CN105070772A - Wet chemical method of preparing uniform reverse pyramid textured structures on the surface of a monocrystalline silicon - Google Patents
Wet chemical method of preparing uniform reverse pyramid textured structures on the surface of a monocrystalline silicon Download PDFInfo
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- CN105070772A CN105070772A CN201510550406.1A CN201510550406A CN105070772A CN 105070772 A CN105070772 A CN 105070772A CN 201510550406 A CN201510550406 A CN 201510550406A CN 105070772 A CN105070772 A CN 105070772A
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims abstract description 43
- 239000000126 substance Substances 0.000 title claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 48
- 239000010703 silicon Substances 0.000 claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005530 etching Methods 0.000 claims abstract description 28
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005137 deposition process Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 6
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001432 tin ion Inorganic materials 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract description 2
- 239000002082 metal nanoparticle Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910021418 black silicon Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021426 porous silicon Inorganic materials 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a wet chemical method of preparing uniform reverse pyramid textured structures on the surface of a monocrystalline silicon. The method is use for preparing uniform reverse pyramid textured structures on the surface of a large-size monocrystalline silicon. The method includes the following steps: firstly, placing a monocrystalline silicon chip in a deposition solution for deposition; secondly, placing the silicon chip that has undergone particle deposition processing in an etching solution for etching; thirdly, placing the silicon chip that has undergone etching processing in an alkali solution to conduct anisotropic etching; and fourthly, removing metal on the surface of the silicon chip by means of an acid solution. The method is capable of preparing uniform reverse pyramid textured structures on the surface of a large-size monocrystalline silicon. According to the method, pre-corrosion needs not to be conducted on the surface of a silicon chip, control over the dimensions of hole structures and control over distribution uniformity of the hole structures can be achieved through control during a metal deposition stage, and finally reverse pyramid structures can be evenly distributed over large areas. The method is simple and effective.
Description
Technical field
The present invention relates to a kind of wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface.
Background technology
For crystal silicon photovoltaic battery, increasing silicon chip as far as possible to the absorption of light, is the important step improving conversion efficiency of solar cell.In the method that crystal silicon solar energy battery surface deposition antireflective coating and silicon chip surface texturing are all conventional increase cell light absorptions.For monocrystalline silicon photovoltaic cell, the production technology generally adopted at present is the positive pyramid shape suede structure being etched random distribution by the method for alkali liquid corrosion at silicon chip surface.Compared to positive pyramid matte, in fact also have other multiple silicon chip surface texture body can play the function increasing light absorption, as circular hole matte, cellular matte, inverted pyramid matte etc.This wherein, inverted pyramid matte not only can obtain lower reflectivity and adopt by some high-efficiency battery chip architectures, and, through theory calculate, the silicon chip specific area with the inverted pyramid matte that four <111> crystal faces surround is 1.7 times that amass without matte silicon chip surface, is minimum in various suede structure.The PN junction of crystal silicon battery generates along textured surfaces, and therefore little surface area can reduce photo-generated carrier recombination probability, is conducive to the raising of battery efficiency.Efficiency reaches the PERL battery of 25%, namely have employed this inverted pyramid structure.Therefore, this structure is more suitable for efficient crystal-silicon battery slice.
The wet-chemical technique that monocrystalline silicon piece is prepared inverted pyramid matte or similar light trapping structure has a lot, mainly contains optics imprinting techniques and the large class of etching technique two.Optics imprinting techniques first coats mask glue at silicon chip surface, then carries out photoetching and remove part mask glue, obtain figure, then carry out chemical corrosion, obtains the matte of the inverted pyramid structure of rule.This method by the photovoltaic laboratory of University of New South Wales for the manufacture of various efficient solar battery.But this method is due to needs coating mask and remove mask structure, and step is complicated and cost is high, therefore always cannot mass production.Etching technique mainly adopts the method for metal catalytic to prepare porous silicon hole and groove structure, is generally used for and manufactures black silicon matte, improves battery efficiency by reducing reflectivity.But because the size of porous silicon hole and groove is generally between 100-300 nanometer, and the diffusion junctions degree of depth is in 200-300 nanometer, therefore black silicon face is caused to produce a large amount of diffusion death layers, and the strong complex effect of dead layer significantly limit the lifting of efficiency, the method making monocrystalline make black silicon is never applied to battery and produces line.Up to the present, adopt metal catalysed processes to make large-area monocrystalline silicon piece inverted pyramid matte, or blank out, be the technology commanding elevation that photovoltaic enterprise is pursued.
Summary of the invention
The present invention proposes a kind of wet chemical method can preparing even inverted pyramid matte at monocrystalline silicon surface first, can prepare even inverted pyramid matte on large size single crystal silicon chip (156mm × 156mm) surface.The present invention does not need to do pre-etching to silicon chip surface, by the control to metal deposition stage, realizes the uniformity controlling of size to pore space structure and distribution, finally realizes the Large-Area-Uniform distribution of inverted pyramid structure, simply effectively.
For achieving the above object, technical scheme of the present invention is a kind of wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface of design, for preparing even inverted pyramid matte at large size single crystal silicon chip surface, described large size single crystal silicon chip is for being not less than the monocrystalline silicon piece of 156mm × 156mm, and described wet chemical method comprises the steps:
1) monocrystalline silicon silicon chip is placed in deposit solution and carries out deposition processes, at silicon chip surface depositing metallic nanoparticles;
2) silicon chip after particle deposition process is placed in etching solution and carries out etching processing, etch nanometer pectination hole array at silicon chip surface;
3) silicon chip after etching processing is placed in aqueous slkali and carries out anisotropic etch processes, etch the matte with even inverted pyramid structure at silicon chip surface, each inwall of described inverted pyramid structure is <111> crystal face;
4) silicon chip surface metal is removed with acid solution cleaning.
Preferably, the described process preparing even inverted pyramid matte at large size single crystal silicon chip surface is carried out at low temperatures, and described low temperature is 12 ~ 40 DEG C.
Preferably, described deposit solution, having allocated on the basis of metal ion and hydrofluoric acid, also added appropriate sodium chloride and polyvinylpyrrolidone; The molecular weight of described polyvinylpyrrolidone is 3000 ~ 50000; Described metal ion is one or more in gold, silver, nickel, zinc, tin ion.
Preferably, described metal ion provides primarily of the slaine allocated in deposit solution, and described slaine is complex salts or silver sulfate.
Preferably, described deposit solution has allocated the hydrofluoric acid of 0.05% ~ 1%, the complex salts of 0.002% ~ 0.1% or silver sulfate, the polyvinylpyrrolidone of 0.001% ~ 2%, the sodium chloride of 0.001% ~ 3% into; Wherein, described percentage is mass percent, and described complex salts is the thiosulfate of silver.
Preferably, described etching solution has allocated the hydrofluoric acid of 20% ~ 40%, the hydrogen peroxide of 5% ~ 20% into; Wherein, described percentage is mass percent.
Preferably, the alkali in described aqueous slkali is one or more in NaOH, potassium hydroxide, Tetramethylammonium hydroxide, sodium carbonate, sodium acid carbonate; In described aqueous slkali, paper mill wastewater is 3 ~ 12%.
Preferably, the temperature of described deposition processes is 12 ~ 40 DEG C, and the time is 5 ~ 60min.
Preferably, the reaction temperature of described etching processing is 12 ~ 22 DEG C, and the time is 2 ~ 10min.
Preferably, the temperature of described anisotropic etch processes is 20 ~ 40 DEG C, and the time is 5 ~ 15min.
The present invention, in the first step depositional phase, just adopts special deposit solution for metal nanoparticle in the deposition of silicon face.3000 ~ 50000) and sodium chloride the present invention by adding the polyvinylpyrrolidone (molecular weight: of specific molecular structure in deposit solution, change charged ion concentration in solution, thus control the concentration class at metal nanoparticle formation initial stage and intergranular decentralization.In addition, because polyvinylpyrrolidone is multidentate ligand, the interior acyl group energy contained in its molecular structure and metal ion are combined by coordination, play effect that is sterically hindered and control metallic growth pattern simultaneously.Further, polyvinylpyrrolidone can be used as surfactant, is easily adsorbed on silicon face.And chloride ion has the function impelling metallic atom to assemble in growth course, it can utilize the skeleton structure of polyvinylpyrrolidone, impels metallic atom cluster at each growing point, and then improves aggregation extent, increases metal nanoparticle size.And hydrofluoric acid can allow the reduction reaction chain of metal continue certain hour, impel and deposit successfully.Finally, the metal nanoparticle of silicon chip surface deposition, is more evenly distributed, and particle size is larger, and particle size difference is less.
The present invention, in second step etch stages, makes full use of the above-mentioned metal nanoparticle in silicon chip surface deposition, coordinates hydrofluoric acid and hydrogen peroxide, etches, etch nanometer pectination hole array at silicon chip surface to monocrystalline silicon.The aperture in each hole, and hole is in the distribution of silicon chip surface, all directly related with metal nanoparticle.Due to metal nanoparticle, be more evenly distributed, particle size is larger, and particle size difference is less; So the nanometer pectination hole array etched, be more evenly distributed, aperture is larger, and aperture difference is less.
The present invention is in the 3rd step anisotropic etching stage, also can make full use of above-mentioned at the nanometer pectination hole array that silicon chip surface etches, coordinate aqueous slkali, monocrystalline silicon is etched further, based on the array of nanometer pectination hole, etch conical pit (inverted pyramid structure) at silicon chip surface.The shape of conical pit, and conical pit is in the distribution of silicon chip surface, all directly related with nanometer pectination hole array.Due to nanometer pectination hole array, be more evenly distributed, aperture is larger, and aperture difference is less; So the conical pit etched, be more evenly distributed.And because aperture, nanometer pectination hole is larger, so the degree of depth in nanometer pectination hole very deeply need not can etch the conical pit of large-size smoothly in the process of etching conical pit, the weight-loss ratio of silicon chip can reduce thereupon.
The present invention, at the 4th step wash phase, adopts hydrochloric acid solution (concentration range is 20% ~ 36%) or salpeter solution (concentration range is 30% ~ 70%) soaking and washing 15 ~ 20 minutes at room temperature 10 ~ 20 DEG C, removes the metal nanoparticle that silicon chip surface is residual.
Described on end, the process of monocrystalline silicon surface texture divides four steps to carry out successively by the present invention, and the processing procedure often walked is controlled, the result of back process gained, the basis of a step process after being, pre-process and post-process step is coordinated mutually, produces forward comprehensive effect.
The present invention has following features:
The present invention forms the initial stage at metal nanoparticle, and with regard to its concentration class of optimal control and intergranular decentralization, what ensure etch topography from source is controlled.
The compound suede structure that the present invention obtains evenly.
The present invention is in the anisotropic etching stage, by composite to aqueous slkali, the inching to conical pit cone angle can be realized, to adapt to the etching in different depth nanometer pectination hole, the nanometer pectination hole making the degree of depth not dark is not merged and remain as small size inverted pyramid structure in the anisotropic etching stage, can adapt to the trend that existing photovoltaic technology monocrystalline silicon piece thickness is day by day thinning.
The present invention is particularly conducive to the conical pit structure preparing large-size aperture, and this, to road diffusion and silk screen printing process after coupling, improves battery efficiency very useful.
The present invention can control weight-loss ratio while the inverted pyramid matte that preparation is suitable, and this is very effective to the crystal silicon chip of minimal thickness.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is further described.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
The invention provides a kind of wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface, for preparing even inverted pyramid matte at large size single crystal silicon chip surface, described large size single crystal silicon chip is for being not less than the monocrystalline silicon piece of 156mm × 156mm, and described wet chemical method comprises the steps:
1) monocrystalline silicon silicon chip is placed in deposit solution and carries out deposition processes, at silicon chip surface depositing metallic nanoparticles; Described deposit solution, having allocated on the basis of metal ion and hydrofluoric acid, also added appropriate sodium chloride and polyvinylpyrrolidone; The molecular weight of described polyvinylpyrrolidone is 3000 ~ 50000; Described metal ion is one or more in gold, silver, nickel, zinc, tin ion; Described metal ion provides primarily of the slaine allocated in deposit solution, and described slaine is complex salts or silver sulfate;
2) silicon chip after particle deposition process is placed in etching solution and carries out etching processing, etch nanometer pectination hole array at silicon chip surface; Described etching solution has allocated appropriate hydrofluoric acid and hydrogen peroxide into;
3) silicon chip after etching processing is placed in aqueous slkali and carries out anisotropic etch processes, etch the matte with even inverted pyramid structure at silicon chip surface, each inwall of described inverted pyramid structure is <111> crystal face; Alkali in described aqueous slkali is one or more in NaOH, potassium hydroxide, Tetramethylammonium hydroxide, sodium carbonate, sodium acid carbonate;
4) silicon chip surface metal is removed with acid solution cleaning;
The whole process preparing even inverted pyramid matte at large size single crystal silicon chip surface is carried out at low temperatures, and described low temperature is 12 ~ 40 DEG C.
Certain/some embodiment in, deposit solution has allocated the hydrofluoric acid of 0.05% ~ 1%, the complex salts of 0.002% ~ 0.1% or silver sulfate, the polyvinylpyrrolidone of 0.001% ~ 2%, the sodium chloride of 0.001% ~ 3% into; Wherein, described percentage is mass percent, and described complex salts is the thiosulfate of silver;
Certain/some embodiment in, etching solution has allocated the hydrofluoric acid of 20% ~ 40%, the hydrogen peroxide of 5% ~ 20% into; Wherein, described percentage is mass percent.
Certain/some embodiment in, in aqueous slkali, paper mill wastewater is 3 ~ 12%.
Certain/some embodiment in, the temperature of deposition processes is 12 ~ 40 DEG C, and the time is 5 ~ 60min.
Certain/some embodiment in, the reaction temperature of etching processing is 12 ~ 22 DEG C, and the time is 2 ~ 10min.
Certain/some embodiment in, the temperature of anisotropic etch processes is 20 ~ 40 DEG C, and the time is 5 ~ 15min.
Certain/some embodiment in, the concrete steps removing silicon chip surface metal with acid solution cleaning are: at room temperature 10 ~ 20 DEG C, adopt hydrochloric acid solution (concentration range is 20% ~ 36%) or salpeter solution (concentration range is 30% ~ 70%) soaking and washing 15 ~ 20 minutes, remove the metal nanoparticle that silicon chip surface is residual.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the wet chemical method of even inverted pyramid matte is prepared at monocrystalline silicon surface, for preparing even inverted pyramid matte at large size single crystal silicon chip surface, described large size single crystal silicon chip is for being not less than the monocrystalline silicon piece of 156mm × 156mm, it is characterized in that, described wet chemical method comprises the steps:
1) monocrystalline silicon silicon chip is placed in deposit solution and carries out deposition processes, at silicon chip surface depositing metallic nanoparticles;
2) silicon chip after particle deposition process is placed in etching solution and carries out etching processing, etch nanometer pectination hole array at silicon chip surface;
3) silicon chip after etching processing is placed in aqueous slkali and carries out anisotropic etch processes, etch the matte with even inverted pyramid structure at silicon chip surface, each inwall of described inverted pyramid structure is <111> crystal face;
4) silicon chip surface metal is removed with acid solution cleaning.
2. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 1, it is characterized in that, the described process preparing even inverted pyramid matte at large size single crystal silicon chip surface is carried out at low temperatures, and described low temperature is 12 ~ 40 DEG C.
3. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 2, it is characterized in that, described deposit solution, having allocated on the basis of metal ion and hydrofluoric acid, also added appropriate sodium chloride and polyvinylpyrrolidone; The molecular weight of described polyvinylpyrrolidone is 3000 ~ 50000; Described metal ion is one or more in gold, silver, nickel, zinc, tin ion.
4. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 3, it is characterized in that, described metal ion provides primarily of the slaine allocated in deposit solution, and described slaine is complex salts or silver sulfate.
5. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 4, it is characterized in that, described deposit solution has allocated the hydrofluoric acid of 0.05% ~ 1%, the complex salts of 0.002% ~ 0.1% or silver sulfate, the polyvinylpyrrolidone of 0.001% ~ 2%, the sodium chloride of 0.001% ~ 3% into; Wherein, described percentage is mass percent, and described complex salts is the thiosulfate of silver.
6. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 5, is characterized in that, described etching solution has allocated the hydrofluoric acid of 20% ~ 40%, the hydrogen peroxide of 5% ~ 20% into; Wherein, described percentage is mass percent.
7. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 6, it is characterized in that, the alkali in described aqueous slkali is one or more in NaOH, potassium hydroxide, Tetramethylammonium hydroxide, sodium carbonate, sodium acid carbonate; In described aqueous slkali, paper mill wastewater is 3 ~ 12%.
8. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 7, is characterized in that, the temperature of described deposition processes is 12 ~ 40 DEG C, and the time is 5 ~ 60min.
9. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 8, is characterized in that, the reaction temperature of described etching processing is 12 ~ 22 DEG C, and the time is 2 ~ 10min.
10. the wet chemical method preparing even inverted pyramid matte at monocrystalline silicon surface according to claim 9, is characterized in that, the temperature of described anisotropic etch processes is 20 ~ 40 DEG C, and the time is 5 ~ 15min.
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| CN106067488A (en) * | 2016-08-16 | 2016-11-02 | 苏州阿特斯阳光电力科技有限公司 | A kind of preparation method of the suede structure of crystal silicon solar energy battery |
| CN106158996A (en) * | 2016-09-26 | 2016-11-23 | 淮海工学院 | A kind of monocrystalline silicon-based nano inverted pyramid structure back of the body passivating solar battery and preparation method thereof |
| CN106521635A (en) * | 2016-11-17 | 2017-03-22 | 上海交通大学 | All-solution preparation method of nanoscale pyramid suede on silicon surface |
| WO2017185592A1 (en) * | 2016-04-29 | 2017-11-02 | 南京工业大学 | Texturing method of polycrystalline silicon wafer cut by diamond wire |
| CN107924836A (en) * | 2016-05-26 | 2018-04-17 | 南京中云新材料有限公司 | A kind of textured method of monocrystalline silicon sheet surface |
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| CN108447942A (en) * | 2018-03-09 | 2018-08-24 | 常州时创能源科技有限公司 | The polishing process for etching of the black silicon PERC batteries of polycrystalline |
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| CN112251817A (en) * | 2019-07-05 | 2021-01-22 | 松山湖材料实验室 | Inverted pyramid auxiliary texturing additive and application thereof |
| CN116004232A (en) * | 2022-11-25 | 2023-04-25 | 常州君合科技股份有限公司 | Monocrystalline silicon polishing alkali etching additive and application thereof |
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| WO2017185592A1 (en) * | 2016-04-29 | 2017-11-02 | 南京工业大学 | Texturing method of polycrystalline silicon wafer cut by diamond wire |
| CN107924836B (en) * | 2016-05-26 | 2021-09-21 | 南京中云新材料有限公司 | Method for texturing surface of monocrystalline silicon wafer |
| CN107924836A (en) * | 2016-05-26 | 2018-04-17 | 南京中云新材料有限公司 | A kind of textured method of monocrystalline silicon sheet surface |
| CN108630786A (en) * | 2016-06-27 | 2018-10-09 | 苏州阿特斯阳光电力科技有限公司 | A kind of preparation method of crystal silicon solar energy battery suede structure |
| CN106024988A (en) * | 2016-07-26 | 2016-10-12 | 南京科乃迪科环保科技有限公司 | One-step wet black silicon preparation and surface treatment method |
| CN106067488B (en) * | 2016-08-16 | 2017-11-03 | 苏州阿特斯阳光电力科技有限公司 | A kind of preparation method of the suede structure of crystal silicon solar energy battery |
| CN106067488A (en) * | 2016-08-16 | 2016-11-02 | 苏州阿特斯阳光电力科技有限公司 | A kind of preparation method of the suede structure of crystal silicon solar energy battery |
| CN106158996A (en) * | 2016-09-26 | 2016-11-23 | 淮海工学院 | A kind of monocrystalline silicon-based nano inverted pyramid structure back of the body passivating solar battery and preparation method thereof |
| CN106521635A (en) * | 2016-11-17 | 2017-03-22 | 上海交通大学 | All-solution preparation method of nanoscale pyramid suede on silicon surface |
| CN108305915A (en) * | 2018-02-02 | 2018-07-20 | 浙江晶科能源有限公司 | A kind of silicon wafer fine hair making method |
| CN108447942A (en) * | 2018-03-09 | 2018-08-24 | 常州时创能源科技有限公司 | The polishing process for etching of the black silicon PERC batteries of polycrystalline |
| CN112251817A (en) * | 2019-07-05 | 2021-01-22 | 松山湖材料实验室 | Inverted pyramid auxiliary texturing additive and application thereof |
| CN112251817B (en) * | 2019-07-05 | 2022-08-05 | 松山湖材料实验室 | Inverted pyramid auxiliary texturing additive and application thereof |
| CN111864013A (en) * | 2020-07-16 | 2020-10-30 | 江苏海洋大学 | Dry-wet mixed preparation method of monocrystal silicon-based inverted pyramid suede |
| CN116004232A (en) * | 2022-11-25 | 2023-04-25 | 常州君合科技股份有限公司 | Monocrystalline silicon polishing alkali etching additive and application thereof |
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