CN104409322A - Preparation method of sub-wavelength silicon nanowire array - Google Patents
Preparation method of sub-wavelength silicon nanowire array Download PDFInfo
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- CN104409322A CN104409322A CN201410614911.3A CN201410614911A CN104409322A CN 104409322 A CN104409322 A CN 104409322A CN 201410614911 A CN201410614911 A CN 201410614911A CN 104409322 A CN104409322 A CN 104409322A
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- nanowire array
- silicon nanowire
- sub
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- silicon
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 108
- 239000010703 silicon Substances 0.000 title claims abstract description 108
- 239000002070 nanowire Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 37
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000005530 etching Methods 0.000 claims abstract description 23
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000002923 metal particle Substances 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 39
- 229920005591 polysilicon Polymers 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 101710134784 Agnoprotein Proteins 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000003491 array Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 14
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000010931 gold Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00214—Processes for the simultaneaous manufacturing of a network or an array of similar microstructural devices
-
- 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 preparation method of a sub-wavelength silicon nanowire array and belongs to the nano material technical field. According to the preparation method of the invention, a cheap commercial polycrystalline silicon sheet is adopted as a raw material; a catalytic effect of nano metal particles including Ag, Pd, Au, Pt and Cu is utilized; one or two steps of a metal nanoparticle assisted etching method is utilized to perform etching, so that a large-scale (156*156mm<2>) silicon nanowire array of a single crystal structure can be prepared; the silicon nanowire array is subjected to secondary corrosion, so that a large-scale thin-tipped nanowire array of a sub-wavelength structure can be effectively obtained; and silicon nanowire arrays of different structures can be prepared through adjusting and controlling parameters such as the size of metal nanoparticles, the concentration of hydrofluoric acid, corrosion time and the concentration of lye. The large-scale nanowire array of the sub-wavelength structure obtained through adopting the method has excellent anti-reflection properties for light, so that silicon nanowires have a bright application prospect in the solar photovoltaic field.
Description
Technical field
The present invention relates to a kind of preparation method of sub-wavelength silicon nanowire array, belong to technical field of nano material.
Background technology
In recent years, silicon nanowires is as a kind of novel semi-conducting material, the characteristics such as huge specific area, quantum limitation effect, skin effect are possessed because of it, make them in optical, electrical, thermal and magnetic and catalytic reaction etc., show peculiar physicochemical properties, thus show very important utilization potentiality in fields such as luminescence generated by light, large scale integrated circuit, single-electron device, nano-sensors.
The direction of growth according to silicon nanowires is divided, and usual its preparation method mainly divides " from bottom to top " and " from top to bottom " two kinds." from bottom to top " refer to from atom and molecule level, utilize catalyst to grow, in Material growth process, its structure, component and size etc. are controlled.Although the method for this type disposablely can grow fairly large silicon nanowires sample, it is difficult to the located growth realizing silicon nanowires, for the application of later stage electronic device brings great difficulty." from top to bottom " refer to from body material, utilize laser or nanometer etching technology to prepare nano-material, metal nanoparticle auxiliary etch method is as typical " from top to bottom " technology of preparing of one, because of its have that equipment requirement is low, technique is simple, growth parameter(s) is easy to control, reproducible, can low cost synthesis high-sequential, the advantage such as the silicon nanowire array of high length-diameter ratio and receiving much concern.The people such as Tsing-Hua University Peng Qing Kui utilize two single metal nano particle auxiliary etch legal systems for the monocrystalline silicon nano line array (patent publication No.: CN 1693191 A) of single axial arranging; Chinese patent CN 103572374 A discloses a kind of two single metal nano particle auxiliary etch legal systems for the method for silicon nanowires, utilizes ion sputtering film coating method at silicon chip surface depositing metallic nanoparticles, at HF/H
2o
2in corrosive liquid, etching single crystal silicon chip prepares silicon nanowires; Patent CN 102040192 A proposes to adopt the monocrystalline silicon piece being oriented to <111> to be raw material, adopts a single metal nano particle auxiliary etch method to realize the preparation of bending silicon nanowire array.The people such as North China Electric Power University Li Mei one-tenth utilize N-shaped monocrystalline silicon for raw material, two single metal nano particle auxiliary etch are adopted to prepare the silicon nanowire array with sub-wavelength structure, and find that it shows superior anti-reflection characteristic, application prospect (patent publication No.: CN 103030100 A) is shown in high performance solar batteries field.
But although existing about the report of metal nano auxiliary etch legal system for silicon nanowire array at present, raw materials is still based on monocrystalline silicon piece.Compared to monocrystalline silicon polysilicon chip, there is lower cost, can realize if just think with polysilicon chip be substrate prepare extensive silicon nanowire array for reduction silicon nanowires be of great significance at the commercial application tool in the fields such as transducer, opto-electronic device, catalytic science.In addition, because polysilicon chip is still the main material of solar cell generation, by introducing the silicon nanowire array with sub-wavelength structure on its surface, greatly can improve the anti-reflection effect of polysilicon chip, this makes silicon nanowire array also show huge utilization prospect in the photovoltaic field except the fields such as nano-sensor, opto-electronic device, nano-catalytic.
Summary of the invention
The object of the invention is to the preparation method proposing a kind of sub-wavelength silicon nanowire array, the method with the commercial polysilicon chip of cheapness for raw material, by the catalytic action of nano metal particles (Ag, Pd, Au, Pt, Cu), use the standby silicon nanowire array on a large scale with mono-crystalline structures of one-step or two-step metal nanoparticle auxiliary etch legal system, through obtaining the anticaustic of silicon nanowire array, there is sub-wavelength structure nano-wire array on a large scale, and it shows good antireflection characteristic to light.
The preparation method of sub-wavelength silicon nanowire array of the present invention, specifically comprises the following steps:
(1) by polysilicon chip successively with acetone, toluene, ethanol, deionized water is ultrasonic cleans 1 ~ 20 minute respectively, the polysilicon chip cleaned up is put into by H
2sO
4and H
2o
2soak 1 ~ 60 minute in the solution be mixed to get for the ratio of 3:1 by volume, being placed on concentration is soak 1 ~ 120min in the hydrofluoric acid solution of 0.1 ~ 40wt%, for subsequent use after clean with deionized water rinsing after taking-up;
(2) by the catalytic action of metal nanoparticle Ag, Pd, Au, Pt or Cu, adopt one-step or two-step metal nanoparticle auxiliary etch method, etch at silicon chip surface, form extensive silicon nanowire array;
(3) the extensive silicon nanowire array containing nano metal particles obtained in step (2) is placed in oxidizing solution immersion 10 ~ 600min that concentration is 0.1 ~ 90wt%, obtains silicon nanowire array with after washed with de-ionized water;
(4) silicon nanowire array obtained in step (3) is placed in etching agent etching 0.01 ~ 48h at 10 ~ 100 DEG C, dry up the silicon nanowire array that can obtain and have sub-wavelength structure with a large amount of washed with de-ionized water, nitrogen afterwards, etching agent chooses the hydrofluoric acid mixed solution that alkaline solution that concentration is 0.1 ~ 90wt% or oxycompound concentration are 0.1 ~ 50wt%.
In a single metal nano particle auxiliary etch method of the present invention, etching agent is the mixed solution of HF and slaine composition, and in mixed solution, the concentration of HF is 0.1 ~ 33mol/L, the concentration of slaine is 0.01 ~ 10mol/L, and described slaine is AgNO
3, KAuCl
4, HAuCl
4, K
2ptCl
6, H
2ptCl
6or CuNO
3, the etching reaction time is 0.5 ~ 600min.
Two single metal nano particle auxiliary etch methods of the present invention comprise the steps: to carry out metal nanoparticle deposition in the mixed solution first formed at HF and slaine, and described slaine is AgNO
3, KAuCl
4, HAuCl
4, K
2ptCl
6, H
2ptCl
6or CuNO
3in mixed solution, the concentration of HF is 0.1 ~ 33mol/L, the concentration of slaine is 0.001 ~ 10mol/L, and sedimentation time is 0.5 ~ 60min; Be positioned over by HF and H after afterwards the polysilicon chip depositing metal nanoparticle being rinsed
2o
2, HNO
3, Fe (NO
3)
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8etch in the etching liquid of composition, in etching liquid, the dense of HF is 0.1 ~ 33mol/L, H
2o
2, HNO
3, Fe (NO
3)
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8concentration be 0.01 ~ 20mol/L, etch period is 0.5 ~ 600min.
If reaction system have chosen HF/AgNO in one-step or two-step metal nanoparticle auxiliary etch method of the present invention
3system, its reaction unit should do lucifuge process.
In step of the present invention (3), oxidizing solution is the one in nitric acid, hydrogen peroxide, ammoniacal liquor.
Described in step of the present invention (4), alkaline solution is NaOH or potassium hydroxide solution; Oxide is H
2o
2, HNO
3, Fe (NO
3)
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8.
In a single metal nano particle auxiliary etch method of the present invention, the deposition of metal nanoparticle and being etched in same reaction system of silicon chip are carried out simultaneously.
In two single metal nano particle auxiliary etch methods of the present invention, the deposition of metal nanoparticle and silicon chip separately carry out.
The beneficial effect of this law:
(1) the present invention adopts the metal nanoparticle auxiliary etch technology of low cost, with commercial rollout polysilicon chip for raw material, effectively can reduce the preparation cost of monocrystalline silicon nano line further;
(2) the present invention introduces sub-wavelength structure by secondarily etched in silicon nanowire array, shows good anti-reflection characteristic to sunlight, and this makes silicon nanowire array show huge utilization prospect in photovoltaic field.
Accompanying drawing explanation
The silicon nanowire array that Fig. 1 has sub-wavelength structure prepares schematic diagram;
Fig. 2 is (left side) (right side) sample surfaces afterwards before embodiment 1 polysilicon chip surface silicon nano-wire array is introduced;
Fig. 3 is sample surfaces after embodiment 2 polysilicon chip surface silicon nano-wire array is introduced;
Fig. 4 is that embodiment 3 polysilicon chip surface silicon nano-wire array introduces sample reflection rate sign before and after sub-wavelength structure silicon nanowire array.
Embodiment
Introduce the present invention in detail below by accompanying drawing and instantiation, but following example is only limitted to explain the present invention, protection scope of the present invention should comprise all the elements in claims.
Embodiment 1
The preparation method of sub-wavelength silicon nanowire array described in the present embodiment, specifically comprises the following steps:
(1) 156 × 156mm will be of a size of
2, doping type is p-type, resistance 1 Ω, thickness are 220 μm commercial solar-grade polysilicon sheet uses acetone, toluene, ethanol, deionized water Ultrasonic Cleaning silicon chip 10 minutes successively;
(2) H is put into
2sO
4and H
2o
2volume ratio is soak 1 minute in the solution of 3:1, and being placed on concentration is soak 10min in the hydrofluoric acid solution of 10wt%, for subsequent use after a large amount of deionized water rinsing after taking out;
(3) 500mlHF/AgNO is prepared
3corrosive liquid, HF and AgNO
3concentration be respectively 2.3mol/L and 5mol/L; Moved to darkroom after the polysilicon chip cleaned up is put into corrosive liquid and left standstill the silicon nanowire array that 50min obtains metal ion;
(4) have the silicon nanowire array of metal ion to put into HNO that concentration is 80wt% is taken out
3middle immersion 20min, obtains silicon nanowire array with after washed with de-ionized water;
(5) taking out silicon nanowire array, to be placed in concentration be that the sodium hydroxide solution of 50wt% etches 0.01h, takes out a large amount of deionized water rinsing of silicon chip afterwards, nitrogen dries up, can obtain the monocrystalline silicon nano line array of large area sub-wavelength structure.Result as shown in Figure 2, contrast can find that before and after etching, polysilicon chip surface demonstrates the change of obvious color, before corrosion, polysilicon chip demonstrates the metallic luster of high brightness, and after the silicon nanowire array introducing of sub-wavelength structure, polysilicon chip surface presentation goes out uniform brown.
Embodiment 2
The preparation method of sub-wavelength silicon nanowire array described in the present embodiment, specifically comprises the following steps:
(1) 156 × 156mm will be of a size of
2, doping type is p-type, resistance 2 Ω, thickness are 210 μm commercial solar-grade polysilicon sheet uses acetone, toluene, ethanol, deionized water Ultrasonic Cleaning silicon chip 10 minutes successively;
(2) H is put into
2sO
4and H
2o
2volume ratio is soak 10 minutes in the solution of 3:1, and being placed on concentration is soak 120min in the hydrofluoric acid solution of 0.1wt%, for subsequent use after a large amount of deionized water rinsing after taking out;
(3) 500mlHF/H is prepared
2ptCl
6corrosive liquid, HF and H
2ptCl
6concentration be respectively 15mol/L and 5mol/L; The polysilicon chip cleaned up is put into corrosive liquid and leave standstill the silicon nanowire array that 5min obtains metal ion;
(4) have the silicon nanowire array of metal ion to put into H that concentration is 50wt% is taken out
2o
2middle immersion 300min, obtains silicon nanowire array with after washed with de-ionized water;
(5) taking out silicon nanowire array, to be placed in concentration be that the potassium hydroxide solution of 90wt% etches 0.1h, takes out a large amount of deionized water rinsing of silicon chip afterwards, nitrogen dries up, can obtain the monocrystalline silicon nano line array of large area sub-wavelength structure.As shown in Figure 3, after the silicon nanowire array introducing of sub-wavelength structure, polysilicon chip surface presentation goes out pitchy to result.
Embodiment 3
The preparation method of sub-wavelength silicon nanowire array described in the present embodiment, specifically comprises the following steps:
(1) 156 × 156mm will be of a size of
2, doping type is p-type, resistance 3 Ω, thickness are 180 μm commercial solar-grade polysilicon sheet uses acetone, toluene, ethanol, deionized water Ultrasonic Cleaning silicon chip 10 minutes successively;
(2) H is put into
2sO
4and H
2o
2volume ratio is soak 2 minutes in the solution of 3:1, and being placed on concentration is soak 20min in the hydrofluoric acid solution of 5wt%, for subsequent use after a large amount of deionized water rinsing after taking out;
(3) 500mlHF/KAuCl is prepared
4corrosive liquid, HF and KAuCl
4concentration be respectively 0.1mol/L and 10mol/L; Moved to darkroom after the polysilicon chip cleaned up is put into corrosive liquid and left standstill 600min;
(4) after, the silicon nanowire array depositing gold is taken out and put into HF/H
2o
2in solution, its concentration is respectively 2.3mol/L and 5mol/L, and etch period is 10min, with the silicon nanowire array obtaining golden nanometer particle after washed with de-ionized water;
(5) taking-up has the silicon nanowire array of gold particle with after a large amount of deionized water rinsing, is placed on HF/HNO
3300min is etched, HF and HNO in solution
3concentration be respectively 1mol/L and 10mol/L, take out silicon chip a large amount of deionized water rinsing afterwards, nitrogen dry up, the monocrystalline silicon nano line array of large area sub-wavelength structure can be obtained.Before and after etching, the reflectance test result of sample as shown in Figure 4, can find out that the anti-reflection efficiency of the introducing sample along with sub-wavelength nanostructure significantly improves.
Embodiment 4
The preparation method of sub-wavelength silicon nanowire array described in the present embodiment, specifically comprises the following steps:
(1) 156 × 156mm will be of a size of
2, doping type is p-type, resistance 1 Ω, thickness are 190 μm commercial solar-grade polysilicon sheet uses acetone, toluene, ethanol, deionized water Ultrasonic Cleaning silicon chip 10 minutes successively;
(2) H is put into
2sO
4and H
2o
2volume ratio is soak 4 minutes in the solution of 3:1, and being placed on concentration is soak 40min in the hydrofluoric acid solution of 10wt%, for subsequent use after a large amount of deionized water rinsing after taking out;
(3) 500mlHF/CuNO is prepared
3corrosive liquid, HF and CuNO
3concentration be respectively 33mol/L and 0.01mol/L; Moved to darkroom after the polysilicon chip cleaned up is put into corrosive liquid and left standstill 300min; Obtain the silicon nanowire array having copper nano-particle;
(4) taking out the silicon nanowire array depositing copper particle, to put into concentration be that the ammoniacal liquor of 0.1wt% soaks 600min, obtains silicon nanowire array with after washed with de-ionized water;
(5) take out silicon nanowire array and be placed in HF/H
2o
248h is etched, HF and H in solution
2o
2concentration be respectively 4.6mol/L and 0.1mol/L, take out silicon chip a large amount of deionized water rinsing afterwards, nitrogen dry up, the monocrystalline silicon nano line array of large area sub-wavelength structure can be obtained.
Embodiment 5
The preparation method of sub-wavelength silicon nanowire array described in the present embodiment, specifically comprises the following steps:
(1) 156 × 156mm will be of a size of
2, doping type is p-type, resistance 1 Ω, thickness are 210 μm commercial solar-grade polysilicon sheet uses acetone, toluene, ethanol, deionized water Ultrasonic Cleaning silicon chip 10 minutes successively;
(2) H is put into
2sO
4and H
2o
2volume ratio is soak 6 minutes in the solution of 3:1, and being placed on concentration is soak 50min in the hydrofluoric acid solution of 20wt%, for subsequent use after a large amount of deionized water rinsing after taking out;
(3) 500mlHF/AgNO is prepared
3deposit fluid, HF and AgNO
3concentration be respectively 0.1mol/L and 10mol/L; Moved to darkroom after the polysilicon chip cleaned up is put into deposit fluid and left standstill 0.5min, afterwards the polysilicon chip depositing silver is positioned over 500mlHF/H
2o
2etch in etching liquid, HF and H
2o
2concentration be respectively 33mol/L and 0.01mol/L; Etch period is 0.5min;
(4) being taken out by silicon nanowire array after and putting into concentration is that the nitric acid of 60wt% soaks 200min, obtains silicon nanowire array with after washed with de-ionized water;
(5) take out silicon nanowire array with after a large amount of deionized water rinsing, be placed on HF/Na
2s
2o
8etch 1min in the sodium hydroxide solution of solution, a large amount of deionized water rinsing of taking-up silicon chip, nitrogen dry up afterwards, can obtain the monocrystalline silicon nano line array of large area sub-wavelength structure.
Embodiment 6
The preparation method of sub-wavelength silicon nanowire array described in the present embodiment, specifically comprises the following steps:
(1) 156 × 156mm will be of a size of
2, doping type is p-type, resistance 2 Ω, thickness are 200 μm commercial solar-grade polysilicon sheet uses acetone, toluene, ethanol, deionized water Ultrasonic Cleaning silicon chip 10 minutes successively;
(2) H is put into
2sO
4and H
2o
2volume ratio is soak 15 minutes in the solution of 3:1, and being placed on concentration is soak 50min in the hydrofluoric acid solution of 30wt%, for subsequent use after a large amount of deionized water rinsing after taking out;
(3) 500mlHF/H is prepared
2ptCl
6deposit fluid, HF and H
2ptCl
6concentration be respectively 33mol/L and 0.001mol/L; Moved to darkroom after the polysilicon chip cleaned up is put into deposit fluid and left standstill 60min; Afterwards the polysilicon chip depositing platinum particles is positioned over 500mlHF/ Fe (NO
3)
3etch in etching liquid, HF and Fe (NO
3)
3concentration be respectively 0.1mol/L and 20mol/L; Etch period is 300min;
(4) after, concentration being put in the silicon nanowire array having platinum particles deposit taking-up is that the hydrogen peroxide of 40wt% soaks 500min, obtains silicon nanowire array with after washed with de-ionized water;
(5) taking-up silicon nanowire array is placed in taking-up silicon nanowire array and is placed in HF/Na
2s
2o
8200min is etched, HF and Na in solution
2s
2o
8concentration be respectively 4.6mol/L and 20mol/L, take out silicon chip a large amount of deionized water rinsing afterwards, nitrogen dry up, the monocrystalline silicon nano line array of large area sub-wavelength structure can be obtained.
Embodiment 7
The preparation method of sub-wavelength silicon nanowire array described in the present embodiment, specifically comprises the following steps:
(1) 156 × 156mm will be of a size of
2, doping type is p-type, resistance 1 Ω, thickness are 210 μm commercial solar-grade polysilicon sheet uses acetone, toluene, ethanol, deionized water Ultrasonic Cleaning silicon chip 10 minutes successively;
(2) H is put into
2sO
4and H
2o
2volume ratio is soak 17 minutes in the solution of 3:1, and being placed on concentration is soak 80min in the hydrofluoric acid solution of 40wt%, for subsequent use after a large amount of deionized water rinsing after taking out;
(3) 500mlHF/ KAuCl is prepared
4deposit fluid, HF and KAuCl
4concentration be respectively 20mol/L and 5mol/L; Moved to darkroom after the polysilicon chip cleaned up is put into deposit fluid and left standstill 30min; Afterwards the polysilicon chip depositing silver is positioned over 500mlHF/KMnO
4etch in etching liquid, HF and KMnO
4concentration be respectively 18mol/L and 10mol/L; Etch period is 600min,
(4) put into there being the silicon nanowire array of gold to take out the HNO that concentration is 50wt%
3middle immersion 10min, obtains silicon nanowire array with after washed with de-ionized water;
(5) taking-up silicon nanowire array is placed in taking-up silicon nanowire array and is placed in HF/Fe (NO
3)
348h is etched, HF and Fe (NO in solution
3)
3concentration be respectively 4.6mol/L and 0.1mol/L, take out silicon chip a large amount of deionized water rinsing afterwards, nitrogen dry up, take out a large amount of deionized water rinsing of silicon chip afterwards, nitrogen dries up, the monocrystalline silicon nano line array of large area sub-wavelength structure can be obtained.
Claims (8)
1. a preparation method for sub-wavelength silicon nanowire array, is characterized in that: specifically comprise the following steps:
(1) by polysilicon chip successively with acetone, toluene, ethanol, deionized water is ultrasonic cleans 1 ~ 20 minute respectively, the polysilicon chip cleaned up is put into by H
2sO
4and H
2o
2soak 1 ~ 60 minute in the solution be mixed to get for the ratio of 3:1 by volume, being placed on concentration is soak 1 ~ 120min in the hydrofluoric acid solution of 0.1 ~ 40wt%, for subsequent use after clean with deionized water rinsing after taking-up;
(2) by the catalytic action of metal nanoparticle Ag, Pd, Au, Pt or Cu, adopt one-step or two-step metal nanoparticle auxiliary etch method, etch at silicon chip surface, form extensive silicon nanowire array;
(3) the extensive silicon nanowire array containing nano metal particles obtained in step (2) is placed in oxidizing solution immersion 10 ~ 600min that concentration is 0.1 ~ 90wt%, obtains silicon nanowire array with after washed with de-ionized water;
(4) silicon nanowire array obtained in step (3) is placed in etching agent etching 0.01 ~ 48h at 10 ~ 100 DEG C, dry up the silicon nanowire array that can obtain and have sub-wavelength structure with a large amount of washed with de-ionized water, nitrogen afterwards, etching agent chooses the hydrofluoric acid mixed solution that alkaline solution that concentration is 0.1 ~ 90wt% or oxycompound concentration are 0.1 ~ 50wt%.
2. the preparation method of sub-wavelength silicon nanowire array according to claim 1, it is characterized in that: in a described single metal nano particle auxiliary etch method, etching agent is the mixed solution of HF and slaine composition, in mixed solution, the concentration of HF is 0.1 ~ 33mol/L, the concentration of slaine is 0.01 ~ 10mol/L, and described slaine is AgNO
3, KAuCl
4, HAuCl
4, K
2ptCl
6, H
2ptCl
6or CuNO
3, the etching reaction time is 0.5 ~ 600min.
3. the preparation method of sub-wavelength silicon nanowire array according to claim 1, it is characterized in that: described two single metal nano particle auxiliary etch methods comprise the steps: to carry out metal nanoparticle deposition in the mixed solution first formed at HF and slaine, and described slaine is AgNO
3, KAuCl
4, HAuCl
4, K
2ptCl
6, H
2ptCl
6or CuNO
3in mixed solution, the concentration of HF is 0.1 ~ 33mol/L, the concentration of slaine is 0.001 ~ 10mol/L, and sedimentation time is 0.5 ~ 60min; Be positioned over by HF and H after afterwards the polysilicon chip depositing metal nanoparticle being rinsed
2o
2, HNO
3, Fe (NO
3)
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8etch in the etching liquid of composition, in etching liquid, the dense of HF is 0.1 ~ 33mol/L, H
2o
2, HNO
3, Fe (NO
3)
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8concentration be 0.01 ~ 20mol/L, etch period is 0.5 ~ 600min.
4. the preparation method of sub-wavelength silicon nanowire array according to claim 1, is characterized in that: if reaction system have chosen HF/AgNO in described one-step or two-step metal nanoparticle auxiliary etch method
3system, its reaction unit should do lucifuge process.
5. the preparation method of sub-wavelength silicon nanowire array according to claim 1, is characterized in that: in described step (3), oxidizing solution is the one in nitric acid, hydrogen peroxide, ammoniacal liquor.
6. the preparation method of sub-wavelength silicon nanowire array according to claim 1, is characterized in that: described in step (4), alkaline solution is NaOH or potassium hydroxide solution; Oxide is H
2o
2, HNO
3, Fe (NO
3)
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8.
7. the preparation method of sub-wavelength silicon nanowire array according to claim 3, is characterized in that: in a described single metal nano particle auxiliary etch method, the deposition of metal nanoparticle and being etched in same reaction system of silicon chip are carried out simultaneously.
8. the preparation method of sub-wavelength silicon nanowire array according to claim 4, is characterized in that: in described two single metal nano particle auxiliary etch methods, the deposition of metal nanoparticle and silicon chip separately carry out.
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