CN108459060A - One-dimensional silicon substrate gas sensitive of polypyrrole surface modification and preparation method thereof - Google Patents
One-dimensional silicon substrate gas sensitive of polypyrrole surface modification and preparation method thereof Download PDFInfo
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- CN108459060A CN108459060A CN201710090800.0A CN201710090800A CN108459060A CN 108459060 A CN108459060 A CN 108459060A CN 201710090800 A CN201710090800 A CN 201710090800A CN 108459060 A CN108459060 A CN 108459060A
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- silicon
- polypyrrole
- dimensional
- surface modification
- silicon substrate
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 160
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000010703 silicon Substances 0.000 title claims abstract description 159
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 74
- 230000004048 modification Effects 0.000 title claims abstract description 52
- 239000000758 substrate Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000002715 modification method Methods 0.000 title abstract description 4
- 239000002070 nanowire Substances 0.000 claims abstract description 68
- 238000012986 modification Methods 0.000 claims abstract description 48
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 37
- 238000003486 chemical etching Methods 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000012545 processing Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 43
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- 230000035945 sensitivity Effects 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000005477 sputtering target Methods 0.000 claims description 6
- 239000013077 target material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 2
- 206010011224 Cough Diseases 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 9
- 239000005416 organic matter Substances 0.000 abstract description 6
- 239000002114 nanocomposite Substances 0.000 abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000010276 construction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 210000000270 basal cell Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
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Abstract
The present invention discloses one-dimensional silicon substrate gas sensitive of polypyrrole surface modification and preparation method thereof, and monocrystalline silicon piece is handled using chemical etching and secondary chemical etching, so that monocrystalline silicon sheet surface generates one-dimensional silicon nanowire array and carries out secondarily etched microstructure modifying processing；Initiator solution and pyrrole monomer solution are successively spin-coated on the monocrystalline silicon piece handled through step 2, so that causing pyrroles in one-dimensional silicon nanowire array Central Plains position aggregates into polypyrrole.Based on the method for the present invention, organic matter polypyrrole particle can be made to form uniform modification in surface of silicon nanowires, obtain the composite modified effective one-dimensional silicon substrate nano composite air-sensitive material of organic matter, which may be implemented to NH3The instantaneous detection of gas at room temperature, and have good selectivity.
Description
Technical field
The invention belongs to gas sensor technical fields, more particularly, are related to a kind of utilization anisotropy secondary quarter
Lose working and room temperature gas sensitive and its method that microstructure modifying technology constructs polypyrrole uniform outer surface modification one-dimensional silicon substrate.
Background technology
In recent years, since gas sensor is in environmental Kuznets Curves and protection, the manufacture of modern industrial and agricultural products, anti-terrorism point
Son, even in the extensive use in the fields such as medical diagnosis on disease, increasingly by the depth of people pay close attention to.One, Dimensional Semiconductor Nano Materials
It is concerned due to the fundamental property of low-dimensional materials, and in the potential researching value of nano-device.Such as metal oxide one
Dimension semiconductor nano material is widely used in gas sensor.But since it is incompatible with semiconductor technology, limit depth
The development of level.Silicon nanowires is a kind of novel One, Dimensional Semiconductor Nano Materials, due to quantum limitation effect, is shown and this
The different physical property of body material.Monocrystalline silicon nano line is lived with very high specific surface area and with extraordinary surface
Property, it is very suitable for making various sensor components, therefore had received widespread attention in recent years.Silicon nanowires (SiNWs) is made
Preparation Method includes：Hydro-thermal method, solwution method, chemical vapor deposition, metal Assisted Chemical Etching Process method, wherein metal assistant chemical is carved
Erosion method etching, which prepares silicon nanowires, has preparation process simple, and manufacturing cost is cheap, is suitble to the notable excellent of large-scale industrial production
Point.Silicon nanowires is applied to gas sensor field, room temperature sensitive capability and material system
Its advantage protruded, however, at room temperature, remolding sensitivity is relatively low when the response gas of silicon nanowires, limits it in high sensitivity
Application in low pow consumption gas sensor.Modification moves towards must walking for practical application as silicon nanowires base gas sensor
Suddenly.Traditional modification is mainly modified by material morphology improvement, noble metal surface and the methods of doping realization.With
The discovery and research of conducting polymer composite, the high molecular gas-sensitive property of conjugated conductive cause the great interest of people, gather
Aniline, polypyrrole and polythiophene equiconjugate conducting polymer composite are used for the detection of various gases.Wherein polypyrrole (PPy)
With conductivity is high, toxicity is low, environmental stability is strong, good biocompatibility, prepares many merits such as simple, cheap.Room
When the lower polypyrrole contact gas of temperature, there is the strong interaction of chemical change and weak mutual without chemical change with gas molecule
Effect, causes self-conductive or other physicochemical properties to change.Compared to inorganic semiconductor material, macromolecule air-sensitive material
Material have many advantages, such as can room temperature detection, processability is good, it is simple, of low cost to prepare, develop it is very rapid, have become sensitivity at present
One of research hotspot of material.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide secondarily etched microstructure modifying using anisotropy
Technology constructs the working and room temperature gas sensitive and its method of polypyrrole uniform outer surface modification one-dimensional silicon substrate,.Based on the inventive method,
Organic matter polypyrrole particle can be made to form uniform modification in surface of silicon nanowires, obtained composite modified effective organic
The one-dimensional silicon substrate nano composite air-sensitive material of object-, the sensitive material may be implemented to NH3The instantaneous detection of gas at room temperature, and
And it has good selectivity.
The technical purpose of the present invention is achieved by following technical proposals：
One-dimensional silicon substrate gas sensitive of polypyrrole surface modification and preparation method thereof, is prepared as steps described below：
Step 1, monocrystalline silicon piece is handled using chemical etching, so that monocrystalline silicon sheet surface is generated perpendicular to monocrystalline silicon sheet surface
One-dimensional silicon nanowire array；
Step 2, the monocrystalline silicon piece handled through step 1 is handled using chemical etching, so that one-dimensional silicon nanowire array carries out
Secondarily etched microstructure modifying processing；
Step 3, initiator solution and pyrrole monomer solution are successively spin-coated on the monocrystalline silicon piece handled through step 2, so that
Cause pyrroles in one-dimensional silicon nanowire array Central Plains position and aggregate into polypyrrole, being formed has polypyrrole surface modification One Dimension Silicon nanometer
The one-dimensional silicon substrate gas sensitive of the monocrystalline silicon piece of linear array, as polypyrrole surface modification.
In the above-mentioned technical solutions, it is arranged on the monocrystalline silicon piece with the one-dimensional silicon nanowire array of polypyrrole surface modification
Platinum electrode, and be connected with test system.
In the above-mentioned technical solutions, (10-15 Ω .cm) silicon chip (100) is lightly doped in monocrystalline silicon piece selection p-type, when carrying out
It is handled first, by silicon chip in volume ratio 4:It is cleaned by ultrasonic 10min in 1 hydrogen peroxide and the concentrated sulfuric acid, then successively by silicon chip
It is placed in ultrasound in acetone solvent, absolute ethyl alcohol, deionized water and is respectively washed 5-10min, remove surface and oil contaminant and organic matter is miscellaneous
Matter is placed in infrared baking oven and thoroughly dries.
In the above-mentioned technical solutions, in step 1, chemical etching solution is the hydrofluoric acid aqueous solution of silver nitrate, hydrofluoric acid
A concentration of 3M -6M, silver nitrate concentration is 0.02M -0.03M (M mol/L), by the adjustment of chemical etching time to realize
The adjustment (increasing with etch period, nanowire length increases) of silicon nanowires length, etch period is 90-180min.
In the above-mentioned technical solutions, after the chemical etching for completing step 1, obtained silicon chip is cleaned with deionized water
It is put into the impurity that 10min in the aqueous solution of nitric acid of 30vol% is used to remove silicon chip surface afterwards, is dried after then rinsing；It will drying
Silicon chip afterwards is put into 60s in the hydrofluoric acid aqueous solution of 1wt%, to remove the oxide layer of surface of silicon nanowires.
In the above-mentioned technical solutions, in step 2, the potassium hydroxide that monocrystalline silicon piece is put into 10wt% -30wt% is water-soluble
Secondarily etched microstructure modifying processing is carried out in liquid, the time is 10-30s.
In the above-mentioned technical solutions, in step 3, the aqueous solution of initiator solution position ammonium persulfate, pyrrole monomer solution
For pyrrole monomer, the aqueous solution of dodecyl benzene sulfonic acid, the molar ratio of pyrrole monomer, dodecyl benzene sulfonic acid and ammonium persulfate is
(0.15—0.6)：(0.05—0.2)：(0.025-0.1), initiator solution and pyrrole monomer solution are isometric, and solute
It is evenly dispersed in a solvent.
In the above-mentioned technical solutions, in step 3, spin coating rotating speed is 600-800r/min, and polymerization time 0.5-4 is small
When, preferably 1-3 hours.
It is 1-2cm that two spacing, which are arranged, in the uniformly modified One Dimension Silicon base array surface of the polypyrrole of preparation, and size is
The electrode of 2mm*2mm forms the Ohmic contact of electrode and silicon substrate sensitive material.The metal platinum of use is as sputtering target material, argon gas
As working gas, sputtering time 4min, it is 160-240nm to form thickness of electrode, and the quality purity of target metal platinum is
99.95%, the quality purity of sputter gas argon gas is 99.999%, and ontology vacuum degree is 1-4.0 × 10-4pa。
As shown in the picture, silicon nanowires, the average length of silicon nanowires are generated in monocrystalline silicon sheet surface after chemical etching
About 35 μm -40 μm, average diameter is 700nm -900nm, and surface of silicon nanowires shows coarse after secondarily etched processing
The average diameter of structure, the polypyrrole nano-particle (i.e. in-situ polymerization generates polypyrrole) of modification is 8-12nm, uniform to be distributed
In in coarse one-dimensional silicon substrate formed surface bulge (i.e. the average length of silicon nanowires ten a few to tens of microns the order of magnitude,
The order of magnitude of the average diameter at hundreds of nanometers；The average diameter of polypyrrole nano-particle is in 10 rans), i.e. polypyrrole nanometer
Particle is embedded among the coarse lines that rough surface is formed, this also demonstrates this coarse structure and is more advantageous to electric polypyrrole
Surface modification, to be more advantageous to the capture to NH3 gases and absorption.It is analyzed again with rxd, characteristic diffraction peak is 20 degree and arrives
30 degree of steamed bun peaks being formed about prove the presence of amorphous polypyrrole, characteristic diffraction peak is 32.865 degree, 43.334 degree,
53.112 degree, 61.101 degree of presence for demonstrating monocrystalline silicon and silica.Element detection is carried out it is found that containing in region with EDS
There is multiple element C, N, O, Si in nano wire, as shown in the table, this also shows experiment and completes polypyrrole surface modification indirectly
The preparation of the nanocomposite of one-dimensional silicon substrate.
| Element | Weight percent | Atomic percent |
| C K | 14.58 | 27.41 |
| N K | 0.69 | 1.12 |
| O K | 5.51 | 7.77 |
| SI K | 79.22 | 63.70 |
| Total amount | 100.00 | 100 |
Compared with prior art, it is constructed using the secondarily etched microstructure modifying technology of anisotropy the present invention provides a kind of
The preparation method of the One Dimension Silicon basal cell temperature work gas sensitive of polypyrrole uniform outer surface modification.It is repaiied with existing noble metal surface
Traditional air-sensitive method of modifying such as decorations, pattern improvement, doping is different, and the present invention is surface modified modification using organic matter, and
Achieve good effect.Using the method for the present invention, organic polypyrrole is realized in the uniform of inorganic One Dimension Silicon base array surface
It is sensitive in the uniformly modified high-performance organic-inorganic composite construction of One Dimension Silicon base array surface to obtain polypyrrole particle for polymerization
Material.The secondarily etched microstructure modifying technology of anisotropy makes nanowire surface be roughened, the high density surface activity poly provided
It closes site and is conducive to homogeneous polymerization modification of the organic matter on one-dimensional silica-base material surface；Significantly reduce one-dimensional silicon based array simultaneously
Array density, so that liquid phase organic monomer is uniformly coated one-dimensional silicon substrate, obtain surface and uniformly modify having for polypyrrole nano particle
Beneficial effect.In terms of air-sensitive performance improvement, hetero-junctions possessed by the composite construction gas sensitive using the method for the present invention formation
Special band structure can speed up the transmission speed of electron hole, improve the sensitivity of gas reaction, huge specific surface
Product provides more gas absorption active sites, its sensitivity can be significantly improved by being contacted with gas.The array of one-dimensional silicon based array
The reduction of density significantly improves the diffusivity of gas wherein, reduces response recovery time and polypyrrole itself to gas
Body has capture effect, and the synergistic effect of the two is so that reducing senor operating temperature, the sensitivity for improving sensor and sound
Prodigious research space will be had in terms of answering resume speed.The sensitive material formed using the inventive method is at room temperature to ammonia
Equal gases have very high sensitivity, instantaneous response and quickly restore.
Description of the drawings
Fig. 1 is the plane and section SEM photograph of the one-dimensional silicon based array for the smooth surface that in the present invention prepared by chemical etching,
Scale is respectively 300nm and 1 μm；Scanning electron microscope is Hitachi scanning electron microscope Hitachi-S4800FESEM.
Fig. 2 is plane pattern photo and the section for the silicon based array figure for not going desilver that in the present invention prepared by chemical etching
Pattern photo, scale are respectively 1um and 2um.Wherein left figure is plan view, and right figure is sectional view.
Fig. 3 is that the plane pattern of the one-dimensional silicon based array/polypyrrole for the smooth surface that in the present invention prepared by chemical etching shines
Piece and Cross Section Morphology photo (1), scale 200nm.
Fig. 4 is the one-dimensional silicon based array plane after secondary chemical etching before and after the modification of polypyrrole uniform outer surface in the present invention
Figure.
Fig. 5 is the structural schematic diagram of polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive in the present invention, wherein (1) is
P-type silicon substrate；(2) it is the one-dimensional silicon nanowire array after etching；(3) it is the polypyrrole nano-particle of surface modification；(4) it is
Platinum electrode forms good contact with nano wire；(5) it is UT70D resistance detection equipment, the variation of real-time detection resistance；(6) it is
Gas sensor is placed in ammonia atmosphere by ammonia atmosphere.
Fig. 6 is the XRD spectra of polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive in the present invention.
Fig. 7 is polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive of the present invention at room temperature to 5ppm-100ppm
The dynamic continuous response curve of NH3 gases.
Fig. 8 is polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive of the present invention at room temperature to the selection of gas with various
Property.
Fig. 9 is that (i.e. polypyrrole uniform outer surface is repaiied for silicon nanowires and silicon nanowires/polypyrrole nano composite structure in the present invention
Adorn one-dimensional silicon substrate gas sensitive) to low concentration ammonia Sensitivity comparison figure.
Figure 10 is the air-sensitive test device structural schematic diagram that the present invention uses.
Specific implementation mode
The technical solution further illustrated the present invention with reference to specific embodiment.Silicon chip uses monocrystalline silicon piece：Resistivity：
10-15 Ω 2cm, crystal orientation：<100>± 0.5 °, thickness：400μm.The quality purity of target metal platinum is 99.95%.Sputter gas
The quality purity of argon gas is 99.999%.The ontology vacuum degree of sputtering is 4.0 × 10-4Pa。
Embodiment 1
(1) cleaning of monocrystalline silicon piece
By silicon chip in volume ratio 4:1 hydrogen peroxide (aqueous solution of the hydrogen peroxide of 10wt%) and the concentrated sulfuric acid (quality percentage
Number 98wt%) in be cleaned by ultrasonic 10min, it is clear respectively to be then successively placed in acetone solvent, absolute ethyl alcohol, deionized water ultrasound
5-10min is washed, surface and oil contaminant and organic impurities is removed, is placed in infrared baking oven and thoroughly dries.
(2) chemical etching solution is configured
Silver nitrate is dissolved in hydrofluoric acid aqueous solution, hydrofluoric acid concentration is 5M in acquired solution, and silver nitrate concentration is
0.025M.(3) metal Assisted Chemical Etching Process
Silicon chip is put into the solution that step (2) has configured and is performed etching, etch period 150min.
(4) silicon chip after etching
It is put into 10min in the aqueous solution of nitric acid of 30vol% after the silicon chip obtained in step (3) is cleaned with deionized water,
To remove the impurity of silicon chip surface, such as Ag of attachment dries after then cleaning, obtains the one-dimensional silica-based nanowire battle array of smooth surface
Row.
(5) oxide layer of surface of silicon nanowires is removed
The silicon chip obtained in step (4) is put into 60s in the hydrofluoric acid aqueous solution of 1wt%.
(6) secondarily etched microstructure modifying processing
The silicon chip obtained in step (5) is put into 20s in the potassium hydroxide aqueous solution of 20wt% and carries out secondarily etched micro- knot
Structure modification forms rough surface, in order to the in-situ polymerization of polypyrrole.
(7) organic pyrroles's polymeric solution is configured
The dodecyl benzene sulfonic acid of the pyrrole monomer of 0.3mmol and 0.1mmol is dissolved in the aqueous solution of 2.5ml, ultrasound
Wave stirring 5min obtains mixed solution 1.The ammonium persulfate of 0.05mmol is dissolved in the aqueous solution of 2.5ml, 5min is stirred by ultrasonic
Obtain mixed solution 2.
(8) preparation of polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive
The mixed solution 2 obtained in step (7) is spun on the silicon chip surface that step (6) obtains, and is dried.It then will step
Suddenly the mixed solution 1 that (7) obtain is spun on silicon chip surface.The rotating speed of spin coating twice is 800r/min, Celsius in room temperature 20-25
The lower polyase 13 h of degree, obtains the composite construction of one-dimensional silicon nanowires/polypyrrole.
(9) air-sensitive performance test electrode is prepared
The silicon chip platinized electrode that step (8) is obtained, it is 1cm that two spacing are formed on one-dimensional silicon nanowire array, greatly
The small electrode for 2mm*2mm forms the Ohmic contact between electrode and silicon chip surface nano wire.The metal platinum of use is as sputtering target
Material, argon gas is as working gas, and sputtering time 4min, it is 200nm to form thickness of electrode.
Embodiment 2
(1) cleaning of monocrystalline silicon piece
By silicon chip in volume ratio 4:1 hydrogen peroxide (aqueous solution of the hydrogen peroxide of 10wt%) and the concentrated sulfuric acid (quality percentage
Number 98wt%) in be cleaned by ultrasonic 10min, it is clear respectively to be then successively placed in acetone solvent, absolute ethyl alcohol, deionized water ultrasound
5-10min is washed, surface and oil contaminant and organic impurities is removed, is placed in infrared baking oven and thoroughly dries.
(2) chemical etching solution is configured
Silver nitrate is dissolved in hydrofluoric acid aqueous solution, hydrofluoric acid concentration is 3M in acquired solution, and silver nitrate concentration is
0.02M。
(3) metal Assisted Chemical Etching Process
Silicon chip is put into the solution that step (2) has configured and is performed etching, etch period 180min.
(4) silicon chip after etching
It is put into 10min in the aqueous solution of nitric acid of 30vol% after the silicon chip obtained in step (3) is cleaned with deionized water,
To remove the impurity of silicon chip surface, such as Ag of attachment dries after then cleaning, obtains the one-dimensional silica-based nanowire battle array of smooth surface
Row.
(5) oxide layer of surface of silicon nanowires is removed
The silicon chip obtained in step (4) is put into 60s in the hydrofluoric acid aqueous solution of 1wt%.
(6) secondarily etched microstructure modifying processing
The silicon chip obtained in step (5) is put into 10s in the potassium hydroxide aqueous solution of 30wt% and carries out secondarily etched micro- knot
Structure modification forms rough surface, in order to the in-situ polymerization of polypyrrole.
(7) organic pyrroles's polymeric solution is configured
The dodecyl benzene sulfonic acid of the pyrrole monomer of 0.15mmol and 0.05mmol is dissolved in the aqueous solution of 2.5ml, is surpassed
Sonic agitation 5min obtains mixed solution 1.The ammonium persulfate of 0.025mmol is dissolved in the aqueous solution of 2.5ml, is stirred by ultrasonic
5min obtains mixed solution 2.
(8) preparation of polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive
The mixed solution 2 obtained in step (7) is spun on the silicon chip surface that step (6) obtains, and is dried.It then will step
Suddenly the mixed solution 1 that (7) obtain is spun on silicon chip surface.The rotating speed of spin coating twice is 600r/min, Celsius in room temperature 20-25
Degree is lower to polymerize 4h, obtains the composite construction of one-dimensional silicon nanowires/polypyrrole.
(9) air-sensitive performance test electrode is prepared
The silicon chip platinized electrode that step (8) is obtained, it is 2cm that two spacing are formed on one-dimensional silicon nanowire array, greatly
The small electrode for 2mm*2mm forms the Ohmic contact between electrode and silicon chip surface nano wire.The metal platinum of use is as sputtering target
Material, argon gas is as working gas, and sputtering time 4min, it is 200nm to form thickness of electrode.
Embodiment 3
(1) cleaning of monocrystalline silicon piece
By silicon chip in volume ratio 4:1 hydrogen peroxide (aqueous solution of the hydrogen peroxide of 10wt%) and the concentrated sulfuric acid (quality percentage
Number 98wt%) in be cleaned by ultrasonic 10min, it is clear respectively to be then successively placed in acetone solvent, absolute ethyl alcohol, deionized water ultrasound
5-10min is washed, surface and oil contaminant and organic impurities is removed, is placed in infrared baking oven and thoroughly dries.
(2) chemical etching solution is configured
Silver nitrate is dissolved in hydrofluoric acid aqueous solution, hydrofluoric acid concentration is 6M in acquired solution, and silver nitrate concentration is
0.03M。
(3) metal Assisted Chemical Etching Process
Silicon chip is put into the solution that step (2) has configured and is performed etching, etch period 90min.
(4) silicon chip after etching
It is put into 10min in the aqueous solution of nitric acid of 30vol% after the silicon chip obtained in step (3) is cleaned with deionized water,
To remove the impurity of silicon chip surface, such as Ag of attachment dries after then cleaning, obtains the one-dimensional silica-based nanowire battle array of smooth surface
Row.
(5) oxide layer of surface of silicon nanowires is removed
The silicon chip obtained in step (4) is put into 60s in the hydrofluoric acid aqueous solution of 1wt%.
(6) secondarily etched microstructure modifying processing
The silicon chip obtained in step (5) is put into 30s in the potassium hydroxide aqueous solution of 10wt% and carries out secondarily etched micro- knot
Structure modification forms rough surface, in order to the in-situ polymerization of polypyrrole.
(7) organic pyrroles's polymeric solution is configured
The dodecyl benzene sulfonic acid of the pyrrole monomer of 0.6mmol and 0.2mmol is dissolved in the aqueous solution of 2.5ml, ultrasound
Wave stirring 5min obtains mixed solution 1.The ammonium persulfate of 0.1mmol is dissolved in the aqueous solution of 2.5ml, ultrasonic agitation 5min is obtained
To mixed solution 2.
(8) preparation of polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive
The mixed solution 2 obtained in step (7) is spun on the silicon chip surface that step (6) obtains, and is dried.It then will step
Suddenly the mixed solution 1 that (7) obtain is spun on silicon chip surface.The rotating speed of spin coating twice is 700r/min, Celsius in room temperature 20-25
The lower polymerase 10 .5h of degree, obtains the composite construction of one-dimensional silicon nanowires/polypyrrole.
(9) air-sensitive performance test electrode is prepared
The silicon chip platinized electrode that step (8) is obtained, it is 1cm that two spacing are formed on one-dimensional silicon nanowire array, greatly
The small electrode for 2mm*2mm forms the Ohmic contact between electrode and silicon chip surface nano wire.The metal platinum of use is as sputtering target
Material, argon gas is as working gas, and sputtering time 4min, it is 160nm to form thickness of electrode.
Embodiment 4
(1) cleaning of monocrystalline silicon piece
By silicon chip in volume ratio 4:1 hydrogen peroxide (aqueous solution of the hydrogen peroxide of 10wt%) and the concentrated sulfuric acid (quality percentage
Number 98wt%) in be cleaned by ultrasonic 10min, it is clear respectively to be then successively placed in acetone solvent, absolute ethyl alcohol, deionized water ultrasound
5-10min is washed, surface and oil contaminant and organic impurities is removed, is placed in infrared baking oven and thoroughly dries.
(2) chemical etching solution is configured
Silver nitrate is dissolved in hydrofluoric acid aqueous solution, hydrofluoric acid concentration is 4M in acquired solution, and silver nitrate concentration is
0.025M。
(3) metal Assisted Chemical Etching Process
Silicon chip is put into the solution that step (2) has configured and is performed etching, etch period 120min.
(4) silicon chip after etching
It is put into 10min in the aqueous solution of nitric acid of 30vol% after the silicon chip obtained in step (3) is cleaned with deionized water,
To remove the impurity of silicon chip surface, such as Ag of attachment dries after then cleaning, obtains the one-dimensional silica-based nanowire battle array of smooth surface
Row.
(5) oxide layer of surface of silicon nanowires is removed
The silicon chip obtained in step (4) is put into 60s in the hydrofluoric acid aqueous solution of 1wt%.
(6) secondarily etched microstructure modifying processing
The silicon chip obtained in step (5) is put into 30s in the potassium hydroxide aqueous solution of 20wt% and carries out secondarily etched micro- knot
Structure modification forms rough surface, in order to the in-situ polymerization of polypyrrole.
(7) organic pyrroles's polymeric solution is configured
The dodecyl benzene sulfonic acid of the pyrrole monomer of 0.5mmol and 0.15mmol is dissolved in the aqueous solution of 2.5ml, ultrasound
Wave stirring 5min obtains mixed solution 1.The ammonium persulfate of 0.06mmol is dissolved in the aqueous solution of 2.5ml, 5min is stirred by ultrasonic
Obtain mixed solution 2.
(8) preparation of polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive
The mixed solution 2 obtained in step (7) is spun on the silicon chip surface that step (6) obtains, and is dried.It then will step
Suddenly the mixed solution 1 that (7) obtain is spun on silicon chip surface.The rotating speed of spin coating twice is 800r/min, Celsius in room temperature 20-25
Degree is lower to polymerize 1h, obtains the composite construction of one-dimensional silicon nanowires/polypyrrole.
(9) air-sensitive performance test electrode is prepared
The silicon chip platinized electrode that step (8) is obtained, it is 1cm that two spacing are formed on one-dimensional silicon nanowire array, greatly
The small electrode for 2mm*2mm forms the Ohmic contact between electrode and silicon chip surface nano wire.The metal platinum of use is as sputtering target
Material, argon gas is as working gas, and sputtering time 4min, it is 240nm to form thickness of electrode.
Using polypyrrole uniform outer surface modification one-dimensional silicon substrate gas sensitive prepared by above-described embodiment air-sensitive survey is carried out as sample
Examination is analyzed with the average result of air-sensitive test, and the air-sensitive test device that the present invention uses, 1 is air admission hole, by micro
Injectant enters the tested gas of test volume；2 be gas sensor element, is connected with platinum electrode by probe, with external detection
Equipment connects；3 be that can heat and keep to the platform for needing temperature；4 be to take the test sealing container made, and is 30L capacity；5
For mini fan, gas diffusion is helped, gas is made to be dispersed in cube container；6 be gas outlet；7 be controllable adjustment temperature
Electronic control equipment；8 be excellent Leadd B.V UT70D resistance detection equipment, the resistance value of real-time display probe junction, and
It exports to computer equipment；9 be the computer terminal that the resistance variations measured are recorded as to table and display；It is set by sealing container top
The air admission hole set micro injection into sealing container is tested gas, passes through mini fan and the collective effect of gas outlet so that
Tested gas is further spread in sealing container, makes tested gas diffusion to the gas sensor member being placed on heating platform
On part, electronic control equipment passes through biography by the temperature of temperature pilot real-time control heating platform, gas sensor element
Sensing unit conducting wire is connected with the UT70D resistance detection equipment of excellent Leadd B.V, to the resistance value of real-time display probe junction,
And by corresponding resistance test data transfer to computer terminal, by computer terminal by whole resistance test numerical value summary records at
Table.
As shown in the picture, polypyrrole surface modification silicon nanowires high-performance gas sensor shows extraordinary gas to ammonia
Body selectivity (test condition：14 DEG C of temperature, humidity 38%), hence it is evident that it is sensitive in other gases (acetone, hydrogen, methanol, methane and
Ethyl alcohol), and it is apparently higher than pure silicon nano wire (the surface setting silicon nanowires prepared using chemical etching for the sensitivity of ammonia
Monocrystalline silicon piece).The polypyrrole surface modification silicon nanowires high-performance gas sensor of preparation to 5ppm, 10ppm, 30ppm,
The dynamic response of 50ppm, 100ppm ammonia is as schemed, and according to (Rn-Rg)/Rg*100% calculating, (wherein Rn is gas sensor in sky
Resistance value in gas, Rg are resistance value of the gas sensor in ammonia atmosphere), sensitivity is respectively：50.5%, 70.2%,
152.8%, 400.3%, 450.1%.Polypyrrole surface modification silicon nanowires high-performance gas sensor based on the present invention is 14
DEG C, the sensitivity to 5~100ppm ammonias is up to 450.1%, and most short response time is 1s~3s, and the quick performance of the ammonia is obviously excellent
In the performance data for the quick element of the ammonia based on same type of material reported.
The adjustment of preparation technology parameter is carried out according to present disclosure, and the One Dimension Silicon nanometer on monocrystalline silicon piece can be achieved
The preparation of line and the in-situ polymerization of polypyrrole realize the sensitivity technique for ammonia.The present invention has been done illustratively above
Description, it should explanation, in the case where not departing from core of the invention, it is any it is simple deformation, modification or other
Field technology personnel can not spend the equivalent replacement of creative work to each fall within protection scope of the present invention.
Claims (10)
1. the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification, which is characterized in that produced in monocrystalline silicon sheet surface after chemical etching
The average length of raw silicon nanowires, silicon nanowires is 35 μm -40 μm, and average diameter is 700nm -900nm, through secondarily etched place
Surface of silicon nanowires shows coarse structure after reason, and the average diameter that in-situ polymerization generates polypyrrole particle is 8-12nm, uniformly
Be distributed in coarse one-dimensional silicon substrate and form surface bulge, prepared as steps described below：
Step 1, monocrystalline silicon piece is handled using chemical etching, so that monocrystalline silicon sheet surface is generated perpendicular to the one of monocrystalline silicon sheet surface
Tie up silicon nanowire array；
Step 2, the monocrystalline silicon piece handled through step 1 is handled using chemical etching, so that the progress of one-dimensional silicon nanowire array is secondary
Etch microstructure modifying processing；
Step 3, initiator solution and pyrrole monomer solution are successively spin-coated on the monocrystalline silicon piece handled through step 2, so that one
Cause pyrroles in situ in dimension silicon nanowire array and aggregate into polypyrrole, being formed has the one-dimensional silicon nanowires battle array of polypyrrole surface modification
The one-dimensional silicon substrate gas sensitive of the monocrystalline silicon piece of row, as polypyrrole surface modification.
2. the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification according to claim 1, which is characterized in that in step 1,
Chemical etching solution is the hydrofluoric acid aqueous solution of silver nitrate, and hydrofluoric acid concentration is 3M -6M, and silver nitrate concentration is 0.02M -
0.03M (M mol/L), by the adjustment of chemical etching time to realize that the adjustment of silicon nanowires length (increases with etch period
Add, nanowire length increases), etch period is 90-180min.
3. the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification according to claim 1, which is characterized in that in step 2,
Monocrystalline silicon piece is put into the potassium hydroxide aqueous solution of 10wt% -30wt% and carries out secondarily etched microstructure modifying processing, time
For 10-30s.
4. the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification according to claim 1, which is characterized in that in step 3,
The aqueous solution of initiator solution position ammonium persulfate, pyrrole monomer solution be pyrrole monomer, dodecyl benzene sulfonic acid aqueous solution, pyrrole
The molar ratio for coughing up monomer, dodecyl benzene sulfonic acid and ammonium persulfate is (0.15-0.6)：(0.05—0.2)：(0.025—
0.1), initiator solution and pyrrole monomer solution are isometric, and solute is evenly dispersed in a solvent；In step 3, spin coating turns
Speed is 600-800r/min, polymerization time 0.5-4 hours, preferably 1-3 hours.
5. the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification according to claim 1, which is characterized in that complete step
After 1 chemical etching, it is put into 10min in the aqueous solution of nitric acid of 30vol% after obtained silicon chip is cleaned with deionized water and uses
In the impurity of removal silicon chip surface, dried after then rinsing；Silicon chip after drying is put into the hydrofluoric acid aqueous solution of 1wt%
60s, to remove the oxide layer of surface of silicon nanowires；It is arranged two in the uniformly modified One Dimension Silicon base array surface of the polypyrrole of preparation
A spacing is 1-2cm, and size is the electrode of 2mm*2mm, forms the Ohmic contact of electrode and silicon substrate sensitive material.The metal of use
Platinum is as sputtering target material, and argon gas is as working gas, and sputtering time 4min, it is 160-240nm, target gold to form thickness of electrode
The quality purity for belonging to platinum is 99.95%, and the quality purity of sputter gas argon gas is 99.999%, ontology vacuum degree is 1-4.0 ×
10-4pa。
6. the preparation method of the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification, which is characterized in that made as steps described below
It is standby：
Step 1, monocrystalline silicon piece is handled using chemical etching, so that monocrystalline silicon sheet surface is generated perpendicular to the one of monocrystalline silicon sheet surface
Tie up silicon nanowire array；
Step 2, the monocrystalline silicon piece handled through step 1 is handled using chemical etching, so that the progress of one-dimensional silicon nanowire array is secondary
Etch microstructure modifying processing；
Step 3, initiator solution and pyrrole monomer solution are successively spin-coated on the monocrystalline silicon piece handled through step 2, so that one
Cause pyrroles in situ in dimension silicon nanowire array and aggregate into polypyrrole, being formed has the one-dimensional silicon nanowires battle array of polypyrrole surface modification
The one-dimensional silicon substrate gas sensitive of the monocrystalline silicon piece of row, as polypyrrole surface modification.
7. the preparation method of the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification according to claim 6, which is characterized in that
In step 1, chemical etching solution is the hydrofluoric acid aqueous solution of silver nitrate, and hydrofluoric acid concentration is 3M -6M, and silver nitrate concentration is
0.02M -0.03M (M mol/L), by the adjustment of chemical etching time to realize the adjustment of silicon nanowires length (with etching
Time increases, and nanowire length increases), etch period is 90-180min.
8. the preparation method of the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification according to claim 6, which is characterized in that
In step 2, monocrystalline silicon piece is put into the potassium hydroxide aqueous solution of 10wt% -30wt% and carries out secondarily etched micro-structure and changes
Property processing, the time be 10-30s.
9. the preparation method of the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification according to claim 6, which is characterized in that
In step 3, the aqueous solution of initiator solution position ammonium persulfate, pyrrole monomer solution are pyrrole monomer, dodecyl benzene sulfonic acid
Aqueous solution, the molar ratio of pyrrole monomer, dodecyl benzene sulfonic acid and ammonium persulfate is (0.15-0.6)：(0.05—0.2)：
(0.025-0.1), initiator solution and pyrrole monomer solution are isometric, and solute is evenly dispersed in a solvent；In step 3
In, spin coating rotating speed is 600-800r/min, polymerization time 0.5-4 hours, preferably 1-3 hours.
10. application of the one-dimensional silicon substrate gas sensitive of polypyrrole surface modification as described in claim 1 in detecting ammonia, special
Sign is that, at 14 DEG C, the sensitivity to 5~100ppm ammonias is up to 450.1%, and most short response time is 1s~3s.
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