CN111364092B - Preparation method of silver-porous silicon-based surface enhanced Raman scattering biological detection chip - Google Patents
Preparation method of silver-porous silicon-based surface enhanced Raman scattering biological detection chip Download PDFInfo
- Publication number
- CN111364092B CN111364092B CN202010222052.9A CN202010222052A CN111364092B CN 111364092 B CN111364092 B CN 111364092B CN 202010222052 A CN202010222052 A CN 202010222052A CN 111364092 B CN111364092 B CN 111364092B
- Authority
- CN
- China
- Prior art keywords
- porous silicon
- silver
- raman scattering
- enhanced raman
- surface enhanced
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
Abstract
The invention relates to a preparation method of a silver-porous silicon-based surface enhanced Raman scattering biological detection chip. A preparation method of a silver-porous silicon-based surface enhanced Raman scattering biological detection chip comprises the following steps of S10: placing a silicon wafer as an anode and a platinum sheet as a cathode in electrolyte for anodic corrosion reaction to obtain a multilayer Bragg porous silicon substrate; s20: and placing the multilayer Bragg porous silicon substrate in a silver nitrate solution for immersion treatment, taking out and drying, and then performing heat treatment to obtain the silver-porous silicon substrate surface enhanced Raman scattering biological detection chip. The invention uses porous silicon as photonic crystal and silver particles as medium for enhancing electromagnetic field, has the characteristics of high amplification factor, stable property, long-term use, wide application range, simple and convenient operation and small artificial operation error, can effectively amplify Raman signals to millions of times and reduce the interference of fluorescence, and greatly improves the quality guarantee period and repeatability.
Description
Technical Field
The invention belongs to the technical field of biological signal detection materials, and particularly relates to a preparation method of a silver-porous silicon-based surface enhanced Raman scattering biological detection chip.
Background
The enhancement of the raman signal is through the interaction between the noble metal nanoparticle substrate and the absorbed target molecule due to localized surface plasmon resonance [ LSPR ] of these plasmonic nanostructures]And generates a stronger Raman signal, namely Surface Enhanced Raman Scattering (SERS). SERS has two enhancement modes, one chemical and one structural. Among the most effective methods of structure enhancement is plasma coupling between adjacent nanoparticles, resulting in a significant increase in LSPR (i.e., "hot spots") in the gap regions between adjacent nanostructures. The regularly arranged silver nanoparticles synthesized on the regularly arranged porous silicon can well realize LSPR enhancement; the heat treatment may then achieve chemical strengthening. In recent years many researchers have prepared by means of heat treatmentThe SERS substrate has a strong Raman signal. For example, HeguangLiu, YadongXu et al, increase SERS signals by heat treating gold nanoparticle modified polystyrene substrates; dandanyanyan, WuQiu et al, by targeting a bulk MoS2The high-performance SERS substrate is realized by further heat treatment, and a very effective hot spot can be provided by the heat treatment to enhance the Raman signal of the SERS substrate; AgnesPurwidylanti et al obtain adjustable plasma-excited "hot spots" by heat-treating the Au film on the nanospheres. Plasma coupling between adjacent nanoparticles is well established by thermal processing, resulting in a significant increase in the electric field (i.e., "hot spot") in the gap region between adjacent nanostructures. Therefore, the SERS substrate with good enhancement effect and good biocompatibility is prepared by applying the heat treatment process to the porous silicon substrate. Porous Silicon (PSi) is an ideal surface-enhanced Raman substrate, and is simple in preparation process and good in biocompatibility due to large surface area and is suitable for detection of biomacromolecules. Futamate et al, for example, have implemented SERS detection of rhodamine 6G (R6G) molecules on single-layer porous silicon substrates. Wanglajia et al developed porous silicon surface gratings and used them for SERS research. The porous silicon photonic crystal structure has the characteristics of increasing the action time of light on substances due to unique optical characteristics and periodic change of refractive index, enhancing the magnetization intensity, having strong local surface plasmon resonance and the like, and can be prepared into various optical devices.
Although the surface modification methods for porous silicon are numerous at present: nonmetal surface modification, precious metal surface modification, transition metal surface modification, semiconductor composite modification and the like, but the preparation process is complex, the repeatability is poor, the quality guarantee period is short, and the wide application is greatly limited.
In view of this, the invention provides a preparation method of a silver-porous silicon-based surface enhanced raman scattering biological detection chip.
Disclosure of Invention
The invention aims to provide a preparation method of a biological detection chip for silver-porous silicon-based surface enhanced Raman scattering, which prepares a chip for silver nanoparticle modified multilayer porous silicon surface enhanced Raman scattering,the porous silicon with the multilayer Bragg structure in regular spatial arrangement has stronger surface plasma spatial distribution enhancement, and simultaneously adds a high-temperature annealing process, and a layer of very thin Ag is coated on the surface of the Ag nano particles2And the repeatability is greatly enhanced and the quality guarantee period is prolonged due to the O shell.
In order to realize the purpose, the adopted technical scheme is as follows:
a preparation method of a silver-porous silicon-based surface enhanced Raman scattering biological detection chip comprises the following steps:
s10: taking a silicon wafer as an anode and a platinum sheet as a cathode, and placing the anode and the cathode in electrolyte to carry out anodic corrosion reaction to obtain a multilayer Bragg porous silicon substrate;
s20: and placing the multilayer Bragg porous silicon substrate in a silver nitrate solution for immersion treatment, taking out and drying, and then performing heat treatment to obtain the silver-porous silicon substrate surface enhanced Raman scattering biological detection chip.
Further, the silicon wafer is of an N type;
the electrolyte is composed of HF and C3H5OH is as follows 1: 1 in volume ratio.
Further, before the anodic corrosion reaction, the silicon wafer needs to be chemically cleaned, and the specific steps are as follows: boiling in the mixed solution 1 for 10min, boiling in the mixed solution 2 for 10min, and sequentially adding 99.5% CH3COCH3Ultrasonic cleaning with deionized water for 15 min;
wherein the mixed solution 1 is prepared from H2O、H2O2And 28 mass percent of NH3·H2Composition of O, H thereof2O：H2O2：NH3·H2The volume ratio of O is 5: 1: 1;
the mixed solution 2 is prepared from H2O、H2O2And 38% by mass of HCl, H thereof2O：H2O2: the volume ratio of HCl is 6: 2: 1.
further, the anodic corrosion is reversed to constantApplying a DC voltage source while stirring at constant temperature, and applying a current density of 100mA/cm to the low refractive index layer2Etching for 2s, and coating with high refractive index at current density of 40mA/cm2The etching time is 3s, and the interval time is 3 s; the characteristic photonic band gap, multilayer structure is designed to fifteen periods.
Further, the molar weight concentration of silver nitrate in the silver nitrate solution is 0.01 mol/L;
the heat treatment method comprises the following steps: heating in a muffle furnace with air atmosphere, preserving heat, and cooling to room temperature.
Further, the time of the dipping treatment is 30-60 s;
the temperature of the heating treatment is 250-350 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 1 h.
Further, the time of the dipping treatment is 50 s;
the temperature of the heating treatment is 300 ℃, and the heating rate is 10 ℃/min.
A biological detection chip of silver-porous silicon-based surface enhanced Raman scattering is prepared by adopting the preparation method.
The silver-porous silicon-based surface enhanced Raman scattering biological detection chip is used for detecting trace organic matters (the concentration is 10)- 6mol/L) in rapid detection.
Further, the application in the rapid detection of the molecules is the application in amplifying rhodamine 6G and characteristic Raman signal peaks in serum.
The invention has the beneficial effects that:
(1) compared with single-layer porous silicon, the porous silicon with the multilayer Bragg structure has stronger surface plasma space enhancement effect.
(2) According to the invention, the silver nanoparticles with the size of 10-20nm are deposited on the multi-layer Bragg structure porous silicon, and the Raman signal enhancement effect is improved through the surface plasma resonance effect of silver.
(3) After the multilayer porous silicon with the Bragg structure is prepared and obtained, silver nitrate is used as a silver source, the multilayer porous silicon with the Bragg structure obtained after anode corrosion is placed in a silver nitrate solution, the interface end of the porous silicon has reducibility, silver ions in the solution can be reduced into silver nanoparticles, and finally the sample is taken out and is annealed at high temperature to firmly modify the silver nanoparticles on the surface of the nano porous silicon, so that the prepared chip for modifying the multilayer porous silicon surface with the silver nanoparticles, which is enhanced by the Raman scattering chip, has high Raman signal enhancing capability and good repeatability and shelf life.
The surface of the silver nano-particles is coated with a layer of Ag by high-temperature annealing2The shell of O enhances the surface enhanced Raman scattering effect, and simultaneously hinders the slow oxidation of the nano silver in the air, thereby greatly improving the quality guarantee period and the repeatability.
In the traditional method, a single-layer porous silicon is used, but the single-layer porous silicon cannot be enhanced by utilizing the surface plasma space distribution in the photonic crystal theory, so that the enhanced signal is weak; or the silver is directly used after reduction, the repeatability is poor, and the effective period is only 1 month.
(4) The silver-porous silicon-based surface-enhanced Raman scattering biological detection chip material prepared by the invention can be widely applied to detection of trace organic pollutants in medical treatment, food safety and environmental water, has stable properties, can be used for a long time, and is safe and environment-friendly.
(5) The silver-porous silicon-based surface enhanced Raman scattering biological detection chip material can be widely applied to biological signal trace detection, medicine signal trace detection and harmful substance trace detection in environmental water, has high amplification factor and stable property, and can be used for a long time. Under the irradiation of 532nm laser, the silver surface modified porous silicon-based surface enhanced Raman scattering chip material can amplify a Raman characteristic signal of rhodamine 6G by 1000000 times, and amplify a characteristic Raman signal in serum of a breast cancer patient by 5000 times, and shows excellent enhancement effect and stability.
Drawings
FIG. 1 shows the concentration of R6G in the chip material for bioassay of Ag-porous Si-based Surface Enhanced Raman Scattering (SERS) of example 10-6-10-13SERS spectra of ranges; wherein, (b) the logarithmic concentration and pointing characteristic peak (614.304 cm) of R6G-1) A linear fit graph between;
FIG. 2 shows Raman enhancement effect of multilayer Ag-Bragg porous silicon chip and single layer Ag-Bragg porous silicon chip on R6G;
FIG. 3 is an SEM image and an EDS spectrum of the silver-porous silicon-based surface enhanced Raman scattering biological detection chip material prepared in example 1;
FIG. 4 is XPS spectrum of the chip material for detecting biology of surface enhanced Raman scattering of silver-porous silicon-based prepared in example 1;
FIG. 5 is a characteristic peak amplification spectrum of the silver-porous silicon-based surface-enhanced Raman scattering bioassay chip material prepared in example 1 on serum of a breast cancer patient;
FIG. 6 is an enhancement spectrum of the Raman peak of rhodamine 6G after the thermal treatment at 300 ℃ of the silver-porous silicon-based surface enhanced Raman scattering biological detection chip material prepared in example 1.
Detailed Description
In order to further illustrate the preparation method of the silver-porous silicon-based surface-enhanced raman scattering biological detection chip of the present invention and achieve the intended purpose of the invention, the following detailed description is provided with reference to the preferred embodiments of the preparation method of the silver-porous silicon-based surface-enhanced raman scattering biological detection chip according to the present invention, and the specific implementation, structure, features and efficacy thereof are described in detail below. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The preparation method of the silver-porous silicon-based surface enhanced raman scattering biological detection chip of the present invention will be further described in detail with reference to the following specific examples:
the technical scheme for preparing the silver-porous silicon-based surface enhanced Raman scattering biological detection chip comprises the following steps:
s10: and (3) taking a silicon wafer as an anode and a platinum sheet as a cathode, and placing the anode and the cathode in electrolyte to carry out anodic corrosion reaction to obtain the multilayer Bragg porous silicon substrate.
According to the invention, the multilayer Bragg porous silicon substrate is prepared through an anodic corrosion reaction, and compared with a signal obtained after the multilayer porous silicon and silver nitrate are soaked and then are subjected to heat treatment, the multilayer structure has a stronger surface plasma space enhancement effect.
S20: and placing the multilayer Bragg porous silicon substrate in a silver nitrate solution for immersion treatment, taking out and drying, and then performing heat treatment to obtain the silver-porous silicon substrate surface enhanced Raman scattering biological detection chip.
The interface end of the prepared multilayer Bragg porous silicon substrate has better reducibility, and silver ions in the solution can be reduced into silver nanoparticles attached to the surface of the multilayer porous silicon by being placed in a silver nitrate solution.
Preferably, the silicon wafer is of an N type;
the electrolyte is composed of HF and C3H5OH is as follows 1: 1 in volume ratio.
Preferably, before the anodic corrosion reaction, the silicon wafer needs to be chemically cleaned, and the specific steps are as follows: boiling in the mixed solution 1 for 10min, boiling in the mixed solution 2 for 10min, and sequentially adding 99.5% CH3COCH3Ultrasonic cleaning with deionized water for 15 min;
wherein the mixed solution 1 is prepared from H2O、H2O2And 28 mass percent of NH3·H2Composition of O, H thereof2O：H2O2：NH3·H2The volume ratio of O is 5: 1: 1;
the mixed solution 2 is prepared from H2O、H2O2And 38% by mass of HCl, H thereof2O：H2O2: the volume ratio of HCl is 6: 2: 1.
according to the invention, the silicon wafer is chemically cleaned before the anodic corrosion reaction is carried out, so that impurities such as grease on the surface of the silicon wafer can be effectively removed, the influence on the sensitivity of the product is avoided, and the preparation of the nano-scale material is facilitated.
Preferably, the anodic corrosion reaction adopts a constant-voltage direct-current power supply and is accompanied with constant-temperature stirring, and the low-refractive index layer adopts a current density of 100mA/cm2Etching for 2s, and coating with high refractive index at current density of 40mA/cm2The etching time is 3s, and the interval time is 3 s; the characteristic photonic band gap, multilayer structure is designed to fifteen periods.
Preferably, the molar weight concentration of silver nitrate in the silver nitrate solution is 0.01 mol/L;
the heat treatment method comprises the following steps: heating in a muffle furnace with air atmosphere, preserving heat, and cooling to room temperature.
According to the invention, after the sample is taken out, the silver nanoparticles are firmly modified on the surface of the nano-porous silicon through high-temperature annealing, and the surface of the silver nanoparticles is coated with a layer of Ag2The shell of O ensures that the prepared silver nanoparticle modified multilayer porous silicon surface enhanced Raman scattering chip has higher Raman signal enhancing capability, also prevents the slow oxidation of the nano silver in the air, and greatly improves the quality guarantee period and the repeatability.
More preferably, the time of the impregnation treatment is 30-60 s;
the temperature of the heating treatment is 250-350 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 1 h. Suitable heat treatment temperatures can improve the consistency and stability of the silver nanoparticles.
Still more preferably, the time for the immersion treatment is 50 s;
the temperature of the heating treatment is 300 ℃, and the heating rate is 10 ℃/min.
Example 1.
The specific operation steps are as follows:
(1) preprocessing an N-type silicon wafer: boiling with mixture 1 for 10min, boiling with mixture 2 for 10min, and adding 99.5 wt% CH3COCH3Ultrasonic cleaning for 15min, and finally ultrasonic cleaning with deionized water for 15 min.
the mixed solution 2 is composed of H2O、H2O2And 38% by mass of HCl according to a 6: 2: 1 in volume ratio.
(2) Taking a metal Pt sheet as a cathode, taking a silicon wafer obtained by pretreatment in the step (1) as an anode, setting the distance between the two electrodes to be 7cm, and placing the anode in a solution of HF and C3H5OH is as follows 1: and carrying out electrochemical anodic corrosion in the mixed solution with the volume ratio of 1 to obtain the multilayer Bragg porous silicon substrate.
The electrochemical anodic corrosion is periodically corroded according to the sequence of high current density and low current density (low refraction rate and high refraction rate). The low refractive index layer used has a current density of 100mA/cm2Etching for 2s, and coating with high refractive index at current density of 40mA/cm2The etching time was 3s and the interval time was 3 s. To achieve high quality, well characterized photonic bandgaps, the multilayer structure is designed to have fifteen periods.
(3) Weighing solid silver nitrate, putting the solid silver nitrate into an aqueous solution, and obtaining the silver nitrate with the concentration of 0.01mol/L after the solid silver nitrate is completely dissolved. And (3) immersing the multilayer Bragg porous silicon substrate prepared in the step (2), standing for 50s, taking out and drying.
(4) And heating to 300 ℃ in an air atmosphere by adopting a muffle furnace, keeping the temperature for 1h at the heating rate of 10 ℃/min, and cooling along with the furnace to obtain the silver-porous silicon-based surface enhanced Raman scattering biological detection chip.
Example 2.
The application of the silver-porous silicon-based surface enhanced Raman scattering biological detection chip prepared in the embodiment 1 in Raman signal amplification of rhodamine 6G and Raman characteristic peak amplification in serum of a breast cancer patient specifically comprises the following steps:
respectively configured with a concentration of 10-6，10-7，10-8，10-9，10-10，10-11，10-12，10-1350ml of each mol/L rhodamine 6G solution, and biological detection of the silver-porous silicon-based surface enhanced Raman scatteringThe chips were put into the solution for 3 hours respectively and then taken out. 50 mWNd: a YAG laser and a He-Ne laser of 633nm light were used as the HORIBA micro raman spectrometer (HORIBA jobinbyvon, kyoto, japan) of the excitation radiation to obtain SERS spectra.
To avoid the sample heating effect, a low laser power of 2.5mW was used, and the laser spot focused on the sample surface had a diameter of about 2 μm. The SERS spectrum of R6G was completed at an excitation wavelength of 532 nm. The data acquisition time for each accumulation was 3 s. The experimental results are shown in fig. 1, 3, 4 and 5.
As can be seen from FIG. 1, the chip for enhancing Raman scattering by the silver-modified porous silicon-based surface after heat treatment is a SERS substrate with high sensitivity, and can be used for quantitative detection of R6G. It can also be seen that the results show excellent linearity (R) over a wide concentration range2＝0.9918)。
As can be seen from fig. 3, silver nanoparticles were also well attached or embedded on porous silicon, and EDS spectra showed the presence of Ag, Si and O in the sample.
As can be seen from FIG. 4, the surface of the sample mainly contains three elements of Si, O and Ag, and the valence of Ag is Ag besides simple substance Ag2The existence of O proves that the surface of the Ag particles has trace Ag2And O is generated.
As can be seen in fig. 5, the silver surface modified porous silicon-based surface enhanced raman scattering chip can amplify the raman characteristic peak in the serum of a breast cancer patient by more than 5000 times.
Comparative example 1.
The Raman signal enhancement test of rhodamine 6G is carried out on the single-layer porous silicon and the multilayer porous silicon with the Bragg structure, and the experimental result is shown in figure 2.
As can be seen from FIG. 2, the Raman signal amplification effect of the single-layer porous silicon and the multilayer porous silicon with the Bragg structure on rhodamine 6G can be seen, and the multilayer structure has the strength which is more than 3 times higher than that of the single-layer structure.
Comparative example 2.
The specific procedure was the same as in example 1 except for the point of step (4). The method specifically comprises the following steps:
the chip is heated to 100 ℃, 200, 300 (namely embodiment 1), 400 and 500 ℃ in the air atmosphere respectively, the heating rate is 10 ℃/min, and after heat preservation is carried out for 1h, the chip is cooled along with the furnace, so that different silver-modified porous silicon-based surface enhanced Raman scattering chips are obtained.
As shown in FIG. 6, the reinforcing effect at 300 ℃ was the best.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a silver-porous silicon-based surface enhanced Raman scattering biological detection chip is characterized by comprising the following steps:
s10: taking a silicon wafer as an anode and a platinum sheet as a cathode, and placing the anode and the cathode in electrolyte to carry out anodic corrosion reaction to obtain a multilayer Bragg porous silicon substrate;
s20: placing the multilayer Bragg porous silicon substrate in a silver nitrate solution for immersion treatment, taking out and drying, and then performing heat treatment to obtain the silver-porous silicon substrate surface enhanced Raman scattering biological detection chip;
the heat treatment method comprises the following steps: after the heating treatment is carried out in a muffle furnace with an air atmosphere, the temperature of the heating treatment is 250-350 ℃, the heat preservation time is 1h, and the furnace is cooled to the room temperature.
2. The production method according to claim 1,
the silicon wafer is of an N type;
the electrolyte is composed of HF and C3H5OH is as follows 1: 1 in volume ratio.
3. The production method according to claim 1,
saidBefore carrying out anodic corrosion reaction, the silicon wafer needs to be chemically cleaned, and the method comprises the following specific steps: boiling in the mixed solution 1 for 10min, boiling in the mixed solution 2 for 10min, and sequentially adding 99.5% CH3COCH3Ultrasonic cleaning with deionized water for 15 min;
wherein the mixed solution 1 is prepared from H2O、H2O2And 28 mass percent of NH3·H2Composition of O, H2O：H2O2：NH3·H2The volume ratio of O is 5: 1: 1;
the mixed solution 2 is prepared from H2O、H2O2And 38% by mass of HCl, H2O：H2O2: the volume ratio of HCl is 6: 2: 1.
4. the production method according to claim 1,
the anodic corrosion reaction adopts a constant-voltage direct-current power supply and is accompanied with constant-temperature stirring, and the low-refractive-index layer uses a current density of 100mA/cm2Etching for 2s, and coating with high refractive index at current density of 40mA/cm2The etching time is 3s, and the interval time is 3 s; the characteristic photonic band gap, multilayer structure is designed to fifteen periods.
5. The production method according to claim 1,
the molar weight concentration of silver nitrate in the silver nitrate solution is 0.01 mol/L.
6. The production method according to claim 5,
the time of the dipping treatment is 30-60 s;
the heating rate of the heating treatment is 5-10 ℃/min.
7. The production method according to claim 6,
the time of the dipping treatment is 50 s;
the temperature of the heating treatment is 300 ℃, and the heating rate is 10 ℃/min.
8. A biological detection chip with a silver-porous silicon-based surface enhanced Raman scattering function is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The application of the silver-porous silicon-based surface enhanced Raman scattering biological detection chip of claim 8 in trace organic matter rapid detection.
10. The application of claim 9, wherein the application in the rapid detection of trace organics is the application in amplifying rhodamine 6G and characteristic Raman signal peaks in serum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010222052.9A CN111364092B (en) | 2020-03-26 | 2020-03-26 | Preparation method of silver-porous silicon-based surface enhanced Raman scattering biological detection chip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010222052.9A CN111364092B (en) | 2020-03-26 | 2020-03-26 | Preparation method of silver-porous silicon-based surface enhanced Raman scattering biological detection chip |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111364092A CN111364092A (en) | 2020-07-03 |
| CN111364092B true CN111364092B (en) | 2021-06-08 |
Family
ID=71202664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010222052.9A Active CN111364092B (en) | 2020-03-26 | 2020-03-26 | Preparation method of silver-porous silicon-based surface enhanced Raman scattering biological detection chip |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111364092B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08285776A (en) * | 1995-04-19 | 1996-11-01 | Hitachi Ltd | Inspection method for amorphous carbon and product produced using metal material inspected thereby |
| CN103364390A (en) * | 2012-04-10 | 2013-10-23 | 国家纳米科学中心 | Surface-enhanced Raman substrate, preparation method and application thereof |
| CN103526288A (en) * | 2013-10-10 | 2014-01-22 | 宋玉军 | Method for interface effect induced self-assembly of high-density nano array |
| CN103604796A (en) * | 2013-11-29 | 2014-02-26 | 苏州大学 | Preparation method for silicon-based surface-enhanced Raman scattering (SERS) substrate |
| CN105403551A (en) * | 2015-10-30 | 2016-03-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of thin film with Raman enhancing performance |
| CN105424674A (en) * | 2015-11-03 | 2016-03-23 | 华南师范大学 | Method for preparing surface Raman reinforced active substrate on basis of ion etching |
| CN105823769A (en) * | 2016-05-12 | 2016-08-03 | 清华大学 | In-situ detection surface enhanced raman substrate and preparation and recycling method |
| CN105866096A (en) * | 2016-04-01 | 2016-08-17 | 新疆大学 | Method for manufacturing highly sensitive surface-enhanced Raman scattering porous silicon photonic crystal biosensor |
| CN107177874A (en) * | 2017-03-27 | 2017-09-19 | 肇庆市华师大光电产业研究院 | A kind of superhigh-density ordered silver nanoparticle ball array and its application |
| CN107309422A (en) * | 2017-05-18 | 2017-11-03 | 中国科学院合肥物质科学研究院 | A kind of porous electrum nano material and preparation method and application |
| CN109187486A (en) * | 2018-09-20 | 2019-01-11 | 天津理工大学 | A kind of Nano silver piece and preparation method thereof and purposes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8900524B2 (en) * | 2008-03-25 | 2014-12-02 | Waseda University | Optical sensor |
-
2020
- 2020-03-26 CN CN202010222052.9A patent/CN111364092B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08285776A (en) * | 1995-04-19 | 1996-11-01 | Hitachi Ltd | Inspection method for amorphous carbon and product produced using metal material inspected thereby |
| CN103364390A (en) * | 2012-04-10 | 2013-10-23 | 国家纳米科学中心 | Surface-enhanced Raman substrate, preparation method and application thereof |
| CN103526288A (en) * | 2013-10-10 | 2014-01-22 | 宋玉军 | Method for interface effect induced self-assembly of high-density nano array |
| CN103604796A (en) * | 2013-11-29 | 2014-02-26 | 苏州大学 | Preparation method for silicon-based surface-enhanced Raman scattering (SERS) substrate |
| CN105403551A (en) * | 2015-10-30 | 2016-03-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of thin film with Raman enhancing performance |
| CN105424674A (en) * | 2015-11-03 | 2016-03-23 | 华南师范大学 | Method for preparing surface Raman reinforced active substrate on basis of ion etching |
| CN105866096A (en) * | 2016-04-01 | 2016-08-17 | 新疆大学 | Method for manufacturing highly sensitive surface-enhanced Raman scattering porous silicon photonic crystal biosensor |
| CN105823769A (en) * | 2016-05-12 | 2016-08-03 | 清华大学 | In-situ detection surface enhanced raman substrate and preparation and recycling method |
| CN107177874A (en) * | 2017-03-27 | 2017-09-19 | 肇庆市华师大光电产业研究院 | A kind of superhigh-density ordered silver nanoparticle ball array and its application |
| CN107309422A (en) * | 2017-05-18 | 2017-11-03 | 中国科学院合肥物质科学研究院 | A kind of porous electrum nano material and preparation method and application |
| CN109187486A (en) * | 2018-09-20 | 2019-01-11 | 天津理工大学 | A kind of Nano silver piece and preparation method thereof and purposes |
Non-Patent Citations (1)
| Title |
|---|
| Enhanced morphological stability of silver nanoparticles supported on rough substrates at high temperatures;Ryan D. Scherzer 等;《Micro & Nano Letters》;20171222;第13卷(第4期);第498–501页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111364092A (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Photoinduced shape conversion and reconstruction of silver nanoprisms | |
| Kvítek et al. | Noble metal nanostructures influence of structure and environment on their optical properties | |
| Samal et al. | Size Tunable Au@ Ag core–shell nanoparticles: synthesis and surface-enhanced raman scattering properties | |
| Yang et al. | One-pot synthesis of monodispersed silver nanodecahedra with optimal SERS activities using seedless photo-assisted citrate reduction method | |
| Hao et al. | Modified Ag nanoparticles on the regular array structure to improve the optical properties | |
| Coman et al. | Green synthesis of gold nanoparticles by Allium sativum extract and their assessment as SERS substrate | |
| Gupta et al. | Au-spotted zinc oxide nano-hexagonrods structure for plasmon-photoluminescence sensor | |
| Wang et al. | Insights into direct plasmon-activated eletrocatalysis on gold nanostar via efficient photothermal effect and reduced activation energy | |
| Li et al. | Controlled preparation of uniform TiO2-catalyzed silver nanoparticle films for surface-enhanced Raman scattering | |
| Jiao et al. | Aligned TiO2 nanorod arrays decorated with closely interconnected Au/Ag nanoparticles: Near-infrared SERS active sensor for monitoring of antibiotic molecules in water | |
| Yin et al. | Plasmon enhanced quantum dots fluorescence and energy conversion in water splitting using shell-isolated nanoparticles | |
| Liu et al. | Polypyrrole-coated flower-like Pd nanoparticles (Pd NPs@ PPy) with enhanced stability and heat conversion efficiency for cancer photothermal therapy | |
| Fu et al. | Silver-decorated hierarchical cuprous oxide micro/nanospheres as highly effective surface-enhanced Raman scattering substrates | |
| Tang et al. | Hexagonally arranged arrays of urchin-like Ag-nanoparticle decorated ZnO-nanorods grafted on PAN-nanopillars as surface-enhanced Raman scattering substrates | |
| Shi et al. | SERS-active WO3-x thin films with tunable surface plasmon resonance induced by defects from thermal treatment | |
| Huang et al. | Construction of ternary multifunctional Fe3O4/Cu2O/Au nanocomposites: SERS detection and visible light driven photocatalysis for organic dyes | |
| Lu et al. | Au@ Ag nanorod horizontal arrays: Self-assembly preparation and in situ monitoring SERS of plasmonic catalytic reaction | |
| Dong et al. | Preparation of Ag/Au bimetallic nanostructures and their application in surface‐enhanced fluorescence | |
| Satheeshkumar et al. | Photochemical decoration of silver nanoparticles on ZnO nanowires as a three‐dimensional substrate for surface‐enhanced Raman scattering measurement | |
| Zhai et al. | Arrays of Ag-nanoparticles decorated TiO2 nanotubes as reusable three-dimensional surface-enhanced Raman scattering substrates for molecule detection | |
| CN111364092B (en) | Preparation method of silver-porous silicon-based surface enhanced Raman scattering biological detection chip | |
| Ma et al. | Design of a thermally stable and highly active SERS optical sensor for the ultrasensitive detection of dye molecules at high-temperature | |
| JP6037624B2 (en) | Method for producing metal nanoparticle modified substrate and metal nanoparticle modified substrate | |
| Jiang et al. | Harvesting the lost photon by plasmonic enhanced hematite-upconversion nanocomposite for water splitting | |
| Naranji et al. | Surface structured silver-copper bimetallic nanoparticles by irradiation of excimer laser pulses to bilayer thin films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |