CN107119252B - A kind of preparation method of silicon substrate surface enhancing Raman substrate - Google Patents

A kind of preparation method of silicon substrate surface enhancing Raman substrate Download PDF

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Publication number
CN107119252B
CN107119252B CN201710384578.5A CN201710384578A CN107119252B CN 107119252 B CN107119252 B CN 107119252B CN 201710384578 A CN201710384578 A CN 201710384578A CN 107119252 B CN107119252 B CN 107119252B
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monocrystalline silicon
pyramid
orderly
preparation
silicon
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CN201710384578.5A
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CN107119252A (en
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满石清
叶巧云
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Yunnan Normal University
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Yunnan Normal University
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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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • 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
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons

Abstract

The invention discloses a kind of preparation method of silicon substrate surface enhancing Raman substrate, the monocrystalline silicon obtains orderly pyramid structure by method prepared by surface micro-structure, and one layer of golden film is coated on orderly pyramid；Preparation method includes: (1) using the alkaline solution corrosion acquisition orderly pyramid structure of monocrystalline silicon surface；(2) certain thickness golden film is plated in the monocrystalline silicon surface of orderly pyramid structure using ion sputtering film coating method.The composite nanoparticle that this method obtains has good chemical stability, can detect low concentration substance, concentration is down to 10‑7Mol/L, gained abosrption spectrogram is almost unchanged for a long time for storage.The preparation method is easy to operate, low in cost, favorable repeatability and easily controllable pyramid size and golden film thickness.

Description

A kind of preparation method of silicon substrate surface enhancing Raman substrate
Technical field
The present invention relates to a kind of preparation methods of silicon substrate surface enhancing Raman substrate.
Background technique
Silicon is a very important semiconductor material, and an important role is played the part of in modern industry.The surface of silicon Chemical Physics structure feature causes extensive interest not only in physics and chemistry subject, but also nano material, biomedicine etc. Subject causes attention.Recently, monocrystalline silicon is also found to be widely used in the generation of solar cell and deep processing manufacture, nanometer material The preparation of material, biochemical sensor, integrated circuit, semiconductor separation part etc..And then set up wanting for a higher silicon face Modification is asked, causes the research interest of a new wave in the surface appearance feature of silicon.
There are commonly Electrochemical roughening electrode, noble metal colloidal sol and vacuum evaporation gold for surface reinforced Raman active substrate Belong to.Surface enhanced Raman spectroscopy technology has had sensitivity very high, and Raman signal is up to 106~1014Times, can improve monolayer or The surface molecular of sub- monolayer structural information abundant, solves that raman spectral signal is weak, and scattering section very little can only provide It is adsorbed on the deficiency of the information of monolayer.
Preparing the surface enhanced active substrate that size shape is controllable, stability is high, favorable reproducibility, enhancing ability are strong is to obtain The key of Raman spectrum.So far, scraped using nanosphere imprint lithography be successfully prepared with template it is as characterized above Active substrate.But somewhat expensive, therefore prepare the monocrystalline silicon active substrate that price is low and stability is good and be necessary.
Summary of the invention
In view of the deficiency of the prior art, the object of the present invention is to provide a kind of stabilization and low-cost silicon substrate tables Face enhances the preparation method of Raman substrate, and this method is easy to operate, and technical process is easy to control, low in cost, favorable repeatability, system Standby compound particle is with good stability.
To achieve the above object the present invention the following technical schemes are provided:
A kind of preparation method of silicon substrate surface enhancing Raman substrate, monocrystalline silicon are obtained by method prepared by surface micro-structure Orderly pyramid structure is coated with one layer of golden film on orderly pyramid particle.
Further, the diameter of the monocrystalline silicon surface pyramid nanoparticle is 0.5-1.5 μm, the thickness of the golden film For 50-200 nm.
A kind of preparation method of silicon substrate surface enhancing Raman substrate, comprising the following steps:
(1) the orderly pyramid structure of monocrystalline silicon surface is obtained using alkaline solution corrosion；
(2) one layer of golden film is plated in the monocrystalline silicon surface of orderly pyramid structure using ion sputtering film coating method.
Further, it is that 1-3 Ω cm is cut into size that step (1), which includes: first by silicon single crystal wafer p-type<100>its resistivity, 1.6cm × 1.6cm is used as corrosion experiment, pre-processes before reaction to monocrystalline silicon, removes surface impurity and oxide；With it is equal from Sub- cleaning device cleans 10min, is successively put into ultrasound 5min in pure water and dehydrated alcohol, is immersed in 60s in the HF that solubility is 4%, then 5min is cleaned with ultrapure water ultrasound, is dried for standby, ultrapure water resistivity is 18.25 M Ω cm；Configuration solubility is 10wt%K2CO3 And 2wt%K2SiO3Solution, magnetic stirring apparatus temperature are set as 85 DEG C, close being put by pretreated monocrystalline silicon piece when reaching temperature It closes and reacts 20min in container, reaction end ultrapure water is cleaned by ultrasonic repeatedly, is dried for standby.
Further, step (2) includes: in the substrate frame that the monocrystalline silicon piece after corrosion is put into ion sputtering film coating machine, Change gold-palladium sputtering into；Rotary speed is adjusted, enables gold particle uniform sputter to pyramid surface, as container chamber pressure 0.08mb When start plated film, coating film thickness can be adjusted by changing sputtering time and size of current.
The invention has the following advantages over the prior art:
(1) above-mentioned to plate one layer of gold nano on the silicon face of orderly pyramid structure using traditional ion sputtering process The method of particle, obtained compound particle have good chemical stability, storage for a long time gained abosrption spectrogram almost without Variation.
(2) this method is easy to operate, technical process is easy to control, low in cost, favorable repeatability and can easily be accommodated pyramid Size and golden film thickness.
(3) monocrystalline silicon has semiconductor property, is used as semiconductor material and utilizes solar energy power generating, heat supply etc., and With unique optical property and electrical properties, it is widely used in diode grade, rectifying device grade, circuit-level and solar-electricity The production and deep processing manufacture of pond grade single crystal product article, subsequent product integrated circuit and semiconductor separation part are widely used to Every field.
Detailed description of the invention
Fig. 1 is the scanning electricity for the pyramid structure that size is about 1.35 μm after the monocrystalline silicon of the method for the present invention preparation corrodes
Mirror photo.
Fig. 2 is the stereoscan photograph of Si/Au composite nanoparticle of the invention；
Fig. 3 is the silicon wafer light reflectogram of the silicon wafer of the invention after excessive erosion and different sputtering time gold nanoparticles.
Fig. 4 is that concentration of the invention is 10-5Mol/L methylene blue (a) Surface enhanced Raman spectroscopy and (b) methylene blue second The Raman spectrogram of alcoholic solution.
Fig. 5 is the Surface enhanced Raman spectroscopy figure of the methylene blue solution of various concentration of the invention；Wherein solubility is 10-3-10-7Mol/L, plated film time 330s.
Fig. 6 is different sputtering times detection 10 of the invention-5The surface-enhanced Raman of mol/L methylene blue ethanol solution Figure.
Specific embodiment
Embodiment
1) silicon single crystal wafer p-type<100>its resistivity is first cut into size 1.6cm × 1.6cm for 1-3 Ω cm to be used as Corrosion experiment pre-processes monocrystalline silicon before reaction, removes surface impurity and oxide.It is cleaned with plasma cleaning instrument 10min is successively put into ultrasound 5min in pure water and dehydrated alcohol, is immersed in 60s in the HF that concentration is 4%, then ultrasonic with ultrapure water 5min is cleaned, is dried for standby.Ultrapure water resistivity is 18.25 M Ω cm；
2) configuration solubility is 10wt%K2CO3And 2wt%K2SiO3Solution, magnetic stirring apparatus temperature are set as 85 degrees Celsius, reach React 20 minutes when to temperature being put into closed container by pretreated monocrystalline silicon, it is repeatedly ultrasonic with ultrapure water to react end Cleaning, is dried for standby；
3) using the pyramid structure shape characteristic of Zeiss EVO MA15 type scanning electron microscope characterization monocrystalline silicon surface.Such as figure Shown in 1, pyramid area coverage is big, of uniform size, and average-size is about 1.35 μm.
4) monocrystalline silicon piece after making herbs into wool is put into ion sputtering film coating machine (Cressington Sputter Coater In substrate frame 108auto), gold target is changed.Rotary speed is adjusted, starts plated film when pressure is 0.08mb, by condition of the same race The monocrystalline silicon piece that lower making herbs into wool obtains is successively that 30mA sputters different time in size of current.
5) surface topography of gold-plated pyramid structure is characterized using Zeiss EVO MA15 type scanning electron microscope.Such as Fig. 2 institute Show, pyramid structure structure is uniform.
6) characterized using UV-2600 type UV, visible light near infrared spectrometer the monocrystalline silicon piece reflectivity after making herbs into wool and Monocrystalline silicon piece reflectivity after gold-plated.Fig. 3 show it is gold-plated after silicon wafer light wave be 500-900nm and not gold-plated silicon wafer herein Range light reflectivity intensity has very big difference.To enhance the detection of Raman signal.
7) various concentration (10 is detected using the portable Raman of marine optics-3-10-7Mol/L methylene blue ethyl alcohol) is molten Liquid；Fig. 4 and Fig. 5 is the Raman spectrum that sputtering time is 330s, and the methylene blue that can detect that low concentration can be observed from figure Solution.Fig. 6 is that different sputtering time detection solubility are 10-5The methylene blue solution of mol/L illustrates the intensity of Raman detection signal There is very big relationship with the time of sputtering.

Claims (2)

1. a kind of preparation method of silicon substrate surface enhancing Raman substrate, it is characterised in that monocrystalline silicon is prepared by surface micro-structure Method obtains orderly pyramid structure, and one layer of golden film is coated on orderly pyramid particle；
The diameter of the monocrystalline silicon surface pyramid nanoparticle be 0.5-1.5 μm, the golden film with a thickness of 50-200 nm；
The preparation method of silicon substrate surface enhancing Raman substrate the following steps are included:
(1) the orderly pyramid structure of monocrystalline silicon surface is obtained using alkaline solution corrosion；
(2) one layer of golden film is plated in the monocrystalline silicon surface of orderly pyramid structure using ion sputtering film coating method；
Step (1) include: first by silicon single crystal wafer p-type<100>its resistivity be 1-3 Ω cm be cut into size 1.6cm × 1.6cm is used as corrosion experiment, pre-processes before reaction to monocrystalline silicon, removes surface impurity and oxide；Use plasma cleaning Instrument cleans 10min, is successively put into ultrasound 5min in pure water and dehydrated alcohol, is immersed in solubility for 60s in 4% HF, then with ultrapure Water ultrasound cleans 5min, is dried for standby, and ultrapure water resistivity is 18.25 M Ω cm；Configuration solubility is 10wt%K2CO3And 2wt% K2SiO3Solution, magnetic stirring apparatus temperature are set as 85 DEG C, are put into closed container pretreated monocrystalline silicon piece is passed through when reaching temperature Middle reaction 20min, reaction end ultrapure water are cleaned by ultrasonic repeatedly, are dried for standby.
2. a kind of preparation method of silicon substrate surface enhancing Raman substrate according to claim 1, it is characterised in that step (2) Include:
Monocrystalline silicon piece after corrosion is put into the substrate frame in ion sputtering film coating machine, changes gold-palladium sputtering into；Adjust turntable speed Degree, enables gold particle uniform sputter to pyramid surface, starts plated film as container chamber pressure 0.08mb, coating film thickness can lead to Change sputtering time and size of current are crossed to adjust.
CN201710384578.5A 2017-05-26 2017-05-26 A kind of preparation method of silicon substrate surface enhancing Raman substrate Expired - Fee Related CN107119252B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111876813A (en) * 2020-07-29 2020-11-03 长春理工大学 Substrate material, Raman surface enhanced substrate, preparation method and application

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CN107748159A (en) * 2017-11-15 2018-03-02 兰州大学 A kind of surface enhanced Raman substrate and preparation method thereof
CN108760714A (en) * 2018-03-05 2018-11-06 华南理工大学 The method that noble metal quenching fluorescence is used in Raman spectrum

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CN102864414B (en) * 2012-10-18 2014-04-02 中山大学 Method for preparing Fe film with pyramid structure
CN103033496B (en) * 2012-12-17 2015-11-25 南开大学 A kind of wide area surface strengthens the preparation method of Raman scattering substrate
CN103112816B (en) * 2013-01-30 2015-05-13 中国科学院大学 Method for preparing pyramid array on monocrystalline silicon substrate
CN103604795B (en) * 2013-11-27 2016-02-10 中国科学院重庆绿色智能技术研究院 A kind of across yardstick thermometal collaborative enhancing Raman scattering chip and preparation method thereof
CN105842227A (en) * 2016-03-30 2016-08-10 中国科学院物理研究所 Preparation method for surface-enhanced Raman substrate and surface-enhanced Raman substrate structure
CN106442460A (en) * 2016-09-05 2017-02-22 山东师范大学 Gold @ silver nano-particles/pyramidal silicon three-dimensional Raman reinforced substrate and preparing method and application thereof

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CN111876813A (en) * 2020-07-29 2020-11-03 长春理工大学 Substrate material, Raman surface enhanced substrate, preparation method and application
CN111876813B (en) * 2020-07-29 2021-06-29 长春理工大学 Substrate material, Raman surface enhanced substrate, preparation method and application

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