CN108996471A - The graphical preparation method of silicon nanowires and preparation method thereof, silicon nanowires - Google Patents
The graphical preparation method of silicon nanowires and preparation method thereof, silicon nanowires Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 114
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 93
- 239000010703 silicon Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000005530 etching Methods 0.000 claims abstract description 58
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 58
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004332 silver Substances 0.000 claims abstract description 47
- 229910052709 silver Inorganic materials 0.000 claims abstract description 47
- 230000008021 deposition Effects 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000002161 passivation Methods 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 12
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 238000001259 photo etching Methods 0.000 claims description 6
- 230000000007 visual effect Effects 0.000 claims description 5
- 238000001312 dry etching Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- 238000001039 wet etching Methods 0.000 claims description 4
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910003978 SiClx Inorganic materials 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 56
- 238000000151 deposition Methods 0.000 description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 22
- 238000012876 topography Methods 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910021426 porous silicon Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The present invention provides a kind of preparation method of silicon nanowires, comprising the following steps: (1) provides monocrystalline silicon piece, monocrystalline silicon piece is soaked in progress hydrogen Passivation Treatment in HF solution；(2) will by step (1) treated, monocrystalline silicon piece is soaked in deposition of silver liquid so that the surface of monocrystalline silicon piece plates Silver nano-particle layer, the deposition of silver liquid includes the AgNO of 0.005~0.02mol/L3With the HF of 1.2~9.6mol/L, silver deposition time is 15~120S；(3) will by step (2) treated, monocrystalline silicon piece is soaked in etching solution is etched, obtain silicon nanowires.Wherein, the etching solution includes the H of 0.2~0.4mol/L2O2With the Fe (NO of the HF or 0.07~0.42mol/L of 2.4~9.6mol/L3)3With the HF of 2.4~9.6mol/L, etching period is 15~120min.The preparation of silicon nanowires can be realized in the preparation method at normal temperatures and pressures, and operating process is simple, and is patterned processing to silicon chip surface on this basis, realizes silicon nanowires and grows in designated position.
Description
Technical field
The present invention relates to technical field of nano material more particularly to a kind of silicon nanowires and preparation method thereof, silicon nanowires
Graphical preparation method.
Background technique
Nano material is greatly paid close attention to, mainly due to its special physical property.Because the size when material subtracts
As low as Nano grade when, small-size effect, quantum size effect, macro quanta tunnel effect, coulomb blockade effect, surface
The specific physical property that the block materials such as effect do not have will show.As constituent content seniority among brothers and sisters second on the earth
Silicon is extremely important semiconductor material, has been widely used in various Communication Equipments and micro- electricity in the information age instantly
Among subcomponent.However the forbidden bandwidth of silicon only has 1.12e V, very narrow, this makes it in device application process
It is restricted.If Semiconducting Silicon Materials sized nanostructures are made it have the distinctive superior physical properties of nano material, this
It will be undoubtedly made to generate higher application value.
The existing preparation method in relation to silicon nanowires generally requires to realize under conditions of high temperature and pressure, equipment used
It is required that high, preparation cost is high, and it is unfavorable that these are all that silicon nanowires industrial application is brought.And silicon nanowires is in device
In part when practical application, only need to grow nanowire structure at certain special positions of silicon wafer sometimes.
Summary of the invention
In view of the foregoing, it is necessary to which a kind of preparation side of simple silicon nanowires operated at normal temperatures and pressures is provided
The graphical preparation method of method and silicon nanowires.
The present invention provides a kind of preparation method of silicon nanowires comprising following steps:
(1) monocrystalline silicon piece is provided, monocrystalline silicon piece is soaked in progress hydrogen Passivation Treatment in HF solution；
(2) will by step (1) treated, monocrystalline silicon piece is soaked in deposition of silver liquid so that the surface of monocrystalline silicon piece is plated
Upper Silver nano-particle layer, the deposition of silver liquid include the AgNO of 0.005~0.0.02mol/L3With the HF of 1.2~9.6mol/L,
Silver deposition time is 15~120S；
(3) will by step (2) treated, monocrystalline silicon piece is soaked in etching solution is etched, obtain silicon nanometer
Line.Wherein, the etching solution includes the H of 0.2~0.4mol/L2O2With the HF or 0.07~0.42mol/ of 2.4~9.6mol/L
Fe (the NO of L3)3With the HF of 2.4~9.6mol/L, etching period is 15~120min；
Preferably, AgNO in the deposition of silver liquid3Concentration be 0.01mol/L.
Preferably, sign is, the concentration of HF is 4.8~9.6mol/L in the deposition of silver liquid.
Preferably, H in the etching solution2O2Concentration be 0.4mol/L.
Preferably, the concentration of HF is 4.8~9.6mol/L in the etching solution.
Preferably, after the step (3) further comprising the steps of (4): will monocrystalline silicon piece impregnates by step (3) treated
In dust technology, to remove the silver nano-grain in the silicon nanowires.
Preferably, further comprising the steps of after the step (4): to by step (4) treated, monocrystalline silicon piece is carried out
Cleaning, drying.
The present invention also provides silicon nanowires made from a kind of preparation method as the silicon nanowires.
The present invention also provides a kind of graphical preparation methods of silicon nanowires comprising following steps:
(a) monocrystalline silicon piece is provided, monocrystalline silicon piece is heated at 900~1200 DEG C, makes the Surface Oxygen metaplasia of monocrystalline silicon piece
At silicon dioxide layer, silicon nitride layer is plated again in silicon dioxide layer；
(b) photomask board is provided, using photoetching technique by the pattern transfer of photomask board to by handling by step (a)
The surface of monocrystalline silicon piece afterwards；
(c) it is successively gone to by the visuals for needing to grow silicon nanowires on step (b) treated monocrystalline silicon piece
Silicon nitride and silica；
(d) make to eliminate the figure after silicon nitride and silica on monocrystalline silicon piece using the preparation method of the silicon nanowires
Shape some growth silicon nanowires.
Preferably, the step (c) includes: after removing silicon nitride using dry etching, then using wet etching removal two
Silica.
Compared with prior art, the present invention provides a kind of preparation method of silicon nanowires, will be after hydrogen Passivation Treatment
Silicon wafer is in HF and AgNO3Mixed solution in deposit Argent grain, then silicon wafer is immersed in oxidizing solution and be etched, and uses dilute nitre
Silicon nanowires is obtained after acid removal Argent grain.The preparation of silicon nanowires can be realized in the preparation method at normal temperatures and pressures, operation
Process is simple, and is patterned processing to silicon chip surface on this basis, realizes silicon nanowires and grows in designated position.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of the preparation method of silicon nanowires provided by the invention.
Fig. 2 is the different AgNO that one embodiment of the invention provides3The surface topography map of silicon nanowires obtained under concentration.
Fig. 3 is the different AgNO that one embodiment of the invention provides3The cross-section morphology figure of silicon nanowires obtained under concentration.
Fig. 4 is the different H that one embodiment of the invention provides2O2The surface topography map of silicon nanowires obtained under concentration.
Fig. 5 is the different H that one embodiment of the invention provides2O2The cross-section morphology figure of silicon nanowires obtained under concentration.
The table of silicon nanowires obtained by the deposition of silver liquid containing different HF concentration that Fig. 6 provides for one embodiment of the invention
Face shape appearance figure.
Silicon nanowires obtained by the deposition of silver liquid containing different HF concentration that Fig. 7 provides for one embodiment of the invention breaks
Face shape appearance figure.
The surface of silicon nanowires obtained by the etching solution containing different HF concentration that Fig. 8 provides for one embodiment of the invention
Shape appearance figure.
The section of silicon nanowires obtained by the etching solution containing different HF concentration that Fig. 9 provides for one embodiment of the invention
Shape appearance figure.
Figure 10 contains different Fe (NO for what one embodiment of the invention provided3)3Silicon nanowires obtained by the etching solution of concentration
Cross-section morphology figure.
Figure 11 is the monocrystalline silicon piece for the growing patterned silicon nanowires that one embodiment of the invention provides in different times magnifications
Surface topography map under several.
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment.Obviously, described
Embodiment be only some embodiments of the invention, rather than whole embodiment.Based on the embodiment party in the present invention
Formula, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all belongs to
In the scope of protection of the invention.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.The title of used technological means is intended merely to retouch in the description of the invention
State the purpose of specific embodiment, it is not intended that in the limitation present invention.
Referring to Fig. 1, the present invention provides a kind of preparation method of silicon nanowires, comprising the following steps:
S1., monocrystalline silicon piece is provided, monocrystalline silicon piece is soaked in progress hydrogen Passivation Treatment in HF solution.Preferably, HF solution
Concentration be 4%~6%, soaking time be 2~4min.
After monocrystalline silicon piece is carried out hydrogen Passivation Treatment, monocrystalline silicon sheet surface will form si-h bond, that is, hydrogen stop layer, hydrogen
Stop layer can guarantee that sample surfaces clean, and be conducive to the preparation of nano wire pattern.
S2. will by step S1, treated that monocrystalline silicon piece is soaked in deposition of silver liquid so that the surface of monocrystalline silicon piece is plated
Upper Silver nano-particle layer, the deposition of silver liquid include the AgNO of 0.005~0.02mol/L3With the HF of 1.2~9.6mol/L, silver
Sedimentation time is 15~120S.Preferably, AgNO in the deposition of silver liquid3Concentration be 0.01mol/L, the concentration of HF is 4.8
~9.6mol/L.
S3. it will impregnate in etching solution and be etched by step S2 treated monocrystalline silicon piece, and obtain silicon nanowires.
The etching solution includes the H of 0.2~0.4mol/L2O2With the Fe of the HF or 0.07~0.42mol/L of 2.4~9.6mol/L
(NO3)3With the HF of 2.4~9.6mol/L, etching period is 15~120min.Preferably, H in the etching solution2O2Concentration be
The concentration range of 0.4mol/L, HF are 4.8~9.6mol/L.
Preferably, the further comprising the steps of S4 after step S3: will treated that monocrystalline silicon piece is soaked in by step S3
In dust technology, to remove the silver nano-grain in the silicon nanowires.Preferably, soaking time is 115~125min, dust technology
Concentration be 0.01~0.03mol/L.
Preferably, further comprising the steps of after step s4: clear to being carried out by step S4 treated monocrystalline silicon piece
It washes, dry.
Preferably, further include following steps before step S1: monocrystalline silicon piece is sequentially placed into acetone, alcohol and distilled water
In be cleaned by ultrasonic, then monocrystalline silicon piece is immersed again and carries out depth cleaning in the mixed solution of hydrogen peroxide and the concentrated sulfuric acid,
Finally cleaned repeatedly with distilled water again.
The present invention also provides a kind of graphical preparation methods of silicon nanowires, include the following steps:
S101., monocrystalline silicon piece is provided, monocrystalline silicon piece is heated at 900~1200 DEG C, makes the surface oxidation of monocrystalline silicon piece
Silicon dioxide layer is generated, plates silicon nitride layer again in silicon dioxide layer.
S102. photomask board is provided, using photoetching technique by the pattern transfer of photomask board to by passing through step S101
The surface of treated monocrystalline silicon piece.
S103. the visuals by needing to grow silicon nanowires on step S102 treated monocrystalline silicon piece is successively gone
Silicon nitride and silica.Preferably, after removing silicon nitride using dry etching, then using wet etching removal titanium dioxide
Silicon.
S104. made after eliminating silicon nitride and silica on monocrystalline silicon piece using the preparation method of the silicon nanowires
Visuals grow silicon nanowires.
Specifically described below with reference to embodiment silicon nanowires of the invention preparation method and silicon nanowires it is graphical
Preparation method.
Embodiment 1
Cleaning monocrystalline silicon is put into after impregnating 3min in the HF solution that concentration is 5% after clean, is then placed in deposition of silver
60S is impregnated in liquid, is then placed in etching solution again and impregnates 30min, and wherein the HF concentration in deposition of silver liquid and etching solution is
4.8mol/L, H in etching solution2O2Concentration is 0.4mol/L, AgNO in deposition of silver liquid3Concentration range is 0.001~0.04mol/L.
Fig. 2 and Fig. 3 are please referred to, Fig. 2 and Fig. 3 are respectively different AgNO3The surface of silicon nanowires obtained under concentration
Shape appearance figure and cross-section morphology figure, AgNO3Concentration is respectively a) 0.001mol/L, b) 0.003mol/L, c) 0.005mol/L, d)
0.01mol/L,e)0.02mol/L,f)0.03mol/L,g)0.04mol/L.Work as AgNO3Concentration be 0.001mol/L when, sample
Product break surface topography without nanowire structure feature.At this point, Argent grain only can etch shallow hole pattern in silicon chip surface；Section shape
Looks show that a small number of Argent grains can still be etched into position deeper in silicon wafer, about 18 μm away from surface.Work as AgNO3Concentration increase
When being added to 0.003mol/L, the surface topography on the surface of sample is between porous silicon pattern and nano wire pattern；From section shape
Looks it can also be seen that, nano wire is not formed completely at this time.Work as AgNO3When concentration is 0.005mol/L, it is already possible to observe bright
The surface appearance feature of aobvious nano wire, cross-section morphology show that nano wire has basically formed at this time, but institute at this concentration
The nano wire etched is very coarse.AgNO3Concentration is the sample of 0.01mol/L, still from disconnected either from surface
Face observation, has had been provided with the disconnected surface characteristics of nano wire most standard, as shown in the d figure in Fig. 2 and Fig. 3, has lost under this concentration
The nano wire carved is neat and uniform, and the discreteness and stretching of nano wire are all relatively good.AgNO3If concentration continues growing,
The appearance of nano wire cluster pattern is had, the spacing of cluster also can gradually increase, and nanowire surface becomes more and more sparse.With
Front silver deposition time extend, etching period increase, etch temperature increase etc. during occur nano wire cluster unlike,
AgNO3Contained nanometer quantity is many less in the nano wire cluster that concentration occurs during increasing.It can be with from the g figure in Fig. 3
Find out, AgNO3Concentration is the sample of 0.04mol/L, and the nano wire in cross-section morphology is different in size, irregular.Therefore, silver-colored
Deposit AgNO in liquid3Concentration be preferably 0.01mol/L.
Embodiment 2
By cleaning monocrystalline silicon it is clean after be put into HF solution impregnate after, be then placed in deposition of silver liquid and impregnate 60S, then
It is placed in etching solution again and impregnates 30min, wherein the HF concentration in deposition of silver liquid and etching solution is 4.8mol/L, in deposition of silver liquid
AgNO3Concentration is 0.01mol/L, H in etching solution2O2Concentration range be 0.05~1.00mol/L.
Fig. 4 and Fig. 5 are please referred to, Fig. 4 and Fig. 5 are respectively different H2O2The surface shape of silicon nanowires obtained under concentration
Looks figure and cross-section morphology figure, H2O2Concentration is respectively a) 0.05mol/L, b) 0.20mol/L, c) 0.30mol/L, d) 0.40mol/
L,e)0.50mol/L,f)1.00mol/L.From figure 3, it can be seen that working as H2O2When concentration only has 0.05mol/L, surface topography is situated between
Between porous silicon pattern and nano wire pattern, it appears it is very dense, it is also quite tiny.H2O2Concentration reaches 0.20mol/L
Afterwards, the surface topography of nano wire has complied with standard feature, and concentration continues growing, and nanowire size size is gradually increased.Nano wire
Discreteness and stretching become to become better and better, H2O2The discreteness of nano wire and stretching reach when concentration value reaches 0.40mol/L
To optimum state.Work as H2O2When concentration is more than 0.40mol/L, there is apparent nanocluster pattern.The size meeting of nano wire
Continue to increase with the increase of concentration, but the distribution of nano wire then can be more and more sparse.From fig. 5, it can be seen that working as H2O2Concentration
When for 0.05mol/L, the nano wire of formation is very short and small, and average length only has 1.88 μm.With H2O2The increase of concentration, nanometer
Line gradually increases.This is primarily due to, H2O2Concentration is higher, and the oxidisability of solution is stronger, so that Si is easier to be oxidized erosion
It carves.In unit time, Si is easier to be oxidized etching then etch depth increase, eventually leads to nanowire length with H2O2Concentration increases
And elongated phenomenon.Work as H2O2When concentration is no more than 0.40mol/L, the discreteness and stretching of nano wire are preferable, more in this way
It is consistent with the conclusion obtained during Analysis of Surface Topography.Work as H2O2Concentration is more than point of nano wire after 0.40mol/L
Vertical property and stretching are deteriorated, and planarization also will receive destruction.Therefore, the H in etching solution2O2Concentration be preferably 0.4mol/L.
Embodiment 3
By cleaning monocrystalline silicon it is clean after be put into HF solution impregnate after, be then placed in deposition of silver liquid and impregnate 60S, then
It is placed in etching solution again and impregnates 30min, wherein AgNO in deposition of silver liquid3Concentration is 0.01mol/L, and the HF concentration in etching solution is
4.8mol/L, H in etching solution2O2Concentration be 0.4mol/L, HF concentration range is 1.2~9.6mol/L in deposition of silver liquid.
Fig. 6 and Fig. 7 are please referred to, Fig. 6 and Fig. 7 are respectively silicon nanometer obtained by the deposition of silver liquid containing different HF concentration
The surface topography map and cross-section morphology figure of line, HF concentration are respectively a) 0.0mol/L, b) 1.2mol/L, c) 2.4mol/L, d)
4.8mol/L,e)7.2mol/L,f)9.6mol/L.As can be seen from Figures 6 and 7, when not containing HF in deposition of silver liquid, sample is carved
Nano wire pattern cannot be obtained after erosion, can only form Porous Silicon structures pattern.In addition, HF concentration is increased to from 1.2mol/L
In the process of 9.6mol/L, there is no too big changes for the surface topography of silicon nanowires, and only HF concentration is in 4.8~9.6mol/L
Interval range in prepare nanowire discreteness and stretching it is more preferable.Therefore, the HF concentration range in deposition of silver liquid is preferred
For 4.8~9.6mol/L.
Embodiment 4
By cleaning monocrystalline silicon it is clean after be put into HF solution impregnate after, be then placed in deposition of silver liquid and impregnate 60S, then
It is placed in etching solution again and impregnates 30min, wherein AgNO in deposition of silver liquid3Concentration is 0.01mol/L, and HF concentration is in deposition of silver liquid
4.8mol/L, H in etching solution2O2Concentration be 0.4mol/L, the HF concentration range in etching solution is 1.2~9.6mol/L.
Fig. 8 and Fig. 9 are please referred to, Fig. 8 and Fig. 9 are respectively silicon nanowires obtained by the etching solution containing different HF concentration
Surface topography map and cross-section morphology figure, HF concentration is respectively a) 0.0mol/L, b) 1.2mol/L, c) 2.4mol/L, d)
4.8mol/L,e)7.2mol/L,f)9.6mol/L.From figure 7 it can be seen that being carved when HF concentration is 1.2mol/L in etching solution
Surface appearance feature out is lost between Porous Silicon structures nanowire structure.When HF concentration reaches 2.4mol/L in etching solution,
Nano wire pattern basically forms.After HF concentration is more than 4.8mol/L in etching solution, nanowire surface pattern hardly happens change
Change, all has preferable stretching.From figure 8, it is seen that when the concentration of HF is 1.2mol/L in etching solution, etching silicon wafer
Depth is very shallow, and only 2 μm or so.The silicon wafer etched at this concentration, section is very coarse, and the structure of class nanometer threadiness is long
It is short different, it is irregular.When the concentration of HF in etching solution increases to 2.4mol/L, etching depth increases, and reaches 6 μm or so.
But the cross-section morphology planarization of nano wire is poor at this time, nano wire length is very uneven.The concentration of HF increases in etching solution
Planarization, stretching, the preferable nano wire pattern of discreteness can be formed after 4.8mol/L.As the concentration of HF in etching solution increases
Add, the length of nano wire is declined slightly, but diameter variation is less, in 130nm or so.
Embodiment 5
Unlike Examples 1 to 4, the present embodiment uses Fe (NO3)3Mixed solution with HF, will be single as etching solution
Crystal silicon chip is put into HF solution after immersion after cleaning up, and is then placed in deposition of silver liquid and is impregnated 60S, is then placed in etching solution again
Middle immersion 45min, wherein AgNO in deposition of silver liquid3Concentration is 0.01mol/L, and the HF concentration in deposition of silver liquid and etching solution is
4.8mol/L, the Fe (NO in etching solution3)3Concentration range is 0.07~0.42mol/L.
Figure 10 is please referred to, Figure 10 is containing different Fe (NO3)3The section of silicon nanowires obtained by the etching solution of concentration
Shape appearance figure, Fe (NO3)3Concentration is respectively a) 0.07mol/L, b) 1.4mol/L, c) 0.28mol/L, d) 0.42mol/L.Work as Fe
(NO3)3When concentration increases, the length of silicon nanowires is consequently increased, but increased amplitude gradually becomes smaller.In Fe (NO3)3Concentration
The length for reaching nano wire after 0.28mol/L almost no longer changes.Silicon nanowires is with Fe (NO3)3The increase of concentration and it is elongated main
It is due to Fe (NO3)3The oxidisability of etching solution becomes strong after concentration increase, so that silicon chip surface is easier to aoxidize, the silicon of oxidation
It can be dissolved and immerse in etching solution.Silicon wafer is easier to be oxidized the rate for also meaning Argent grain etching silicon wafer and can become larger, therefore works as
In Fe (NO in etching solution3)3When concentration increases, the length of silicon nanowires also can be elongated.It follows that in Fe (NO3)3Concentration pair
The influence of silicon nanowires length and H2O2Influence of the concentration to nano wire is similar, only Fe (NO3)3Oxidisability does not have H2O2That
It is strong, thus (the NO containing Fe3)3The silicon nanowires that etches of etching solution it is shorter and smaller.
Embodiment 6
It first uses acetone, alcohol, distilled water to be successively cleaned by ultrasonic monocrystalline silicon piece, then puts into dense H2SO4With H2O2Middle mixing
In solution, cleaning is boiled in heating, is reused distilled water after taking-up and is cleaned repeatedly.Monocrystalline silicon piece is once purged, in 1000 DEG C of height
Under temperature, thermal oxide generates layer of silicon dioxide layer, and the thickness of silicon dioxide layer is about 500nm.Existed using low-pressure chemical deposition
Silicon nitride film is plated in silicon dioxide layer, film thickness is about 150nm.One layer of photoetching is first coated on needing patterned surface
Glue recycles photoetching technique that will be pre-designed in the pattern transfer to surface on the mask plate processed.By development operation it
Afterwards, the figure on mask plate will be retained on the surface.Windowing processing is carried out to the graphics field for requiring growth nano wire,
After first removing silicon nitride using dry etching, then using wet etching removal silica, it will finally remain in the photoetching on surface
Glue washes.
Next monocrystalline silicon piece is put into HF solution and is impregnated, be then placed in deposition of silver liquid and impregnate 60S, be then placed in again
15min is impregnated in etching solution, wherein the HF concentration in deposition of silver liquid and etching solution is 4.8mol/L, AgNO in deposition of silver liquid3
Concentration is 0.01mol/L, H in etching solution2O2Concentration range be 0.4mol/L.Figure 11 is please referred to, Figure 11 is growing patterned silicon
Surface topography map of the monocrystalline silicon piece of nano wire under different amplification, amplification factor is respectively a) 90 times, b) 250 times, c)
5000 times, d) 60000 times.From fig. 10 it can be seen that monocrystalline silicon sheet surface completes graphical treatment, orderly given birth in graphics field
Silicon nanowires is grown.
Embodiment of above is only for interpreting the claims.Right protection scope of the present invention is not limited to illustrate
Book.Anyone skilled in the art within the technical scope of the present disclosure, the variation that can readily occur in or
Replacement, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon nanowires, which comprises the following steps:
(1) monocrystalline silicon piece is provided, monocrystalline silicon piece is soaked in progress hydrogen Passivation Treatment in HF solution；
(2) will by step (1) treated, monocrystalline silicon piece is soaked in deposition of silver liquid so that the surface of monocrystalline silicon piece plates silver
Nano-particle layer, the deposition of silver liquid include the AgNO of 0.005~0.02mol/L3With the HF of 1.2~9.6mol/L, deposition of silver
Time is 15~120S；
(3) will by step (2) treated, monocrystalline silicon piece is soaked in etching solution is etched, obtain silicon nanowires,
Wherein, the etching solution includes the H of 0.2~0.4mol/L2O2With the HF or 0.07~0.42mol/L of 2.4~9.6mol/L
Fe(NO3)3With the HF of 2.4~9.6mol/L, etching period is 15~120min.
2. the preparation method of silicon nanowires as described in claim 1, which is characterized in that AgNO in the deposition of silver liquid3Concentration
For 0.01mol/L.
3. the preparation method of silicon nanowires as described in claim 1, which is characterized in that the concentration of HF is in the deposition of silver liquid
4.8~9.6mol/L.
4. the preparation method of silicon nanowires as described in claim 1, which is characterized in that H in the etching solution2O2Concentration be
0.4mol/L。
5. the preparation method of silicon nanowires as described in claim 1, which is characterized in that the concentration of HF is in the etching solution
4.8~9.6mol/L.
6. the preparation method of silicon nanowires as described in claim 1, which is characterized in that after step (3) further include following step
Suddenly (4): passing through step (3), treated, and monocrystalline silicon piece is soaked in dust technology, to remove the Yin Na in the silicon nanowires
Rice grain.
7. the preparation method of silicon nanowires as claimed in claim 6, which is characterized in that after the step (4) further include following
Step: to monocrystalline silicon piece cleaned, is dried by step (4) treated.
8. silicon nanowires made from a kind of preparation method of the silicon nanowires as described in claim 1~7 any one.
9. a kind of graphical preparation method of silicon nanowires, which comprises the steps of:
(a) monocrystalline silicon piece is provided, monocrystalline silicon piece is heated at 900~1200 DEG C, the surface oxidation of monocrystalline silicon piece is made to generate two
Silicon oxide layer plates silicon nitride layer again in silicon dioxide layer；
(b) photomask board is provided, using photoetching technique by the pattern transfer of photomask board to by treated by step (a)
The surface of monocrystalline silicon piece；
(c) it successively goes to denitrogenate to by the visuals for needing to grow silicon nanowires on step (b) treated monocrystalline silicon piece
SiClx and silica；
(d) make to eliminate nitrogen on monocrystalline silicon piece using the preparation method of the silicon nanowires as described in claim 1~7 any one
Visuals after SiClx and silica grows silicon nanowires.
10. the graphical preparation method of silicon nanowires as claimed in claim 9, which is characterized in that the step (c) includes:
After removing silicon nitride using dry etching, then using wet etching removal silica.
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| CN104649273A (en) * | 2013-11-25 | 2015-05-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of low-doped porous P-type silicon nanowire |
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| CN101266919A (en) * | 2008-04-25 | 2008-09-17 | 华东师范大学 | A method for selectively etching silicon nano line |
| CN102086024A (en) * | 2010-12-31 | 2011-06-08 | 上海集成电路研发中心有限公司 | Method for preparing silicon nanowire |
| CN103342337A (en) * | 2013-07-11 | 2013-10-09 | 昆明理工大学 | Method for preparing mesoporous silicon nanowire by metal nanoparticle auxiliary etching method |
| CN104649273A (en) * | 2013-11-25 | 2015-05-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of low-doped porous P-type silicon nanowire |
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