hydrogen peroxide to corrode the described silicon chip that has deposited metallic particles, at described silicon chip surface, forms suede structure.
The matte preparation method that the embodiment of the present invention provides, can be referred to as metal catalytic silicon etch.At scientific research field, metal catalytic silicon etch is mainly used to prepare silicon nanostructure at present, as quantum dot, and porous silicon, nano wire etc.Its cardinal principle is under strong oxidizing property HF acid solution environment, metallic particles is as catalyzer, make the silicon face generation oxidation that contacts with metallic particles by electrochemical reaction, zone of oxidation is corroded by HF, be accompanied by the conversion of electrochemical energy and mechanical energy, metallic particles moves downward, and further corrodes the silicon face that contacts with metallic particles.Deposited silver (Ag) particle as example take silicon chip surface, when surface deposition silicon chip immersion HF and the H of Ag particle
2O
2Mixing solutions the time, as shown in Fig. 4 (a), at the Ag particle surface, cathodic reaction occurs:
H
2O
2+2H++2e-→2H
2O
And anodic reaction, the silicon face generation oxidation that contacts with the Ag particle occur in the silicon face under the Ag particle:
Si+2H
2O→SiO
2+4H
++4e-
Then, as shown in Fig. 4 (b) and Fig. 4 (c), SiO
2Layer is corroded by HF, and is accompanied by the conversion of electrochemical energy and mechanical energy, and the Ag particle moves downward, and further corrodes the silicon face that contacts with the Ag particle:
SiO
2+6HF→H
2SiF
6+2H2O
Si+6HF→H
2SiF
6+4H
++4e-
The total reaction that occurs in corrosive fluid is:
Si+2H
2O
2+6HF→H
2SiF
6+4H
2O
, according to different processing parameter proportionings,, by above-mentioned reaction process, will form different morphologies at silicon chip surface.And experiment finds that the silicon corrosion by metal catalytic is anisotropic, and its corrosion position is perpendicular to (100) face of silicon chip, and the pattern of the silicon of metal catalytic corrosion depends on the geomery of metallic particles and etching time.Therefore,, by controlling geomery and the etching time of metallic particles, make the less and etching time of the size of metallic particles more in short-term, just can form undersized suede structure at silicon chip surface.
Based on above-mentioned principle, the preparation method of the matte that the embodiment of the present invention provides,, by controlling geomery and the etching time of metallic particles, can access the suede structure of the finer silicon single crystal of size, in the situation that comparable with incident wavelength, effectively reduced the reflection loss of incident light; And, the preparation method that the embodiment of the present invention provides, the formation speed of matte is fast, has effectively saved the process time, has improved production capacity.
It is pointed out that wherein in order to form the concavo-convex suede structure that replaces, the metallic particles that the S11 step in the embodiment of the present invention deposits is discrete in the distribution of silicon chip surface according to the principle of above-mentioned metal catalytic silicon corrosion.Determining the size of suede structure due to the size of metallic particles, and fine suede structure can effectively reduce the loss of incident light, therefore, make the less and fine and closely woven arrangement of the metal particle size of deposition, preferably, the metallic particles that deposits is the metallic particles of nanometer scale.In addition,, for the performance of the battery of follow-up preparation, guarantee the homogeneity of matte pattern, the metallic particles of deposition is evenly distributed at silicon chip surface.
Wherein, the metallic particles of S11 step deposition can be metallic gold (Au) particle or Ag particle or platinum (Pt) particle etc.
Further; the S11 step can adopt several different methods at the discrete metallic particles of silicon chip surface deposition; such as adopting physical vaporous deposition (sputtering method or vapour deposition method etc.) to deposit discrete metallic particles or adopt the method for plating or electroless plating to deposit discrete metallic particles etc. at silicon chip surface at silicon chip surface at the gelatinoid that silicon chip surface deposits discrete metallic particles or adopts printing, spraying or spin coating to comprise metallic particles;, if the quantity of the metallic particles of the method for plating or electroless plating deposition is more, can reduce metallic particles quantity by dilution.
Further, silicon corrosion principle based on previously described metal catalytic, the process that the S12 step is concrete is: with the S11 step deposition silicon chip of metallic particles immerse mixing solutions, under the katalysis of described metallic particles, the silicon chip surface that contacts with described metallic particles is corroded by described mixing solutions, at described silicon chip surface, forms suede structure.Metallic particles can move down along the silicon face that erodes, and the silicon face that contacts with described metallic particles can further be corroded.
It should be noted that in addition in the S12 step HF and H in corrosive fluid
2O
2Concentration can be according to the practical situation setting, to set etching time to the silicon chip of metal refining particle according to the concentration of corrosive fluid and practical situation etc., etching time is unsuitable long, and long etching time easily causes excessive corrosion, can not obtain desirable suede structure.
Due to metallic particles in the S12 step as catalyzer, therefore after the S12 step, also comprise the step of removing metallic particles.Usually the silicon chip that the S12 step was corroded immerses in iodized salt or nitrate solution, and then with hydrochloric acid (HCl) solution, cleans to remove metallic particles.
, in order to make those skilled in the art better understand technical scheme of the present invention, below by a specific embodiment, the present invention is described in further detail.
Embodiment one
The preparation method of the matte that the present embodiment provides, schema as shown in Figure 5, comprise the following steps:
S21, carry out standard cleaning to silicon chip;
S21, the method for employing electroless plating, immerse HF and Silver Nitrate (AgNO with silicon chip
3) mixing solutions in, at the discrete Ag particle of silicon chip surface deposition.
This step is at room temperature carried out, and the reaction times is 1min, the HF of employing and AgNO
3Mixing solutions in, the concentration of HF is 10%, AgNO
3Concentration be 0.01～0.03Mol/L.Through after this step, silicon chip surface will deposit discrete, the Ag particle that is evenly distributed.After this step, as shown in Figure 6, in figure, the white particulate thing is the Ag particle of deposition to the pattern of silicon chip surface, and as seen from the figure, the Ag particle that deposits is discrete, the densification that is evenly distributed, and granular size is about 60～200nm.
S23, immerse HF and H with silicon chip
2O
2Mixing solutions in corrode;
The etching time of this step is 20 seconds, and in the mixing solutions of employing, the concentration of HF is 10%, H
2O
2Concentration be 0.6%.
S24, remove the Ag particle;
The method of the removal Ag particle that this step adopts is: the silicon chip after the corrosion of S23 step is immersed 3min in the KNO3 aqueous solution that concentration is 0.05Mol/L, then take out silicon chip and immerse HCl solution again and clean.
S25, carry out washed with de-ionized water and dry silicon chip.
Like this, the present embodiment has been completed the whole flow process for preparing suede structure, prepared suede structure as shown in Figure 7, as seen from the figure, the suede structure of the present embodiment preparation presents hole and the protruding pattern that replaces, the degree of depth of its Hole is that depth of corrosion is about 180～240nm, and the erosion rate that represents the S23 step is 9～12nm/s.
For the suede structure of the verifying the present embodiment preparation improvement ability to emittance, sample to preparation has carried out the test of reflectivity, and with prior art, adopt the reflectivity of the suede structure of alkaline solution corrosion preparation to contrast, result as shown in Figure 8, as shown in Figure 8, in 300～1100nm wavelength region, the suede structure that the reflection loss of the suede structure of the present embodiment preparation all prepares less than caustic corrosion.
In sum, the preparation method of matte provided by the invention, can access finer suede structure, improved the reflectivity of suede structure, effectively reduced reflection loss; And the time of corrosion is short, and the formation speed of matte is fast, has effectively saved the process time, has improved production capacity.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; can expect easily changing or replacing, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion by described protection domain with claim.
Claims (4)
1. the preparation method of a monocrystalline silicon suede structure, is characterized in that, comprising:
Adopt the method for electroless plating, silicon chip is immersed in the mixing solutions of hydrofluoric acid and Silver Nitrate, at the discrete metallic particles of silicon chip surface deposition, wherein the concentration of hydrofluoric acid is 10%, the concentration of Silver Nitrate is 0.01～0.03Mol/L;
Utilize the mixing solutions of hydrofluoric acid and hydrogen peroxide to corrode the described silicon chip that has deposited metallic particles, form suede structure at described silicon chip surface, wherein, in the mixing solutions of described hydrofluoric acid and hydrogen peroxide, the concentration of hydrofluoric acid is 10%, the concentration of hydrogen peroxide is 0.6%, and erosion rate is 9～12nm/s.
2. method according to claim 1, is characterized in that, described metallic particles is the metallic particles of nanometer scale.
3. method according to claim 1, it is characterized in that: the described mixing solutions of hydrofluoric acid and hydrogen peroxide that utilizes is specially the step that the described silicon chip that has deposited metallic particles corrodes:
The described silicon chip that has deposited metallic particles is immersed described mixing solutions, and under the katalysis of described metallic particles, the silicon chip surface that contacts with described metallic particles is corroded by described mixing solutions, at described silicon chip surface, forms suede structure.
4. method according to claim 1, is characterized in that, the time that the described silicon chip that has deposited metallic particles is corroded is 20 seconds.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102534622B (en) * | 2012-03-20 | 2014-01-08 | 常州比太科技有限公司 | Method for forming solar dry textured black silicon by plasma excitation |
| CN102683439A (en) * | 2012-05-04 | 2012-09-19 | 友达光电股份有限公司 | Optical anti-reflection structure and manufacturing method thereof as well as solar battery containing optical anti-reflection structure |
| CN102738308A (en) * | 2012-07-11 | 2012-10-17 | 辽宁朝阳太阳能科技有限公司 | Hollow borosilicate glass bead doped nanometer suede solar battery manufacturing method |
| CN102738309A (en) * | 2012-07-11 | 2012-10-17 | 辽宁朝阳太阳能科技有限公司 | Manufacturing method of double PN crystalline silicon solar cell with double high-efficiency trap light nanometer suede surfaces |
| CN103337560B (en) * | 2013-07-08 | 2015-10-28 | 苏州大学 | For the preparation method of the three-dimensional silicon nano structure of solar cell |
| CN103746038A (en) * | 2014-01-09 | 2014-04-23 | 上海交通大学 | Preparation method of porous silicon template |
| CN105428432B (en) * | 2015-11-06 | 2017-04-12 | 上海师范大学 | Preparation method for porous light-trapping structure on surface of silicon solar cell |
| CN105696084B (en) * | 2016-02-01 | 2018-07-24 | 浙江晶科能源有限公司 | A kind of etching method of diamond wire silicon chip and application |
| CN105655448B (en) * | 2016-04-06 | 2018-01-09 | 广东爱康太阳能科技有限公司 | A kind of efficiently colored polycrystalline solar cell and preparation method thereof |
| CN105839193B (en) * | 2016-04-27 | 2018-09-21 | 新疆中硅科技有限公司 | A kind of preparation method of textured mono-crystalline silicon |
| CN107598183B (en) * | 2017-08-14 | 2020-06-12 | 嘉兴尚能光伏材料科技有限公司 | Macroscopic quantity preparation method of nano-silver particles |
| CN107737917B (en) * | 2017-09-27 | 2019-08-16 | 西安理工大学 | A kind of preparation method of sheet suede structure magnetism microwave absorption |
| CN109444710A (en) * | 2018-09-26 | 2019-03-08 | 上海神舟新能源发展有限公司 | The method for testing polysilicon grain crystal orientation by selective corrosion |
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| CN101475173A (en) * | 2009-01-20 | 2009-07-08 | 吉林大学 | Method for preparing super-hydrophobic antireflex micron and nano composite structure surface |
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