CN110044870A - The method for preparing SERS substrate is restored based on laser irradiation - Google Patents

The method for preparing SERS substrate is restored based on laser irradiation Download PDF

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Publication number
CN110044870A
CN110044870A CN201910343577.5A CN201910343577A CN110044870A CN 110044870 A CN110044870 A CN 110044870A CN 201910343577 A CN201910343577 A CN 201910343577A CN 110044870 A CN110044870 A CN 110044870A
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sers substrate
laser irradiation
copper sheet
restores
backing material
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CN110044870B (en
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唐建设
唐曦璞
项丽
吴焕乐
崔兆行
严政
王一
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Anhui Jianzhu University
Anhui University of Architecture
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Anhui University of Architecture
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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

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Abstract

The invention discloses a kind of methods for being restored based on laser irradiation and preparing SERS substrate, comprising: the clean flat and smooth copper sheet surface of oxidation induces the copper sheet backing material of surface Cu oxide；Copper sheet backing material is placed in silica ware, sulfide is added, laser irradiation forms the copper sheet backing material of surface copper oxysulfide；Copper sheet backing material is cleaned again, is placed in silica ware, argentum reagent is added, continues laser irradiation, obtains the SERS substrate of surface copper oxysulfide hybridization silver nano-grain.The invention has the advantages that there is prepared semiconductor SERS substrate good SERS to enhance performance, and production method is simple, reproducible, uniform surface；Because introducing semiconductor material, control the size of semiconductor, pattern, forbidden bandwidth and in terms of also there is certain advantage than the SERS substrate of Typical precious metal nano particle, and prepared by the method SERS substrate, in the rule for exploring Chemical enhancement effect, new SERS base material is also provided.

Description

The method for preparing SERS substrate is restored based on laser irradiation
Technical field
The present invention relates to analysis technical fields, and in particular to the method for preparing SERS substrate is restored based on laser irradiation.
Background technique
(surface enhancement of Raman scattering, surface increase the SERS of plasmon nanostructure Strong Raman scattering) substrate, need to have chemical stability, it is easily prepared, repeatable, spatially uniform the features such as, it is prior It is to have high enhancement factor.
Metal nanoparticle is used and become shortly after SERS effect is found grinds a kind of SERS base to make internal disorder or usurp extensively Bottom.SERS substrate can be divided into metal nanoparticle solution, fix the substrate of metal nanoparticle on support, directly in solid Three kinds of nanostructure are synthesized in substrate.Either directly synthesized by the support anchoring base of self assembly or the surface of solids Nanometer supporting body structure, have its is easy to use, reinforcing effect is good, be easy to save etc. unique advantages.
However, single metal nano material limits SERS in the application in nonmetallic field.Subsequent semiconductor material SERS substrate all shows wide application prospect in the field SERS and Material Field, and having compared to metal material substrate can Control, richer intrinsic property, becomes the active material in the field SERS.Semiconductor not only have good surface stability, It is easier to surface modification and modification, and its amount can be regulated and controled by size, pattern, forbidden bandwidth and the doping of control semiconductor The characteristics such as sub- confinement effect, surface defect state explore the action rule to Chemical enhancement effect.
The important one kind of chalcogen compound/noble metal composite substrate as semiconductor material SERS substrate, is either related to The oxides such as metal Ti, Zn, Cu or nonmetallic SiO2, preparation method be intended to by chemical reaction and nanoassemble skill Art, the preparation method of this SERS substrate, belongs to chemistry redox method.Problem is that conventional preparation method exists: 1) anti- Special chemical reaction condition and synthetic environment should be needed in the process, technically be difficult to control, be difficult to meet in realization condition；2) Complicated chemical treating process, needs a variety of chemical reducing agents, reaction stabilizer and multi-solvents, to be readily incorporated various The reproducibility of impurity, efficiency and preparation method to material has a significant impact；3) use of many chemical reagent, is unfavorable for ring It protects, and also will increase the cost of substrate synthesis.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for being restored based on laser irradiation and preparing SERS substrate, are thus made and increase Strong energy dissipating is good, the uniform surface Cu semiconductor-Ag nano grain surface compound substrate for SERS enhancing.
The present invention through the following technical solutions to achieve the above objectives:
A kind of method that laser irradiation reduction prepares SERS substrate, including
Step 1: the clean flat and smooth copper sheet surface of oxidation induces the copper sheet backing material of surface Cu oxide；
Step 2: the copper sheet backing material obtained in step 1 is placed in silica ware, and sulfide solution is added, and is passed through Laser irradiation forms the copper sheet backing material of surface copper oxysulfide；
Step 3: the copper sheet backing material obtained in step 2 being cleaned, is placed in silica ware, and argentum reagent is added, after It is continuous to pass through laser irradiation, obtain the SERS substrate of surface copper oxysulfide hybridization silver nano-grain.
Further improvement lies in that the clean flat and smooth copper sheet surface of oxidation, oxidant used includes hydrogen peroxide, hydrogen peroxide Mass percentage concentration be 5%~30%, aoxidize soaking time 30min~2h, acid condition, and H+Concentration is 1M.
Further improvement lies in that the sulfide solution is the organic compound rolled into a ball containing sulfydryl, and sulfide solution is dense Degree is 2~20mM.
Further improvement lies in that the organic compound containing sulfydryl group is thioacetic acid, mercaptopropionic acid or sulfydryl second Amine.
Further improvement lies in that the argentum reagent is silver nitrate or silver acetate, and the concentration of argentum reagent is 0.01~0.3g/ mL。
Further improvement lies in that one or more mixing of the laser irradiation between wavelength 350nm~670nm.
Further improvement lies in that the laser irradiation is controlled in the time of deposition sulphur copper compound in 20min~1h, and institute It is 80~1000mW with laser power.
Further improvement lies in that the laser irradiation is controlled in the time of deposition silver nano-grain in 20min~1h, and institute It is 80~1000mW with laser power.
A kind of semiconductor SERS substrate, the SERS substrate be using the above method prepare be compounded with copper sulfide and The SERS substrate of silver nano-grain.
The beneficial effects of the present invention are: there is prepared semiconductor SERS substrate good SERS to enhance performance, and Have many advantages, such as that production method is simple, reproducible, uniform surface.In addition, because introducing semiconductor material, in control semiconductor Size, pattern, forbidden bandwidth and doping etc. also have than the SERS substrate of Typical precious metal nano particle it is certain excellent Gesture, and prepared by the method SERS substrate also provide new SERS base in the rule for exploring Chemical enhancement effect Bottom material.
Detailed description of the invention
Fig. 1 is the copper sheet surface irradiation reduction silver nano-grain structure and morphology that sulfide is deposited without laser irradiation；
Fig. 2 is the copper sheet surface irradiation reduction silver nano-grain structure and morphology that sulfide is deposited by laser irradiation；
Fig. 3 is that different materials compare the SERS reinforcing effect of R6G.
Specific embodiment
The application is described in further detail with reference to the accompanying drawing, it is necessary to it is indicated herein to be, implement in detail below Mode is served only for that the application is further detailed, and should not be understood as the limitation to the application protection scope, the field Technical staff can make some nonessential modifications and adaptations to the application according to above-mentioned application content.
Embodiment 1:
Solution used: AgNO3Solution, mercaptoacetic acid solution, R6G solution；
Select laser: green (light) laser；
Laser irradiation: mercaptoacetic acid solution being added into quartz colorimetric utensil, is put into sample copper sheet, is shone using green (light) laser Penetrate 30min；Sample copper sheet is moved to, AgNO is added3In another quartz colorimetric utensil of solution, green (light) laser is equally used Irradiate same site 30min.
A kind of method that laser irradiation reduction prepares SERS substrate, including the following steps:
A., the long strip type sample copper sheet that copper sheet is cut into 30mm*5mm, is polished sample with metallurgical polishing powder, and vacuum is protected It deposits spare；
B. the AgNO of 10mM mercaptoacetic acid solution and 0.3g/mL is prepared3Solution；
C. (laser power 500mW) sample copper sheet is irradiated with green (light) laser, continues 30min, copper sheet is placed in 10mM sulfydryl In acetic acid solution；Sample copper sheet is taken out, air dry oven is put into and is dried；
D. sample (laser power 500mW) product copper sheet is irradiated with green (light) laser, continues 30min, copper sheet is placed in 0.3g/mL's AgNO3In solution；Sample copper sheet is taken out, air dry oven is put into and is dried；
E. R6G solution is added dropwise respectively, is put into air dry oven and is dried；Using Raman spectrometer, Raman spectrum is scanned.
Embodiment 2:
Solution used: AgNO3Solution, mercaptoethylmaine, R6G solution；
Select laser: blue laser；
Laser irradiation: mercaptoethylmaine solution is added into quartz colorimetric utensil, is put into sample copper sheet, is shone using blue laser Penetrate 50min；Sample copper sheet is moved to, AgNO is added3In another quartz colorimetric utensil of solution, blue laser is equally used Irradiate same site 50min.
A kind of method that laser irradiation reduction prepares SERS substrate, including the following steps:
A., the long strip type sample copper sheet that copper sheet is cut into 30mm*5mm, is polished sample with metallurgical polishing powder, and vacuum is protected It deposits spare；
B. the AgNO of 10mM mercaptoethylmaine solution and 0.3g/mL is prepared3Solution；
C. (laser power 800mW) sample copper sheet is irradiated with blue laser, continues 50min, copper sheet is placed in 10mM sulfydryl In ethylamine solution；Sample copper sheet is taken out, air dry oven is put into and is dried；
D. sample (laser power 800mW) product copper sheet is irradiated with blue laser, continues 50min, copper sheet is placed in 0.3g/mL's AgNO3In solution；Sample copper sheet is taken out, air dry oven is put into and is dried；
E. R6G solution is added dropwise respectively, is put into air dry oven and is dried；Using Raman spectrometer, Raman spectrum is scanned.
Embodiment 3:
Solution used: C2H3AgO2Solution, mercaptoacetic acid solution, R6G solution；
Select laser: green (light) laser；
Laser irradiation: mercaptoacetic acid solution being added into quartz colorimetric utensil, is put into sample copper sheet, is shone using green (light) laser Penetrate 20min；Sample copper sheet is moved to, C is added2H3AgO2In another quartz colorimetric utensil of solution, green laser is equally used Device irradiates same site 20min.
A kind of method that laser irradiation reduction prepares SERS substrate, including the following steps:
A., the long strip type sample copper sheet that copper sheet is cut into 30mm*5mm, is polished sample with metallurgical polishing powder, and vacuum is protected It deposits spare；
B. the C of 10mM mercaptoacetic acid solution and 0.1g/mL is prepared2H3AgO2Solution；
C. (laser power 1000mW) sample copper sheet is irradiated with green (light) laser, continues 20min, copper sheet is placed in 20mM sulfydryl In acetic acid solution；Sample copper sheet is taken out, air dry oven is put into and is dried；
D. sample (laser power 1000mW) product copper sheet is irradiated with green (light) laser, continues 20min, copper sheet is placed in 0.1g/mL C2H3AgO2In solution；Sample copper sheet is taken out, air dry oven is put into and is dried；
E. R6G solution is added dropwise respectively, is put into air dry oven and is dried；Using Raman spectrometer, Raman spectrum is scanned.
Silver nanoparticle is restored without the copper sheet surface irradiation of laser irradiation deposition sulfide as shown in Figure 1, showing Kernel structure pattern；Silver nanoparticle is restored by the copper sheet surface irradiation of laser irradiation deposition sulfide as shown in Fig. 2, showing Kernel structure pattern.
As shown in figure 3, show that different materials compare the SERS reinforcing effect of R6G, wherein used respectively R6G, Cu+R6G, Cu+S+R6G, Cu+Ag+R6G as a comparison, by comparing result as can be seen that semiconductor prepared by the present invention There is SERS substrate good SERS to enhance performance.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.

Claims (9)

1. a kind of laser irradiation restores the method for preparing SERS substrate, it is characterised in that: including
Step 1: the clean flat and smooth copper sheet surface of oxidation induces the copper sheet backing material of surface Cu oxide；
Step 2: the copper sheet backing material obtained in step 1 is placed in silica ware, sulfide solution is added, by laser Irradiation forms the copper sheet backing material of surface copper oxysulfide；
Step 3: the copper sheet backing material obtained in step 2 being cleaned, is placed in silica ware, and argentum reagent is added, continues on through Laser irradiation is crossed, the SERS substrate of surface copper oxysulfide hybridization silver nano-grain is obtained.
2. a kind of laser irradiation according to claim 1 restores the method for preparing SERS substrate, it is characterised in that: oxidation is clean Net flat and smooth copper sheet surface, oxidant used include hydrogen peroxide, and the mass percentage concentration of hydrogen peroxide is 5%~30%, oxygen Change soaking time 30min~2h, acid condition, and H+Concentration is 1M.
3. a kind of laser irradiation according to claim 1 restores the method for preparing SERS substrate, it is characterised in that: the sulphur Compound solution is the organic compound rolled into a ball containing sulfydryl, and sulfide solution concentration is 2~20mM.
4. a kind of laser irradiation according to claim 3 restores the method for preparing SERS substrate, it is characterised in that: described to contain The organic compound for having sulfydryl to roll into a ball is thioacetic acid, mercaptopropionic acid or mercaptoethylmaine.
5. a kind of laser irradiation according to claim 1 restores the method for preparing SERS substrate, it is characterised in that: the silver Reagent is silver nitrate or silver acetate, and the concentration of argentum reagent is 0.01~0.3g/mL.
6. a kind of laser irradiation according to claim 1 restores the method for preparing SERS substrate, it is characterised in that: described to swash Light irradiates one or more mixing between wavelength 350nm~670nm.
7. a kind of laser irradiation according to claim 1 restores the method for preparing SERS substrate, it is characterised in that: described to swash Light irradiation is controlled in the time of deposition sulphur copper compound in 20min~1h, and laser power used is 80~1000mW.
8. a kind of laser irradiation according to claim 1 restores the method for preparing SERS substrate, it is characterised in that: described to swash Light irradiation is controlled in the time of deposition silver nano-grain in 20min~1h, and laser power used is 80~1000mW.
9. a kind of semiconductor SERS substrate, which is characterized in that the SERS substrate is to be prepared using such as claim 1-8 either method The SERS substrate for being compounded with copper sulfide and silver nano-grain obtained.
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Citations (8)

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US9279759B2 (en) * 2012-05-01 2016-03-08 University Of Maryland, College Park Nanoparticle array with tunable nanoparticle size and separation
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CN106493381A (en) * 2016-09-21 2017-03-15 宁波大学 A kind of preparation method and applications of silver/cuprous oxide micro-nano structure composite
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