CN117071020A - Preparation method of porous gallium nitride composite substrate with surface Raman enhancement characteristic - Google Patents
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- 239000000758 substrate Substances 0.000 title claims abstract description 111
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 57
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 40
- 238000005530 etching Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000151 deposition Methods 0.000 claims abstract description 16
- 230000008021 deposition Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 24
- 238000001514 detection method Methods 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 16
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 13
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000004317 sodium nitrate Substances 0.000 claims description 12
- 235000010344 sodium nitrate Nutrition 0.000 claims description 12
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 10
- 229940043267 rhodamine b Drugs 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
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- 238000012512 characterization method Methods 0.000 claims description 3
- -1 nano silver ions Chemical class 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 2
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- 239000002082 metal nanoparticle Substances 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
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- 238000004544 sputter deposition Methods 0.000 description 3
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- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000009610 hypersensitivity Effects 0.000 description 1
- 238000011898 label-free detection Methods 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C25D3/00—Electroplating: Baths therefor
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- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/12—Etching of semiconducting materials
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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 relates to a preparation method of a porous gallium nitride composite substrate with surface Raman enhancement characteristics, which comprises the following steps: preparing porous gallium nitride by light-assisted electrochemical etching, wherein an etching solution is potassium hydroxide, immersing a GaN sheet in a KOH solution and placing the GaN sheet in front of a xenon lamp, and heating to 60 ℃; after etching for 30Min, cleaning the GaN sheet by using ethanol and deionized water, and drying by using nitrogen to obtain porous gallium nitride; preparing a mixed solution of a deposition solution; soaking porous gallium nitride in the mixed solution for ultrasonic vibration; taking soaked porous gallium nitride as a cathode, taking a platinum sheet as an anode, and performing electrodeposition by using a direct current power supply to obtain a composite substrate sample; rinsing with ethanol, washing with deionized water, drying with cold air, and preserving in vacuum bag to obtain the porous gallium nitride and nano silver particle composite substrate with Raman enhancement property. The porous gallium nitride and nano silver particle composite substrate prepared by the method has wide application, long storage life and can be reused by simple cleaning.
Description
Technical Field
The invention relates to the field of material analysis, in particular to a preparation method and application of a porous gallium nitride composite substrate with surface Raman enhancement characteristics.
Background
Surface Enhanced Raman Scattering (SERS) is an efficient, non-destructive technique for detecting chemical and biological compounds by unique vibratory fingerprinting. SERS plays an important role in high-sensitivity label-free detection in the fields of material science, biophysics, medical diagnostics, molecular biology, and the like. By introducing the metal nano particles, the spectral Raman characteristics can be greatly amplified, and a means is provided for surface enhanced Raman scattering.
Localized Surface Plasmon Resonance (LSPRs) due to silver nanostructures can increase scattering efficiency and provide detection of hypersensitivity. The combination of porous semiconductor and metal nanoparticle deposition is a component of a metal dielectric nanostructure material, a nanocomposite material with great potential in photonics and optoelectronics.
The Chinese patent application No. 201910930515 discloses a surface enhanced Raman scattering substrate based on porous gallium nitride and a preparation method thereof. The substrate in this patent comprises a porous gallium nitride substrate and a gold/silver composite surface inner layer to form a roughened surface, the maximum effect of raman enhancement being achieved by the coupling of metal particles to the underlying porous gallium nitride.
However, the above-described techniques including the above-described invention patents currently have the following disadvantages:
(1) The particles formed in the film layer formed by the electron beam deposition or sputtering method are coarse and affect the reinforcing effect.
(2) The etching process can be influenced by the addition of no light source in the etching reaction, and the etching efficiency is high without light assistance.
(3) The acid etching may have a small porosity, and it is difficult to use the porosity by vapor deposition sputtering, and the porous gallium nitride has an unclear meaning as a substrate.
Based on the requirement, the technical personnel develop a new substrate with the surface enhanced Raman scattering and a preparation method.
Disclosure of Invention
The invention aims to prepare a porous gallium nitride/nano silver particle composite substrate capable of carrying out biological and chemical detection, so as to achieve the purposes of easy preparation and repeated utilization. The preparation method of the invention can improve the etching efficiency, and the obtained composite substrate can obtain better biological detection, has long-time SERS activity and prolongs the service life.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the porous gallium nitride composite substrate with the surface Raman enhancement characteristic comprises the steps of:
porous gallium nitride preparation link:
firstly, preparing porous gallium nitride by light-assisted electrochemical etching, wherein an etching solution is potassium hydroxide KOH, immersing a GaN piece in a reactor containing KOH solution, vertically placing the GaN piece in front of a 200-400W xenon lamp, placing the reactor on a rotary heating table, rotating the reactor by a rotor and heating the reactor to 40-60 ℃;
setting the output voltage of the power supply direct current instrument as V1, simultaneously turning on power switches of the xenon lamp and the power supply direct current instrument and starting timing, and setting the etching time as T1;
thirdly, rinsing the GaN sheet with ethanol after etching, ultrasonically cleaning with deionized water, and drying with nitrogen after cleaning to obtain porous gallium nitride;
and (3) preparing a composite substrate:
step four, preparing a mixed solution of a deposition solution, wherein the deposition solution comprises silver nitrate and citric acid, and the silver nitrate and the citric acid are stirred until transparent, and then sodium nitrate is added to form the mixed solution;
fifthly, pre-soaking the etched porous gallium nitride in a mixed solution of silver nitrate, sodium citrate and sodium nitrate, and performing ultrasonic vibration for a period of time t to enable the mixed solution to enter into pores of the porous gallium nitride;
sixthly, taking the soaked porous gallium nitride as a cathode, taking a platinum sheet as an anode, and performing electrodeposition by using a direct current power supply, wherein the deposition voltage is selected to be V2, and the deposition time is T2, so as to obtain a composite substrate sample;
and seventh, rinsing the obtained composite substrate sample with ethanol, washing with deionized water, drying with cold air, and preserving in a vacuum bag to obtain the composite substrate of porous gallium nitride and nano silver particles with Raman enhancement characteristics.
In the preparation method of the porous gallium nitride composite substrate with the surface Raman enhancement characteristic, the concentration of the potassium hydroxide KOH of the etching liquid in the first step is 2mol/l, and the etching temperature is 60 ℃.
In the fourth step, the silver nitrate solution and sodium citrate powder are mixed together until white precipitate appears, stirring is continued until the white precipitate disappears, then the sodium nitrate solution is added, and finally the mixed solution is added into an electrochemical deposition tank.
In the preparation method of the porous gallium nitride composite substrate with the surface Raman enhancement characteristic, the dosage of the silver nitrate in the fourth step is 25ml, the dosage of the sodium citrate is 0.0294g, and the dosage of the sodium nitrate is 10ml.
In the preparation method of the porous gallium nitride composite substrate with the surface Raman enhancement characteristic, the preparation method further comprises an eighth step of measuring the Raman enhancement factor of the composite substrate:
raman enhancement factor
Wherein N is surface N is the number of molecules adsorbed on the SERS-active substrate VOL Respectively representing the total number of molecules of the analyte in the test volume, I SERS And I Raman Represents the intensity of the spectrum enhanced without Ag nanostructure and the intensity of the same mode in raman spectrum, N is estimated from the laser spot size, reagent concentration and Ag distribution ratio surface Is a value of (2). This step is used to evaluate the properties of the substrate material, and can be compared with other materials as an evaluation criterion.
Further, in testing performance, rhodamine B solution concentration gradient 10 was configured -7 M，10 -9 M，10 -11 M，10 -13 M is filled with 50mL centrifuge tubes, the prepared composite substrate is immersed in the centrifuge tubes for 5min, and Raman detection is carried out after drying; at the same time, a blank substrate sample without silver nano particles is at 10 -3 M immersion, determination of detection limit of 10 for Ag-NPs/NP-GaN substrate by measuring rhodamine B at different concentrations -13 。
Further, a blank substrate sample was selected and tested at 10 -13 The concentration in the sample is used as the molecular number, the intensity ratio is 0.1 by taking the peak integral difference of the two as the result, 20% of coverage area is selected by nano silver ions, and finally EF value is calculated to be 2 multiplied by 10 9 。
In the preparation method of the porous gallium nitride composite substrate with the surface Raman enhancement characteristic, the preparation method further comprises a ninth step of firstly taking and immersing the prepared composite substrate sample in 50ml of 10-concentration solution -7 And (3) taking out the composite substrate and drying the composite substrate in a mol/l BSA solution for 5min, carrying out Raman characterization on the composite substrate and a blank substrate without silver nano particles by using a 633 excitation light source, and carrying out high-signal detection on chemical and biological reagents.
Based on the technical scheme, the preparation method of the composite substrate has the following technical advantages compared with the prior art:
1. according to the preparation method, the alkaline etching liquid is adopted to replace the traditional acidic etching liquid, and the etching is performed in a light-assisted mode, wherein the etching effect of the alkaline solution is stronger than that of the acidic solution, the formed pores can better enable nano silver particles to be adsorbed in the alkaline solution, the opportunity of contact with air is reduced, the electrochemical etching is performed in a light-assisted mode, the etching efficiency can be improved, the chemical analysis of a sample is more convenient, and the biomedical value is higher.
2. Compared with the traditional sputtering mode, the composite substrate has the advantages of high adsorption speed and uniform adsorption, and the process required by the electrodeposition method is simpler, the size of the deposited particles can be controlled, and the cost is low.
3. The composite substrate prepared by the invention can be widely applied to detection of biomolecules and chemical residues, besides the function of detection results, the introduction of the porous layer can prolong the storage life of the substrate, and the extent of reutilization can be achieved by simply cleaning the substrate.
4. Compared with the prior art that the substrate activity is protected by the Jin Yinfu cover layer, the composite substrate prepared by the method has higher utilization rate and longer preservation life, regular hexagonal pores are formed after alkaline etching, silver nano particles can be better adsorbed in the regular hexagonal pores to reduce the exposure area with air, the oxidation process is further delayed, and in addition, the introduction of the pores can adsorb molecules to be tested more to enhance the test signal.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a porous GaN composite substrate with surface Raman enhancement characteristics.
FIG. 2 is a schematic photograph of samples at different deposition times in a method for preparing a porous GaN composite substrate with surface Raman enhancement features according to the present invention.
FIG. 3 is a sample 10 of a method for preparing a porous GaN composite substrate with surface Raman enhancement features according to the present invention -7 SERS profile of BSA at mol/l concentration.
Detailed Description
The following describes in further detail a method for preparing a porous gallium nitride composite substrate with surface raman enhancement property according to the present invention, with reference to the accompanying drawings and specific examples, in order to more clearly understand the structural composition and working procedure, but not to limit the scope of the present invention.
The invention relates to a preparation method of a porous gallium nitride composite substrate with surface Raman enhancement characteristics, which is characterized in that nano silver particles with uniform particles are formed in gaps and surfaces of gallium nitride to be used as a substrate with high enhancement factors and semiconductor metal composite Raman enhancement characteristics. Compared with the existing SERS material, the substrate prepared by the invention can be widely applied to detection of biomolecules and chemical residues, besides the function of detection results, the preservation life of the substrate can be prolonged by introducing the porous layer, and the extent of reutilization can be achieved by simply cleaning the substrate.
As shown in fig. 1, the preparation method of the invention comprises a porous gallium nitride preparation link and a preparation link of a composite substrate:
in the porous gallium nitride preparation link:
firstly, preparing porous gallium nitride by light-assisted electrochemical etching, wherein an etching solution is potassium hydroxide KOH, immersing a GaN piece in a reactor containing KOH solution, vertically placing the reactor in front of a 300W xenon lamp, placing the reactor on a rotary heating table, rotating and heating to 60 ℃ by a rotor, wherein the concentration of the potassium hydroxide KOH in the etching solution is 2mol/l, and the etching temperature is 60 ℃.
And secondly, setting the output voltage of the power supply direct current instrument to be 20V, turning on power switches of the xenon lamp and the power supply direct current instrument, starting timing, and setting the etching time to be 30Min.
And thirdly, rinsing the GaN sheet with ethanol, ultrasonically cleaning with deionized water for 30Min, and drying with nitrogen after cleaning to obtain the porous gallium nitride NP-GaN.
In the composite substrate preparation link:
fourthly, preparing a deposition solution which comprises 0.01mol/L silver nitrate and citric acid, stirring the silver nitrate and the citric acid until the silver nitrate and the citric acid are transparent, and then adding 0.5mol/L sodium nitrate to form a mixed solution. Specifically, the silver nitrate solution and the sodium citrate powder are mixed together until white precipitation appears, stirring is continued until the white precipitation disappears, then the sodium nitrate solution is added, and finally the mixed solution is added into an electrochemical deposition tank. In the mixed solution, the dosage of the silver nitrate is 25ml, the dosage of the sodium citrate is 0.0294g, and the dosage of the sodium nitrate is 10ml.
Fifth, pre-soaking the etched NP-GaN in silver nitrate (AgNO) 3 ) Carrying out ultrasonic vibration for 3min in the solution and the mixed solution of sodium citrate and sodium nitrate to enable the mixed solution to enter the pores of NP-GaN;
sixthly, taking the soaked porous gallium nitride as a cathode, taking a platinum sheet as an anode, and performing electrodeposition by using a direct current power supply, wherein the deposition voltage is 8V, the deposition time is 4Min, and a composite substrate sample is obtained preliminarily;
and seventhly, rinsing the obtained composite substrate sample with ethanol, washing with deionized water, drying with cold air at 20 ℃, and preserving in a vacuum bag to obtain the composite substrate of porous gallium nitride and nano silver particles with Raman enhancement characteristics.
The preparation method of the porous gallium nitride composite substrate with the surface Raman enhancement characteristic further comprises an eighth step, wherein the eighth step is used for evaluating the performance of the substrate material as a step which is necessary to prepare, and the eighth step can be compared with other materials as a general evaluation standard. The raman enhancement factor measurement formula of the composite substrate is set as follows:
raman enhancement factor
Wherein N is surface N is the number of molecules adsorbed on the SERS-active substrate VOL Respectively representing the total number of molecules of the analyte in the test volume, I SERS And I Raman Represents the intensity of the spectrum enhanced without Ag nanostructure and the intensity of the same mode in raman spectrum, N is estimated from the laser spot size, reagent concentration and Ag distribution ratio surface Is a value of (2).
Further, in testing performance, rhodamine B solution concentration gradient 10 was configured -7 M，10 -9 M，10 -11 M，10 -13 M is filled with 50mL centrifuge tubes, the prepared composite substrate is immersed in each centrifuge tube for 5min, and the composite substrate is taken out for Raman detection after being dried; at the same time, a blank substrate sample without silver nano particles is at 10 -3 M immersion, determination of detection limit of 10 for Ag-NPs/NP-GaN substrate by measuring rhodamine B at different concentrations -13 。
Further, a blank substrate sample was selected and tested at 10 -13 The concentration in the sample is used as the molecular number, the intensity ratio is 0.1 by taking the peak integral difference of the two as the result, 20% of coverage area is selected by nano silver ions, and finally EF value is calculated to be 2 multiplied by 10 9 。
In the preparation method of the porous gallium nitride composite substrate with the surface Raman enhancement characteristic, the preparation method further comprises a ninth step of firstly taking and immersing the prepared composite substrate sample in 50ml of 10-concentration solution -7 And (3) in a mol/l BSA solution for 5min, taking out and drying the composite substrate, and carrying out Raman characterization on the composite substrate and a blank substrate without silver nano particles by using a 633 excitation light source, thereby carrying out high-signal detection on chemical and biological reagents.
The preparation method provided by the invention is a semiconductor metal composite structure substrate with enhanced Raman enhancement characteristics, and can be directly used for detecting chemical reagents after drying.
The invention also provides a method for preparing the semiconductor metal composite structure substrate with enhanced Raman enhancement characteristics, and the porous gallium nitride/nano silver particle composite substrate prepared by the method has two main Raman enhancement mechanisms: specifically, localized surface plasmon resonance enhancement (LSPR) and a specific charge transfer mechanism after metal nano-and semiconductor are compounded can more effectively amplify Raman scattering signals. The surface plasma is a collective oscillation mode, and the electric field intensity is several orders of magnitude larger than the common electric field intensity, so that the processes of vibration, rotation or expansion and contraction of molecules adsorbed on the surface can be greatly enhanced, and obvious Raman scattering signals can be generated. In the charge transfer mechanism, when the incident photon does not have enough energy to directly transfer the excited electron of Ag into the LUMO of the molecule to be measured, gaN acts as a "bridge" to indirectly transfer the electron in Ag to the LUMO level of the molecule to be measured, where the lowest unoccupied molecular orbital is among the unoccupied molecular orbitals of electrons, and the molecular orbital with the lowest energy is called the Lowest Unoccupied Molecular Orbital (LUMO).
The method of the invention can control the size of the metal particles to achieve the optimal detection signal, so that parameters of the size (voltage, solution concentration and deposition time) of the silver nano particles in the electrodeposition process are controlled, the specific particle size capable of achieving the optimal SERS enhancement can be prepared according to specific molecules to be detected and selected excitation wavelength, the prepared sample can be exposed in the air for a long time, and the prepared sample can still maintain higher substrate activity after simple water washing. The characteristic that the composite substrate can be used by simple water washing expresses the reusability of the composite substrate, the substrate material can be subjected to experiments for many times without causing interference, and more complex cleaning means can be required along with the change of the form of the molecular solution to be detected, but the invention can improve the detection efficiency and the detection speed by simple cleaning.
Example 1
The embodiment provides a preparation method of a semiconductor metal composite structure substrate with enhanced Raman enhancement characteristics, and the flow is shown in figure 1.
Fig. 2 is a physical diagram of a semiconductor metal composite structure substrate with enhanced raman enhancement characteristics prepared in this embodiment. FIG. 2 showsThe Ag-NPs/NP-GaN samples were deposited for 1 minute, 2 minutes, and 4 minutes at different deposition times, respectively. The performance of the semiconductor metal composite structure substrate with the enhanced Raman enhancement characteristic prepared by the embodiment is detected. Test conditions: preparation of rhodamine B solution concentration gradient 10 -7 M，10 -9 M，10 -11 M，10 -13 M is filled with 50mL centrifuge tubes, the prepared substrates are immersed in the centrifuge tubes for 5min, and Raman detection is carried out after drying; blank substrate (without silver nanoparticles) at 10 -3 And (3) immersing under M. The detection limit of the Ag-NPs/NP-GaN substrate was determined to be 10 by measuring rhodamine B at different concentrations -13 。
According to the Raman enhancement factorN surface N is the number of molecules adsorbed on the SERS-active substrate VOL Respectively the total number of molecules of the analyte in the test volume. I SERS And I Raman Indicating the enhanced spectral intensity without Ag nanostructures and the intensity of the same mode in raman spectra. Estimating N according to laser spot size, reagent concentration and Ag distribution proportion surface Is a value of (2).
Finally, it was found that the ratio of their molecular numbers was largely dependent on the concentration of the reagent. Therefore, a blank sample is selected and a sample is selected at 10 -13 The concentration in the sample was 0.1 as the number of molecules, and the intensity ratio was 0.1 as the peak integral difference between the two, and the coverage area of 20% was selected in consideration of the silver distribution ratio. The final value of EF calculated is 2X 10 9 . EF is a common standard for performance judgment.
Example 2
The present embodiment provides for recycling the available raman signal after the prepared substrate is placed in an environment in contact with air for 80 days.
Test conditions: after the primary rhodamine B test, the dried sample cartridges were left for 80 days by ultrasonic 5min deionized water rinse. Taking out after 80 days, carrying out Raman test, washing with deionized water, and soaking in 10 -11 Solution of MThe phenomenon of re-immersion to rhodamine reagent and appearance of a distinct peak after 80 days indicates that the activity of Ag-NPs is retained in the presence of prolonged exposure to air. Different washing means may be required depending on the reagent to be tested, and more complicated washing means may be required in the oil-soluble solution.
Example 3
The embodiment provides an application of a semiconductor metal composite structure substrate with surface enhanced Raman characteristics in biological protein detection.
Test conditions: immersing the freshly prepared sample in 50ml of the solution at a concentration of 10 -7 Taking out and drying the blank substrate (without silver nano particles) and 10 by using 633 excitation light source after 5min in mol/l BSA solution -7 The BSA of (c) is raman-characterized, as shown in fig. 3, wherein the coordinates represent specific functional groups, the specific structure of the test molecule is analyzed by the change of the signal of the functional groups, and the curve represents the intensity of each signal peak under different abscissa, i.e. different functional groups. The substrate proved to be useful for biological detection of proteins and the like. For example, a signal of phe-phenylalanine is generated at a position of 1000cm-1, trp-tryptophan is generated at a position of 1600cm-1, and a functional group of CH2 of about 1446cm-1 and the like indicate that the substrate can detect a very low concentration of protein.
The signal enhancement due to 633nm wavelength in this embodiment may be due to a charge transfer transition mechanism generated after the semiconductor and metal are combined. The composite material as semiconductor and metal nano particles can be subjected to surface Raman enhancement through two main mechanisms, and can be used for detecting high signals of chemical and biological reagents. Through the test, the substrate sample is wider in test application, and can be explored on the monitoring of biological proteins. There is no excellent concrete representation in biological monitoring, and the obtained EF calculation value is an excellent value compared with other previous samples.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (8)
1. The preparation method of the porous gallium nitride composite substrate with the surface Raman enhancement characteristic is characterized in that the porous gallium nitride composite substrate forms nano silver particles with uniform particles in gaps and surfaces of gallium nitride, and the preparation method comprises a porous gallium nitride preparation link and a composite substrate preparation link:
porous gallium nitride preparation link:
firstly, preparing porous gallium nitride by light-assisted electrochemical etching, wherein an etching solution is potassium hydroxide KOH, immersing a GaN piece in a reactor containing KOH solution, vertically placing the GaN piece in front of a 200-400W xenon lamp, placing the reactor on a rotary heating table, rotating the reactor by a rotor and heating the reactor to 40-60 ℃;
setting the output voltage of the power supply direct current instrument as V1, simultaneously turning on power switches of the xenon lamp and the power supply direct current instrument and starting timing, and setting the etching time as T1;
thirdly, rinsing the GaN sheet with ethanol after etching, ultrasonically cleaning with deionized water, and drying with nitrogen after cleaning to obtain porous gallium nitride;
and (3) preparing a composite substrate:
step four, preparing a mixed solution of a deposition solution, wherein the deposition solution comprises silver nitrate and citric acid, and the silver nitrate and the citric acid are stirred until transparent, and then sodium nitrate is added to form the mixed solution;
fifthly, pre-soaking the etched porous gallium nitride in a mixed solution of silver nitrate, sodium citrate and sodium nitrate, and performing ultrasonic vibration for a period of time t to enable the mixed solution to enter into pores of the porous gallium nitride;
sixthly, taking the soaked porous gallium nitride as a cathode, taking a platinum sheet as an anode, and performing electrodeposition by using a direct current power supply, wherein the deposition voltage is selected to be V2, and the deposition time is T2, so as to obtain a composite substrate sample;
and seventh, rinsing the obtained composite substrate sample with ethanol, washing with deionized water, drying with cold air, and preserving in a vacuum bag to obtain the composite substrate of porous gallium nitride and nano silver particles with Raman enhancement characteristics.
2. The method for preparing a porous gallium nitride composite substrate with surface raman enhancement property according to claim 1, wherein in the first step, the concentration of the etching solution potassium hydroxide KOH is 2mol/l, and the etching temperature is 60 ℃.
3. The method for preparing a porous gallium nitride composite substrate with surface raman enhancement according to claim 1, wherein in the fourth step, the silver nitrate solution and sodium citrate powder are mixed together until white precipitate appears, stirring is continued until white precipitate disappears, then sodium nitrate solution is added, and finally the mixed solution is added into an electrochemical deposition tank.
4. A method for producing a porous gallium nitride composite substrate having surface raman enhancement property according to claim 3, wherein in the fourth step, the amount of silver nitrate is 25ml, the amount of sodium citrate is 0.0294g, and the amount of sodium nitrate added is 10ml.
5. The method for preparing a porous gallium nitride composite substrate with surface raman enhancement property according to claim 1, further comprising an eighth step of measuring raman enhancement factor of the composite substrate:
raman enhancement factor
Wherein N is surface N is the number of molecules adsorbed on the SERS-active substrate VOL Respectively representing the total number of molecules of the analyte in the test volume, I SERS And I Raman Indicating enhanced spectral intensity without Ag nanostructuresAnd intensity of the same mode in Raman spectrum, estimating N according to laser spot size, reagent concentration and Ag distribution proportion surface Is a value of (2).
6. The method for preparing a porous GaN composite substrate with surface Raman enhancement property according to claim 5, wherein rhodamine B solution concentration gradient 10 is configured in testing performance -7 M，10 -9 M，10 -11 M，10 -13 M is filled with 50mL centrifuge tubes, the prepared composite substrate is immersed in the centrifuge tubes for 5min, and Raman detection is carried out after drying; at the same time, a blank substrate sample without silver nano particles is at 10 -3 M immersion, determination of detection limit of 10 for Ag-NPs/NP-GaN substrate by measuring rhodamine B at different concentrations -13 。
7. The method for preparing a porous GaN composite substrate with surface Raman enhancement property according to claim 5, wherein a blank substrate sample is selected and used at 10 -13 The concentration in the sample is used as the molecular number, the intensity ratio is 0.1 by taking the peak integral difference of the two as the result, 20% of coverage area is selected by nano silver ions, and finally EF value is calculated to be 2 multiplied by 10 9 。
8. The method for preparing a porous GaN composite substrate with surface Raman enhancement property according to claim 5, further comprising a ninth step of immersing the prepared composite substrate sample in a solution having a concentration of 10 of 50ml -7 And (3) taking out the composite substrate and drying the composite substrate in a mol/l BSA solution for 5min, carrying out Raman characterization on the composite substrate and a blank substrate without silver nano particles by using a 633 excitation light source, and carrying out high-signal detection on chemical and biological reagents.
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