CN111398248A - Preparation method of nanogold film SERS substrate based on multi-morphology silver modification - Google Patents
Preparation method of nanogold film SERS substrate based on multi-morphology silver modification Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 61
- 239000004332 silver Substances 0.000 title claims abstract description 61
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 51
- 239000000758 substrate Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000012986 modification Methods 0.000 title claims abstract description 9
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- 229910052737 gold Inorganic materials 0.000 claims abstract description 141
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 134
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 239000013078 crystal Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 35
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims description 34
- 239000000523 sample Substances 0.000 claims description 32
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 30
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
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- 239000012744 reinforcing agent Substances 0.000 claims description 16
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- 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
Abstract
The invention discloses a preparation method of a nano-gold film SERS substrate based on multi-morphology silver modification, which comprises the following steps: step 1, preparing a flat porous nano gold film; step 2, preparing a corrugated porous nano gold film; step 3, preparing a silver-modified flat porous nano gold film; step 4, preparing a silver-modified wrinkled porous nano gold film; and 5, carrying out detection analysis. The prepared nano-structure substrate mainly comprises two kinds of porous nano-gold films, namely a flat type and a wrinkled type, after silver modification, the two kinds of shapes can form a composite multi-hot-spot hole structure, and through comparison analysis, the wrinkled type silver-modified porous gold film has better SERS sensitivity, is simple to manufacture, good in repeatability, more uniform in surface signal sensitivity and strong in stability.
Description
Technical Field
The invention relates to the technical field of nanometer, in particular to a preparation method of a nanogold film SERS substrate based on multi-morphology silver modification, belonging to the preparation and application of patterned nanomaterials.
Background
With the synchronous exploration of a large number of experiments and theoretical researches, the SERS technology is gradually developed into a material characterization and analysis tool which is high in sensitivity, can monitor in real time, is reliable and effective, the SERS active substrate is a precondition for obtaining Raman signals, and factors such as composition, structure, morphology and size of the SERS active substrate can directly influence the SERS activity.
A large number of experiments show that when the nanometer structure is changed into different shapes such as a nanowire, a nanorod, a nanocube and the like from particles, a hot spot area is correspondingly changed into a hot line, a hot surface and the like along with the change of a nanometer gap, and the SERS effect is gradually enhanced due to the increase of the area of the hot spot. The porous gold film can be used as a precursor for effectively preparing the SERS active substrate due to the advantages of uniform pore size distribution, large surface roughness, rich hot spots and the like, and can also obtain a patterned structure by virtue of the deformation of a metal film on a heat shrinkage film (PS film) under the action of thermal stress. Silver is the metal with the best SERS activity in the single-metal material, so that the silver is an ideal modified material. By combining the two contents, the optimized SERS active substrate can be prepared by reasonably utilizing the characteristics of large surface roughness, strong uniformity and the like of the porous plane structure and the fold structure of the pattern.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-gold film SERS substrate based on multi-morphology silver modification.
In order to realize the purpose of the invention, the invention adopts the following technical scheme: a preparation method of a nanogold film SERS substrate based on multi-morphology silver modification comprises the following steps: step 1, preparing a flat porous nano gold film, which specifically comprises the following steps: step (1-1), sequentially placing the glass slide in acetone, absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, then rinsing with ultrapure water for several times, and drying with nitrogen for later use;
cutting a thermal shrinkage (PS) film to a proper size, sequentially placing the film in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, and storing the film in the ultrapure water for later use after the ultrasonic cleaning is finished;
step (1-3), carefully transferring the 12K gold-silver alloy film to an A4 paper interlayer, and cutting the film with scissors for later use;
step (1-4), dipping a small amount of ultrapure water on a glass slide, transferring the gold-silver alloy film into concentrated nitric acid by utilizing electrostatic adsorption for corrosion;
step (1-5), after the corrosion is finished, transferring the film into ultrapure water by using a glass slide, and rinsing for multiple times; after the cleaning is finished, transferring the film to a PS film, and naturally airing for later use to obtain a flat porous nano gold film;
and 5, carrying out detection analysis: and quantitatively analyzing the sample by adopting an Energy Dispersive Spectrometer (EDS), taking crystal violet as probe molecules, respectively dripping quantitative crystal violet on the surface of the sample, standing, slowly leaching for many times by using ultrapure water, naturally drying, and detecting and analyzing SERS activity of different samples by using a Raman instrument.
Preferably, in the step 1, a glass slide is sequentially placed in acetone, absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, then is rinsed with ultrapure water for multiple times and is dried by blowing with nitrogen for standby, a heat shrinkage (PS) film is cut to the size of 1.5cm × 1.5.5 cm and is sequentially placed in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, after cleaning is finished, the glass slide is stored in ultrapure water for standby, a 12K gold-silver alloy film is carefully transferred to an A4 paper interlayer, the thickness of the 12K gold-silver alloy film is 100 nm and is 50 wt% Au, the glass slide is cut into the size of 1cm × 1cm by using scissors for standby, the glass slide is dipped with a small amount of ultrapure water and is transferred to concentrated nitric acid by electrostatic adsorption for corrosion for 1h, after corrosion is finished, the film is rinsed in the ultrapure water by the glass slide for multiple times, after cleaning, the film is transferred to the PS film, and is naturally dried in the air, and the standby porous nano gold film is obtained.
Preferably, in step 2, the porous gold film is horizontally placed in an electrothermal blowing dry box with the temperature of 120 ℃ and dried for 15 min.
Preferably, in the step 3, under the condition of keeping out of the sun, the silver reinforcing agent A and the initiator B are mixed according to the volume ratio of 1: 1, the flat gold nano porous film obtained in the step 1 is placed in a mixed solution, and is soaked for different time periods of 1min to 10 min; and then all samples are rinsed by ultrapure water and dried by nitrogen, and the flat porous nano gold film modified by silver is obtained.
Preferably, in the step 4, under the condition of keeping out of the sun, the silver reinforcing agent A and the initiator B are mixed according to the volume ratio of 1: 1, the wrinkled gold nano porous film obtained in the step 2 is placed in the mixed solution, and is soaked for different time of 1-12 min; and then all samples are rinsed by ultrapure water and dried by nitrogen, and the silver-modified wrinkled porous nano gold film is obtained.
Preferably, in step 5, the sample is quantitatively analyzed by an energy spectrometer (EDS), and crystal violet is used as a probe molecule, and is respectively dripped on the surface of the sample to be quantitatively analyzed, wherein the concentration of the crystal violet is 10-4Standing the crystal violet of M for 30 min, then slowly leaching the crystal violet with ultrapure water for multiple times, naturally drying the crystal violet, detecting and analyzing SERS (surface enhanced Raman scattering) activities of different samples by using a Raman spectrometer, and exciting the Raman spectrumThe wavelength is 785nm, the integration time is 7 s, and the Raman spectra of crystal violet on the multi-morphology nanogold film and the silver-modified nanogold film are analyzed and compared by using the crystal violet as a probe molecule, so that the silver-modified wrinkled nanogold film has stronger SERS activity and shows higher sensitivity.
Compared with the prior art, the preparation method of the multi-morphology silver modified nano-gold film SERS substrate based on the technical scheme has the following beneficial effects:
the preparation method of the multi-morphology silver-modified-based nanogold film SERS substrate is obtained through a nitric acid dealloying method, thermal shrinkage, self-assembly and other links, the preparation is simple and easy to operate, the repeatability is good, the obtained structure is stable, and good detection uniformity is shown;
secondly, the multi-morphology nanogold film SERS substrate is provided with a porous structure, is modified by silver, further grows into a composite hole structure, can provide more abundant multiple hot points for electromagnetic field enhancement, and is good in SERS sensitivity and strong in stability.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of a preparation method of a multi-morphology silver-modified nanogold film SERS substrate according to the invention;
FIG. 2 is EDS spectra of the 12K gold-silver alloy thin film and the porous nanogold film obtained by etching in the present example;
FIG. 3 is a line graph showing the variation of gold and silver concentration of the silver-modified porous nanogold film substrate in the present example;
FIG. 4 is a surface topography of a 12K gold-silver alloy thin film, a porous nanogold film obtained by etching and a silver-modified porous nanogold film in the embodiment under a scanning electron microscope;
FIG. 5 is a surface topography of the silver-modified flat porous nanogold film in this example under a scanning electron microscope;
FIG. 6 is a surface topography of the silver-modified wrinkled porous nano-Au film in the present embodiment under a scanning electron microscope;
FIG. 7 is a graph showing the result of Raman spectroscopy on the porous nanogold film substrate containing the probe molecular crystal violet in this example;
FIG. 8 is a graph of the result of the Raman spectroscopy performed on the silver-modified porous nanogold film substrate containing the probe molecule crystal violet according to the present example;
FIG. 9 is a graph of the results of Raman spectroscopy on a target product containing the probe molecule crystal violet at different locations on the substrate in this example.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
As shown in fig. 1, a schematic flow chart of a preparation method of a multi-morphology silver-modified nanogold film SERS substrate is shown, and the preparation method comprises the following steps: step 1, preparing a flat porous nano gold film, which specifically comprises the following steps: step (1-1), sequentially placing the glass slide in acetone, absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, then rinsing with ultrapure water for several times, and drying with nitrogen for later use;
cutting a thermal shrinkage (PS) film to a proper size, sequentially placing the film in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, and storing the film in the ultrapure water for later use after the ultrasonic cleaning is finished;
fig. 4 shows a surface topography of a 12K gold-silver alloy thin film, a porous nanogold film obtained by etching, and a silver-modified porous nanogold film by a scanning electron microscope, wherein (a) the initial gold-silver alloy thin film; (b) a flat porous gold film; (c) the corrugated porous nano gold film.
Step (1-3), carefully transferring the 12K gold-silver alloy film to an A4 paper interlayer, and cutting the film with scissors for later use, as shown in FIG. 4 (a);
and (1-4) dipping a small amount of ultrapure water on the glass slide, and transferring the gold-silver alloy film into concentrated nitric acid for corrosion by utilizing electrostatic adsorption. As shown in fig. 2, EDS spectra of the 12K gold-silver alloy thin film and the porous nano-gold film obtained by etching are shown, wherein (a) the initial gold-silver alloy thin film; (b) corroding with concentrated nitric acid for 1h to obtain a porous nano gold film;
step (1-5), after the corrosion is finished, transferring the film into ultrapure water by using a glass slide, and rinsing for multiple times; after the cleaning, the film is transferred to a PS film, and naturally dried for use, so as to obtain a flat porous nanogold film, as shown in fig. 4 (b).
And 5, carrying out detection analysis: performing quantitative analysis on a sample by using an Energy Dispersive Spectrometer (EDS), taking crystal violet as probe molecules, respectively dripping quantitative crystal violet on the surface of the sample, standing, slowly rinsing with ultrapure water for multiple times, naturally drying, and detecting and analyzing SERS activity of different samples by using a Raman spectrometer, wherein as shown in fig. 7, a representation result graph of the porous nano gold film substrate containing the probe molecule crystal violet by using the Raman spectrometer is shown, wherein (a) the SERS spectrum graph of the flat porous gold film; (b) and SERS spectra of the corrugated porous gold thin film. Fig. 8 is a graph showing the characterization results of a silver-modified porous nanogold film substrate containing probe molecular crystal violet using a raman spectrometer, wherein (a) the SERS spectrum of the silver-modified flat porous gold film; (b) SERS spectra of silver-modified pleated porous gold films.
Example 1:
the preparation method comprises the following steps of 1, preparing a flat porous nanogold film, namely, sequentially placing a glass slide in acetone, absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, then rinsing with ultrapure water for multiple times, drying with nitrogen for standby, cutting a heat shrinkage (PS) film to the size of 1.5cm × 1.5cm, sequentially placing the glass slide in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, after cleaning, storing the glass slide in the ultrapure water for standby, carefully transferring a 12K gold-silver alloy film into an A4 paper interlayer, using the 12K gold-silver alloy film with the thickness of 100 nm and using 50 wt% of Au, cutting the Au film into the size of 1cm × 1cm by using a pair of scissors for standby, as shown in a picture 4 (a), dipping a small amount of the glass slide in the gold-silver alloy film, transferring the alloy film into concentrated nitric acid by electrostatic adsorption, corroding for 1h, transferring the film into the standby water for standby after corrosion, rinsing the film in the standby × cm, and naturally drying the gold-silver film after finishing corrosion, as shown in a picture 4, and obtaining the porous nanogold as a natural drawing.
And 5, carrying out detection analysis: quantitatively analyzing the sample by an energy spectrometer (EDS), and respectively dripping quantitative crystal violet with the concentration of 10 on the surface of the sample by taking the crystal violet as a probe molecule-4Standing the crystal violet of M for 30 min, slowly rinsing the crystal violet with ultrapure water for multiple times, naturally drying the crystal violet, detecting and analyzing SERS activity of different samples by using a Raman spectrometer, wherein the excitation wavelength of a Raman spectrum is 785nm, and the integration time is 7 s, as shown in 1min and 2min in fig. 8 (a), and as shown in 1min and 3min in fig. 8 (b).
Example 2:
the preparation method comprises the following steps of 1, preparing a flat porous nanogold film, namely, sequentially placing a glass slide in acetone, absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, then rinsing with ultrapure water for multiple times, drying with nitrogen for standby, cutting a heat shrinkage (PS) film to the size of 1.5cm × 1.5cm, sequentially placing the glass slide in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, after cleaning, storing the glass slide in the ultrapure water for standby, carefully transferring a 12K gold-silver alloy film into an A4 paper interlayer, using the 12K gold-silver alloy film with the thickness of 100 nm and using 50 wt% of Au, cutting the Au film into the size of 1cm × 1cm by using a pair of scissors for standby, as shown in a picture 4 (a), dipping a small amount of the glass slide in the gold-silver alloy film, transferring the alloy film into concentrated nitric acid by electrostatic adsorption, corroding for 1h, transferring the film into the standby water for standby after corrosion, rinsing the film in the standby × cm, and naturally drying the gold-silver film after finishing corrosion, as shown in a picture 4, and obtaining the porous nanogold as a natural drawing.
And 5, carrying out detection analysis: quantitatively analyzing the sample by an energy spectrometer (EDS), and respectively dripping quantitative crystal violet with the concentration of 10 on the surface of the sample by taking the crystal violet as a probe molecule-4Standing crystal violet of M for 30 min, and slowly leaching with ultrapure water for multiple timesAfter drying, detecting and analyzing SERS activity of different samples by using a Raman spectrometer, wherein the excitation wavelength of a Raman spectrum is 785nm, and the integration time is 7 s, as shown in 3min and 5min in fig. 8 (a), and as shown in 5min, 6min and 7min in fig. 8 (b).
Example 3:
the preparation method comprises the following steps of 1, preparing a flat porous nanogold film, namely, sequentially placing a glass slide in acetone, absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, then rinsing with ultrapure water for multiple times, drying with nitrogen for standby, cutting a heat shrinkage (PS) film to the size of 1.5cm × 1.5cm, sequentially placing the glass slide in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, after cleaning, storing the glass slide in the ultrapure water for standby, carefully transferring a 12K gold-silver alloy film into an A4 paper interlayer, using the 12K gold-silver alloy film with the thickness of 100 nm and using 50 wt% of Au, cutting the Au film into the size of 1cm × 1cm by using a pair of scissors for standby, as shown in a picture 4 (a), dipping a small amount of the glass slide in the gold-silver alloy film, transferring the alloy film into concentrated nitric acid by electrostatic adsorption, corroding for 1h, transferring the film into the standby water for standby after corrosion, rinsing the film in the standby × cm, and naturally drying the gold-silver film after finishing corrosion, as shown in a picture 4, and obtaining the porous nanogold as a natural drawing.
And 5, carrying out detection analysis: quantitatively analyzing the sample by an energy spectrometer (EDS), and respectively dripping quantitative crystal violet with the concentration of 10 on the surface of the sample by taking the crystal violet as a probe molecule-4Standing the crystal violet of M for 30 min, slowly rinsing the crystal violet with ultrapure water for multiple times, naturally drying the crystal violet, detecting and analyzing SERS activity of different samples by using a Raman spectrometer, wherein the excitation wavelength of a Raman spectrum is 785nm, and the integration time is 7 s, as shown in 7min and 10min in fig. 8 (a), and as shown in 8min, 9min and 12min in fig. 8 (b).
Test example 1: detection by energy spectrometer
The components and contents of the 12K gold-silver alloy thin film, the etched porous nanogold film and the silver-modified porous nanogold film used in examples 1 to 3 were measured by an energy spectrometer, and the results are shown in fig. 2 and 3. Fig. 2 (a) is an EDS spectrum of the gold-silver alloy thin film, and it is confirmed that the alloy material contains only two metals, i.e., gold and silver, and that the mass ratio of gold to silver can be determined to be 50: 50 from quantitative elemental analysis. Fig. 2 (b) shows the porous gold nano-film obtained by chemical etching using a nitric acid dealloying method, and it can be seen that the Ag component is not present at this time, and a gold nano-porous film with high purity is indeed obtained.
Fig. 3 is a line graph showing the variation of gold and silver concentration of the silver-modified porous nanogold film substrate, wherein (a) is the line graph showing the variation of gold and silver concentration of the silver-modified flat porous gold film, and six points of the line graph respectively correspond to the immersion time in silver AB: 1. 2, 3, 5, 7 and 10min, it can be seen that the silver content in the film increases significantly with time. When the reaction time is increased to 10min, the mass ratio of gold to silver in the silver-modified porous gold film is 56: 44, and a large number of silver particles are proved to be agglomerated on the porous gold film. (b) The gold and silver concentration change line graph of the silver-modified fold type porous gold film is characterized in that eight points respectively correspond to the soaking time in the silver AB: 1. 3, 5, 6, 7, 8, 9 and 12min, it can be seen that the silver content in the film increases significantly with time. However, the deposition rate of silver particles on the wrinkled gold film is significantly slower than that of the flat gold film.
Test example 2: scanning by electron microscope
The 12K gold-silver alloy thin film, the etched porous nanogold film and the silver-modified porous nanogold film used in examples 1 to 3 were respectively subjected to electron microscope scanning, and the results were shown in fig. 4, 5 and 6. In fig. 4 (a), the original gold-silver alloy thin film has a flat surface and no hollow structure. FIG. 4 (b) is a schematic diagram of a porous nanogold film, which is chemically etched by a nitric acid dealloying method to obtain a porous structure on the surface of the film, wherein the size of pores is concentrated in a range of 20-30 nm and is uniform; fig. 4 (c) shows the corrugated porous nano-gold film, which mainly utilizes the thermal shrinkage of the PS film to deform the gold film thereon under thermal induction to form corrugations, and thus, the micron-sized corrugated pattern can greatly improve the surface roughness of the structure, which is beneficial to enhancing the SERS activity.
FIG. 5 shows a silver-modified planar porous gold film, wherein (a) - (f) correspond to the time for immersing the porous gold film in silver AB: 1. 2, 3, 5, 7 and 10min, it can be seen that the silver nanoparticles reduced on the gold ligament have small size and have little influence on the size of the original pores when the reaction is carried out for 1 and 2min, and therefore, hot spots are still concentrated in the porous gold film area. With the enhancement of the soaking time, the silver particles cover and grow the original holes, when the reaction time is increased to 5min (corresponding to the figure (d)), composite holes with the silver particles as inner walls and the gold holes as bottoms are formed among the silver particles accumulated at the edges of the holes, and the hole structure has a three-dimensional shape, so that the surface structure is further roughened. However, the time is continuously increased, the gold-silver composite holes are gradually blocked due to the excessive accumulation of the particles, and the hot spot structure is damaged. Therefore, as shown in the graph (f), when the reaction time is as long as 10min, the grown silver particles are adhered to form a large-size morphology uniformly distributed on the surface of the film, and the pore structure is weakened.
FIG. 6 shows a silver-modified pleated porous gold membrane, wherein (a) - (h) correspond to the time for soaking the porous gold membrane in silver AB: 1. 3, 5, 6, 7, 8, 9 and 12min, it can be seen that the corrugated porous gold film has the modes of bending, breaking and the like, the films are staggered and stacked, and the difference of micrometer scale between the peak and the valley forms an effective three-dimensional space. Under the soaking of silver AB, certain particles are deposited on the same fold-type gold film, but due to the shielding of the fold part on the gold film, the deposition speed of the silver particles is slightly slower than that of a flat porous gold film, but as the time increases (corresponding to a graph (d) (e) (f)), the reduced silver particles can be attached to the crack of the ridge in the fold and the porous film slit area between the fold ridges, so that the gold film is rich in three hot areas of points, lines and surfaces, the SERS sensitivity is highest, and after the time is too long (corresponding to a graph (g) (h)), the surface is changed from fine holes into large-scale convergence, namely, the hot point structure is damaged due to the excessive accumulation and growth of the particles, and the three-dimensional hole structure is weakened.
Test example 3: applied analysis for crystal violet detection
And (3) detecting SERS activity by taking crystal violet as a probe molecule. The samples were each added dropwise to the surface in a fixed amount and at a concentration of 10-4And (3) standing the crystal violet of M for 30 min, then slowly leaching the crystal violet with ultrapure water for several times, naturally drying the crystal violet, and detecting and analyzing SERS activity of different samples by using a Raman instrument. The excitation wavelength of the raman spectrum is 785nm, and the integration time is 7 s, so that the raman spectrometer characterization results shown in fig. 7, 8 and 9 are obtained.
Fig. 7 shows SERS spectra of (a) a flat porous gold film and (b) a wrinkled porous gold film, respectively. It can be obtained from spectrogram, and the two structures can detect characteristic peak of crystal violet adsorbed thereon, with comparison of 1161 cm-1The intensity of the peak at the characteristic peak indicates that the latter is the signal intensity of the formerMore than 2 times. This indicates that the corrugated structure has better SERS activity than the flat structure under the precondition of the same size of the porous gold film.
Fig. 8 shows SERS spectra of (a) a silver-modified flat porous gold film and (b) a silver-modified wrinkled porous gold film, respectively. The spectrogram can obtain that the SERS activity of the silver-modified porous gold film is obviously superior to that of a pure porous gold film, and the silver-modified porous gold film shows a trend of signal change which is firstly enhanced and then weakened along with the increase of time. And it can be seen that the SERS signal of the silver-modified wrinkled porous gold film is stronger than that of the silver-modified flat porous gold film. The numerical comparison yields: the SERS signal of the silver-modified folded porous gold film is 50 times that of the folded gold film which is not modified by silver and 6 times that of the silver-modified flat porous gold film, so that the effectiveness of the synergy of gold and silver in the structure is proved to be optimal.
As shown in fig. 9, which is a graph of the results of the characterization of the target product containing the probe molecule crystal violet using a raman spectrometer at different locations on the substrate, fig. 9 is a graph further depicting the repeatability and uniformity of the SERS signal to optimize the substrate: for a 7-minute silver-modified wrinkled porous gold film as an example, 20 detection points are randomly selected on the same substrate for SERS detection (a picture), and the length of the detection points is 1161 cm-1Relative Standard Deviation (RSD) values and mean values of SERS signal intensity were calculated at the peak positions (b plot). The RSD value of the crystal violet characteristic peak is less than 10 percent through calculation, and the porous structure has good SERS repeatability. Although the gold film flower type corrugated fold is different in shape in the nanometer scale from the surface appearance, certain uncontrollable exists. However, the porous gold film and the PS film can be tightly attached, the heat shrinkage of the PS film is very stable, and a large number of uniform and effective hot spot structures exist on the surface of the metal corrugated film within the size (micron-sized) range of Raman laser detection light spots, so that the good repeatability and uniformity of SERS signals are shown.
The foregoing is a preferred embodiment of the present invention, and it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (6)
1. A preparation method of a nanogold film SERS substrate based on multi-morphology silver modification is characterized by comprising the following steps: the method comprises the following steps: step 1, preparing a flat porous nano gold film, which specifically comprises the following steps: step (1-1), sequentially placing the glass slide in acetone, absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, then rinsing with ultrapure water for several times, and drying with nitrogen for later use;
cutting a thermal shrinkage (PS) film to a proper size, sequentially placing the film in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning, and storing the film in the ultrapure water for later use after the ultrasonic cleaning is finished;
step (1-3), carefully transferring the 12K gold-silver alloy film to an A4 paper interlayer, and cutting the film with scissors for later use;
step (1-4), dipping a small amount of ultrapure water on a glass slide, transferring the gold-silver alloy film into concentrated nitric acid by utilizing electrostatic adsorption for corrosion;
step (1-5), after the corrosion is finished, transferring the film into ultrapure water by using a glass slide, and rinsing for multiple times; after the cleaning is finished, transferring the film to a PS film, and naturally airing for later use to obtain a flat porous nano gold film;
step 2, preparing the corrugated porous nano gold film, which comprises the following steps: horizontally placing the porous gold film obtained in the step 1 in an electric heating air blast drying oven for drying, taking out and naturally cooling for later use to obtain a wrinkle type porous nano gold film;
step 3, preparing the silver-modified flat porous nano gold film, which comprises the following steps: under the condition of keeping out of the sun, placing the flat gold nano porous film obtained in the step 1 into a mixed solution of a silver reinforcing agent and an initiator, and soaking for different times; then, leaching all samples with ultrapure water, and drying the samples with nitrogen to obtain the silver-modified flat porous nano gold film;
step 4, preparing the silver-modified wrinkled porous nano gold film, which comprises the following steps: placing the pleated gold nano porous film obtained in the step 2 in a mixed solution of a silver reinforcing agent and an initiator under the condition of keeping out of the sun, and soaking for different times; then, leaching all samples with ultrapure water, and drying the samples with nitrogen to obtain the silver-modified wrinkled porous nano gold film;
and 5, carrying out detection analysis: and quantitatively analyzing the sample by adopting an Energy Dispersive Spectrometer (EDS), taking crystal violet as probe molecules, respectively dripping quantitative crystal violet on the surface of the sample, standing, slowly leaching for many times by using ultrapure water, naturally drying, and detecting and analyzing SERS activity of different samples by using a Raman instrument.
2. The preparation method of the nanotopography silver-modified nano gold film SERS substrate based on claim 1 is characterized in that in step 1, a glass slide is sequentially placed in acetone, absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, then rinsed with ultrapure water for multiple times, dried with nitrogen for standby, a heat-shrinkable (PS) film is cut to the size of × 1.5.5 cm 891.5 cm, sequentially placed in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 20min, and stored in ultrapure water for standby after cleaning, a 12K gold-silver alloy film is carefully transferred into an A4 paper interlayer, the 12K gold-silver alloy film adopts the thickness of 100 nm and is cut into the size of × 1cm by scissors for standby after cleaning, a small amount of ultrapure water is dipped in the glass slide, the gold-silver alloy film is transferred into concentrated nitric acid by electrostatic adsorption and is corroded for 1h, after corrosion is finished, the film is transferred into ultrapure water for multiple times by using the glass slide, after cleaning is finished, the film is transferred onto the film, and is naturally dried in the standby glass slide, and the gold nano gold film is obtained.
3. The preparation method of the multi-morphology silver modified nanogold film SERS substrate according to claim 1, characterized in that: in step 2, the porous gold film is horizontally placed in an electrothermal blowing drying oven with the temperature of 120 ℃ and dried for 15 min.
4. The preparation method of the multi-morphology silver modified nanogold film SERS substrate according to claim 1, characterized in that: in the step 3, under the condition of keeping out of the sun, mixing the silver reinforcing agent A and the initiator B in a volume ratio of 1: 1, placing the flat gold nano porous film obtained in the step 1 into a mixed solution, and soaking for different times of 1-10 min; and then all samples are rinsed by ultrapure water and dried by nitrogen, and the flat porous nano gold film modified by silver is obtained.
5. The preparation method of the multi-morphology silver modified nanogold film SERS substrate according to claim 1, characterized in that: in the step 4, under the condition of keeping out of the sun, mixing the silver reinforcing agent A and the initiator B according to the volume ratio of 1: 1, placing the wrinkled gold nano porous film obtained in the step 2 into a mixed solution, and soaking for different time of 1-12 min; and then all samples are rinsed by ultrapure water and dried by nitrogen, and the silver-modified wrinkled porous nano gold film is obtained.
6. The preparation method of the multi-morphology silver modified nanogold film SERS substrate according to claim 1, characterized in that: in step 5, a sample is quantitatively analyzed by an energy spectrometer (EDS), crystal violet is taken as a probe molecule, and the surface of the sample is respectively dripped with quantitative samples with the concentration of 10-4And (3) standing the crystal violet of M for 30 min, then slowly leaching the crystal violet with ultrapure water for multiple times, naturally drying the crystal violet, and detecting and analyzing SERS (surface enhanced Raman scattering) activities of different samples by using a Raman spectrometer, wherein the excitation wavelength of the Raman spectrum is 785nm, and the integration time is 7 s.
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