CN107101988B - Gold film covered high-density nanometer needle tip array and application thereof - Google Patents
Gold film covered high-density nanometer needle tip array and application thereof Download PDFInfo
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Abstract
The invention discloses a gold film covered high-density nanometer needle tip array and application thereof, and the preparation method of the gold film covered high-density nanometer needle tip array comprises the following steps: preparing a glass substrate single-layer polystyrene colloidal crystal array; etching the glass substrate single-layer polystyrene colloidal crystal array by adopting a reactive ion etching method, and removing the single-layer polystyrene colloidal crystal array on the glass substrate to obtain a high-density nanometer needle tip array; and taking the high-density nanometer needle tip array as a template, and depositing a layer of gold film with the thickness of 10-50 nm on the surface of the template by adopting a physical deposition method, thereby preparing the high-density nanometer needle tip array covered by the gold film. The high-density nanometer needle tip array covered by the gold film can be directly used as a substrate material of a surface enhanced Raman effect. The invention has the advantages of large construction area, good uniformity, clean surface, high detection sensitivity, simple preparation method, convenient operation, low cost, economy and environmental protection.
Description
Technical Field
The invention relates to the field of substrate materials with Surface-enhanced Raman scattering (SERS), in particular to a gold film covered high-density nanometer needle tip array and application thereof.
Background
Triphenylphosphine (C18H15P) is not only an important basic raw material of rhodium phosphine and gold phosphine complex catalyst, but also can be used as a brightener of dye technology, an antioxidant for color film development, a stabilizer for poly-epoxy, and an analytical reagent for chemical analysis, so that the triphenylphosphine has wide application in the fields of medicine industry, organic synthesis, chemical analysis and the like. Since triphenylphosphine causes environmental pollution and harm to human body, in many fields using triphenylphosphine, it is necessary to perform on-site, rapid trace detection of triphenylphosphine concentration.
At present, methods for detecting the concentration of triphenylphosphine mainly comprise a gas chromatography method, an electrochemical method and the like, but the existing detection methods have the defects of low sensitivity, poor selectivity, long time consumption and the like, so that the rapid trace detection of the concentration of triphenylphosphine is difficult to realize. The existing research finds that: the noble metal nanoparticles (such as gold nanoparticles, silver nanoparticles and the like) have excellent plasmon effect and can generate stronger surface enhanced Raman effect, and the concentration detection method based on the surface enhanced Raman effect has the advantages of high sensitivity, quick response, fingerprint effect and the like, and can provide molecular structure information adsorbed on the surface of the noble metal, so that the rapid trace detection of the concentration of triphenylphosphine is expected to be realized.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a gold film covered high-density nanometer needle tip array and application thereof, which not only have large construction area, good uniformity, clean surface, high sensitivity and good detection performance, but also can be directly used as a substrate material with high-activity surface enhanced Raman effect, and have simple preparation method, convenient operation, low cost, economy and environmental protection.
The purpose of the invention is realized by the following technical scheme:
a high-density nanometer pinpoint array covered by a gold film is prepared by the following steps:
step A, preparing a single-layer polystyrene colloidal crystal array which is tightly arranged on a glass substrate so as to obtain the single-layer polystyrene colloidal crystal array of the glass substrate;
b, etching the glass substrate single-layer polystyrene colloidal crystal array by adopting a reactive ion etching method, and removing the single-layer polystyrene colloidal crystal array on the glass substrate to obtain a high-density nano needle tip array;
and step C, taking the high-density nanometer needle tip array as a template, and depositing a layer of gold film with the thickness of 10-50 nm on the surface of the template by adopting a physical deposition method, thereby preparing the high-density nanometer needle tip array covered by the gold film.
Preferably, the etching the glass substrate single-layer polystyrene colloidal crystal array by using the reactive ion etching method comprises: and (2) etching the glass substrate single-layer polystyrene colloidal crystal array by using sulfur hexafluoride as a working gas, wherein the gas flow is controlled to be 20-50 scc/min, the gas pressure is maintained to be 1-4 Pa, the etching power is controlled to be 150-250W, and the etching time is 15-60 s.
Preferably, the removing of the single-layer polystyrene colloidal crystal array on the glass substrate comprises: soaking the etched glass substrate single-layer polystyrene colloidal crystal array in a cleaning solvent for 5-20 min of ultrasonic treatment, and then cleaning with deionized water to remove the single-layer polystyrene colloidal crystal array on the glass substrate; wherein the cleaning solvent is at least one of dichloromethane, toluene, ethylbenzene, xylene and chloroform.
Preferably, the preparation of the densely arranged monolayer polystyrene colloidal crystal array on the glass substrate comprises the following steps:
step A1, sequentially putting the glass substrate into acetone, ethanol, the first mixed solution and deionized water for ultrasonic cleaning, drying the cleaned glass substrate, and then putting the glass substrate into an ultraviolet ozone cleaning machine for irradiation for 10-40 min to obtain the glass substrate with a hydrophilic surface; the first mixed solution is formed by mixing concentrated sulfuric acid with the mass concentration of 1.84g/ml and hydrogen peroxide with the mass concentration of 1.1g/ml according to the volume ratio of 3: 1;
and A2, putting the glass substrate treated in the step A1 into an ethanol diluent of polystyrene colloidal spheres, and preparing a single-layer polystyrene colloidal crystal array which is arranged closely on the glass substrate by adopting a gas-liquid interface self-assembly method.
Preferably, the polystyrene colloidal sphere ethanol diluent is prepared by the following method: and taking the polystyrene colloidal sphere suspension with the colloidal sphere diameter of 120-300 nm, mixing the polystyrene colloidal sphere suspension with ethanol in the same volume, and performing ultrasonic oscillation for 10-30 min to prepare the uniformly dispersed polystyrene colloidal sphere ethanol diluent.
Preferably, the physical deposition method comprises magnetron sputter deposition, thermal evaporation deposition or electron beam evaporation deposition.
The concentration detection method of triphenylphosphine adopts the high-density nanometer needle tip array covered by the gold film in the technical scheme to directly serve as a substrate material with a surface enhanced Raman effect to carry out the concentration detection of the triphenylphosphine.
According to the technical scheme provided by the invention, the high-density nanometer needle point array covered by the gold film provided by the embodiment of the invention is obtained by adopting sulfur hexafluoride gas as working gas to carry out reactive ion etching on a glass substrate single-layer polystyrene colloidal crystal array, then removing the single-layer polystyrene colloidal crystal array on the glass substrate to obtain the high-density nanometer needle point array, and then depositing a layer of gold film with the thickness of 10-50 nm on the surface of a template by adopting a physical deposition method by adopting the high-density nanometer needle point array as the template, so that the high-density nanometer needle point array covered by the gold film is prepared. The high-density nanometer needle tip array covered by the gold film can be directly used as a substrate material with a high-activity surface enhanced Raman effect and used for detecting the concentration of triphenylphosphine. Therefore, the gold film covered high-density nanometer needle tip array provided by the invention has the advantages of large construction area, good uniformity, clean surface, high sensitivity and good detection performance, can be directly used as a substrate material with a high-activity surface enhanced Raman effect, and has the advantages of simple preparation method, convenience in operation, low cost, economy and environmental friendliness.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a schematic view of the shapes of the glass substrate single-layer polystyrene colloidal crystal array prepared in step b, the high-density nano needle tip array prepared in step d, and the gold film-covered high-density nano needle tip array prepared in step e in example 1 of the present invention.
Fig. 2 is a scanning electron microscope photograph (FESEM image) obtained by observing the glass substrate single-layer polystyrene colloidal crystal array prepared in step b and the high-density nano-needle tip array prepared in step d respectively by using a Sirion 200 field emission scanning electron microscope when a polystyrene colloidal sphere suspension with a colloidal sphere diameter of 120nm is used as a raw material in step b of example 1 of the present invention.
Fig. 3 is a light absorption spectrum diagram obtained by controlling the thickness of the gold film deposited on the surface of the template shown in step E and detecting the light absorption performance of the high-density nano needle tip array covered with the gold film prepared in step E by using a Cary-5E ultraviolet-visible-near infrared spectrometer when the polystyrene colloidal sphere suspension with the colloidal sphere diameter of 120nm is used as the raw material in step b of example 1 of the present invention.
Fig. 4 is a diagram showing an electromagnetic field intensity distribution diagram obtained by performing FDTD (Finite-Difference Time-Domain) simulation using the high-density nanoprobe array covered with the gold film obtained in step e when the polystyrene colloidal ball suspension having a colloidal ball diameter of 120nm is used as a raw material in step b of example 1 of the present invention.
Fig. 5 is a surface enhanced raman spectrum obtained by directly using the gold film-covered high-density nano needle tip array obtained in step e as a substrate material for the surface enhanced raman effect, respectively soaking the substrate material in 500ml of triphenylphosphine ethanol solutions with different concentrations for three hours, and then respectively detecting the surface enhanced raman spectrum of the substrate material by using a Renishaw inVia Reflex raman spectrometer, when a polystyrene colloidal sphere suspension with a colloidal sphere diameter of 120nm is used as a raw material in step b of example 1 of the present invention.
FIG. 6 shows that when polystyrene colloidal sphere suspension with a colloidal sphere diameter of 120nm is used as a raw material in step b of example 1 of the present invention, 5ul of high density nanoprobe tip array covered with gold film prepared in step e is added dropwise to the gold film prepared in step e, respectively, at a concentration of 10- 4mol/L triphenylphosphine solution and 5ul concentration of 10-1And (3) respectively detecting the surface enhanced Raman spectrums of the substrate materials by using a Raman spectrometer through the mol/L triphenylphosphine solution, thereby obtaining the surface enhanced Raman spectrums.
Fig. 7 is a scanning electron microscope photograph (FESEM image) obtained by observing the glass substrate single-layer polystyrene colloidal crystal array prepared in step b and the high-density nano-needle tip array prepared in step d respectively by using a Sirion 200 field emission scanning electron microscope when a polystyrene colloidal sphere suspension with a colloidal sphere diameter of 300nm is used as a raw material in step b of example 1 of the present invention.
FIG. 8 shows that when the polystyrene colloidal sphere suspension with a colloidal sphere diameter of 120nm is used as the raw material in step b of example 1, the gold film covered high-density nanoprobe tip array prepared in step e is directly used as the substrate material for the Surface Enhanced Raman Scattering (SERS) effect and is immersed in the solution with a concentration of 10-6And (3) in a triphenylphosphine ethanol solution, exciting by using different excitation wavelengths (such as 532nm, 633nm and 785nm), and testing the surface enhanced Raman spectrum, thereby obtaining the surface enhanced Raman spectrum.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The gold film covered high density nanoprobe tip array and the application thereof provided by the present invention are described in detail below.
A high-density nanometer pinpoint array covered by a gold film is prepared by the following steps:
step A, preparing a single-layer polystyrene colloidal crystal array which is arranged closely on a glass substrate, thereby obtaining the single-layer polystyrene colloidal crystal array of the glass substrate.
Specifically, the preparation of a densely arranged single-layer polystyrene colloidal crystal array on a glass substrate comprises the following steps:
and A1, sequentially putting a glass substrate (for example, the glass substrate can be a glass sheet made of common glass) into acetone, ethanol, the first mixed solution and deionized water for ultrasonic cleaning, drying the cleaned glass substrate, and then putting the glass substrate into an ultraviolet ozone cleaning machine for irradiation for 10-40 min to obtain the glass substrate with a hydrophilic surface. The first mixed solution is formed by mixing concentrated sulfuric acid with the mass concentration of 1.84g/ml and hydrogen peroxide with the mass concentration of 1.1g/ml according to the volume ratio of 3: 1.
And A2, putting the glass substrate treated in the step A1 into an ethanol diluent of polystyrene colloidal spheres, and preparing a single-layer polystyrene colloidal crystal array which is arranged closely on the glass substrate by adopting a gas-liquid interface self-assembly method. In practical application, polystyrene colloidal sphere suspension with the colloidal sphere diameter of 120-300 nm is taken and mixed with ethanol in equal volume, and ultrasonic oscillation is carried out for 10-30 min, so that uniformly dispersed polystyrene colloidal sphere ethanol diluent can be prepared; the polystyrene colloidal sphere suspension can be purchased commercially.
And step B, etching the glass substrate single-layer polystyrene colloidal crystal array by adopting a reactive ion etching method, and removing the single-layer polystyrene colloidal crystal array on the glass substrate to obtain the high-density nanometer needle tip array.
Specifically, the etching the glass substrate single-layer polystyrene colloidal crystal array by using the reactive ion etching method may include: and etching the glass substrate single-layer polystyrene colloidal crystal array by using sulfur hexafluoride as a working gas, wherein the gas flow is controlled to be 20-50 scc/min, the gas pressure is maintained to be 1-4 Pa, the etching power is controlled to be 150-250W, and the etching time is 15-60 s, so that the etched glass substrate single-layer polystyrene colloidal crystal array is obtained. The method for removing the single-layer polystyrene colloidal crystal array on the glass substrate comprises the following steps: soaking the etched glass substrate single-layer polystyrene colloidal crystal array in a cleaning solvent for 5-20 min of ultrasonic treatment, and then cleaning with deionized water, thereby removing the single-layer polystyrene colloidal crystal array on the glass substrate; in practical application, the cleaning solvent is at least one of dichloromethane, toluene, ethylbenzene, xylene and chloroform.
And step C, taking the high-density nanometer needle tip array as a template, and depositing a layer of gold film with the thickness of 10-50 nm on the surface of the template by adopting a physical deposition method, thereby preparing the high-density nanometer needle tip array covered by the gold film. The physical deposition method comprises magnetron sputtering deposition, thermal evaporation deposition or electron beam evaporation deposition.
In addition to the technical scheme, the invention also provides a triphenylphosphine concentration detection method, which adopts the gold film-covered high-density nano needle tip array as a substrate material with a surface enhanced Raman effect to directly detect the concentration of triphenylphosphine, can quickly and sensitively detect the concentration of triphenylphosphine, shortens the detection time and reduces the detection cost.
Compared with the prior art, the high-density nanometer pinpoint array covered by the gold film has at least the following advantages:
(1) the gold film covered high-density nanometer needle tip array provided by the embodiment of the invention has a plurality of nanometer needle tips, so that the gold film covered high-density nanometer needle tip array has a strong surface enhanced Raman effect.
(2) The gold film covered high-density nanometer needle tip array provided by the embodiment of the invention can be directly used as a substrate material for the surface enhanced Raman effect, the needle tip density and the period of the high-density nanometer needle tip array can be effectively regulated and controlled by changing the size of the polystyrene colloid sphere, the smaller the size of the polystyrene colloid sphere, the higher the needle tip density of the high-density nanometer needle tip array is, and the possibility of exploring the concentration detection of triphenylphosphine in a solution by the high-density nanometer needle tip arrays with different needle tip densities is provided.
(3) When the gold film covered high-density nano needle tip array provided by the embodiment of the invention is used as a substrate material of a surface enhanced Raman effect to detect the concentration of triphenylphosphine, the sensitivity is high, the detection limit is low, the detection concentration range is wide, and the signal uniformity is good.
(4) The gold film covered high-density nanometer needle tip array provided by the embodiment of the invention does not use any surfactant in the preparation process, so that the substrate material with the surface enhanced Raman effect and a clean surface is obtained.
(5) The gold film covered high-density nanometer needle tip array provided by the embodiment of the invention can be constructed in a large area and produced in a large scale, and can be suitable for industrial large-scale application in the aspects of environment, food, medicine and the like in the future.
In conclusion, the embodiment of the invention has the advantages of large construction area, good uniformity, clean surface, high sensitivity and good detection performance, can be directly used as a substrate material with a high-activity surface enhanced Raman effect, and has the advantages of simple preparation method, convenient operation, low cost, economy and environmental protection.
In order to more clearly show the technical solutions and the technical effects provided by the present invention, the gold-covered high-density nanoprobe array and the applications thereof provided by the present invention are described in detail with specific embodiments below.
Example 1
A high-density nanometer pinpoint array covered by a gold film is prepared by the following steps:
a, sequentially putting a glass substrate (the glass substrate is a common glass sheet) into acetone, ethanol, a first mixed solution (the first mixed solution is formed by mixing concentrated sulfuric acid with the mass concentration of 1.84g/ml and hydrogen peroxide with the mass concentration of 1.1g/ml according to the volume ratio of 3: 1) and deionized water for ultrasonic cleaning, carrying out ultrasonic cleaning for 40min in each liquid, and then drying the cleaned glass substrate at the drying temperature of 120 ℃ for 20 min; and after the moisture on the glass substrate is completely evaporated, placing the glass substrate in an ultraviolet ozone cleaning machine for irradiation for 10-40 min, thereby obtaining the glass substrate with a hydrophilic surface.
B, taking 50 microliters of polystyrene colloidal sphere suspension (2.5 wt.%) with the colloidal sphere diameter of 120-300 nm, mixing the suspension with ethanol in the same volume, and performing ultrasonic vibration for 10min to obtain uniformly dispersed polystyrene colloidal sphere ethanol diluent; and c, putting the glass substrate treated in the step a into the polystyrene colloidal sphere ethanol diluent, and preparing a single-layer polystyrene colloidal crystal array which is tightly arranged on the glass substrate by adopting a gas-liquid interface self-assembly method, so as to prepare the single-layer polystyrene colloidal crystal array of the glass substrate.
And c, etching the glass substrate single-layer polystyrene colloidal crystal array prepared in the step b by using sulfur hexafluoride as a working gas, wherein the gas flow is controlled to be 20-50 scc/min, the gas pressure is maintained to be 1-4 Pa, the etching power is controlled to be 150-250W, and the etching time is 15-60 s, so that the etched glass substrate single-layer polystyrene colloidal crystal array is obtained.
And d, soaking the etched glass substrate single-layer polystyrene colloidal crystal array prepared in the step c in a dichloromethane solvent for 20min of ultrasonic treatment, and then cleaning with deionized water, so that the single-layer polystyrene colloidal crystal array on the glass substrate can be removed, and the high-density nano needle tip array is prepared.
And e, taking the high-density nanometer needle tip array prepared in the step d as a template, and depositing a layer of gold film with the thickness of 10-50 nm on the surface of the template by adopting a magnetron sputtering deposition method (the processing current of magnetron sputtering deposition is 20mA, and the processing time of magnetron sputtering deposition is 3min), so as to prepare the high-density nanometer needle tip array covered by the gold film.
Specifically, the following topography observations and performance measurements were made during the practice of example 1 of the present invention:
(1) in the process of implementing embodiment 1 of the present invention, the glass substrate single-layer polystyrene colloidal crystal array prepared in step b, the high-density nano needle tip array prepared in step d, and the gold film-covered high-density nano needle tip array prepared in step e are respectively subjected to topography observation, so as to obtain a topography schematic diagram as shown in fig. 1. Wherein, fig. 1a is a schematic view of a morphology of a glass substrate single-layer polystyrene colloidal crystal array prepared in step b of embodiment 1 of the present invention, fig. 1b is a schematic view of a morphology of a high-density nano-needle tip array prepared in step d of embodiment 1 of the present invention, and fig. 1c is a schematic view of a morphology of a gold film covered high-density nano-needle tip array prepared in step e of embodiment 1 of the present invention. As can be seen from fig. 1a, 1b and 1 c: the morphology of the product of each step is changed in the process of implementing the embodiment 1 of the invention, and finally the high-density nanometer pinpoint array covered by the gold film is obtained.
(2) In the implementation of example 1 of the present invention, when the polystyrene colloidal sphere suspension with a colloidal sphere diameter of 120nm is used as a raw material in step b, the single-layer polystyrene colloidal crystal array with a glass substrate prepared in step b and the high-density nano-needle tip array prepared in step d are observed by using a Sirion 200 field emission scanning electron microscope, so as to obtain a scanning electron microscope photograph (FESEM image) as shown in fig. 2. Wherein, FIG. 2a is a FESEM image of the glass substrate single-layer polystyrene colloidal crystal array prepared in step b when a polystyrene colloidal sphere suspension having a colloidal sphere diameter of 120nm is used as a raw material in step b of example 1 of the present invention, FIG. 2b is a low power top view FESEM image of the high density nanoprobe tip array prepared in step d when polystyrene colloidal sphere suspension with a colloidal sphere diameter of 120nm is used as a raw material in step b of example 1 of the present invention, FIG. 2c is an FESEM image observed at an angle of 45 lower times of the high-density nanoprobe tip array prepared in step d when a polystyrene colloidal sphere suspension having a colloidal sphere diameter of 120nm is used as a raw material in step b of example 1 of the present invention, FIG. 2d is a high power FESEM image of the high density nanoprobe tip array prepared in step d when polystyrene colloidal sphere suspension with a colloidal sphere diameter of 120nm is used as a raw material in step b of example 1 of the present invention. As can be seen from fig. 2a, 2b, 2c and 2 d: the high-density nano needle tip array prepared in the step d of the embodiment 1 of the invention is a nano needle tip with high density, and the period interval is 120 nm.
(3) In the process of implementing embodiment 1 of the present invention, when the polystyrene colloidal sphere suspension with a colloidal sphere diameter of 120nm is used as a raw material in step b, the thickness of the gold film deposited on the surface of the template in step E is controlled, and a Cary-5E ultraviolet-visible-near infrared spectrometer is used to detect the light absorption performance of the high-density nano needle tip array covered by the gold film prepared in step E, so as to obtain a light absorption spectrum diagram shown in fig. 3; in fig. 3, the abscissa is Wavelength (i.e., Wavelength, which is expressed in nm), the ordinate is Normalized absorbance (i.e., Normalized absorbance, which is expressed in a.u.), curve i represents the light absorption curve of the high-density nanoprobe tip array with the gold film thickness of 28nm, curve II represents the light absorption curve of the high-density nanoprobe tip array with the gold film thickness of 35nm, curve III represents the light absorption curve of the high-density nanoprobe tip array with the gold film thickness of 42nm, curve IV represents the light absorption curve of the high-density nanoprobe tip array with the gold film thickness of 49nm, and curve V represents the light absorption curve of the high-density nanoprobe tip array with the gold film thickness of 56 nm. As can be seen from fig. 3: the maximum light absorption value of curve I is 690nm, the maximum light absorption value of curve II is 705nm, the maximum light absorption value of curve III is 715nm, the maximum light absorption value of curve IV is 725nm, and the maximum light absorption value of curve V is 775 nm. That is, the maximum absorption peak of light absorption of the gold film covered high-density nanoprobe tip array prepared in step e of example 1 of the present invention is red-shifted with the increase of the thickness of the gold film.
(4) In the process of carrying out example 1 of the present invention, when the polystyrene colloidal sphere suspension having a colloidal sphere diameter of 120nm was used as a raw material in step b, FDTD (Finite-Difference Time-Domain) simulation was performed using the high-density nanopip array covered with the gold film prepared in step e, thereby obtaining an electromagnetic field intensity distribution pattern as shown in fig. 4. In the process of implementing the embodiment 1 of the present invention, when the polystyrene colloidal sphere suspension with the colloidal sphere diameter of 120nm is used as the raw material in the step b, the high-density nanoprobe tip array covered with the gold film prepared in the step e is directly used as the substrate material of the surface enhanced raman effect, and 500ml of the substrate material with different concentrations (the concentrations are 10 respectively) are respectively placed in the high-density nanoprobe tip array-6mol/L、10-7mol/L、10-8mol/L、10-10mol/L) of the substrate material, soaking the substrate material in a triphenylphosphine ethanol solution for three hours, and then respectively detecting the surface enhanced Raman spectrum of the substrate material by adopting a Renishaw inViaReflex Raman spectrometer, thereby obtaining the surface enhanced Raman spectrum shown in figure 5; in FIG. 5, the horizontal and vertical axes are Raman shifts (i.e., Raman shifts in cm)-1) Intensity (i.e., raman Intensity in a.u.), 10 on the ordinate-6M represents soaking at a concentration of 10-6Surface enhanced Raman spectroscopy of substrate materials in mol/L triphenylphosphine ethanol solutionSpectrogram, 10-7M represents soaking at a concentration of 10-7Surface enhanced Raman spectroscopy of substrate materials in mol/L triphenylphosphine in ethanol solution, 10-8M represents soaking at a concentration of 10-8Surface enhanced Raman spectroscopy of substrate materials in mol/L triphenylphosphine in ethanol solution, 10-10M represents soaking at a concentration of 10-10And (3) a surface enhanced Raman spectrum of the substrate material in a triphenylphosphine ethanol solution of mol/L. As can be seen from fig. 4 and 5: in the embodiment 1, the detection limit of the gold film covered high-density nanometer pinpoint array on triphenylphosphine is 10-10mol/L, and the electromagnetic field is strongest at the nano needle tip at the top end of each small unit.
(5) In the process of implementing example 1 of the present invention, when the polystyrene colloidal sphere suspension with the colloidal sphere diameter of 120nm is used as the raw material in step b, 5ul of the high density nanoprobe tip array covered with the gold film prepared in step e is respectively dropped into the high density nanoprobe tip array with the concentration of 10-4mol/L triphenylphosphine solution and 5ul concentration of 10-1Respectively detecting the surface enhanced Raman spectra of the substrate materials by using a Raman spectrometer with mol/L triphenylphosphine solution to obtain the surface enhanced Raman spectra shown in FIG. 6; in FIG. 6, the horizontal and vertical axes are designated Raman shift (i.e., Raman shift in cm)-1) Intensity (i.e., raman Intensity in a.u.), 10 on the ordinate-4M represents soaking at a concentration of 10-4Surface enhanced Raman spectroscopy of substrate materials in mol/L triphenylphosphine in ethanol solution, 10-1M represents soaking at a concentration of 10-1And (3) a surface enhanced Raman spectrum of the substrate material in a triphenylphosphine ethanol solution of mol/L. As can be seen from fig. 6: the gold film covered high-density nano needle tip array prepared in the step e in the embodiment 1 of the invention has a good enhancement effect on a Raman spectrogram of triphenylphosphine.
(6) In the implementation of example 1 of the present invention, when the polystyrene colloidal sphere suspension with a colloidal sphere diameter of 300nm is used as a raw material in step b, the glass substrate single-layer polystyrene colloidal crystal array prepared in step b and the high-density nanoprobe tip array prepared in step d are observed by using a Sirion 200 field emission scanning electron microscope, respectively, so as to obtain a scanning electron microscope photograph (FESEM image) as shown in fig. 7. Wherein, FIG. 7a is a FESEM image of the glass-based single-layer polystyrene colloidal crystal array prepared in step b when a polystyrene colloidal sphere suspension having a colloidal sphere diameter of 300nm is used as a raw material in step b of example 1 of the present invention, FIG. 7b is a low power top view FESEM image of the high density nanoprobe tip array prepared in step d when polystyrene colloidal sphere suspension with a colloidal sphere diameter of 300nm is used as the raw material in step b of example 1 of the present invention, FIG. 7c is an FESEM image observed at an angle of 45 lower times of the high-density nanoprobe tip array prepared in step d when a polystyrene colloidal sphere suspension having a colloidal sphere diameter of 300nm is used as a raw material in step b of example 1 of the present invention, FIG. 7d is a high power FESEM image of the high density nanoprobe tip array prepared in step d when polystyrene colloidal sphere suspension with a colloidal sphere diameter of 300nm is used as a raw material in step b of example 1 of the present invention. As can be seen from fig. 7a, 7b, 7c and 7 d: the high-density nano needle tip array prepared in the step d of the embodiment 1 of the invention is a nano needle tip with high density, and the periodic interval is 300 nm.
(7) In the process of implementing the embodiment 1 of the present invention, when the polystyrene colloidal sphere suspension with the colloidal sphere diameter of 120nm is used as the raw material in the step b, the high-density nanoprobe tip array covered with the gold film prepared in the step e is directly used as the substrate material of the surface enhanced raman effect and is soaked in the substrate material with the concentration of 10-6In mol/L triphenylphosphine ethanol solution, then exciting with different excitation wavelengths (such as 532nm, 633nm and 785nm), and testing the surface enhanced Raman spectrum of the substrate material, thereby obtaining the surface enhanced Raman spectrum shown in FIG. 8; in FIG. 8, the horizontal and vertical axes are labeled Raman shift (i.e., Raman shift in cm)-1) The ordinate is Intensity (i.e. raman Intensity, unit a.u.), cure I represents the raman spectrum obtained by excitation at 532nm, cure II represents the raman spectrum obtained by excitation at 633nm, and cure III represents the raman spectrum obtained by excitation at 785 nm. As can be seen from fig. 8: the good surface enhanced Raman spectrum can be obtained only when the excitation wavelength is 785nm, which indicates that the invention is implementedExample 1 step e the most suitable excitation wavelength for the gold-coated high density nanoprobe tip array was 785 nm.
In conclusion, the embodiment of the invention has the advantages of large construction area, good uniformity, clean surface, high sensitivity and good detection performance, can be directly used as a substrate material with a high-activity surface enhanced Raman effect, and has the advantages of simple preparation method, convenient operation, low cost, economy and environmental protection.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A high-density nanometer pinpoint array covered by a gold film is characterized in that the preparation method comprises the following steps:
step A, preparing a single-layer polystyrene colloidal crystal array which is tightly arranged on a glass substrate so as to obtain the single-layer polystyrene colloidal crystal array of the glass substrate;
b, etching the glass substrate single-layer polystyrene colloidal crystal array by adopting a reactive ion etching method, and removing the single-layer polystyrene colloidal crystal array on the glass substrate to obtain a high-density nano needle tip array;
step C, taking the high-density nanometer needle tip array as a template, and depositing a layer of gold film with the thickness of 10-50 nm on the surface of the template by adopting a physical deposition method so as to prepare the high-density nanometer needle tip array covered by the gold film;
wherein, the etching the glass substrate single-layer polystyrene colloidal crystal array by adopting a reactive ion etching method comprises the following steps: etching the glass substrate single-layer polystyrene colloidal crystal array by using sulfur hexafluoride as a working gas, wherein the gas flow is controlled to be 20-50 scc/min, the gas pressure is maintained to be 1-4 Pa, the etching power is controlled to be 150-250W, and the etching time is 15-60 s;
the method for removing the single-layer polystyrene colloidal crystal array on the glass substrate comprises the following steps: soaking the etched glass substrate single-layer polystyrene colloidal crystal array in a cleaning solvent for 5-20 min of ultrasonic treatment, and then cleaning with deionized water to remove the single-layer polystyrene colloidal crystal array on the glass substrate; wherein the cleaning solvent is at least one of dichloromethane, ethylbenzene, xylene and chloroform.
2. The gold-coated high-density nanoprobe tip array according to claim 1, wherein the preparation of the densely-arranged single-layer polystyrene colloidal crystal array on the glass substrate comprises the following steps:
step A1, sequentially putting the glass substrate into acetone, ethanol, the first mixed solution and deionized water for ultrasonic cleaning, drying the cleaned glass substrate, and then putting the glass substrate into an ultraviolet ozone cleaning machine for irradiation for 10-40 min to obtain the glass substrate with a hydrophilic surface; the first mixed solution is formed by mixing concentrated sulfuric acid with the mass concentration of 1.84g/ml and hydrogen peroxide with the mass concentration of 1.1g/ml according to the volume ratio of 3: 1;
and A2, putting the glass substrate treated in the step A1 into an ethanol diluent of polystyrene colloidal spheres, and preparing a single-layer polystyrene colloidal crystal array which is arranged closely on the glass substrate by adopting a gas-liquid interface self-assembly method.
3. The gold-coated high-density nanoprobe tip array according to claim 2, wherein the polystyrene colloidal sphere ethanol diluent is prepared by the following method: and taking the polystyrene colloidal sphere suspension with the colloidal sphere diameter of 120-300 nm, mixing the polystyrene colloidal sphere suspension with ethanol in the same volume, and performing ultrasonic oscillation for 10-30 min to prepare the uniformly dispersed polystyrene colloidal sphere ethanol diluent.
4. The gold film covered high density nanoprobe tip array according to claim 1 or 2, wherein the physical deposition method comprises magnetron sputter deposition, thermal evaporation deposition or electron beam evaporation deposition.
5. The gold-film covered high-density nanoprobe tip array of any one of the above claims 1 to 4 directly as a substrate material for surface enhanced Raman effect.
6. A method for detecting the concentration of triphenylphosphine is characterized in that the high-density nanometer needle tip array covered by the gold film according to any one of claims 1 to 4 is directly used as a substrate material of a surface enhanced Raman effect to detect the concentration of the triphenylphosphine.
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| CN108892100A (en) * | 2018-06-25 | 2018-11-27 | 武汉大学 | A kind of preparation method of metal nano needle tip array |
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