CN102304766B - Method for preparing silicon surface light trapping structure through sliver mirror reaction - Google Patents
Method for preparing silicon surface light trapping structure through sliver mirror reaction Download PDFInfo
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Abstract
The invention discloses a preparation method of a silicon surface light trapping structure and belongs to the technical field of solar cells. In the preparation method, a (100) or (111) silicon wafer is used, the sliver mirror reaction is adopted to plate silver on the surface of the silicon wafer, and the silver-plated silicon wafer is soaked in an acidic etching solution to obtain an antireflection light trapping structure. The reflectivity of the light trapping structure is reduced to 3.4% within a spectral range of 300-1000nm. In the method, on the basis of maintaining the etching characteristics of a room-temperature wet process, the sliver mirror reaction is adopted to simplify the precious metal nanoparticle plating process, a silicon surface with higher antireflection effect is obtained, and a new technical means for improving the efficiency of a silicon-based solar cell is provided.
Description
Technical field
The invention belongs to technical field of solar batteries, relate to a kind of silicon surface light trapping structure preparation method in solar battery structure.Be specifically related to silicon face antireflective light trapping structure preparation technology's noble metal nano particles catalysis etching technics technology.
Background technology
Reduce cost and improve the emphasis direction that efficiency of conversion is solar cell research.Silicon solar cell is because raw material sources are extensive, and cost is lower, in occupation of the dominant position in solar cell market.The reflection that reduces incident sunlight on the battery sensitive surface is to improve one of means of the photoelectric transformation efficiency of solar cell.Antireflective measure commonly used mainly contains and adopts traditional method etch silicon substrate, prepares the antireflective coatings such as TiOx (x≤2), SiNx etc. at the sensitive surface of surface of silicon or battery.These methods generally need complex apparatus, running cost higher.Noble metal nano particles catalysis lithographic technique is first in silicon chip surface deposition one deck nano level or the even distribution of submicron order thickness, discrete noble metal layer, then etch silicon in containing the solution of HF.This technology is wet chemical etch at normal temperatures, does not need complicated equipment, favorable repeatability, cost is lower, can be compatible with traditional solar battery process, be easy to combine with industrialized production, and all applicable to silicon single crystal, polysilicon and silicon film, therefore have obvious advantage.For noble metal nano particles catalysis lithographic technique, at the noble metal nano particles of surface deposition the result of final etching is had material impact, usually utilize the means depositing noble metal nanoparticles such as plating, electroless plating, evaporation or self-assembly.Silver mirror reaction is a kind of chemical plating method of ancient silver-plated mirror processed, be characterized in that reaction is simple, cost is lower, limitation is used for silver-plated mirror processed all the time, inhomogeneous with the silverskin that the method plates out, discontinuous, the basement membrane bonding force is little, peel off easily, be unsuitable for the demand of common plated film, but for noble metal nano particles catalysis lithographic technique, silver mirror reaction just satisfies the requirement of the discontinuous metallics of matrix surface, therefore the surperficial discontinuous metal nanoparticle for preparing in the noble metal nano particles lithographic technique by silver mirror reaction is a kind of new approaches, novel method is of very high actual application value.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of silicon surface light trapping structure, adopt silver mirror reaction plating noble metal nano particles to carry out the catalysis etching of noble metal nano particles; The method comprises the steps:
A. cleaning silicon chip, the silicon face that obtains cleaning;
B. silver mirror reaction is silver-plated: in reaction vessel, add silver nitrate solution first, drip gradually again ammoniacal liquor, and constantly concussion, until the precipitation that produces disappears just; Put into the silicon chip after the cleaning, drip again glucose or glutaraldehyde solution, heating in water bath, observe one deck silver and be plated on the silicon chip this moment;
C. adopt noble metal nano particles catalysis etching: the silicon chip after silver-plated is soaked in the acid attack agent, can see the generation of bubble, namely silicon face is in the etching process; Described acid etching liquid adopts 40wt% hydrofluoric acid, 30wt% hydrogen peroxide and deionized water formulated according to 1: 5: 10 volume ratio, to guarantee the reflection preventing ability of etching homogeneity and light trapping structure;
D. silicon chip aftertreatment: the silicon chip nitric acid dousing after the etching, remain in the silver of silicon face with removal, then use deionized water (or ultrapure water) to rinse well, can be observed silicon face has the blackout phenomenon, namely obtain light trapping structure, vacuum-drying at silicon face.
The method of the described cleaning silicon chip of step a is: ultrasonic cleaning in acetone, with deionized water or ultrapure water flushing; Clean with CP-4A solution again, with deionized water or ultrapure water flushing; Clean with hydrofluoric acid solution at last, with deionized water or ultrapure water flushing.The concentration of described hydrofluoric acid solution is 7.3mol/L.
Described CP-4A solution is by HF solution, HNO
3Solution, dehydrated alcohol, H
2O was by 3: 5: 3: 22 volume ratio is formulated, wherein, and HNO
3The massfraction of solution is that the massfraction of 65%～68%, HF solution is 40%.
The concentration of Silver Nitrate described in the step b is 0.05～0.2mol/L, and ammonia concn is 1mol/L; The concentration of described glucose and glutaraldehyde is between 0.1-0.5mol/L, to guarantee severe degree and the corrosive effect of reaction; The temperature of described water-bath is 20-30 ℃.
The time of etching is 3-5min among the step c.
The concentration of nitric acid described in the steps d is 20wt%-40wt%, and soak time is 25-35min, preferred 30min.
Described deionized water and ultrapure resistivity of water are more than 16M Ω cm.
Described noble metal nano particles is silver particles.
Described silicon chip is (100) or (111) oriented single crystal silicon chip, and the resistivity of (100) oriented single crystal silicon chip is at 7～13 Ω cm, and the resistivity of (111) oriented single crystal silicon chip is at 8～13 Ω cm.
The invention has the beneficial effects as follows: the silicon surface light trapping structure that adopts method of the present invention to prepare, dropped to 3.4% at 300nm to the spectral band average reflectance of 1000nm, for the efficient that improves silica-based solar cell provides new technique means, for stable, the efficient application of solar cell proposed new approaches.The feature of the present invention uses that silver mirror reaction has been simplified the technological process of noble metal nano particles plating, the temperature remains within the normal range wet etching obtains the higher anti-reflective effect of silicon face.
Description of drawings
Fig. 1 adopts silver mirror reaction silver-plated at (100) oriented single crystal silicon chip, through acid etch silicon face structure (stereoscan photograph) after 3 minutes.
Fig. 2 adopts silver mirror reaction silver-plated at (100) oriented single crystal silicon chip, carries out the anti-reflective effect of 3 minutes front and back of noble metal nano particles catalysis etching, the average reflectance 3.4% after the etching in 300nm arrives the 1000nm spectral range.
Embodiment
The present invention proposes a kind of silicon face anti-reflection structure preparation method.Below in conjunction with drawings and Examples the present invention is further described.
Embodiment 1
1. adopting resistivity is (100) oriented single crystal silicon chip of 7-13 Ω cm, is put in the acetone normal temperature ultrasonic cleaning 10min; Adopt deionized water rinsing 2min; Then at CP-4A solution soak at room temperature 5min, deionized water rinsing 2min; With 7.3mol/L hydrofluoric acid solution soak at room temperature 2min, deionized water rinsing 2min; Vacuum-drying;
Described CP-4A solution is by HF solution, HNO
3Solution, dehydrated alcohol, H
2O was by 3: 5: 3: 22 volume ratio is formulated, wherein, and HNO
3The massfraction of solution is that the massfraction of 65%, HF solution is 40%.
2. stand-by reaction vessel cleans with hot potassium hydroxide solution first, and deionized water rinsing cleans deionized water rinsing, the reaction environment that obtains cleaning again with salpeter solution; Wherein the concentration of potassium hydroxide solution and salpeter solution is between the 20-40wt% concentration.
3. first splashing into concentration in reaction vessel is the 0.1mol/L silver nitrate solution, drips gradually the ammoniacal liquor that concentration is 1mol/L again, and the pH value is controlled between the 8-9, and constantly concussion, until the precipitation that produces disappears just;
4. put into the silicon chip after the cleaning, drip the glucose solution that several concentration are 0.5mol/L, 25 ℃ of heating in water bath are observed one deck silver and are generated along wall of container after the short period of time, final whole wall of container and the silicon chip that is immersed in the solution of plating;
5. the silicon chip after silver-plated is immersed in the acid etching solution, can see the generation of bubble in the etching process, etching time is 3min, uses the deionized water rinsing silicon chip after etching is finished; Described acid attack agent adopts 40wt% hydrofluoric acid, 30wt% hydrogen peroxide and deionized water formulated according to 1: 5: 10 volume ratio;
6. be 20wt% nitric acid dousing 30min with concentration, remove the silver that remains in silicon face, then rinse well with deionized water, can be observed silicon face has the blackout phenomenon, namely obtains the antireflective light trapping structure of silicon face.
7. vacuumize drying, sample is preserved in moisture eliminator.
The resistivity of water of deionization described in the present embodiment is more than 16M Ω cm.
The silicon surface light trapping structure that present embodiment obtains as shown in Figure 1.Adopt solar cell spectral responsivity, reflectivity and quantum efficiency measurement system to measure, dropped to 3.4% level in the spectral range internal reflection rate of 300～1000nm, reflectance curve as shown in Figure 2.
Embodiment 2
Adopting resistivity is (111) oriented single crystal silicon chip of 8-13 Ω cm, is put in the acetone normal temperature ultrasonic cleaning 10min; Adopt deionized water rinsing 2min; Then at CP-4A solution soak at room temperature 5min, deionized water rinsing 2min; With 7.3mol/L hydrofluoric acid solution soak at room temperature 2min, deionized water rinsing 2min; Vacuum-drying;
Described CP-4A solution is by HF solution, HNO
3Solution, dehydrated alcohol, H
2O was by 3: 5: 3: 22 volume ratio is formulated, wherein, and HNO
3The massfraction of solution is that the massfraction of 68%, HF solution is 40%.
2. stand-by reaction vessel cleans with hot potassium hydroxide solution first, and deionized water rinsing cleans deionized water rinsing, the reaction environment that obtains cleaning again with salpeter solution; Wherein the concentration of potassium hydroxide solution and salpeter solution is between the 20-40wt% concentration.
3. first splash into silver nitrate solution in reaction vessel, concentration is controlled at 0.2mol/L, drips gradually the ammoniacal liquor that concentration is 1mol/L again, and PH is controlled between the 8-9, and constantly concussion, until the precipitation that produces disappears just;
4. put into the silicon chip after the cleaning, drip the glutaraldehyde solution that several concentration are 0.1mol/L, 25 ℃ of heating in water bath are observed one deck silver and are generated along wall of container after the short period of time, final whole wall of container and the silicon chip that is immersed in the solution of plating;
5. the silicon chip after silver-plated is immersed in the acid etching solution, can see the generation of bubble in the etching process, etching time is 5min, uses the deionized water rinsing silicon chip after etching is finished; Described acid attack agent adopts hydrofluoric acid (concentration is 40wt%), hydrogen peroxide (30wt%) and deionized water formulated according to 1: 5: 10 volume ratio;
6. with 40wt% nitric acid dousing 30min, remove the silver that remains in silicon face, then rinse well with deionized water, can be observed silicon face has the blackout phenomenon, namely obtains the antireflective light trapping structure of silicon face;
7. vacuumize drying, sample is preserved in moisture eliminator.
The resistivity of water of deionization described in the present embodiment is more than 16M Ω cm.
The present invention adopts (100) or (111) silicon chip, uses CP-4A method cleaning silicon chip; Reaction vessel cleans with hot potassium hydroxide solution, salpeter solution and deionized water, then adopt silver mirror reaction silver-plated on silicon chip surface, reductive agent is taked two kinds, be respectively glutaraldehyde and glucose, silvering size of particles, thickness, the dispersiveness of two kinds of reductive agent formation have certain difference, so catalytic effect is different; Afterwards the silicon chip after silver-plated is immersed in the acid etching liquid, take different etching times; Sample behind the last etching soaks 30min at salpeter solution and removes residual silver particles, rinses well with deionized water again, and can be observed the surface has the blackout phenomenon, namely obtains silicon surface light trapping structure.
The above; only for the better 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; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (10)
1. method of utilizing silver mirror reaction to prepare silicon surface light trapping structure, it is characterized in that: the method comprises the steps:
A. cleaning silicon chip, the silicon face that obtains cleaning;
B. silver mirror reaction is silver-plated: in reaction vessel, add silver nitrate solution first, drip gradually again ammoniacal liquor, and constantly concussion, until the precipitation that produces disappears just; Put into the silicon chip after the cleaning, drip again glucose or glutaraldehyde solution, heating in water bath;
C. adopt noble metal nano particles catalysis etching: the silicon chip after silver-plated is immersed in the acid etching liquid, and described acid etching liquid adopts 40wt% hydrofluoric acid, 30wt% hydrogen peroxide and deionized water formulated according to the volume ratio of 1:5:10;
D. silicon chip aftertreatment: the silicon chip nitric acid dousing after the etching, remain in the silver of silicon face with removal, then rinse vacuum-drying with deionized water or ultrapure water well.
2. method according to claim 1, it is characterized in that: the method for the described cleaning silicon chip of step a is: ultrasonic cleaning in acetone, with deionized water or ultrapure water flushing; Clean with CP-4A solution again, with deionized water or ultrapure water flushing; Clean with hydrofluoric acid solution at last, with deionized water or ultrapure water flushing.
Described CP-4A solution is by HF solution, HNO3 solution, dehydrated alcohol, H
2It is formulated that O presses the volume ratio of 3:5:3:22, wherein, and HNO
3The massfraction of solution is that the massfraction of 65%～68%, HF solution is 40%.
3. preparation method according to claim 2, it is characterized in that: the concentration of hydrofluoric acid solution described in the step a is 7.3mol/L.
4. method according to claim 1, it is characterized in that: the concentration of silver nitrate solution described in the step b is 0.05～0.2mol/L, ammonia concn is 1mol/L.
5. method according to claim 1, it is characterized in that: the concentration of glucose described in the step b and glutaraldehyde is between 0.1-0.5mol/L.
6. method according to claim 1, it is characterized in that: the temperature of the described water-bath of step b is 20-30 ℃.
7. method according to claim 1, it is characterized in that: the time of etching is 3-5min among the step c.
8. method according to claim 1, it is characterized in that: the concentration of nitric acid described in the steps d is 20wt%-40wt%, soak time is 25-35min.
9. method according to claim 1, it is characterized in that: described silicon chip is (100) or (111) oriented single crystal silicon chip, and the resistivity of (100) oriented single crystal silicon chip is at 7～13 Ω cm, and the resistivity of (111) oriented single crystal silicon chip is at 8～13 Ω cm.
10. method according to claim 1 and 2, it is characterized in that: described deionized water and ultrapure resistivity of water are more than 16M Ω cm.
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| CN102560493B (en) * | 2012-01-18 | 2013-10-30 | 电子科技大学 | Method for preparing silicon nanowire array |
| CN102694076B (en) * | 2012-06-12 | 2015-04-22 | 沈阳大学 | Preparation method of silicon thin film surface antireflection structure |
| CN103103511B (en) * | 2013-02-28 | 2015-04-15 | 华北电力大学 | Method for preparing nanometer silver particles with controllable silicon surface appearances by using silver mirror reaction |
| CN103887367B (en) * | 2014-03-06 | 2016-08-17 | 陕西师范大学 | A kind of preparation method of silver nano-grain auxiliary twice etching silicon micro-nano hole antireflective texture |
| CN103943477A (en) * | 2014-04-01 | 2014-07-23 | 京东方科技集团股份有限公司 | Thin film transistor, manufacturing method thereof, double-face displaying device and single-face displaying device |
| 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 |
| CN107302040B (en) * | 2017-06-22 | 2018-11-20 | 烟台南山学院 | The preparation method of Ag nano wire light trapping structure is inlayed based on wet etching silicon face |
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| CN102157621B (en) * | 2011-03-03 | 2013-03-13 | 郑州大学 | Square silicon nanometer hole and preparation method thereof |
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