CN110294456A - A method of Silver nanorod array structure materials are prepared using silicon nanowires template - Google Patents

A method of Silver nanorod array structure materials are prepared using silicon nanowires template Download PDF

Info

Publication number
CN110294456A
CN110294456A CN201810278879.4A CN201810278879A CN110294456A CN 110294456 A CN110294456 A CN 110294456A CN 201810278879 A CN201810278879 A CN 201810278879A CN 110294456 A CN110294456 A CN 110294456A
Authority
CN
China
Prior art keywords
silicon
template
nanorod array
silver nanorod
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810278879.4A
Other languages
Chinese (zh)
Inventor
白帆
胡赠彬
他德洪
苏海涛
黄蓁
潘媛
黄韵婷
孔涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yunnan Product Quality Supervision And Inspection Institute
Original Assignee
Yunnan Product Quality Supervision And Inspection Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yunnan Product Quality Supervision And Inspection Institute filed Critical Yunnan Product Quality Supervision And Inspection Institute
Priority to CN201810278879.4A priority Critical patent/CN110294456A/en
Publication of CN110294456A publication Critical patent/CN110294456A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B82B3/0014—Array or network of similar nanostructural elements
    • 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
    • B82B3/0038—Manufacturing processes for forming specific nanostructures not provided for in groups B82B3/0014 - B82B3/0033
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention discloses a kind of preparation methods for the Silver nanorod array structure materials for belonging to nano material preparation and method and technology field.The present invention prepares silicon nanowire array template using the N-shaped monocrystalline silicon piece for being orientated (100), coupled ion sputtering method and wet etching technique.Using electrodeless plating method, Silver nanorod array is prepared in silicon nanowire array template surface.The present invention prepares Silver nanorod array using silicon nanowires template for the first time, and the size of prepared Silver nanorod array structure, pattern can be regulated and controled by structural parameters, the electrodeless plating technological parameter of silicon nanowire array template.The preparation process of this operating procedure simply, under normal temperature and pressure conditions, provides new approaches for novel silver nanostructured preparation.

Description

A method of Silver nanorod array structure materials are prepared using silicon nanowires template
Technical field
The invention belongs to preparation method of nano material technical field, in particular to a kind of Silver nanorod array structure materials Preparation method.
Background technique
Silver nanorod array has excellent activity and unique optical property, is design and building novel nano device Basic material.In recent years, using the preparation of Silver nanorod array structure there is the high activity surface enhancing Raman of " hot spot " effect to dissipate Penetrate extensive concern of the base material by researcher.The common preparation method of Silver nanorod array includes vapour deposition method, electrochemistry Sedimentation, hydro-thermal method etc..These methods need the process conditions of high temperature, high pressure and high vacuum, and preparation step is more, and technique is not easy Control, so the parameters such as the pattern of Silver nanorod array structure, size are not easy.Therefore, Silver nanorod array structure The controllable preparation technology of material needs further research.Template is to realize effective way of Silver nanorod array structure controllable preparation Diameter.Silicon nanowires has physical and chemical performance stabilization and the advantages such as mutually compatible with existing silica-base material preparation process, utilizes its nanometer Size characteristic can be used for further exposure mask preparation nano material.In recent years, gold/silicon nucleocapsid knot has been prepared with silicon nanowires template The materials such as structure nano wire, nickel nano wire, silicon oxide nanotube array.The present invention is used using silicon nanowire array as template Electrodeless plating deposition technique, in the tip deposition growing Silver nanorod of silicon nanowires, to obtain Silver nanorod array.It is this Technology of preparing has apparent advantage: on the one hand, technology of preparing does not need expensive filming equipment, does not need high temperature, high pressure, height The condition of vacuum, technological operation step are simple.On the other hand, the size of Silver nanorod array structure can pass through silicon nanowire array The structural parameters and electrodeless plating technological parameter of template carry out Effective Regulation.Therefore, develop normal temperature and pressure, simple process, can The technology of preparing of control has promote meaning to the practical application for pushing Silver nanorod array structure materials.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of Silver nanorod array structure materials, It is characterized in that, uses silicon nanowire array for template, using the electrodeless plating technology under normal temperature and pressure, in silicon nanowire array Template surface prepares Silver nanorod array, the specific steps are as follows:
A. silicon wafer pre-processes: being utilized respectively acetone, ethyl alcohol and deionized water ultrasonic cleaning, removes silicon face oil pollution object. Removing oxide layer is removed using 7.3 mol/L hydrofluoric acid, then is rinsed with deionized water, clean silicon face is obtained；
B. silicon chip surface sputtering sedimentation Ag films: ion sputtering is used, in < 10-4 Under the vacuum condition of mbar, control Sputtering current and sputtering time, in the certain thickness Ag films of silicon chip surface sputtering sedimentation, Ag films should have certain film Shape characteristic；
C. it prepares silicon nanowires template: preparing the etching liquid being made of the hydrofluoric acid and hydrogen peroxide that centainly match, deposition silver is thin Silicon wafer after film is dipped in the etching liquid of 15-25 DEG C of water-bath, is reacted certain time, can be observed silicon chip surface gradually blackening；
D. it removes remaining silver in silicon nanowires template: with 30 ~ 65 wt % nitric acid dousing, 10 ~ 20 min, completely removing and remain in Silver in silicon nanowires template, is then rinsed well with deionized water；
E. silicon nanowires template surface forms hydrogen bond: with 5 wt % hydrofluoric acid dips, 5 ~ 10 min, removing the oxidation of silicon face Layer, and hydrogen bond is formed in silicon nanowires template surface, deionized water is rinsed well, is dried in vacuo；
F. electrodeless plating deposits Silver nanorod array: preparing the electrodeless electricity of the hydrofluoric acid centainly matched and silver nitrate composition Silicon nanowires template is dipped in the electrodeless plating solution of 15-25 DEG C of water-bath by plating liquor, certain time is reacted, in silicon nanometer The surface deposition of line template prepares Silver nanorod array；
G. the preservation of Silver nanorod array: being rinsed well with deionized water, and vacuum drying saves.
The silicon wafer is that (100) are orientated N-shaped monocrystalline silicon piece, and resistivity is in 3 ~ 5 Ω cm.
Sputtering current is 10 ~ 15 mA in the step b, and sputtering time is 45 ~ 60 s.
In the step b Ag films with a thickness of 8 ~ 12 nm, pattern should have the film morphology feature of continuous island.
Etching liquid proportion is 4 ~ 6mol/L HF, 0.1 ~ 0.5 mol/L H in the step c2O2。
Etch period is 1 ~ 5 min in the step c.
Electrodeless plating solution ratio is 4 ~ 5 mol/L HF, 0.01 ~ 0.03 mol/L AgNO in the step f3, In order to obtain Silver nanorod array structure materials.
The reaction time is 20 ~ 60 s(for 25 DEG C of bath temperature in the step f).
The beneficial effects of the invention are as follows can prepare silver nanoparticle under conditions of normal temperature and pressure using method of the invention Stick array obtains the high yield rate of Silver nanorod array structure materials.The preparation process of silicon nanowire array template with it is existing Monocrystalline silicon piece preparation process is mutually compatible with, and the Silver nanorod array structure prepared with silicon nanowire array template is firm, is not easy from silicon The surface of nano-wire array falls off.
Detailed description of the invention
Fig. 1 is the SEM pattern in silicon nanowire array template.
Fig. 2 is to deposit the SEM pattern for the Silver nanorod array structure to be formed in silicon nanowire array template surface.
Specific embodiment
The present invention proposes a kind of preparation method of Silver nanorod array structure materials.With reference to the accompanying drawings and examples to this Invention is further described.
Embodiment.
1. using resistivity for 3 ~ 5 Ω cm, being orientated the N-shaped monocrystalline silicon piece of (100), it is cleaned by ultrasonic 10 in acetone min；It is cleaned by ultrasonic 10min in dehydrated alcohol；It is rinsed 2 times using deionized water, rinses 1 min every time, be then in concentration 5 min are impregnated in the hydrofluoric acid solution of 7.3 mol/L；Deionized water rinses 2 min, vacuum drying.
2. (< 10 in high vacuum conditions-4Mbar), by control ion sputtering parameter, 10 mA of sputtering current, 50 s of sputtering time, silicon chip surface sputtering sedimentation after the pre-treatment obtain the Ag films with a thickness of 10 nm, the shape of Ag films Looks are continuous island film, this is conducive to the formation of silicon nanowire array template in next step.
3. the silicon wafer for being deposited with Ag films immerses etching liquid, etching liquid is by 4 ~ 6 mol/L HF and 0.1 ~ 0.5 mol/L H2O2Composition, reacts certain time under constant temperature conditions, is catalyzed etching by Ag films and prepares silicon nanowire array mould Plate；For example, the silicon wafer for being deposited with Ag films is immersed by 5 mol/L HF and 0.5 mol/L in 25 DEG C of water bath with thermostatic control H2O2In the etching liquid of composition, 2 min are reacted, obtain silicon nanowire array template.
4. removing remaining silver with 30 wt % nitric acid dousing, 15 min, deionized water is rinsed.It is soaked again with 5 wt % hydrofluoric acid 10 min are steeped, after deionized water rinses and dries, the cross-section morphology of silicon nanowire array template is as shown in Figure 1.
5. silicon nanowire array template is immersed electrodeless plating solution, electrodeless plating solution is by 4 ~ 6 mol/L HF With 0.01 ~ 0.03 mol/L AgNO3Composition, reacts certain time, by galvanic interaction in silicon nanometer under constant temperature conditions Linear array surface forms Silver nanorod array；For example, in 25 DEG C of water bath with thermostatic control, by silicon nanowire array template immerse by 4.5 mol/L HF and 0.02 mol/L AgNO3In the electrodeless plating solution of composition, 45 s are reacted, obtain Silver nanorod battle array Column.
6. after deionized water rinses and dries, the pattern of Silver nanorod array is as shown in Figure 2.
The present invention uses the N-shaped monocrystalline silicon piece of orientation (100), uses ion sputtering process after surface clean, passes through sputtering electricity The thickness and pattern of stream and sputtering time control Ag films have the silver of continuous island shape characteristic in silicon chip surface sputtering sedimentation Film.Wet etching technique is used again, by controlling the concentration proportioning and etch period of etching liquid, prepares silicon nanowire array Template.Electrodeless plating method is further used, by control solution ratio and reaction time, in silicon nanowire array template surface Prepare Silver nanorod array.

Claims (9)

1. a kind of preparation method of Silver nanorod array structure materials, which is characterized in that use silicon nanowire array for template, benefit With the electrodeless plating technology under normal temperature and pressure conditions, Silver nanorod array is prepared in silicon nanowire array template surface, is had Steps are as follows for body:
A. silicon wafer pre-processes: it is utilized respectively acetone, ethyl alcohol and deionized water ultrasonic cleaning, removes silicon face oil pollution object, It recycles 7.3 mol/L hydrofluoric acid to remove removing oxide layer, then is rinsed with deionized water, obtain clean silicon face；
B. silicon chip surface sputtering sedimentation Ag films: ion sputtering is used, in < 10-4 Under the vacuum condition of mbar, control is splashed Radio stream is 10~15 mA, and sputtering time is 45~60 s, in silicon chip surface sputtering sedimentation Ag films with a thickness of 8~12 nm；
C. prepare silicon nanowires template: preparing proportion is 4~6 mol/L HF, 0.1~0.5 mol/L H2O2Etching liquid, will Silicon wafer after deposition Ag films is dipped in the etching liquid of 15-25 DEG C of water-bath, reacts 1~5 min；
D. it removes remaining silver in silicon nanowires template: with 30~65 wt% nitric acid dousing, 10~20 min, completely removing and remain in Silver in silicon nanowires template, is then rinsed well with deionized water；
E. silicon nanowires template surface forms hydrogen bond: with 5 wt% hydrofluoric acid dips, 5~10 min, the oxide layer of silicon face is removed, And hydrogen bond is formed in silicon nanowires template surface, deionized water is rinsed well, is dried in vacuo；
F. electrodeless plating deposits Silver nanorod array: preparing proportion is 4~5 mol/L HF, 0.01~0.03 mol/L AgNO3Electroplating solution, silicon nanowires template is dipped in the electrodeless plating solution of 15~25 DEG C of water-baths, reaction 20~ 60s, on the surface of silicon nanowires template, deposition prepares Silver nanorod array；
G. the preservation of Silver nanorod array: being rinsed well with deionized water, and vacuum drying saves.
2. the preparation method of Silver nanorod array structure materials according to claim 1, which is characterized in that the step b For the sputtering current used for 10 mA, sputtering time is 50 s.
3. the preparation method of Silver nanorod array structure materials according to claim 1, which is characterized in that the step b In Ag films with a thickness of 10 nm.
4. the preparation method of Silver nanorod array structure materials according to claim 1, which is characterized in that the step c The middle etching liquid used matches as 5 mol/L HF, 0.5 mol/L H2O2。
5. the preparation method of Silver nanorod array structure materials according to claim 1, which is characterized in that the step c The middle reaction time used is 2 min.
6. the preparation method of Silver nanorod array structure materials according to claim 1, which is characterized in that the step f The middle electrodeless plating solution ratio used is 4.5 mol/L HF, 0.02 mol/L AgNO3。
7. the preparation method of Silver nanorod array structure materials according to claim 1, which is characterized in that the step f The middle reaction time used is 45 s.
8. the preparation method of Silver nanorod array structure materials described in any one of -7 according to claim 1, which is characterized in that The silicon wafer is the N-shaped monocrystalline silicon piece of (100) orientation, and resistivity is 3~5 Ω cm.
9. the preparation method of Silver nanorod array structure materials described in any one of -7 according to claim 1, which is characterized in that Water resistance rate used is more than 16 Ω cm.
CN201810278879.4A 2018-04-03 2018-04-03 A method of Silver nanorod array structure materials are prepared using silicon nanowires template Pending CN110294456A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810278879.4A CN110294456A (en) 2018-04-03 2018-04-03 A method of Silver nanorod array structure materials are prepared using silicon nanowires template

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810278879.4A CN110294456A (en) 2018-04-03 2018-04-03 A method of Silver nanorod array structure materials are prepared using silicon nanowires template

Publications (1)

Publication Number Publication Date
CN110294456A true CN110294456A (en) 2019-10-01

Family

ID=68026290

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810278879.4A Pending CN110294456A (en) 2018-04-03 2018-04-03 A method of Silver nanorod array structure materials are prepared using silicon nanowires template

Country Status (1)

Country Link
CN (1) CN110294456A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114018897A (en) * 2021-10-21 2022-02-08 云南省产品质量监督检验研究院 Preparation method of silicon-based SERS substrate based on double-layer silver nanostructure

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060146323A1 (en) * 2005-01-06 2006-07-06 Alexandre Bratkovski Nanowires for surface-enhanced raman scattering molecular sensors
CN101672786A (en) * 2009-03-12 2010-03-17 中国科学院理化技术研究所 Active substrate with surface provided with enhanced raman scattering effect and production method and application thereof
CN102126724A (en) * 2011-03-31 2011-07-20 上海交通大学 Method for preparing silicon nanowire array with smooth surface
CN103572374A (en) * 2013-11-05 2014-02-12 无锡英普林纳米科技有限公司 Method for preparing silicon nanowire through sputter deposited metal
CN103569961A (en) * 2013-11-20 2014-02-12 中国科学院理化技术研究所 Preparation method for silver nanoparticle chain under inducement of silicon nanowire

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060146323A1 (en) * 2005-01-06 2006-07-06 Alexandre Bratkovski Nanowires for surface-enhanced raman scattering molecular sensors
CN101672786A (en) * 2009-03-12 2010-03-17 中国科学院理化技术研究所 Active substrate with surface provided with enhanced raman scattering effect and production method and application thereof
CN102126724A (en) * 2011-03-31 2011-07-20 上海交通大学 Method for preparing silicon nanowire array with smooth surface
CN103572374A (en) * 2013-11-05 2014-02-12 无锡英普林纳米科技有限公司 Method for preparing silicon nanowire through sputter deposited metal
CN103569961A (en) * 2013-11-20 2014-02-12 中国科学院理化技术研究所 Preparation method for silver nanoparticle chain under inducement of silicon nanowire

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FAN BAI等: "Silicon nanowire arrays coated with electroless Ag for increased surface-enhanced Raman scattering", 《APL MATERIALS》 *
吴永宽: "硅纳米线阵列与银纳米结构的制备及其SERS研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114018897A (en) * 2021-10-21 2022-02-08 云南省产品质量监督检验研究院 Preparation method of silicon-based SERS substrate based on double-layer silver nanostructure

Similar Documents

Publication Publication Date Title
CN104986724B (en) A kind of fexible film surface micronano structure and application thereof
CN105926014B (en) The preparation method of the highly ordered porous oxidation film of large area based on the soft coining of nanometer
CN102910573B (en) Preparation method of SERS (Surface Enhanced Raman Scattering) active substrate of multilevel metal micro-nano structure array with removable protection layer
CN104310372B (en) A kind of method of direct growth carbon nano pipe array in fibrous substrate
CN103274354B (en) Preparation method of gecko structure simulating adhesive
CN100436008C (en) Chemical production of metal nickel nano-line
CN103337449B (en) Method prepared by the transplanting of silicon nanowire array and simple Devices thereof
CN104195518B (en) A kind of black light-absorbing film and preparation method thereof
CN104045054A (en) Method for preparing high-adhesion micro-nano array structure film through wet etching and reverse transfer printing
CN109770438A (en) A kind of plated film silicon-based electronic aerosolization chip and preparation method thereof
CN108190830A (en) A kind of production method of high-aspect-ratio diamond micro nano structure
CN109648096B (en) Method for converting random nanocone array into silver nanosheet constructed micro/nano structure array in situ
CN103979485B (en) A kind of preparation method of micro-nano porous silica material
CN105967139A (en) Method for etching holes on silicon substrate, silicon substrate with holes and semiconductor device
CN103803486A (en) Preparation method of superfine silicon nanowire array
CN103194778A (en) Transfer method of ultrathin porous aluminum oxide template
Cao et al. Inherent superhydrophobicity of Sn/SnOx films prepared by surface self-passivation of electrodeposited porous dendritic Sn
CN110294456A (en) A method of Silver nanorod array structure materials are prepared using silicon nanowires template
CN108033479A (en) A kind of needle-shaped Kocide SD with super-hydrophobicity and preparation method thereof
CN103296141A (en) Method for producing dendritic heterojunction nanowire array structural materials
CN100517063C (en) Method for preparing three-dimensional micro-configuration of unidimensional nanometer material
CN104726920A (en) Method for preparing and transferring ultrathin perforated anode alumina template
CN104766724B (en) A kind of button capacitor microfabrication based on cobaltosic oxide nano structure
CN106927421B (en) The method for manufacturing the silicon nanowires controllably moved towards
CN102856434B (en) Preparation method for square silicon nano-porous array

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20191001