CN107119252A - A kind of silicon substrate surface strengthens the preparation method of Raman substrate - Google Patents
A kind of silicon substrate surface strengthens the preparation method of Raman substrate Download PDFInfo
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- CN107119252A CN107119252A CN201710384578.5A CN201710384578A CN107119252A CN 107119252 A CN107119252 A CN 107119252A CN 201710384578 A CN201710384578 A CN 201710384578A CN 107119252 A CN107119252 A CN 107119252A
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- preparation
- monocrystalline silicon
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- silicon
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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
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- 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 the preparation method that a kind of silicon substrate surface strengthens Raman substrate, the method that the monocrystalline silicon is prepared by surface micro-structure obtains orderly pyramid structure, and one layer of golden film is coated with orderly pyramid；Its preparation method includes：（1）The orderly pyramid structure of monocrystalline silicon surface is obtained using alkaline solution corrosion；（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 is obtained has good chemical stability, can detect low concentration material, and concentration is low up to 10‑7Mol/L, gained abosrption spectrogram is almost unchanged for a long time for storage.The preparation method is easy to operate, with low cost, favorable repeatability and easily controllable pyramid size and golden film thickness.
Description
Technical field
The present invention relates to the preparation method that a kind of silicon substrate surface strengthens Raman substrate.
Background technology
Silicon is a very important semi-conducting material, and an important role is played the part of in modern industry.The surface of silicon
Chemical Physics architectural feature, causes extensive interest not only in physics and chemistry subject, and 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 higher silicon face will
Modification is asked, causes the research interest of a new ripple in the surface appearance feature of silicon.
What surface reinforced Raman active substrate was commonly used has Electrochemical roughening electrode, noble metal colloidal sol and vacuum evaporation gold
Category.SERS technology has had sensitivity very high, and Raman signal is up to 106~1014Times, can improve monolayer or
The abundant structural information of the surface molecular of sub- monolayer, solves that raman spectral signal is weak, and scattering section very little can only be provided
Adsorb the deficiency in the information of monolayer.
Prepare that size shape is controllable, stability is high, the surface enhanced active substrate that 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.
The content of the invention
The deficiency existed for above-mentioned prior art, it is an object of the invention to provide one kind stabilization and low-cost silicon substrate table
Face strengthens the preparation method of Raman substrate, and this method is simple to operate, and technical process is easy to control, with low cost, favorable repeatability, system
Standby compound particle has good stability.
The present invention provides following technical scheme to achieve the above object：
A kind of silicon substrate surface strengthens the preparation method of Raman substrate, and the method that monocrystalline silicon is prepared by surface micro-structure obtains orderly
Pyramid structure, is coated with one layer of golden film on orderly pyramid particle.
Further, a diameter of 0.5-1.5 μm of the monocrystalline silicon surface pyramid nano-particle, the thickness of the golden film
For 50-200 nm.
A kind of silicon substrate surface strengthens the preparation method of Raman substrate, comprises the following steps：
（1）The orderly pyramid structure of monocrystalline silicon surface is obtained using alkaline solution corrosion；
（2）Monocrystalline silicon surface using ion sputtering film coating method in orderly pyramid structure plates last layer golden film.
Further, step（1）Including：First by silicon single crystal wafer p-type< 100 >Its resistivity is that 1-3 Ω cm are cut into size
1.6cm × 1.6cm is used as corrosion experiment, and monocrystalline silicon is pre-processed before reaction, removes surface impurity and oxide；With wait from
Sub- cleaning device cleans 10min, is successively put into ultrasound 5min in pure water and absolute ethyl alcohol, is immersed in 60s in the HF that solubility is 4%, then
With the clean 5min of ultra-pure water ultrasound, dry for standby, ultra-pure water resistivity is 18.25 M Ω cm；Configuration solubility is 10wt%K2CO3
And 2wt%K2SiO3Solution, magnetic stirring apparatus temperature is set to 85 DEG C, reaches that the monocrystalline silicon piece that process is pre-processed during temperature is put into close
Close and 20min is reacted in container, reaction end ultra-pure water is cleaned by ultrasonic repeatedly, dry for standby.
Further, step（2）Including：Monocrystalline silicon piece after corrosion is put into the substrate frame in 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 present invention has the following advantages that compared with prior art：
（1）It is above-mentioned that last layer golden nanometer particle is plated on the silicon face of orderly pyramid structure using traditional ion sputtering process
Method, obtained compound particle has a good chemical stability, and gained abosrption spectrogram is almost unchanged for a long time for storage.
（2）This method is easy to operate, technical process is easy to control, with low cost, favorable repeatability and can easily be accommodated pyramid
Size and golden film thickness.
（3）Monocrystalline silicon has semiconductor property, as semi-conducting material and using solar energy power generating, heat supply etc., and
With unique optical property and electrical properties, it is widely used in diode level, rectifying device level, circuit-level and solar-electricity
The production and deep processing manufacture of pond level single crystal product article, its subsequent product integrated circuit and semiconductor separation part are widely used to
Every field.
Brief description of the drawings
Fig. 1 be the inventive method prepare monocrystalline silicon corrosion after size be about 1.35 μm pyramid structure scanning electricity
Mirror photo.
Fig. 2 is the stereoscan photograph of the Si/Au composite nanoparticles of the present invention；
Fig. 3 is the silicon chip after excessive erosion of the present invention and the silicon chip light reflectogram of different sputtering time golden nanometer particles.
The concentration that Fig. 4 is the present invention is 10-5Mol/L methylene blues (a) SERS and (b) methylene blue second
The Raman spectrogram of alcoholic solution.
Fig. 5 is the SERS figure of the methylene blue solution of the various concentrations of the present invention；Wherein solubility is 10-3-10-7Mol/L, plated film time is 330s.
Fig. 6 is the different sputtering times detection 10 of the present invention-5The surface-enhanced Raman of mol/L methylene blue ethanol solutions
Figure.
Embodiment
Embodiment
1) first by silicon single crystal wafer p-type< 100 >Its resistivity is cut into size 1.6cm × 1.6cm for 1-3 Ω cm and is used as
Corrosion experiment, is pre-processed before reaction to monocrystalline silicon, removes surface impurity and oxide.Cleaned with plasma cleaning instrument
10min, is successively put into ultrasound 5min in pure water and absolute ethyl alcohol, is immersed in 60s in the HF that concentration is 4%, then ultrasonic with ultra-pure water
Clean 5min, dry for standby.Ultra-pure water resistivity is 18.25 M Ω cm；
2) configuration solubility is 10wt%K2CO3And 2wt%K2SiO3Solution, magnetic stirring apparatus temperature is set to 85 degrees Celsius, reaches temperature
The monocrystalline silicon by pretreatment is put into closed container when spending and reacted 20 minutes, ultrasound is clear repeatedly with ultra-pure water for reaction end
Wash, dry for standby；
3）The pyramid structure shape characteristic of monocrystalline silicon surface is characterized using Zeiss EVO MA15 types ESEM.Such as Fig. 1 institutes
Show, pyramid area coverage is big, and size uniform, 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
108auto）Substrate frame on, change gold target.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 is obtained is successively that 30mA sputters different time in size of current.
5）The surface topography of gold-plated pyramid structure is characterized using Zeiss EVO MA15 types ESEM.Such as Fig. 2 institutes
Show, pyramid structure even structure.
6）Characterized using UV-2600 type UV, visible light near infrared spectrometers 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 chip light wave be 500-900nm and not gold-plated silicon chip herein
Scope light reflectivity intensity has very big difference.So as to enhance the detection of Raman signal.
7）Using the portable Raman detection various concentrations of marine optics（10-3-10-7mol/L）Methylene blue ethanol it is molten
Liquid；Fig. 4 and Fig. 5 are the Raman spectrums that sputtering time is 330s, can be observed to can detect that the methylene blue of low concentration from figure
Solution.Fig. 6 is that different sputtering time detection solubility are 10-5Mol/L methylene blue solution, illustrates the intensity of Raman detection signal
There is very big relation with the time of sputtering.
Claims (5)
1. a kind of silicon substrate surface strengthens the preparation method of 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 with orderly pyramid particle.
2. a kind of silicon substrate surface according to claim 1 strengthens the preparation method of Raman substrate, it is characterised in that the list
A diameter of 0.5-1.5 μm of crystal silicon surface pyramid nano-particle, the thickness of the golden film is 50-200 nm.
3. a kind of silicon substrate surface described in claim 1 or 2 strengthens the preparation method of Raman substrate, it is characterised in that including with
Lower step：
（1）The orderly pyramid structure of monocrystalline silicon surface is obtained using alkaline solution corrosion；
（2）Monocrystalline silicon surface using ion sputtering film coating method in orderly pyramid structure plates last layer golden film.
4. a kind of silicon substrate surface according to claim 3 strengthens the preparation method of Raman substrate, it is characterised in that step（1）
Including：
First by silicon single crystal wafer p-type< 100 >Its resistivity is cut into size 1.6cm × 1.6cm for 1-3 Ω cm and is used as corrosion in fact
Test, monocrystalline silicon is pre-processed before reaction, remove surface impurity and oxide；10min is cleaned with plasma cleaning instrument, successively
Ultrasound 5min in pure water and absolute ethyl alcohol is put into, 60s in the HF that solubility is 4% is immersed in, then 5min is cleaned with ultra-pure water ultrasound,
Dry for standby, ultra-pure water resistivity is 18.25 M Ω cm；Configuration solubility is 10wt%K2CO3And 2wt%K2SiO3Solution, magnetic force
Agitator temperature is set to 85 DEG C, reaches to be put into closed container the monocrystalline silicon piece by pretreatment during temperature and reacts 20min, instead
It should terminate repeatedly to be cleaned by ultrasonic with ultra-pure water, dry for standby.
5. a kind of silicon substrate surface according to claim 3 strengthens the preparation method of Raman substrate, it is characterised in that step（2）
Including：
Monocrystalline silicon piece after corrosion is put into the substrate frame in ion sputtering film coating machine, gold-palladium sputtering is changed into；Adjust rotating disk 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 is crossed to adjust.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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