CN106784063A - Monocrystalline silicon piece and its application comprising the suede structure of falling rectangular pyramid - Google Patents
Monocrystalline silicon piece and its application comprising the suede structure of falling rectangular pyramid Download PDFInfo
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- CN106784063A CN106784063A CN201710063021.1A CN201710063021A CN106784063A CN 106784063 A CN106784063 A CN 106784063A CN 201710063021 A CN201710063021 A CN 201710063021A CN 106784063 A CN106784063 A CN 106784063A
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- rectangular pyramid
- monocrystalline silicon
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- silicon chip
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims abstract description 122
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 185
- 229910052710 silicon Inorganic materials 0.000 claims description 185
- 239000010703 silicon Substances 0.000 claims description 185
- 238000004140 cleaning Methods 0.000 claims description 70
- 239000002585 base Substances 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 46
- 239000003513 alkali Substances 0.000 claims description 45
- 230000004048 modification Effects 0.000 claims description 27
- 238000012986 modification Methods 0.000 claims description 27
- 229910021645 metal ion Inorganic materials 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 239000012467 final product Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 abstract description 24
- 235000008216 herbs Nutrition 0.000 abstract description 17
- 210000002268 wool Anatomy 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 163
- 239000008367 deionised water Substances 0.000 description 71
- 229910021641 deionized water Inorganic materials 0.000 description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 71
- 239000000243 solution Substances 0.000 description 57
- 229910017604 nitric acid Inorganic materials 0.000 description 30
- 230000035484 reaction time Effects 0.000 description 28
- 239000013078 crystal Substances 0.000 description 21
- 239000010949 copper Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 101710134784 Agnoprotein Proteins 0.000 description 14
- 238000007654 immersion Methods 0.000 description 14
- 239000002082 metal nanoparticle Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 230000003292 diminished effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002310 reflectometry Methods 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
-
- 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
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention relates to the making herbs into wool structure of monocrystalline silicon piece and its application, more particularly to a kind of monocrystalline silicon piece comprising the suede structure of falling rectangular pyramid and its application in solar cells, belong to technical field of solar batteries.The group of falling rectangular pyramid includes one or more high with the rectangular pyramid that falls that the ratio of the base length of side is 0.7 6: 1.The present invention has further related to the etching method of the monocrystalline silicon piece.
Description
Technical field
The suede structure of falling rectangular pyramid is included the present invention relates to the making herbs into wool structure of monocrystalline silicon piece and its application, more particularly to one kind
Monocrystalline silicon piece and its application in solar cells, belong to technical field of solar batteries.
Background technology
Silica-based solar cell is that industrial quarters produces most commonly used solar cell, and important technology present in it is asked
Topic is that the reflectivity of silicon face is higher.To solve this technical problem, the silicon chip with suede structure is applied to solar energy
It is to reduce solar cell cost and further improve one of effective way of electricity conversion in battery, was sent out from 1998
Since existing, extensively paid attention to by researcher and industrial quarters.
Common suede structure, including irregular projection, silicon nanowire array, porous silicon surface and pyramid and fall
The suede structure on Pyramid surface.Wherein, for pyramid or the suede structure of inverted pyramid structure, gold is generally believed down
The suede structure performance of word tower structure is more excellent.
So-called inverted pyramid structure is the seamed edge length of side positive rectangular pyramid equal with the base length of side, i.e. its high and base side
Ratio long isEtched typically by (100) face, ultimately form and the inverted pyramid knot for falling is enclosed by (111) face
Structure, is randomly formed on the surface of silicon chip by corrasion, and the structure can carry out triple reflection to sunshine, reflect in theory
Rate can be reduced to 5%~15%.
The monocrystalline silicon piece texture structural research of inverted pyramid structure of the prior art is more.
Typically for example, CN201410384313 and CN201420441064 disclose a kind of with inverted pyramid matte
The monocrystalline silicon piece of structure, the making herbs into wool surface has by the pit of multiple inverted pyramid shapes, and the top of the pit depths is in
Round and smooth shape.The opening of the pit is quadrangle, and the length of side of the quadrangle is 1~10 μm, and the depth of the pit is 1~10
μm.The opening of the pit is square.
Such as non-patent literature " Maskless inverted pyramid texturization of silicon " again,
Yan Wang et al., Sci.Rep.5,10843；doi：10.1038/srep10843 (2015), and document " One-step
Cu-assisted Chemical etching on Polycrystalline Silicon ", Yu Dong (Yu Dong) et al.,
Micro-nano electronic technology, in April, 2014, also discloses that similar inverted pyramid structure.
Shape yet with inverted pyramid structure is fixed, is only different size, to the angle of reflection of sunshine
Degree is fixed, and effect and battery efficiency to anti-reflection have been difficult further to be lifted.
The content of the invention
The first aspect of the present invention there is provided a kind of monocrystalline silicon piece comprising the suede structure of falling rectangular pyramid, the silicon chip table
Face random distribution has the group of falling rectangular pyramid, and the group of falling rectangular pyramid includes one or more high and base length of side ratio is 0.7-6: 1
Fall rectangular pyramid.
In currently available technology, for the silicon chip with the suede structure of falling rectangular pyramid, it is typical gold
Word tower structure, i.e. the seamed edge the length of side positive rectangular pyramid equal with the base length of side, i.e. its height are with the ratio of the base length of side
Etched typically by (100) face, ultimately form and enclose the inverted pyramid structure for falling by four faces of family of crystal planes { 111 }.
For the silicon chip with inverted pyramid suede structure for actually obtaining, the ratio of the high and base length of side of rectangular pyramid typically exists
Between 0.7-0.9: 1.
In one embodiment, the monocrystalline silicon piece comprising the suede structure of falling rectangular pyramid, its surface random distribution has
The group of falling rectangular pyramid, the group of falling rectangular pyramid includes one or more high with the rectangular pyramid that falls that the ratio of the base length of side is 1.2-4.4: 1；
The rectangular pyramid is selected from one or more in following rectangular pyramid：
1) ratio a kind of high and the base length of side be 1.2-1.5: 1 between fall rectangular pyramid；
2) and/or a kind of high and the base length of side ratio be 1.9-2.3: 1 between fall rectangular pyramid；
3) and/or a kind of high and the base length of side ratio be 2.5-3.1: 1 between fall rectangular pyramid；
4) and/or a kind of high and the base length of side ratio be 3.2-3.7: 1 between fall rectangular pyramid；
5) and/or a kind of high and the base length of side ratio be 4.0-4.4: 1 between fall rectangular pyramid.
In still another embodiment, it is described fall rectangular pyramid top be selected from it is square, circular, oval or by a plurality of curve
One or more in the closed figures for surrounding.
In another specifically embodiment, four ribs with the ratio of the base length of side between 1.2-1.5: 1 high
Cone, its base length of side is between 90nm-500nm.
In another specifically embodiment, four ribs with the ratio of the base length of side between 1.9-2.3: 1 high
Cone, its base length of side is between 80nm-500nm.
In another specifically embodiment, four ribs with the ratio of the base length of side between 2.5-3.1: 1 high
Cone, its base length of side is between 80nm-500nm.
In another specifically embodiment, four ribs with the ratio of the base length of side between 3.2-3.7: 1 high
Cone, its base length of side is between 60nm-500nm.
In another specifically embodiment, four ribs with the ratio of the base length of side between 4.0-4.4: 1 high
Cone, its base length of side is between 70nm-500nm.
The second aspect of the present invention is to provide a kind of preparation side of the monocrystalline silicon piece comprising the suede structure of falling rectangular pyramid
Method, it includes：
1) monocrystalline silicon piece is positioned in acid Woolen-making liquid, is etched at room temperature, cleaning removal metal ion；
2) being placed in the monocrystalline silicon piece with the suede structure of falling rectangular pyramid after cleaning carries out structural modification in alkali lye, cleaning is
.
In one embodiment, silver ion, 10-200mmol/ comprising 0.5-10mmol/L in the acid Woolen-making liquid
The H of the copper ion of L, the HF of 1-8mol/L and 0.1-8mol/L2O2；Further, 1- is preferably comprised in the acid Woolen-making liquid
The silver ion of 10mmol/L, the copper ion of 20-180mmol/L, the H of the HF of 2-6mol/L and 0.3-5mol/L2O2。
In another embodiment, the alkali lye is the aqueous solution of the hydroxide of alkalies and alkaline earth, for example,
LiOH、NaOH、KOH、RbOH、CsOH、Mg(OH)2、Ca(OH)2、Sr(OH)2And Ba (OH)2；Further, the alkali lye be containing
The aqueous solution of the hydroxide of 1-5% (weight) alkalies and alkaline earth.
In one specifically embodiment, in the acid Woolen-making liquid, the mol ratio of silver ion and copper ion is 1:
5-100, further preferably 1: 20-60.
In one more specifically embodiment, the preparation side of the monocrystalline silicon piece comprising the suede structure of falling rectangular pyramid
Method, it includes：
1) monocrystalline silicon piece is positioned in acid Woolen-making liquid, is etched at 20 DEG C~35 DEG C 1~10 minute, cleaning is gone
Except the metal ion of silicon chip surface；
2) monocrystalline silicon piece with the suede structure of falling rectangular pyramid after cleaning is placed in alkali lye, under the conditions of 20 DEG C~30 DEG C
Structural modification 5-90s is carried out, cleaning is obtained final product.
The third aspect of the present invention is to provide the above-mentioned monocrystalline silicon piece comprising the suede structure of falling rectangular pyramid in solar-electricity
Application in pond.
Brief description of the drawings
Fig. 1：The figures of the monocrystalline silicon piece SEM comprising the suede structure of falling rectangular pyramid without alkali lye modification are shown, is got the bid from figure
Can be seen that suede structure shows the typical structure of falling rectangular pyramid that completion is enclosed by 221 crystal faces, two sides on silicon chip at note
, at 48 ° or so, the height of rectangular pyramid and the ratio of the base length of side are between 1.2-1.5: 1 for angle；The base length of side of rectangular pyramid exists
90nm-512nm or so；It is highly in 125nm-760nm or so.
Fig. 2：The figures of the monocrystalline silicon piece SEM comprising the suede structure of falling rectangular pyramid without alkali lye modification are shown, is got the bid from figure
Can be seen that suede structure shows the typical structure of falling rectangular pyramid that completion is enclosed by 331 crystal faces, two sides on silicon chip at note
, at 40 ° or so, the height of rectangular pyramid and the ratio of the base length of side are between 1.9-2.3: 1 for angle；The base length of side of rectangular pyramid exists
135nm-425nm or so；It is highly in 260nm-980nm or so.
Fig. 3：The figures of the monocrystalline silicon piece SEM comprising the suede structure of falling rectangular pyramid without alkali lye modification are shown, is got the bid from figure
Can be seen that suede structure shows the typical structure of falling rectangular pyramid that completion is enclosed by 441 crystal faces, two sides on silicon chip at note
, at 32 ° or so, the height of rectangular pyramid and the ratio of the base length of side are between 2.5-3.1: 1 for angle；The base length of side of rectangular pyramid exists
95nm-620nm or so；It is highly in 250nm-1840nm or so.
Fig. 4：The figures of the monocrystalline silicon piece SEM comprising the suede structure of falling rectangular pyramid without alkali lye modification are shown, is got the bid from figure
Can be seen that suede structure shows the typical structure of falling rectangular pyramid that completion is enclosed by 551 crystal faces, two sides on silicon chip at note
, at 28 ° or so, the height of rectangular pyramid and the ratio of the base length of side are between 3.2-3.7: 1 for angle；The base length of side of rectangular pyramid exists
95nm-625nm or so；It is highly in 310nm-2300nm or so.
Fig. 5：The figures of the monocrystalline silicon piece SEM comprising the suede structure of falling rectangular pyramid after alkali lye modification are shown, it is by Fig. 1
Silicon chip through alkali lye modify and obtain.Be can be seen that at mark from figure on silicon chip suede structure still show it is typical by
221 crystal faces enclose the structure of falling rectangular pyramid of completion, but size has diminished, two side angles at 48 ° or so, the height of rectangular pyramid
With the ratio of the base length of side between 1.2-1.5: 1, the base length of side of rectangular pyramid is in 90nm-500nm or so；It highly exists
100nm-750nm or so.
Fig. 6：The figures of the monocrystalline silicon piece SEM comprising the suede structure of falling rectangular pyramid after alkali lye modification are shown, it is by Fig. 2
Silicon chip through alkali lye modify and obtain.Be can be seen that at mark from figure on silicon chip suede structure still show it is typical by
331 crystal faces enclose the structure of falling rectangular pyramid of completion, but size has diminished, two side angles at 40 ° or so, the height of rectangular pyramid
With the ratio of the base length of side between 1.9-2.3: 1, the base length of side of rectangular pyramid is in 80nm-500nm or so；It highly exists
150nm-1150nm or so.
Fig. 7：The figures of the monocrystalline silicon piece SEM comprising the suede structure of falling rectangular pyramid after alkali lye modification are shown, it is by Fig. 3
Silicon chip through alkali lye modify and obtain.Be can be seen that at mark from figure on silicon chip suede structure still show it is typical by
441 crystal faces enclose the structure of falling rectangular pyramid of completion, but size has diminished, two side angles at 32 ° or so, the height of rectangular pyramid
With the ratio of the base length of side in 2.5-3.1：Between 1, the base length of side of rectangular pyramid is in 80nm-500nm or so；It highly exists
200nm-1550nm or so.
Fig. 8：The figures of the monocrystalline silicon piece SEM comprising the suede structure of falling rectangular pyramid after alkali lye modification are shown, it is by Fig. 4
Silicon chip through alkali lye modify and obtain.Be can be seen that at mark from figure on silicon chip suede structure still show it is typical by
551 crystal faces enclose the structure of falling rectangular pyramid of completion, but size has diminished, two side angles at 28 ° or so, the height of rectangular pyramid
With the ratio of the base length of side between 3.2-3.7: 1, the base length of side of rectangular pyramid is in 60nm-500nm or so；It highly exists
200nm-1850nm or so.
Specific embodiment
Also the present invention further can be understood by embodiment, wherein the embodiment illustrates that some are prepared or user
Method.It is to be appreciated, however, that these embodiments do not limit the present invention.Currently known or further exploitation change of the invention
Change is considered within the scope of the invention described herein and claimed below.
In currently available technology, for the monocrystalline silicon piece with the suede structure of falling rectangular pyramid, it is typical
Inverted pyramid structure, i.e. the seamed edge the length of side positive rectangular pyramid equal with the base length of side, i.e. its height are with the ratio of the base length of sideEtched typically by (100) face, ultimately form the golden word that falls for being enclosed to fall by four faces of family of crystal planes { 111 }
Tower structure.For the silicon chip with inverted pyramid suede structure for actually obtaining, the ratio of the high and base length of side of rectangular pyramid
Typically between 0.7-0.9: 1, its size is at 1~10 μm or so.Although inverted pyramid suede structure is effective in the prior art
The solar battery efficiency for reducing the reflectivity of monocrystalline silicon piece and being prepared by the type silicon chip also calibration pyramid structure
Monocrystalline silicon piece battery increases, but the battery efficiency of its solar cell for preparing is also only between 17.5-18.8%.And
And prior art improves the follow-up solar cell preparation work of matching inverted pyramid structure monocrystalline silicon piece with being also continually striving to always
Skill, but its battery efficiency cannot break through 19% technical bottleneck.
And the structure of falling rectangular pyramid obtained by the present invention, not only with relatively low reflectivity, what is more important structure is
Submicron order, and surface is smooth, so as to not increase extra Carrier recombination while light absorbs are increased, makes optical gain quilt
Effectively utilize.Further, since the architectural characteristic of the uniqueness of falling rectangular pyramid, allows the slurry in silk-screen printing preferably to fill out
Fill in the structure, obtain more excellent electrode contact, effectively reduce the series resistance of battery, improve fill factor, curve factor.Always
It, the low reflection of the structure of falling rectangular pyramid, low compound, easily filling characteristic so that battery efficiency is significantly improved.
In the present invention, refer to the thin of the depths of falling rectangular pyramid, portion more than top at the top of the rectangular pyramid
It is divided into down the conical section of rectangular pyramid, and the square face opening portion of rectangular pyramid is down the bottom of rectangular pyramid.Four ribs
The top of cone is selected from one or more in closed figures that are square, circular, oval or being surrounded by a plurality of curve.
Be can be seen that under conditions of being modified without alkali lye from accompanying drawing 1-4 of the invention, the suede structure of monocrystalline silicon piece is in
Reveal the typical structure of falling rectangular pyramid, be taper below its bottom, such as Fig. 1 shows the rectangular pyramid that falls that completion is enclosed by 221 crystal faces
Structure, with the difference of etching condition, the structure type of falling rectangular pyramid is also changed, and the structure of falling rectangular pyramid is enclosed by 221 crystal faces
Into the structure of falling rectangular pyramid be changed into the structure of falling rectangular pyramid that 331 crystal faces, 441 crystal faces or 551 crystal faces enclose completion, and four rib
The dimensions of wimble structure also there occurs change, for example, height is deepened, base size dimension expands.And work as monocrystalline silicon piece process
Alkali lye is modified, and monocrystalline silicon piece texture structure becomes more smooth, and the physical dimension of falling rectangular pyramid becomes more uniform, and for example Fig. 2 shows
After the monocrystalline silicon piece for going out is modified through alkali lye, the top and faceted pebble that the structure of falling rectangular pyramid of completion is enclosed by 331 crystal faces become more light
Sliding, the physical dimension of falling rectangular pyramid becomes more uniform, thus the suede structure of monocrystalline silicon piece becomes more smooth, and this point is from figure
Monocrystalline silicon piece texture structure shown in 6 can be seen that.
Surprisingly it has been found that by alkali lye modify the monocrystalline silicon piece comprising the structure of falling rectangular pyramid, it is prepared therefrom too
Positive energy battery efficiency is greatly improved, specific up to more than 19.7%.With the prior art typically list with inverted pyramid structure
Crystal silicon chip (for example, the disclosed monocrystalline silicon pieces with inverted pyramid suede structure of patent CN201410384313) is compared, battery
Efficiency can improve more than 1%.
Monocrystalline silicon piece comprising the suede structure of falling rectangular pyramid of the invention can be entered by various methods known in the art
It is prepared by row.Those skilled in the art can select existing etching method, and preparation is set for according to said structure, it is known that
Method includes but is not limited to chemical etching, mechanical carving groove, photoetching, reactive ion etching, electron beam lithography etc..
In being preferably carried out scheme at one, the suede structure of falling rectangular pyramid of the invention is obtained by method for chemially etching；
Monocrystalline silicon piece is placed in acid Woolen-making liquid after etching, the described matte of falling rectangular pyramid knot can be obtained by simple modification
Structure, specifically includes：
1) monocrystalline silicon piece is positioned in acid Woolen-making liquid, is etched at room temperature, cleaning removal metal ion；
2) being placed in the monocrystalline silicon piece with the suede structure of falling rectangular pyramid after cleaning carries out structural modification in alkali lye, cleaning is
.
Specifically, in the acid Woolen-making liquid comprising the silver ion of 0.5-10mmol/L, 10-200mmol/L copper from
Son, the H of the HF of 1-8mol/L and 0.1-8mol/L2O2；Further, the silver comprising 1-10mmol/L in the acid Woolen-making liquid
Ion, the copper ion of 20-180mmol/L, the H of the HF of 2-6mol/L and 0.3-5mol/L2O2。
In the acid Woolen-making liquid, the concentration of silver ion can be 0.5,1,2,3,4,5,6,7,8,9 or 10mmol/L；
The concentration of copper ion can be 10,20,30,40,50,60,70,80,90,100,110,120,130,140,150,160,170,
180th, 190 or 200mmol/L；The concentration of HF can be 1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5 or
8mol/L；H2O2Concentration can be 0.1,0.2,0.3,0.4,0.5,0.6,0.8,1,1.25,1.5,1.75,2,2.25,2.5,
2.75th, 3,3.25,3.5,3.75,4,4.25,4.5,4.75,5,5.5,6,6.5,7,7.5 or 8mol/L.
The method that acid Woolen-making liquid of the invention is urged altogether using copper silver, it combines silver and is catalyzed the characteristics of with copper catalysis each,
So that the existing big depth-width ratio of structure that etching is obtained, there is relatively open opening, such as the structure of falling rectangular pyramid again.Ag particle masters
It is responsible for etching (borehole) downwards, copper particle auxiliary lateral etching (reaming), therefore the structure of rectangular pyramid can be obtained down, for example
The silicon wafer suede structure for going out as Figure 1-4, and the structure is submicrometer structure.
Present invention discover that in the acid Woolen-making liquid, the optimum mole ratio of silver ion and copper ion is 1: 5-100, enters one
Step ground is preferably 1: 20-60.Specifically, the mol ratio of silver ion and copper ion can be 1: 5,1: 10,1: 15,1: 20,1:
25th, 1: 30,1: 35,1: 40,1: 45,1: 50,1: 55,1: 60,1: 65,1: 70,1: 75,1: 80,1: 85,1: 90,1: 95 or 1:
100。
For fine-hair maring using monocrystalline silicon slice method of the invention, monocrystalline silicon piece can be made to bring preferably effect using alkali lye modification
Really, alkali lye modification can make the monocrystalline silicon sheet surface comprising the suede structure of falling rectangular pyramid more smooth, from make monocrystalline silicon piece with it is rear
Continuous solar cell preparation technology is more matched, and improves battery efficiency.
In the present invention, the alkali lye is the aqueous solution of the hydroxide of alkalies and alkaline earth, for example, LiOH,
NaOH、KOH、RbOH、CsOH、Mg(OH)2、Ca(OH)2、Sr(OH)2And Ba (OH)2；The hydrogen-oxygen of the alkalies and alkaline earth
Compound is preferably NaOH or KOH.
Further, the alkali lye is the aqueous solution of the hydroxide containing 1-5% (weight) alkalies and alkaline earth.Example
Such as, the alkali lye is the aqueous solution of the hydroxide containing 1,2,3,4 or 5% (weight) alkalies and alkaline earth.
In one specifically embodiment, the preparation method comprises the following steps：
1) monocrystalline silicon piece is positioned in acid Woolen-making liquid, is etched at 20 DEG C~35 DEG C 1~10 minute, cleaning is gone
Except the metal ion of silicon chip surface；
2) monocrystalline silicon piece with the suede structure of falling rectangular pyramid after cleaning is placed in alkali lye, under the conditions of 20 DEG C~30 DEG C
Structural modification 5-90s is carried out, cleaning is obtained final product.
Specifically, in step 1) in, etch temperature can for 20,21,22,23,24,25,26,27,28,29,30,
31st, 32,33,34 or 35 DEG C；Etching period can be 1,2,3,4,5,6,7,8,9 or 10 minutes.
In step 2) in, structural modification temperature can be 20,21,22,23,24,25,26,27,28,29 or 30 DEG C；Structure
The modification time can be 5,10,20,30,40,50,60,70,80 or 90s.
In order to obtain optimal technique effect, in the preparation process in accordance with the present invention, monocrystalline silicon piece is inserted into acid Woolen-making liquid
Before, definitely pre-treatment can be carried out to it, for example, monocrystalline silicon piece is placed in into HF and HNO31- is reacted in the solution of composition
10min；Then clean to remove reaction dissolvent with deionized water.The above method is known in the art, people in the art
Member can carry out unrestricted choice according to different situations.
Similarly, after an etching step with to use cleaning fluid to remove metal ion be also existing after alkali lye structural modification step
Have known to technology, for example with HNO3, one or more reagent is prepared into the certain density aqueous solution as clear in HCl or HF
Washing lotion carrys out cleaning silicon chip to remove the metallic particles on silicon chip or metal ion.
Embodiment 1
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 2mmol/L3Cu (the NO of+100mmol/L3)2The HF+0.4mol/L of+1.5mol/L
H2O2, reaction temperature is 30 DEG C, and the reaction time is in 240s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 1%, 90s is reacted at 20 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) monocrystalline silicon piece is obtained after cleaning carries out electron-microscope scanning, as a result as shown in figure 1, by step 5) obtain after cleaning
The monocrystalline silicon piece texture structure for obtaining is as shown in Figure 5.
The typical rectangular pyramid that falls that completion is enclosed by 221 crystal faces is still showed by suede structure on silicon chip after alkali lye modification
Structure, two side angles at 48 ° or so, the height of rectangular pyramid and the ratio of the base length of side between 1.2-1.5: 1, rectangular pyramid
The base length of side in 90nm-500nm or so；It is highly in 100nm-750nm or so.
Embodiment 2
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 2mmol/L3Cu (the NO of+40mmol/L3)2The HF+0.6mol/L's of+2.5mol/L
H2O2, reaction temperature is 25 DEG C, and the reaction time is in 210s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 3%, 40s is reacted at 26 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 1
It is similar.
Embodiment 3
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 3mmol/L3Cu (the NO of+30mmol/L3)2The HF+0.7mol/L's of+3mol/L
H2O2, reaction temperature is 20 DEG C, and the reaction time is in 120s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 2%, 50s is reacted at 30 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 1
It is similar.
It is realApplyExample 4
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 4mmol/L3Cu (the NO of+60mmol/L3)2The HF+1mol/L's of+2.5mol/L
H2O2, reaction temperature is 23 DEG C, and the reaction time is in 100s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 4%, 15s is reacted at 22 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 1
It is similar.
Embodiment 5
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 4mmol/L3Cu (the NO of+80mmol/L3)2The HF+1.5mol/L's of+3mol/L
H2O2, reaction temperature is 25 DEG C, and the reaction time is in 210s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 1%, 80s is reacted at 23 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) monocrystalline silicon piece is obtained after cleaning carries out electron-microscope scanning, as a result as shown in Fig. 2 by step 5) obtain after cleaning
The monocrystalline silicon piece texture structure for obtaining is as shown in Figure 6.
Still showed by suede structure on the monocrystalline silicon piece after alkali lye modification and typically enclose falling for completion by 331 crystal faces
Rectangular pyramid structure, two side angles at 40 ° or so, rectangular pyramid height and the base length of side ratio between 1.9-2.3: 1,
The base length of side of rectangular pyramid is in 80nm-500nm or so；It is highly in 150nm-1150nm or so.
Embodiment 6
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 5mmol/L3Cu (the NO of+80mmol/L3)2The HF+2mol/L's of+3.5mol/L
H2O2, reaction temperature is 26 DEG C, and the reaction time is in 240s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 2%, 60s is reacted at 24 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 5
It is identical.
Embodiment 7
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 6mmol/L3Cu (the NO of+100mol/L3)2The HF+2.5mol/L's of+3.8mol/L
H2O2, reaction temperature is 27 DEG C, and the reaction time is in 160s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 3%, 30s is reacted at 25 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 5
It is identical.
Embodiment 8
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 6mmol/L3Cu (the NO of+100mmol/L3)2The HF+3mol/L's of+4mol/L
H2O2, reaction temperature is 22 DEG C, and the reaction time is in 290s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 5%, 5s is reacted at 25 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) monocrystalline silicon piece is obtained after cleaning carries out electron-microscope scanning, as a result as shown in figure 3, by step 5) obtain after cleaning
The monocrystalline silicon piece texture structure for obtaining is as shown in Figure 7.
Suede structure still shows the typical knot of falling rectangular pyramid that completion is enclosed by 441 crystal faces on the monocrystalline silicon piece for being obtained
Structure, two side angles at 32 ° or so, the height of rectangular pyramid and the ratio of the base length of side between 2.5-3.1: 1, rectangular pyramid
The base length of side is in 80nm-500nm or so；It is highly in 200nm-1550nm or so.
Embodiment 9
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 7mmol/L3Cu (the NO of+120mmol/L3)2The HF+3.5mol/L of+4.5mol/L
H2O2, reaction temperature is 23 DEG C, and the reaction time is in 240s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 2%, 60s is reacted at 25 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 8
It is similar.
Embodiment 10
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 8mmol/L3Cu (the NO of+150mmol/L3)2The HF+3.75mol/L's of+5mol/L
H2O2, reaction temperature is 24 DEG C, and the reaction time is in 210s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 3%, 50s is reacted at 20 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 8
It is similar.
Embodiment 11
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 8mmol/L3Cu (the NO of+170mmol/L3)2The HF+4mol/L's of+5.5mol/L
H2O2, reaction temperature is 21 DEG C, and the reaction time is in 360s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 5%, 10s is reacted at 27 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) monocrystalline silicon piece is obtained after cleaning carries out electron-microscope scanning, as a result as shown in figure 4, by step 5) obtain after cleaning
The monocrystalline silicon piece texture structure for obtaining is as shown in Figure 8.
Suede structure still shows the typical knot of falling rectangular pyramid that completion is enclosed by 551 crystal faces on obtained monocrystalline silicon piece
Structure, but size diminished, and, at 28 ° or so, the ratio of the high and base length of side of rectangular pyramid is in 3.2-3.7: 1 for two side angles
Between, the base length of side of rectangular pyramid is in 60nm-500nm or so；It is highly in 200nm-1850nm or so.
Embodiment 12
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 10mmol/L3Cu (the NO of+200mmol/L3)2The HF+5mol/L's of+7mol/L
H2O2, reaction temperature is 25 DEG C, and the reaction time is in 300s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 3%, 40s is reacted at 25 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 11
It is similar.
Embodiment 13
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 5mmol/L3Cu (the NO of+150mmol/L3)2The HF+2mol/L's of+3.5mol/L
H2O2, reaction temperature is 26 DEG C, and the reaction time is in 80s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 1%, 70s is reacted at 25 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 1
It is identical.
Embodiment 14
1) silicon chip is placed in HF+HNO3Chemical attack is carried out in solution is to remove monocrystalline silicon surface damage layer solution temperature
8 DEG C or so, the reaction time is 3min；Silicon chip is placed in deionized water and is cleaned；
2) will be performed etching in the silicon chip immersion Woolen-making liquid after cleaning and form sub-micron rectangular pyramid with monocrystalline silicon surface
Suede structure, Woolen-making liquid composition is the AgNO of 3mmol/L3Cu (the NO of+105mmol/L3)2The HF+0.7mol/L's of+3mol/L
H2O2, reaction temperature is 20 DEG C, and the reaction time is in 480s；
3) silicon chip is placed in deionized water and is cleaned；Silicon chip after making herbs into wool is immersed into HNO3Cleaned in solution,
Removal surface metal nano particle；Deionized water is cleaned；
4) silicon chip is immersed and is processed in NaOH aqueous slkalis so that silicon chip surface suede structure is smooth, NaOH aqueous slkalis are
The aqueous solution of percentage by weight 3%, 50s is reacted at 28 DEG C；
5) silicon chip is placed in deionized water and is cleaned；Silicon chip after cleaning is placed in HCl+H2O2Carried out in solution clear
Wash, remove silicon sheet surface metal ion；Silicon chip is placed in deionized water to carry out cleaning and obtains final product.
By step 3) and 5) monocrystalline silicon piece that obtains carries out electron-microscope scanning, the suede structure for being obtained and the structure of embodiment 8
It is identical.
Effect example 1
Reflectivity will be determined without the monocrystalline silicon piece after alkali lye modification and alkali lye modification in embodiment 1-14, concrete outcome is such as
Under：
| Reflectivity (R) | Without alkali lye modification | After alkali lye modification |
| Embodiment 1 | 6.6% | 13.5% |
| Embodiment 2 | 6.3% | 13.0% |
| Embodiment 3 | 6.4% | 13.3% |
| Embodiment 4 | 6.2% | 13.6% |
| Embodiment 5 | 5.9% | 12.9% |
| Embodiment 6 | 5.7% | 12.7% |
| Embodiment 7 | 5.8% | 13.0% |
| Embodiment 8 | 4.9% | 10.3% |
| Embodiment 9 | 5.0% | 9.9% |
| Embodiment 10 | 4.8% | 9.3% |
| Embodiment 11 | 4.0% | 7.4% |
| Embodiment 12 | 3.9% | 7.2% |
| Embodiment 13 | 6.5% | 13.4% |
| Embodiment 14 | 4.9% | 9.7% |
Effect example 2
To there is inverted pyramid disclosed in monocrystalline silicon piece and CN201410384313 after alkali lye modification in embodiment 1-14
The monocrystalline silicon piece (comparative example 1) of suede structure is prepared into solar cell according to common process, determines solar cell properties, tool
Body result is as follows：
| Uoc(V) | Isc(A) | FF (%) | Eff. (%) | |
| Embodiment 1 | 0.6420 | 9.348 | 81.17 | 19.94 |
| Embodiment 2 | 0.6396 | 9.439 | 80.21 | 19.82 |
| Embodiment 3 | 0.6426 | 9.261 | 81.50 | 19.85 |
| Embodiment 4 | 0.6437 | 9.289 | 80.39 | 19.72 |
| Embodiment 5 | 0.6412 | 9.361 | 80.40 | 19.79 |
| Embodiment 6 | 0.6439 | 9.297 | 81.17 | 19.87 |
| Embodiment 7 | 0.6413 | 9.380 | 80.30 | 19.77 |
| Embodiment 8 | 0.6400 | 9.463 | 80.17 | 19.87 |
| Embodiment 9 | 0.6396 | 9.428 | 80.24 | 19.8 |
| Embodiment 10 | 0.6433 | 9.352 | 81.41 | 20.04 |
| Embodiment 11 | 0.6489 | 9.478 | 81.55 | 19.90 |
| Embodiment 12 | 0.6503 | 9.522 | 81.72 | 20.16 |
| Embodiment 13 | 0.6419 | 9.369 | 80.52 | 19.71 |
| Embodiment 14 | 0.6439 | 9.497 | 80.46 | 19.82 |
| Comparative example 1 | 0.6387 | 9.028 | 79.10 | 18.84 |
Present invention merely illustrates some claimed specific embodiments, one of them or more skill
Described technical characteristic can be combined with arbitrary one or more technical schemes in art scheme, these are combined and obtain
Technical scheme also in the application protection domain, technical scheme is disclosed in the present invention just as obtained from these are combined
It is specific in content to record the same.
Claims (16)
1. a kind of monocrystalline silicon piece comprising the suede structure of falling rectangular pyramid, the silicon chip surface random distribution has the group of falling rectangular pyramid, institute
State the rectangular pyramid that falls that the group of falling rectangular pyramid ratio with the base length of side high including one or more is 0.7-6: 1.
2. monocrystalline silicon piece according to claim 1, it is characterised in that the group of falling rectangular pyramid include one or more high with
The ratio of the base length of side is 1.2-4.4: 1 rectangular pyramid that falls.
3. monocrystalline silicon piece according to claim 2, it is characterised in that it is described fall rectangular pyramid be selected from it is following fall rectangular pyramid in
One or more：
1) ratio a kind of high and the base length of side be 1.2-1.5: 1 between fall rectangular pyramid；
2) and/or a kind of high and the base length of side ratio be 1.9-2.3: 1 between fall rectangular pyramid；
3) and/or a kind of high and the base length of side ratio be 2.5-3.1: 1 between fall rectangular pyramid；
4) and/or a kind of high and the base length of side ratio be 3.2-3.7: 1 between fall rectangular pyramid；
5) and/or a kind of high and the base length of side ratio be 4.0-4.4: 1 between fall rectangular pyramid.
4. monocrystalline silicon piece according to claim 3, it is characterised in that the ratio with the base length of side high is in 1.2-1.5: 1
Between fall rectangular pyramid, its base length of side is between 90nm-500nm.
5. monocrystalline silicon piece according to claim 3, it is characterised in that the ratio with the base length of side high is in 1.9-2.3: 1
Between fall rectangular pyramid, its base length of side is between 80nm-500nm.
6. monocrystalline silicon piece according to claim 3, it is characterised in that the ratio with the base length of side high is in 2.5-3.1: 1
Between fall rectangular pyramid, its base length of side is between 80nm-500nm.
7. monocrystalline silicon piece according to claim 3, it is characterised in that the ratio with the base length of side high is in 3.2-3.7: 1
Between fall rectangular pyramid, its base length of side is between 60nm-500nm.
8. monocrystalline silicon piece according to claim 3, it is characterised in that the ratio with the base length of side high is in 4.0-4.4: 1
Between fall rectangular pyramid, its base length of side is between 70nm-500nm.
9. the preparation method of the monocrystalline silicon piece of the suede structure of falling rectangular pyramid is included described in a kind of any one of claim 1-8, its bag
Include：
1) monocrystalline silicon piece is positioned in acid Woolen-making liquid, is etched at room temperature, cleaning removal metal ion；
2) being placed in the monocrystalline silicon piece with the suede structure of falling rectangular pyramid after cleaning carries out structural modification in alkali lye, cleaning is obtained final product.
10. the preparation method of monocrystalline silicon piece according to claim 9, it is characterised in that included in the acid Woolen-making liquid
The silver ion of 0.5-10mmol/L, the copper ion of 10-200mmol/L, the H of the HF of 1-8mol/L and 0.1-8mol/L2O2。
The preparation method of 11. monocrystalline silicon pieces according to claim 10, it is characterised in that in the acid Woolen-making liquid preferably
The copper ion of silver ion, 20-180mmol/L, the H of the HF of 2-6mol/L and 0.3-5mol/L comprising 1-10mmol/L2O2。
The preparation method of 12. monocrystalline silicon pieces according to claim 10, it is characterised in that silver ion and copper ion mole
Than being 1: 5-100.
The preparation method of 13. monocrystalline silicon pieces according to claim 10, it is characterised in that silver ion and copper ion mole
Than being 1: 20-60.
The preparation method of 14. monocrystalline silicon pieces according to claim 9, it is characterised in that the alkali lye is containing 1-5% (weights
Amount) alkalies and alkaline earth hydroxide the aqueous solution.
The preparation method of 15. monocrystalline silicon piece according to claim any one of 9-14, it is characterised in that it includes：
1) monocrystalline silicon piece is positioned in acid Woolen-making liquid, is etched at 20 DEG C~35 DEG C 1~10 minute, cleaning removal silicon
The metal ion on piece surface；
2) monocrystalline silicon piece with the suede structure of falling rectangular pyramid after cleaning is placed in alkali lye, is carried out under the conditions of 20 DEG C~30 DEG C
Structural modification 5-90s, cleaning is obtained final product.
Described in 16. claim any one of 1-8 comprising the suede structure of falling rectangular pyramid monocrystalline silicon piece in solar cells should
With.
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