CN104576353A - Method for preparing nano-porous silicon from Cu nano-particles by two-step auxiliary etching - Google Patents
Method for preparing nano-porous silicon from Cu nano-particles by two-step auxiliary etching Download PDFInfo
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- CN104576353A CN104576353A CN201410748516.4A CN201410748516A CN104576353A CN 104576353 A CN104576353 A CN 104576353A CN 201410748516 A CN201410748516 A CN 201410748516A CN 104576353 A CN104576353 A CN 104576353A
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 56
- 238000005530 etching Methods 0.000 title claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 97
- 239000010703 silicon Substances 0.000 claims abstract description 97
- 238000002360 preparation method Methods 0.000 claims abstract description 54
- 239000002086 nanomaterial Substances 0.000 claims abstract description 46
- 239000008367 deionised water Substances 0.000 claims abstract description 43
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005234 chemical deposition Methods 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 20
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 14
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002310 reflectometry Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 2
- 238000000861 blow drying Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 9
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 238000003631 wet chemical etching Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- BVDPFTQTMQKPGQ-UHFFFAOYSA-N ethanol hydrofluoride Chemical compound F.CCO BVDPFTQTMQKPGQ-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
Abstract
The invention relates to a method for preparing nano-porous silicon from Cu nano-particles by two-step auxiliary etching and belongs to the technical field of preparation of nano-materials. The method comprises the following steps: firstly, pre-treating a silicon chip; performing surface oxidation treatment on the pre-treated silicon chip by using a physical or chemical method to form an oxidation layer; preparing a deposition solution and an etching solution; placing the silicon chip with the oxidation layer in the deposition solution for chemical deposition, taking out the silicon chip, placing the silicon chip in the etching solution, completely etching the silicon chip, then soaking the silicon chip into nitric acid, washing the silicon chip by using a great amount of deionized water, and then blow-drying the silicon chip by nitrogen to obtain the nano-porous silicon. The method offers a great help to the improvement of the surface area and the reaction activity of the nano-porous silicon, the surface reflectivity of the nano-porous silicon is greatly reduced, and the method has broad application prospect in the fields of nano-sensors and nano-catalysis.
Description
Technical field
The present invention relates to a kind of method that Cu nano particle two step auxiliary etch prepares nano-structure porous silicon, belong to technical field of nanometer material preparation.
Background technology
In recent decades, along with the development of society, nano material, due to the unique physicochemical properties such as itself nano effect and huge specific area, causes people in the potential utilization prospect of numerous areas and studies interest widely.Along with the progress of science and technology, silicon nano material is as a kind of novel semi-conducting material, the physical characteristic that its quantum limitation effect presented along with the continuous reduction of diameter dimension, skin effect etc. are novel, also make them in optical, electrical, thermal and magnetic and catalytic reaction etc., show the superior character of the physics being significantly different from other materials, thus show very important utilization potentiality in fields such as luminescence generated by light, large scale integrated circuit, single-electron device, nano-sensors.
Prepare pore size controlled, the nano-structure porous silicon that structure is moderate is the target that people pursue always, and a kind of simple and reliable process, nano-structure porous silicon production technology with low cost are significant for realizing its large-scale application.
At present, the preparation method of porous silicon mainly contains wet chemical etching technique method and electrochemical erosion method.Wet chemical etching technique is as a kind of in CN1212989A discloses prepares porous silicon by the method that silica flour is corroded by fluorine ion under hydrothermal conditions, and it is red that this powder porasil can stablize transmitting under ultraviolet excitation, blue or ultraviolet light.It is that the electrochemical method of corrosive liquid prepares porous silicon that CN1974880A discloses a kind of hydrofluoric acid-ethanol that adopts.Electrochemical erosion method discloses a kind of cathodic reduction of porous silicon respectively as CN1396315A and CN1396316A or anodised process for treating surface prepares porous silicon.In addition also have solid heatable catalytic method as CN103508458A discloses a kind of silica flour at high temperature prepare porous silicon by the method for solid copper catalysis.
Wet chemical etching technique fado as above is that noble metal is as Assisted Chemical Etching Process methods such as gold and silver.The problems such as it is high that the use of noble metal makes production process there is production cost, batch production difficulty.The problems such as electrochemical corrosion is prepared porous silicon and be there is complicated process of preparation again, and equipment requirement is high, batch production difficulty.And solid heatable catalytic method needs high temperature and a series of pickling, seriously polluted.
Number of patent application is 2013102896160, name is called that metal nanoparticle auxiliary etch legal system is for nanometer line method, by silicon chip preliminary treatment, carry out surface oxidation treatment again, then be placed in corrosive liquid to leave standstill, be placed in salpeter solution subsequently and soak, dry up with nitrogen with after a large amount of deionized water rinsing again, namely obtain nanometer line.But the method is prepare nanometer line not illustrate the method how preparing nano-structure porous silicon.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of method that Cu nano particle two step auxiliary etch prepares nano-structure porous silicon.The present invention can obtain required nano-structure porous silicon easily by controlling the parameters such as the concentration of hydrofluoric acid in the quantity of metal copper nano granules and size, corrosive liquid and etching time.Certain process is carried out to silicon base and can prepare a large amount of Porous Silicon structures easily, huge help is had to the surface area and reactivity that improve nano-structure porous silicon, also greatly reduce the reflectivity of nanoporous silicon face simultaneously, make it also show wide utilization prospect at nano-sensor and nano-catalytic field, the present invention is achieved through the following technical solutions.
Cu nano particle two step auxiliary etch prepares a method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: by silicon chip successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 10 ~ 20min respectively;
The oxidation processes of step 2, silicon chip surface: the method for silicon chip physics pretreated for step 1 or chemistry is carried out surface oxidation treatment formation oxide layer; Wherein the method for physics or chemistry is that the methods such as conventional thermal oxidation, chemical oxidation, plasma oxidation or photochemical catalytic oxidation carry out oxidation processes to silicon chip surface, such as, adopt chemical oxidization method to be immersed in ultrasonic washing instrument by H by the silicon chip obtained of (1)
2sO
4(15 ~ 90wt.%) and H
2o
2(10 ~ 30wt.%) soaks 10 ~ 20 minutes in the solution of the composition of 3:1, can form layer of oxide layer at silicon chip surface;
The preparation of step 3, deposit solution: be 0.1 ~ 10wt.% copper ion solution by concentration, concentration be 1 ~ 50wt.% hydrofluoric acid and deionized water by volume (0.01 ~ 50): (0.01 ~ 50): (0 ~ 80) preparation obtains deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 1 ~ 50wt.% by concentration, concentration be 1 ~ 50wt.% oxidising agent and deionized water according to volume ratio (0.01 ~ 50): (0.01 ~ 50): (0 ~ 80) preparation obtains etching liquid;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 0 ~ 1000s at temperature is 1 ~ 90 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4,1 ~ 1000min is etched at temperature is 1 ~ 99 DEG C, being put into mass fraction after having etched is take out after soaking 1 ~ 60min in 15 ~ 90wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.
Silicon chip in described step 1 is monocrystalline or polycrystalline, N-shaped or p-type, and the resistivity of silicon chip is 0.001 ~ 2000 Ω/cm, and the crystal orientation of silicon chip can be (100), (110), (111).
In described step 3, copper ion solution is CuCl
2, CuSO
4or Cu (NO
3)
2.
Oxidising agent H in described step 4
2o
2, HNO
3, Fe (NO
3)
3, FeCl
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8.
Detailed process in above-mentioned steps 1 is: be first immersed in by silicon chip in the beaker having acetone soln (99wt.%), ultrasonic cleaning 10 ~ 20 minutes in ultrasonic washing instrument, removes partial organic substances; Then taking-up silicon chip is immersed in and has in the beaker of toluene, and the acetone of silicon chip surface is removed in ultrasonic cleaning 10 ~ 20 minutes in ultrasonic washing instrument; Subsequently taking out silicon chip is immersed in the beaker having ethanol (15 ~ 90wt.%), and ultrasonic cleaning 10 ~ 20 minutes in ultrasonic washing instrument, removes the organic substance of silicon chip surface; Then silicon chip deionized water ultrasonic cleaning 10 ~ 20 minutes is taken out.
The invention has the beneficial effects as follows: this method has that production cost is low, production technology is simple, the hydrogen fluoride be easy in suitability for industrialized production, production process can be recycled, and produces without waste liquid.The pore structure of silicon, size, adjustable porosity, be easy to operation.
Accompanying drawing explanation
Fig. 1 is that the nano-structure porous silicon SEM that the embodiment of the present invention 1 prepares schemes;
Fig. 2 is that the nano-structure porous silicon SEM that the embodiment of the present invention 2 prepares schemes.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
This Cu nano particle two step auxiliary etch prepares the method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: be 0.01 Ω/cm by resistivity, p-type, crystal orientation be that the monocrystalline silicon piece of (100) is successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 20min respectively;
The oxidation processes of step 2, silicon chip surface: silicon chip pretreated for step 1 is immersed in ultrasonic washing instrument by H
2sO
4(15wt.%) and H
2o
2(10wt.%) according to volume ratio be 3:1 composition solution in soak 10 minutes, layer of oxide layer can be formed at silicon chip surface;
The preparation of step 3, deposit solution: be 0.1wt.%Cu (NO by 10ml concentration
3)
2, 20ml concentration is that the 10:20:70 preparation by volume of 40wt.% hydrofluoric acid and deionized water obtains 100ml deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 40wt.% by 20ml concentration, concentration is that 30wt.% oxidising agent and deionized water obtain 100ml etching liquid according to volume ratio 20:5:75 preparation; Wherein oxidant is H
2o
2;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 10s at temperature is 25 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4, be 80 DEG C in temperature to be displaced downwardly in darkroom and to etch 90min, being put into mass fraction after having etched is take out after soaking 10min in 50wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.The nanoporous silicon structure obtained as shown in Figure 1.
Embodiment 2
This Cu nano particle two step auxiliary etch prepares the method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: be 240 Ω/cm by resistivity, p-type, crystal orientation be that the monocrystalline silicon piece of (100) is successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 20min respectively;
The oxidation processes of step 2, silicon chip surface: silicon chip pretreated for step 1 is immersed in ultrasonic washing instrument by H
2sO
4(15wt.%) and H
2o
2(10wt.%) according to volume ratio be 3:1 composition solution in soak 10 minutes, layer of oxide layer can be formed at silicon chip surface;
The preparation of step 3, deposit solution: be 0.1wt.%Cu (NO by 10ml concentration
3)
2, 20ml concentration is that the 10:20:70 preparation by volume of 40wt.% hydrofluoric acid and deionized water obtains 100ml deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 40wt.% by 20ml concentration, concentration is that 30wt.% oxidising agent and deionized water obtain 100ml etching liquid according to volume ratio 20:5:75 preparation; Wherein oxidant is H
2o
2;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 10s at temperature is 25 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4, be 25 DEG C in temperature to be displaced downwardly in darkroom and to etch 90min, being put into mass fraction after having etched is take out after soaking 10min in 50wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.The nanoporous silicon structure obtained as shown in Figure 2.
Embodiment 3
This Cu nano particle two step auxiliary etch prepares the method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: be 0.01 Ω/cm by resistivity, p-type, crystal orientation be that the monocrystalline silicon piece of (100) is successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 20min respectively;
The oxidation processes of step 2, silicon chip surface: silicon chip pretreated for step 1 is immersed in ultrasonic washing instrument by H
2sO
4(15wt.%) and H
2o
2(10wt.%) according to volume ratio be 3:1 composition solution in soak 10 minutes, layer of oxide layer can be formed at silicon chip surface;
The preparation of step 3, deposit solution: be 0.1wt.%Cu (NO by 10ml concentration
3)
2, 20ml concentration is that the 10:20:70 preparation by volume of 40wt.% hydrofluoric acid and deionized water obtains 100ml deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 40wt.% by 20ml concentration, concentration is that 30wt.% oxidising agent and deionized water obtain 100ml etching liquid according to volume ratio 20:5:75 preparation; Wherein oxidant is H
2o
2;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 10s at temperature is 1 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4, be 25 DEG C in temperature to be displaced downwardly in darkroom and to etch 90min, being put into mass fraction after having etched is take out after soaking 10min in 50wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.
Embodiment 4
This Cu nano particle two step auxiliary etch prepares the method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: be 450 Ω/cm by resistivity, p-type, crystal orientation be that the monocrystalline silicon piece of (100) is successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 20min respectively;
The oxidation processes of step 2, silicon chip surface: silicon chip pretreated for step 1 is immersed in ultrasonic washing instrument by H
2sO
4(90wt.%) and H
2o
2(30wt.%) according to volume ratio be 3:1 composition solution in soak 20 minutes, layer of oxide layer can be formed at silicon chip surface;
The preparation of step 3, deposit solution: be 0.1wt.%Cu (NO by 10ml concentration
3)
2, 20ml concentration is that the 10:20:70 preparation by volume of 40wt.% hydrofluoric acid and deionized water obtains 100ml deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 40wt.% by 20ml concentration, concentration is that 30wt.% oxidising agent and deionized water obtain 100ml etching liquid according to volume ratio 20:5:75 preparation; Wherein oxidant is H
2o
2;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 10s at temperature is 90 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4, be 25 DEG C in temperature to be displaced downwardly in darkroom and to etch 90min, being put into mass fraction after having etched is take out after soaking 10min in 50wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.
Embodiment 5
This Cu nano particle two step auxiliary etch prepares the method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: be 0.01 Ω/cm by resistivity, p-type, crystal orientation be that the monocrystalline silicon piece of (100) is successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 15min respectively;
The oxidation processes of step 2, silicon chip surface: silicon chip pretreated for step 1 is immersed in ultrasonic washing instrument by H
2sO
4(50wt.%) and H
2o
2(20wt.%) according to volume ratio be 3:1 composition solution in soak 15 minutes, layer of oxide layer can be formed at silicon chip surface;
The preparation of step 3, deposit solution: be 10wt.%Cu (NO by 50ml concentration
3)
2, 40ml concentration is that the 50:40:10 preparation by volume of 1wt.% hydrofluoric acid and deionized water obtains 100ml deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 50wt.% by 50ml concentration, concentration is that 1wt.% oxidising agent and deionized water obtain 100ml etching liquid according to volume ratio 50:40:10 preparation; Wherein oxidant is HNO
3;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 1s at temperature is 80 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4, be 1 DEG C in temperature to be displaced downwardly in darkroom and to etch 1min, being put into mass fraction after having etched is take out after soaking 1min in 15wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.
Embodiment 6
This Cu nano particle two step auxiliary etch prepares the method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: be 2000 Ω/cm by resistivity, N-shaped, crystal orientation be that the monocrystalline silicon piece of (110) is successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 15min respectively;
The oxidation processes of step 2, silicon chip surface: adopt conventional thermal oxidation can form layer of oxide layer at silicon chip surface silicon chip pretreated for step 1;
The preparation of step 3, deposit solution: be 8wt.%CuCl by 0.01ml concentration
2, 19.99ml concentration is that the 0.01:19.99:80 preparation by volume of 50wt.% hydrofluoric acid and deionized water obtains 100ml deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 1wt.% by 0.01ml concentration, concentration is that 50wt.% oxidising agent and deionized water obtain 100ml etching liquid according to volume ratio 0.01:19.99:80 preparation; Wherein oxidant is Fe (NO
3)
3;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 1000s at temperature is 80 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4, be 99 DEG C in temperature to be displaced downwardly in darkroom and to etch 1000min, being put into mass fraction after having etched is take out after soaking 60min in 90wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.
Embodiment 7
This Cu nano particle two step auxiliary etch prepares the method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: be 1000 Ω/cm by resistivity, N-shaped, crystal orientation be that the monocrystalline silicon piece of (111) is successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 15min respectively;
The oxidation processes of step 2, silicon chip surface: silicon chip using plasma pretreated for step 1 oxidation can be formed layer of oxide layer at silicon chip surface;
The preparation of step 3, deposit solution: be 8wt.%CuCl by 49.99ml concentration
2, 0.01ml concentration is that the 49.99:0.01:50 preparation by volume of 50wt.% hydrofluoric acid and deionized water obtains 100ml deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 5wt.% by 49.99ml concentration, concentration is that 45wt.% oxidising agent and deionized water obtain 100ml etching liquid according to volume ratio 49.99:0.01:50 preparation; Wherein oxidant is Fe (NO
3)
3;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 100s at temperature is 80 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4, be 99 DEG C in temperature to be displaced downwardly in darkroom and to etch 1000min, being put into mass fraction after having etched is take out after soaking 60min in 90wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.
Embodiment 8
This Cu nano particle two step auxiliary etch prepares the method for nano-structure porous silicon, and its concrete steps are as follows:
Step 1, silicon chip preliminary treatment: be 1500 Ω/cm by resistivity, N-shaped, crystal orientation be that the monocrystalline silicon piece of (111) is successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 15min respectively;
The oxidation processes of step 2, silicon chip surface: adopt photochemical catalytic oxidation can form layer of oxide layer at silicon chip surface silicon chip pretreated for step 1;
The preparation of step 3, deposit solution: be 8wt.%CuCl by 50ml concentration
2, 50ml concentration is that the 50:50:0 preparation by volume of 50wt.% hydrofluoric acid and deionized water obtains 100ml deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 5wt.% by 49.99ml concentration, concentration is that 45wt.% oxidising agent and deionized water obtain 100ml etching liquid according to volume ratio 50:50:0 preparation; Wherein oxidant is FeCl
3;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 800s at temperature is 85 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4, be 80 DEG C in temperature to be displaced downwardly in darkroom and to etch 800min, being put into mass fraction after having etched is take out after soaking 50min in 80wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.
By reference to the accompanying drawings the specific embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned execution mode, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (4)
1. Cu nano particle two step auxiliary etch prepares a method for nano-structure porous silicon, it is characterized in that concrete steps are as follows:
Step 1, silicon chip preliminary treatment: by silicon chip successively with acetone, toluene, ethanol, deionized water ultrasonic cleaning 10 ~ 20min respectively;
The oxidation processes of step 2, silicon chip surface: the method for silicon chip physics pretreated for step 1 or chemistry is carried out surface oxidation treatment formation oxide layer;
The preparation of step 3, deposit solution: be 0.1 ~ 10wt.% copper ion solution by concentration, concentration be 1 ~ 50wt.% hydrofluoric acid and deionized water by volume (0.01 ~ 50): (0.01 ~ 50): (0 ~ 80) preparation obtains deposit solution;
The preparation of step 4, etching liquid: be the hydrofluoric acid of 1 ~ 50wt.% by concentration, concentration be 1 ~ 50wt.% oxidising agent and deionized water according to volume ratio (0.01 ~ 50): (0.01 ~ 50): (0 ~ 80) preparation obtains etching liquid;
The preparation of step 5, nano-structure porous silicon: silicon chip step 2 being formed oxide layer is placed in deposit solution in step 3, chemical deposition 0 ~ 1000s at temperature is 1 ~ 90 DEG C, then silicon chip is taken out, silicon chip is placed in the etching liquid of step 4,1 ~ 1000min is etched at temperature is 1 ~ 99 DEG C, being put into mass fraction after having etched is take out after soaking 1 ~ 60min in 15 ~ 90wt.% nitric acid, dries up namely obtain nano-structure porous silicon with nitrogen after a large amount of deionized water rinsing.
2. Cu nano particle two step auxiliary etch according to claim 1 prepares the method for nano-structure porous silicon, it is characterized in that: the silicon chip in described step 1 is monocrystalline or polycrystalline, N-shaped or p-type.
3. Cu nano particle two step auxiliary etch according to claim 1 prepares the method for nano-structure porous silicon, it is characterized in that: in described step 3, copper ion solution is CuCl
2, CuSO
4or Cu (NO
3)
2.
4. Cu nano particle two step auxiliary etch according to claim 1 prepares the method for nano-structure porous silicon, it is characterized in that: the oxidising agent H in described step 4
2o
2, HNO
3, Fe (NO
3)
3, FeCl
3, KMnO
4, KBrO
3, K
2cr
2o
7or Na
2s
2o
8.
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