WO2014044228A1 - 表面增强拉曼基底、制备方法、拉曼光谱仪及检测方法和微调装置 - Google Patents

表面增强拉曼基底、制备方法、拉曼光谱仪及检测方法和微调装置 Download PDF

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Publication number
WO2014044228A1
WO2014044228A1 PCT/CN2013/084136 CN2013084136W WO2014044228A1 WO 2014044228 A1 WO2014044228 A1 WO 2014044228A1 CN 2013084136 W CN2013084136 W CN 2013084136W WO 2014044228 A1 WO2014044228 A1 WO 2014044228A1
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WIPO (PCT)
Prior art keywords
substrate
base
tray
sample
layer
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PCT/CN2013/084136
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English (en)
French (fr)
Inventor
胡建明
Original Assignee
Hu Jianming
Priority date (The priority date 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 date listed.)
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Publication date
Priority claimed from CN201210358471.0A external-priority patent/CN102890077B/zh
Priority claimed from CN201210394955.0A external-priority patent/CN103776812A/zh
Priority claimed from CN2012103976844A external-priority patent/CN102944542A/zh
Priority claimed from CN201310429690.8A external-priority patent/CN103487426B/zh
Application filed by Hu Jianming filed Critical Hu Jianming
Publication of WO2014044228A1 publication Critical patent/WO2014044228A1/zh

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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

Definitions

  • the invention relates to the field of molecular spectroscopic analysis and in particular to a surface-enhanced Raman substrate, a preparation method, a Raman spectrometer, a detection method and a fine adjustment device.
  • the scattered light of the elastic scattering is the same wavelength as the wavelength of the excitation light.
  • the scattered light of the inelastic scattering has a shorter and shorter component than the wavelength of the excitation light, which is called Raman. Effect, the spectrum obtained is called Raman spectroscopy.
  • the Raman spectrum belongs to the molecular vibrational spectrum and is the fingerprint of the material molecule.
  • the Raman spectrometer fabricated according to the Raman effect can be used for quasi-deterministic identification of the sample.
  • Raman spectroscopy analysis methods generally do not require pre-treatment of the sample, and are easy to operate and short in measurement time. It is an analytical technique that can simultaneously perform qualitative and quantitative analysis on samples, and has a wide application prospect. However, its disadvantage is its low sensitivity.
  • SERS Surface-enhanced Raman spectroscopy
  • SERS is a highly sensitive spectral analysis technique developed with the development of nanotechnology in the 1990s. Like Raman spectroscopy, SERS can be used to identify samples with quasi-determinism. SERS has an ultra-high analytical sensitivity, which is about 6-10 orders of magnitude better than ordinary Raman analysis, and can be analyzed for subjects as small as single molecules and as large as cells.
  • the surface-enhanced Raman substrate generally adopts a solid substrate such as a hard glass slide or a silicon wafer, and the surface growth has A material with a certain roughness can be formed by vapor deposition of a noble metal; or a precious metal nanomaterial can be directly attached to a hard carrier to achieve a better reinforcing effect.
  • the above structure of the prior art requires etching on the surface of the solid base material to form a base layer, and then growing the substrate to have a This high, long production cycle, difficult to adapt to the shortcomings of mass production; and solid base materials are hard and brittle, easy to damage, and do not have the characteristics of adapting to the orientation according to environmental conditions.
  • the method of growing nano silver particles is more used in the production of the reinforcing layer on the SERS substrate, and the cost and the reinforcing effect are more cost-effective.
  • an oxide film is formed on the surface of the nano-silver, and the surface properties of the oxidized nano-silver particles are changed, so that the SERS substrate enhancement effect is more obvious, generally reaching in about two days. Less than the desired enhancement; resulting in wasted silver metal and substrate materials.
  • SERS Surface-enhanced Raman spectroscopy
  • SERS is a highly sensitive spectral analysis technique developed with the development of nanotechnology in the 1990s. Like Raman spectroscopy, SERS can be used to identify samples with quasi-determinism. SERS has an ultra-high analytical sensitivity, which is about 6-10 orders of magnitude better than ordinary Raman analysis, and can be analyzed from small to single molecules up to the cell level.
  • the SERS substrate In practical applications, it is a relatively common method to directly drop the sample solution on the SERS substrate.
  • the SERS substrate generally uses solid substrates such as hard slides and silicon wafers, and the surface grows with a certain roughness. Forming a substrate by vapor deposition of a noble metal; or directly attaching a precious metal nanomaterial to a hard carrier can achieve a better reinforcing effect.
  • the above structure of the prior art requires etching on the surface of the solid base material to form a base layer, and then growing the substrate, which has the disadvantages of high cost, long manufacturing cycle, and difficulty in adapting to mass production; and the solid base material is hard and brittle, and is easy to use. Damaged, does not have the characteristics of adapting to the orientation according to environmental conditions.
  • a SERS substrate which directly forms a noble metal surface reinforcing layer on a surface of frosted glass, sandpaper or filter paper having a micron order of roughness, without requiring a base.
  • the etched surface is formed on the base layer, and the noble metal layer is not roughened, and the formed substrate also has excellent reinforcing effect and high analytical sensitivity, and is suitable for detection of ultra-trace samples; fabrication of the SERS substrate of the structure Simple, short production cycle and low cost, suitable for mass production.
  • the SERS may exhibit irregular protrusion within a certain range after being irradiated and reflected, and thus has a certain dispersion in the detection, and the reproducibility is poor, resulting in repeated accuracy of the detection result. Not high, affecting the application of the substrate.
  • a surface-enhanced Raman substrate a preparation method, a spectrometer, a detection method, and a fine adjustment device, which not only have ultra-high analytical sensitivity, but are suitable for detection of ultra-trace samples, and are simple to manufacture, short in production cycle, and low in cost.
  • Suitable for mass production providing conditions for further promotion of SERS technology in a wider range of applications in homeland security, environmental monitoring, food safety and medical care; the preparation of this substrate makes the SERS substrate still have a good enhancement for long-term preservation.
  • the Raman spectrometer using the substrate increases the utilization efficiency of the excitation light, makes full use of the excitation energy, makes it suitable for the detection of ultra-trace samples, and obtains the desired effect; and the detection method adopted not only has ultra-high analytical sensitivity. It is suitable for the detection of ultra-trace samples. It also has high reproducibility, accurate detection results, simple operation and short detection period.
  • the fine-tuning device suitable for this method is simple in structure and low in cost.
  • an object of the present invention is to provide a high performance and low cost surface-enhanced Raman substrate, a preparation method, a Raman spectrometer, a detection method and a fine adjustment device, which not only have ultra-high analytical sensitivity, but are suitable for ultra-trace samples.
  • the detection, and the simple production, short production cycle, low cost, suitable for mass production, provide conditions for further promotion of SERS technology in a wider range of applications in homeland security, environmental monitoring, food safety and medical care;
  • the preparation of the SERS substrate still has a good reinforcing effect for long-term preservation;
  • the Raman spectrometer using the substrate increases the utilization efficiency of the excitation light, and fully utilizes the excitation energy, making it suitable for the detection of ultra-trace samples, and obtaining the desired
  • the detection method adopted not only has ultra-high analytical sensitivity, but also is suitable for the detection of ultra-trace samples, and has high reproducibility, accurate detection results, simple operation, short detection period, and is suitable for the method.
  • the fine adjustment device has a simple structure and a low cost.
  • the frosted glass surface-enhanced Raman substrate of the present invention comprises a base layer and a surface reinforcing layer, the base layer being frosted glass, and a surface reinforcing layer attached to the frosted surface of the frosted glass.
  • the surface enhancement layer is a noble metal layer; the noble metal layer is adhered with a noble metal nano material layer;
  • the roughness of the frosted surface of the frosted glass corresponds to a surface roughness of the 180-5000 mesh metallographic sandpaper
  • the precious metal layer has a thickness of 20-400 nm
  • the precious metal layer is any one of gold, silver and copper.
  • the noble metal nano material layer is one or two or more nano material layers of gold, silver, and copper;
  • the frosted glass is an arc-shaped groove-shaped structure, and the frosted surface is an arc-shaped groove-shaped structure. Inner surface.
  • the invention also discloses a preparation method of a surface-enhanced Raman substrate, comprising the following steps: a. attaching a surface enhancement layer on the surface of the base layer to form a surface-enhanced Raman substrate;
  • step a The surface-enhanced Raman substrate formed in step a is stored in an inert gas.
  • step a a superhydrophobic structure is first formed on a surface of the base layer, and the noble metal nano material layer is attached to the surface of the superhydrophobic structure;
  • the base layer is a smooth groove-shaped structure, and the super-hydrophobic structure is located on the inner surface of the smooth groove.
  • step a the formation process of the surface enhancement layer of the nano silver particles includes the following steps: I.
  • the base layer is immersed in a liquid adhesive for 10-40 minutes and then taken out;
  • the invention also discloses a Raman spectrometer comprising a Raman spectrometer body and a detecting head assembly, the detecting head assembly comprising a housing and a dual optical path assembly disposed in the housing, the dual optical path assembly comprising at least one disposed along the direction of the excitation light a convex lens and a concave mirror, the convex lens being confocal with the concave mirror, and the sample to be detected is located at a focal point of the convex lens and the concave mirror.
  • the housing is provided with a pick-and-place port for picking up and dropping a sample, and the pick-and-place port is provided with a sealing cover for blocking light in an openable manner;
  • the sealing cover is disposed in an articulated manner on the housing to form a gate-shaped structure, and a sealing cover having a sealing cover larger than the pick-and-place opening and a radially outer surface of the edge of the pick-and-place opening is provided with a light-shielding pad; a tray or tray for placing a sample to be inspected and having the sample to be detected at a focal point of the convex lens and the concave mirror, the bracket or tray having a confocal light transmission at least at the convex lens and the concave mirror; the bracket or the tray being fixedly coupled to
  • the sealing cover can be removed or placed in accordance with the opening and closing of the sealing cover; or the bracket or the tray is fixedly disposed in the housing.
  • the tray or the tray is a smooth groove-shaped tray, the opening of the smooth groove-shaped tray is upward and the lowest point of the bottom is located at a focal point of the convex lens and the concave mirror; the inner surface of the smooth groove-shaped tray is a super-hydrophobic structure a surface of the superhydrophobic structure is grown with self-assembled nanomaterials for surface enhancement; a thermal light for volatilizing a solvent of the sample to be detected is introduced into the excitation light; and the Raman signal is introduced in the housing for introducing excitation light and The dichroic mirror is taken out.
  • the invention also discloses a method for detecting surface enhanced Raman spectroscopy, comprising the following steps: a. uniformly coating a sample to be tested on a SERS substrate;
  • c performing multi-point detection on the sample having the sample on the SERS substrate and repeating the step b; d. using the acquired spectral information of the multi-point sample to be tested, and then averaging the background, and measuring according to the average value
  • the spectral information of the multi-point sample to be tested is removed from the minimum and maximum values, and the spectral information of the multi-point sample to be tested is removed and averaged to obtain the Raman spectrum information of the sample to be tested.
  • Raman spectral database that gives qualitative or/and quantitative information about the sample being tested.
  • the sample to be detected is uniformly distributed on the surface of the SERS substrate on the SERS substrate; in the step c, the multi-point detection of the sample is performed in the same range on the SERS substrate.
  • the in-plane moving SERS substrate is implemented; the SERS substrate comprises a base layer and a surface reinforcing layer, the base layer is frosted glass, sandpaper, filter paper or lens paper, and the surface is adhered to the frosted surface of the frosted glass, the working surface of the sandpaper Or the surface of the filter paper.
  • the invention also discloses a fine adjustment device for surface enhanced Raman spectroscopy, comprising a SERS substrate holder for placing a SERS substrate and a drive for driving the SERS substrate to move the substrate in the detection plane Moving components.
  • the SERS substrate holder includes a base assembly and a substrate tray on the base assembly, the base tray is provided with a SERS substrate, the SERS substrate includes a base layer and a surface reinforcing layer, the base layer is frosted glass, Sandpaper, filter paper or lens paper;
  • the base assembly comprises a carriage and a base, the base tray being arranged on the carriage in a manner rotatable about its own axis, the carriage being arranged in a reciprocating manner on the detection plane
  • the drive assembly includes a rotary drive assembly for driving the base tray to rotate about its own axis and a reciprocating drive assembly for driving the carriage to reciprocate in the detection plane; further, the rotary drive assembly includes a drag a rotary drive motor of the plate, a rotary drive gear driven by the rotary drive motor, and a rotary driven gear located on the outer circumference of the base tray and meshed with the rotary drive gear;
  • the reciprocating drive assembly includes a reciprocating drive motor mounted on the base and driven by the reciprocating drive
  • the SERS substrate holder includes a base assembly and a substrate tray on the base assembly, the base tray is provided with a SERS substrate, the SERS substrate includes a base layer and a surface reinforcing layer, the base layer is frosted glass, Sandpaper, filter paper or lens paper;
  • the base assembly includes a y-axis carriage and a base, the base tray being disposed on the y-axis carriage in a manner reciprocable along the X-axis in the detection plane, the y-axis drag
  • the plate is disposed on the base in a reciprocable manner along the y-axis in the detecting plane;
  • the driving assembly includes an X-axis driving assembly for driving the substrate tray to reciprocate along the X-axis and for driving the carriage to reciprocate along the y-axis
  • the y-axis drive assembly includes a X-axis driving assembly for driving the substrate tray to reciprocate along the X-axis and for driving the carriage to reciprocate along the y-axis
  • the substrate of the nanoparticle is protected by an inert gas to ensure that the surface is not oxidized after long-term storage, so that the substrate is preserved for a long time for the SERS substrate, and the substrate has a better reinforcing effect, so that the substrate has Ultra-high analytical sensitivity, suitable for ultra-trace sample detection, simple production, short production cycle, low cost, suitable for mass production, especially for nano-silver particles, thus saving costs;
  • the Raman spectrometer adopts a structure in which a convex lens and a concave mirror are combined, and the sample to be detected is located at its confocal point, and the excited light of the excited sample is reflected and then excited again to realize single-source double-path excitation, and at the same time, in the focusing lens.
  • Convex lens Effectively receive the Raman spectrum of the forward-scattering of the laser-excited sample collected in the solid angle, increase the utilization efficiency of the excitation light without changing the source of the existing Raman spectrometer, and make full use of the excitation energy to make it suitable.
  • ultra-high sensitivity, ie, measurement and display analysis can be realized in the field analysis, which can give qualitative and quantitative results to the ultra-trace samples, and obtain the desired effect with lower cost.
  • the detection method of averaging multiple detections avoids the problem of high dispersion of the prior art detection method, has high reproducibility and ultra-high analytical sensitivity, is suitable for detection of ultra-trace samples, and can also be accurate
  • the detection result is obtained, and the operation is simple and the detection period is short;
  • the method adopts a fine adjustment device to realize the movement of the substrate to perform multi-point detection, and the device has the advantages of simple structure, low cost and simple and convenient operation; the above method and device further promote SERS technology Providing conditions for wider application in areas such as homeland security, environmental monitoring, food safety and health care.
  • FIG. 1 is a schematic structural view of a first embodiment of a substrate of the present invention
  • 2 is a schematic structural view of a second embodiment of the substrate of the present invention (with a noble metal nanomaterial layer attached thereto)
  • FIG. 3 is a 5 L 1 ppm triazophos (5 ng), and a frosted glass having the same roughness as a 1200 mesh metallographic paper.
  • Figure 4 shows the spectrum obtained by a portable Raman spectrometer with 632.8 nm excitation light, SxlO ⁇ mol / 1 Nylan blue, a surface-enhanced Raman substrate based on frosted glass with the same roughness of 3000 mesh metallographic paper.
  • Figure 5 is a SEM photograph of 120 nm silver vapor-deposited frosted glass with the same roughness of 400 mesh metallographic sandpaper;
  • Fig. 6 is a SEM photograph of vapor-deposited 120 nm silver of a frosted glass having the same roughness of 3000 mesh metallographic sandpaper;
  • Figure 7 is a SEM photograph of 120 nm silver deposited on the base layer of the frosted glass with the same roughness of 5000 mesh metallographic sandpaper;
  • Figure 8 is a schematic diagram of the principle of the Raman spectrometer of the present invention.
  • Figure 9 is an enlarged view of the sample at the confocal point of the Raman spectrometer.
  • Figure 10 is a longitudinal sectional view of the Raman spectrometer detecting head assembly
  • Figure 11 is a cross-sectional view taken along line A of Figure 10;
  • Figure 12 is an enlarged view of Figure 11B;
  • Figure 13 is a schematic structural view of the fine adjustment device of the present invention.
  • Figure 14 is a plan view of Figure 13;
  • Figure 15 is a fine adjustment device with a housing
  • Figure 16 is a cross-sectional view taken along line C-C of Figure 15;
  • Figure 17 is an enlarged view of Figure 16D
  • Figure 18 is a schematic view showing another structure of the fine adjustment device of the present invention.
  • FIG. 1 is a schematic structural view of a first embodiment of a substrate of the present invention
  • FIG. 2 is a schematic structural view of a second embodiment of the substrate of the present invention (with a noble metal nanomaterial layer attached thereto)
  • FIG. 3 is a 5 L 1 ppm triazophos (5 ng).
  • Base layer 1200 is formed of the same mesh roughness of sandpaper metallographic frosted glass substrate as the surface-enhanced Raman performed test spectra obtained by the portable Raman spectrometer 785 nm excitation light;
  • FIG. 1 is a schematic structural view of a first embodiment of a substrate of the present invention
  • FIG. 2 is a schematic structural view of a second embodiment of the substrate of the present invention (with a noble metal nanomaterial layer attached thereto)
  • FIG. 3 is a 5 L 1 ppm triazophos (5 ng).
  • FIG. 4 is a Nair 5xl0- 1Q mol 1 Blue, a surface-enhanced Raman substrate based on a frosted glass with the same roughness of 3000 mesh metallographic paper, a spectrogram obtained by a portable Raman spectrometer with 632.8 nm excitation light;
  • Figure 5 is a 400 mesh metallographic sandpaper The frosted glass with the same roughness is the SEM photograph of the base layer evaporation 120 nm silver;
  • Fig. 6 is the SEM photograph of the frosted glass with the same roughness of the 3000 mesh metallographic sandpaper as the base layer evaporation 120 nm silver; Fig.
  • the frosted glass having the same roughness is a SEM photograph of the base layer vapor-deposited 120 nm silver; as shown in the figure: the frosted glass surface-enhanced Raman substrate of the present embodiment includes a base layer and a surface reinforcing layer, and the base layer is frosted glass.
  • the surface reinforcement adheres to the frosted surface of the frosted glass; the frosted glass is frosted glass, smoothing the surface of the prior art, and the other side is similar to the metallographic sandpaper Rough glass; the present invention, the frosted glass is a glass sheet.
  • the surface is reinforced to a precious metal layer.
  • the noble metal layer is adhered with a noble metal nano material layer.
  • the noble metal layer is any one of gold, silver, and copper
  • the noble metal nano material layer is one or two or more nano material layers of gold, silver, and copper.
  • the roughness of the frosted surface of the frosted glass is equivalent to the surface roughness of the metallographic sandpaper of 180 to 5000 mesh, and the range of the embodiment is preferably a roughness of 3000 mesh; through the drawings of FIG. 4, FIG. 5 and FIG.
  • the SEM photograph comparison shows that the roughness of 3000 mesh is optimal; in the above scheme of the embodiment, the complete structure of the frosted glass surface-enhanced Raman substrate is independently formed, and is made of frosted glass, which has low cost and good reproducibility. The use of high performance and mass production is difficult to achieve with other surface-enhanced Raman substrates.
  • the substrate of the present invention that is, the noble metal nano material layer 3 is adhered to the noble metal layer 2 of the above embodiment, as shown in FIG. 2; combined with the surface roughness of the frosted glass, has a two-way reinforcing effect
  • the surface enhancement effect is enhanced, and the analysis sensitivity is further improved compared with the prior art. The result is shown in Figure 3.
  • the noble metal layer 2 has a thickness of 20-400 nm, preferably 120 nm; the thickness can fully exert the bidirectional reinforcing function of the nano material layer and the metallographic sandpaper surface.
  • the noble metal nano material layer 3 may be a gold or silver nano material layer, and the silver material is used in this embodiment; different nano metal particle shapes such as nanorods, nanospheres and other irregularities may be used.
  • the body can achieve the purpose of the invention.
  • the frosted glass is an arc-shaped groove-shaped structure, and the frosted surface is an inner surface of an arc-shaped groove-shaped structure; when used, the sample to be tested is directly located at the lowest point of the bottom by gravity, and has automatic positioning.
  • the effect of the sample, and the concentration of the sample improve the detection sensitivity and improve work efficiency.
  • the substrate of the present invention is prepared by the following method:
  • Embodiment 1 of the substrate preparation method of the present invention a method for preparing a surface-enhanced Raman substrate, comprising the following steps:
  • the frosted glass 1 is washed in an organic solvent to clean the matte surface, and the organic solvent is ethanol or acetone.
  • the organic solvent is ethanol or acetone.
  • ethanol is used;
  • the roughness of the matte surface is the same as that of the 3000-mesh metallographic sandpaper, in this embodiment
  • the test was carried out with roughness of 180 mesh, 400 mesh and 5000 mesh, and the obtained result was slightly inferior to the effect of 3000 mesh;
  • the precious metal is silver
  • the evaporation thickness is 20-400 nm, preferably 120 nm, saving materials and achieving the intended purpose
  • the first embodiment of the preparation method of the present invention comprises the following steps: a. cleaning the frosted glass 1 in an organic solvent to clean the frosted surface; the organic solvent of the embodiment is ethanol or acetone. In this embodiment, ethanol is used; the roughness of the matte surface is the same as that of the 3000-mesh metallographic sandpaper. In this embodiment, the roughness of 180 mesh, 400 mesh, and 5000 mesh is also used for the test, and the result is slightly smaller than the 3000 mesh ratio. Poor
  • the frosted glass 1 is placed on the spin coater.
  • the frosted glass 1 is in the form of a sheet and cut into a size of 1 X 1 inch, and the rotation speed of the spin coater is set between 500 and 3000 rpm.
  • the precious metal layer is coated on the frosted surface of the frosted glass 1, and the coating is not uniformly applied when the height is too high or too low; this embodiment adopts 1000 rpm, and tests are performed at 500 and 3000 rpm, and the obtained result is slightly worse than 1000 rpm.
  • the precious metal salt solution is added dropwise for more than 20 s; in this embodiment, the precious metal salt solution is configured as follows: 15 mL 0.
  • the precious metal salt solution and the reducing solution are divided into 8-13 parts according to the total amount, and the steps c and d are repeated for the dropwise addition.
  • the precious metal salt solution and the reducing liquid are divided into 10 parts according to the total amount, 10 times repeated steps c and d were added dropwise, and divided into 8 parts and 13 parts for the test, the results were not significantly different; the precious metal layer 2 was formed on the frosted surface of the frosted glass 1;
  • the diluted solution of the cleaning solution and the AgN0 3 is 0. 5 mL of ammonia water diluted by 1:1;
  • the noble metal layer 2 is formed by using silver.
  • the method is also applicable to gold and copper, except that the reduction and cleaning medium used are different, and will not be described herein.
  • the first embodiment of the preparation method of the present invention comprises the following steps: a. cleaning the frosted glass 1 in an organic solvent to clean the frosted surface; the organic solvent of the embodiment is ethanol or acetone. In this embodiment, ethanol is used; the roughness of the matte surface is the same as that of the 3000-mesh metallographic sandpaper. In this embodiment, the roughness of 180 mesh, 400 mesh, and 5000 mesh is also used for the test, and the result is slightly smaller than the 3000 mesh ratio. Poor
  • the precious metal salt solution is configured as follows: 15 mL 0. 1M AgN0 3 , add 7.5 mL of O. 8M ⁇ , add concentrated ammonia water dropwise to the solution to clarify, the proportion of each component can be added 5 ⁇ ;
  • the reducing solution is reduced or increased according to the need;
  • the precious metal salt solution and the reducing solution are divided into 8-13 parts according to the total amount, and the b-spraying and reduction are repeated by repeating b.
  • This embodiment is divided into 10 parts, and at the same time, it is divided into 8 parts and 13 parts, and the result is obtained. There is no significant difference; a precious metal layer is formed on the frosted surface of the frosted glass 1;
  • the noble metal layer 2 is formed by using silver.
  • the method is also applicable to gold and copper, except that the reduction and cleaning medium used are different, and will not be described herein.
  • the first embodiment of the preparation method of the present invention comprises the following steps: a. cleaning the frosted glass 1 in an organic solvent to clean the surface of the matte, and the organic solvent is ethanol or acetone. Ethanol is used; the metallographic sandpaper is 3000 mesh; in this embodiment, 180 mesh, 400 mesh and 5000 mesh sandpaper are also used for the test, and the obtained result is slightly inferior to the 3000 mesh ratio; b.
  • the precious metal salt solution and the reducing solution are proportional In this embodiment, the precious metal salt solution is configured as follows: 15 mL 0. 1M AgN0 3 , add 7.5 mL of O.
  • the frosted glass 1 forming the noble metal layer is immersed in the secondary distilled water, and washed 3-5 times, this embodiment is 4 times, and this embodiment is 4 times, and the number of times of washing can be changed as needed.
  • the noble metal layer 2 is formed by using silver.
  • the method is also applicable to gold and copper, except that the reduction and cleaning medium used are different, and will not be described herein.
  • the method further includes the method of attaching the precious metal nano material layer 3 on the noble metal layer 2, and the method is applicable to the precious metal layer formed by the above two methods, and specifically includes the following steps:
  • the frosted glass 1 to which the precious metal layer 2 is attached is placed in a liquid adhesive for 10-40 minutes and then taken out. This embodiment uses 20 minutes. In this embodiment, the experiment is further performed by soaking for 10 minutes and soaking for 40 minutes. There is no significant difference between the results obtained; the binder is any one of the hydrolyzate of dithiol, mercapto and aminosilicone. In this embodiment, a hydrolyzate of aminosilicone is used;
  • the surface roughness of the frosted surface of the frosted glass 1 is important, and the surface roughness similar to the 3000 mesh metallographic paper is optimal, and the effect is deteriorated if the temperature is too high or too low. . This is because too high or too low will reduce the number of SERS hotspots.
  • the formation of the enhanced Raman substrate on the surface of the frosted glass can also be formed by coating with a coating machine, including an ion beam sputtering coating machine, a thermal evaporation coating machine or an electron beam evaporation coating machine, generally coating for 10-50 minutes to form 20-400 nm.
  • a coating machine including an ion beam sputtering coating machine, a thermal evaporation coating machine or an electron beam evaporation coating machine, generally coating for 10-50 minutes to form 20-400 nm.
  • the noble metal film layer the coating film may also be plated with two precious metal layers, the first layer is silver, the second layer is gold, the silver layer is thick, and the gold layer is thin; both can achieve the object of the invention.
  • the method for preparing a surface-enhanced Raman substrate of the present invention comprises the following steps:
  • the base layer is a base layer for forming a substrate, and the base layer 1 may adopt any of the already disclosed base layers in the prior art. , including organic materials, etc.;
  • step a The surface-enhanced Raman substrate formed in step a is stored in an inert gas.
  • the base layer 1 needs to be cleaned as necessary to ensure the adhesion effect.
  • a superhydrophobic structure 2 is first formed on the surface of the base layer 1, and the surface enhancement layer 3 of the nano silver particles is attached to the surface of the superhydrophobic structure; it may be formed by direct surface treatment or may be added with superhydrophobicity.
  • Membrane using a superhydrophobic structure to make the aqueous sample form approximately spherical, increasing the storm
  • the surface area exposed to the air not only makes the solvent easy to volatilize, but also achieves purification; and the concentrated concentration is at the bottom, and the components in the sample are concentrated, which is beneficial to improve the detection accuracy of trace and ultra-trace components; superhydrophobic structure and nano-Ag
  • the enhancement effect is better; the outer surface of the outermost self-assembled nanomaterial layer can also be modified to separate and enrich the sample self-assembled molecular film; when it is produced, it has the functions of separation and enrichment and internal reference, forming a matching High sensitivity and high reliability SERS substrate.
  • the roughness of the surface of the base layer 1 for forming the superhydrophobic structure 2 is equivalent to the surface roughness of the metallographic sandpaper of 180 to 5000 mesh; having a good bonding strength, and capable of forming a superhydrophobic structure by itself,
  • the manufacturing cost is saved and the manufacturing process is saved; in this embodiment, frosted glass or metallographic sandpaper is used; the etching formation in the prior art can be avoided, and the above structure of the prior art is required to be etched on the surface of the solid base material.
  • the formation of the base layer and the subsequent growth of the substrate have the disadvantages of high cost, long production cycle, and difficulty in adapting to mass production; and the solid base material is hard and brittle, easy to be damaged, and does not have the characteristics of adapting to the orientation according to environmental conditions, etc. Disadvantages.
  • the superhydrophobic structure is directly formed on frosted glass or metallographic sandpaper, and the etched surface is not required to be formed on the base layer.
  • the formed substrate also has excellent reinforcing effect and high analytical sensitivity, and is suitable for ultra-trace samples. Inspection, most prominently, the SERS substrate is simple to manufacture, short in production cycle, low in cost, and suitable for mass production. Since there is no etched surface, the application will not interfere with Raman enhancement and analysis process. The prior art SERS substrate preparation method cannot be achieved.
  • the base layer 1 is a smooth groove-shaped structure, and the super-hydrophobic structure 2 is located on the inner surface of the smooth groove; when used, the sample to be tested is directly located at the bottom of the bottom by gravity. With automatic positioning effect, improve work efficiency.
  • the inert gas is nitrogen gas, which is low in cost and easily available.
  • the nano silver particle surface enhancement layer forming process comprises the following steps: I.
  • the base layer is placed in a liquid adhesive for 10-40 minutes and then taken out; this embodiment takes 20 minutes.
  • the experiment is further performed by immersing for 10 minutes and immersing for 40 minutes, and the results obtained are not significantly different;
  • the binder is any one of hydrolyzed products of dithiol, mercapto and aminosilicone.
  • II. Wash with secondary deionized water and immerse in silver nanomaterial water mixture for 60-180 minutes; this embodiment uses 100 minutes, in this embodiment, it is also immersed for 60 minutes and soaked for 80 minutes.
  • the silver nanomaterial aqueous mixture refers to a water mixed liquid formed by reducing silver nanoparticles in the silver nitrate solution and trisodium citrate reaction;
  • the surface roughness of the frosted surface of the base layer is important, and the surface roughness similar to that of the 3000 mesh metallographic paper is optimal, and the effect is deteriorated if the surface is too high or too low. This is because too high or too low will reduce the number of SERS hotspots.
  • FIG. 8 is a schematic diagram of the principle of the spectrometer of the present invention
  • FIG. 9 is an enlarged view of the sample at the confocal point of the spectrometer
  • FIG. 10 is a longitudinal sectional view of the head assembly of the spectrometer
  • FIG. 11 is a cross-sectional view taken along line A of FIG. 10
  • FIG. 12 is a cross-sectional view taken along line A of FIG.
  • the dual-range Raman spectrometer of the present embodiment comprises a Raman spectrometer body 6 and a detection head assembly, the detection head assembly comprising a casing 12 and a dual optical path assembly disposed in the casing 12,
  • the optical path assembly includes at least one convex lens 17 and one concave mirror 19 disposed along the direction of the excitation light.
  • the convex lens 17 may be several, which does not affect the realization of the object of the present invention; the convex lens 17 is confocal with the concave mirror 19, and the sample to be detected 9 is located at the focal point of the convex lens 17 and the concave mirror 19, and the excitation light emitted by the light source 7 is incident after being condensed by the convex lens 17, and then the sample 9 to be detected is excited, and after being reflected by the concave mirror 19, the sample 9 is again excited to realize excitation light.
  • the secondary utilization while enhancing the signal intensity of the Raman effect of the components in the sample 9 to be tested.
  • the housing 12 is provided with a pick-and-place port 12a for picking up and dropping a sample, and the pick-and-place port 12a is provided with a sealing cover 15 for blocking light in an openable manner; .
  • the sealing cover 15 is hingedly disposed on the housing 12 to form a door-shaped structure. As shown, the sealing cover 15 is hinged to the side of the housing 12, and the end of the body is buckled. 14 buckled, A light-shielding seal is formed; a cover of the seal cover 15 is larger than the pick-and-place port 12a and a light-shielding pad 16 is disposed between the radially outer surface of the edge of the pick-and-place port 12a. As shown, the light-shielding pad 16 may be made of a flexible material such as rubber.
  • the utility model has the advantages of simple structure, easy operation, easy positioning, and shielding from the outside through the light shielding pad, which is favorable for the accuracy of the detection result.
  • a bracket or a tray for placing the sample 9 to be detected and having the sample 9 to be detected located at the focal point of the convex lens 17 and the concave mirror 19 is provided in the housing 12, and the tray or tray is at least at the convex lens 17 Confocal light transmission with the concave mirror 19; in this embodiment, the bracket or the tray can be made transparent as a whole to reduce interference with the excitation light.
  • the bracket or tray is fixedly connected to the sealing cover 15 can be removed or placed with the sealing cover 15 open, as shown, the bracket or tray is fixedly connected to the sealing cover 15 through the connecting frame 13; It is convenient to take out and put in the sample, and the operation is simple.
  • the fixed position of the tray or the bracket is realized by the orientation of the sealing cover 15, and the sample 9 to be detected is placed at the confocal point to realize double path excitation;
  • the bracket or the tray is fixedly disposed in the housing; has a relatively stable positioning effect, and does not affect the positioning accuracy with the long period of use of the device.
  • the tray or the tray is a smooth groove-shaped tray 18 (ie, the substrate of the present invention), the opening of the smooth groove-shaped tray 18 is upward and the bottom point of the bottom is located at the focal point of the convex lens 17 and the concave mirror 19
  • a hemispherical structure tray is used, which is similar to a bowl shape; after the sample 9 to be tested is placed in a smooth grooved tray, the gravity is directly located at the lowest point of the bottom, and the effect of automatic positioning is improved, thereby improving work efficiency.
  • the inner surface of the smooth grooved tray 18 is a superhydrophobic structure, which may be formed by direct surface treatment or may be a superhydrophobic film; using a superhydrophobic structure, the aqueous solution sample is formed into a substantially spherical shape, and the exposure is increased.
  • the surface area in the air not only makes the solvent easy to volatilize, but also achieves purification; and it is concentrated at the bottom, and the components in the sample are concentrated, which is beneficial to improve the detection accuracy of trace and ultra-trace components.
  • the surface of the superhydrophobic structure is grown with self-assembled nano-materials 10 for surface enhancement.
  • self-assembled gold, silver, copper nanomaterials, etc. can generate surface enhanced Raman scattering (SERS).
  • SERS surface enhanced Raman scattering
  • the metal, both located in the superhydrophobic film, is best enhanced by the enhancement effect of Ag; the outermost self-assembly
  • the outer surface of the nano-material layer can also be modified to separate and enrich the sample self-assembled molecular film; when fabricated, it has the functions of separation and enrichment and internal reference, and forms a SERS substrate with high sensitivity and high reliability.
  • the excitation light emitted by the light source 7 introduces hot light for volatilizing the solvent of the sample to be detected, and the thermal light can heat the light which evaporates the water solvent; in this embodiment, infrared light is used as the thermal light, Infrared light volatilizes the sample to be tested to increase the relative content of the components, facilitating the detection and making the results accurate.
  • the housing 12 is provided with a dichroic mirror 4 for introducing excitation light and extracting Raman signal light, which simplifies the structure and facilitates carrying; the dichroic mirror 4 is reflected as shown in the figure.
  • the Raman optical signal enters the body of the Raman spectrometer through a convex lens 5 for spectral analysis.
  • a notch filter is disposed between the dichroic mirror 4 and the convex lens 5, and the purpose is to eliminate the excitation source to Raman. The effect of the signal.
  • the detection method of the invention has high sensitivity and high reproducibility, and the detection method of the highly sensitive and highly reproducible surface enhanced Raman spectrum comprises the following steps:
  • the sample to be tested is uniformly coated on the SERS substrate; the coating method may be distributed in a dot-like manner or distributed in a plane;
  • c. Perform multi-point detection on the sample with the sample on the SERS substrate and repeat the step b; d. Using the acquired spectral information of the multi-point sample to be tested, go to the background and average, according to the average The measured spectral information of the multi-point sample to be tested removes the minimum and maximum values, and the spectral information of the multi-point sample to be tested with the minimum and maximum values is removed and averaged to obtain the Raman spectrum information of the sample to be tested.
  • a Raman spectroscopy database is available to obtain qualitative or/and quantitative information on the sample to be tested; the average is calculated from the data obtained.
  • step a the sample to be detected is distributed on the surface of the SERS substrate on the SERS substrate; the distribution pattern of the structure solution facilitates random selection of monitoring points, and the operation is relatively convenient.
  • step c the sample is in the range of the sample on the SERS substrate.
  • Point detection is achieved by moving the SERS substrate in the same plane; easy to operate, avoid refocusing, and improve work efficiency.
  • the SERS substrate comprises a base layer and a surface reinforcing layer, the base layer is frosted glass, sandpaper or filter paper, and the surface is adhered to the frosted surface of the frosted glass, the working surface of the sandpaper, the surface of the filter paper or Lens paper, etc.; this embodiment uses a frosted glass base layer.
  • Figure 13 is a schematic view of the fine adjustment device of the present invention
  • Figure 14 is a plan view of Figure 13
  • Figure 15 is a trimming device with a housing
  • Figure 16 is a cross-sectional view taken along line CC
  • Figure 17 is an enlarged view of Figure 16D
  • the invention also discloses a fine adjustment device for highly sensitive, highly reproducible surface enhanced Raman spectroscopy, comprising a SERS substrate holder for placing a SERS substrate and a drive for driving the SERS substrate to move the substrate in the detection plane
  • the component, the detection plane refers to the plane where the SERS photofocus point is located, and there are more planes passing through the point, just driving the SERS base frame to move the substrate in any one of the planes.
  • the SERS base frame includes a base assembly and a base tray 3c on the base assembly, the base tray 3c is for placing a base;
  • the base assembly includes a carriage 2c and a base lc, the base
  • the tray 3c is disposed on the carriage 2c in such a manner as to be rotatable about its own axis, the carriage 2c being disposed on the base lc in a reciprocable manner in the detection plane;
  • the drive assembly includes means for driving the base tray 3c about its own axis The rotating rotary drive assembly and the reciprocating drive assembly for driving the carriage 2c to reciprocate in the detection plane;
  • the base assembly and the drive assembly drive the base tray 3c for rotation and reciprocation, so that the entire substrate has no blind spots for detection.
  • the rotary drive assembly includes a rotary drive motor mounted on the carriage 2c, a rotary drive gear 5c driven by the rotary drive motor 6c, and a rotation of the outer circumference of the base tray 3c and meshed with the rotary drive gear 5c.
  • the base tray 3c and the rotary driven gear 4c are integrally formed, and the structure is simple and easy to manufacture;
  • the reciprocating drive assembly includes a reciprocating drive motor 9c mounted to the base lc, a ball screw 8c driven by the reciprocating drive motor 9c, and a nut 7c that is drivingly coupled to the ball screw 8c and disposed on the carriage 2c; the gear meshing pair and the ball are used
  • the drive structure of the lead screw is precise and controllable, and the detection point is controlled by the method of driving the process to make the detection point controllable.
  • the fine adjustment device further includes a housing 10c, and the housing 10c is provided for pick and place
  • the pick-and-place port 10ca of the sample, the pick-and-place port 10ca is provided with a sealing cover 12c for light-shielding in an openable manner;
  • the base lc is fixedly disposed on the sealing cover 12c, and in fact, the base lc is fixed to the sealing cover 12c and After the sealing cover 12c is closed, the SERS base frame a is entirely located in the casing 10c, and the base tray 3c is located in the detecting plane of the Raman spectrometer;
  • the base tray 3c is fixedly connected to the sealing cover 12c and can be opened and closed with the sealing cover 12c.
  • the metal tray 3c is fixedly connected to the sealing cover 12c through the connecting frame 14 as shown in the figure; the sample is taken out and placed, the operation is simple, and the tray or the bracket is realized by the orientation of the sealing cover 12c. Fixed positioning;
  • the base lc can also be fixedly disposed in the housing 10c and fixedly connected to the housing 10c.
  • the base tray 3c can be located in the detection plane of the Raman spectrometer, and the object of the invention can also be achieved.
  • the sealing cover 12c is hingedly disposed on the casing 10c to form a gate-shaped structure. As shown, the sealing cover 12c is hinged to the side of the casing 10c, and the end of the body is buckled. 11 is fastened to form a light-shielding seal; a sealing cover 12c having a cover size larger than the pick-and-place port 10ca and a radially outer surface of the edge of the pick-and-place port 10ca is provided with a light-shielding pad 13c. As shown, the light-shielding pad 13c can be used. Flexible material such as rubber; simple structure, easy to operate, easy to position, and shielded from the outside by a light-shielding pad, which is conducive to the accuracy of the detection results.
  • the base lc is frame-shaped, and the corresponding two sides of the frame form two parallel tracks, and the carriage 2c forms two carriage branches corresponding to the track and slidingly matched with the same, as shown in the figure.
  • the two carriage branches respectively form a chute and are directly slidably engaged with the rail through the chute; the nut extends laterally to form an extension and is fixedly connected to the two carriage branches respectively; the frame structure is adopted to facilitate the passage of the laser It is especially suitable for the dual-path Raman spectrometer to further improve the sensitivity to adapt to the detection of trace samples.
  • the reciprocating drive motor 9c and the ball screw 8c are located between the two rails for driving the nut.
  • the bottom of the base tray is coaxially provided with a circular protrusion and the two carriage branches are respectively provided with a sliding groove for rotating cooperation with the circular protrusion, that is, the bottom of the base tray is formed Similar to the circular circular protrusion, the circular protrusion is placed on the two carriage branches, and the carriage branch is provided with a sliding groove for accommodating the circular protrusion, forming a sliding fit and capable of restraining the base tray Radial displacement; the base tray can only be rotated relative to the carriage to ensure the controllability of the detection point; as shown in the figure, the rotary drive motor is fixed to one of the carriage branches, and the structure is simple and compact; Block lc passes along its longitudinal The two connecting brackets 14 are connected to the sealing cover 12c.
  • the base tray 3c is transparent or centrally placed; to accommodate the dual-path Raman spectrometer (application number: 201210358471), to obtain a higher sensitivity detection result.
  • the fine adjustment device of the invention drives the rotary drive motor and the reciprocating drive motor to drive the base tray to reciprocate, rotate and combine the same, thereby realizing the fine adjustment of the substrate tray and the substrate, thereby realizing the detection of the sample distributed on the substrate;
  • the drive motor and the rotary drive motor are both servo motors.
  • the automatic control system automatically controls and drives the rotation according to the input external command. The sample detection of the set position has been obtained, and will not be described here.
  • FIG. 18 is another schematic structural view of the fine adjustment device of the present invention.
  • the structure of the mechanism is different from that of the above embodiment only in that the driving manner of the substrate tray is different, the substrate tray is no longer rotated, but is on the X-axis and the y-axis.
  • the upper and lower reciprocating motions are fine-tuned to meet the needs of the present invention, and the specific differences are as follows:
  • the SERS substrate holder includes a base assembly and a substrate tray on the base assembly, the base tray is provided with a SERS substrate, the SERS substrate includes a base layer and a surface reinforcing layer, the base layer is frosted glass, sandpaper, filter paper Or a lens paper;
  • the base assembly includes a y-axis carriage and a base, and the structure of the y-axis carriage and the base is the same as that of the carriage and the base of the above embodiment;
  • the base tray has an inner edge in the detection plane
  • the X-axis reciprocating manner is disposed on the y-axis carriage, the y-axis carriage is disposed on the base in a reciprocable manner along the y-axis in the detection plane;
  • the drive assembly includes a base tray for driving along the X-axis a reciprocating X-axis drive assembly and a y-axis drive assembly for driving the carriage to reciprocate along the y-axis.
  • the y-axis drive assembly is identical to the reciprocating drive assembly of the above embodiment, that is, the drive of the y-axis carriage is completely
  • the carriage driving of the above embodiment is the same, and will not be described again here;
  • the y-axis carriage is provided with two X-axis rails 15c, and the base tray is matched with the two X-axis rails 15c along the two X-axis rails 15c on the x-axis.
  • Reciprocating motion and the X-axis drive motor 6ca is provided on the y-axis carriage, and the x-axis drive motor 6ca drives the x-axis ball screw 5ca to rotate, and the X-axis nut 4ca on the base tray is reciprocated along the X-axis to drive the base tray. Reciprocating along the X axis.

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Abstract

一种表面增强拉曼基底、制备方法、拉曼光谱仪及检测方法和微调装置，基底采用在具有微米数量级粗糙度的磨砂玻璃（1）上直接形成贵金属表面增强层（2），不需要在基础层上形成刻蚀表面，且不需要将贵金属层粗糙化，形成的基底同样具有极好的增强效果和超高的分析灵敏度，适用于超痕量样品的检测；纳米颗粒的基底采用惰性气体保护保存的方式；拉曼光谱仪实现单光源双光程激发，同时，也能在聚焦透镜（凸透镜）（17）有效接收立体角内收集到激光激发的样品向前散射的拉曼光谱，在不改变现有拉曼光谱仪光源的前提下，增加激发光的利用效率，充分利用激发能量；并且检测方法具有高重现性和超高的分析灵敏度，适用于超痕量样品的检测。

Description

表面增强拉曼基底、 制备方法、 拉曼光谱仪及检测方法和微调装置 技术领域
本发明涉及分子光谱分析检测领域， 具体涉及一种表面增强拉曼基底、 制备方法、 拉曼光谱仪及检测方法和微调装置。
背景技术
光照射到物质上发生弹性散射和非弹性散射， 弹性散射的散射光是与 激发光波长相同的成分， 非弹性散射的散射光有比激发光波长长的和短的 成分， 称之为拉曼效应， 所获得的光谱称之为拉曼光谱。 拉曼光谱属于分 子振动光谱， 是物质分子的指紋， 依据拉曼效应制作的拉曼光谱仪可以用于准 确定性鉴别样品。拉曼光谱的分析方法一般不需要对样品进行前处理， 并且 在分析过程中操作简便， 测定时间短， 是一种可以对样品同时进行定性和定 量的分析技术， 具有极为广泛的应用前景。 但其缺点是灵敏度较低。
表面增强拉曼光谱 （SERS ) 是一种在 20世纪 90年代随着纳米技术发展而 发展起来的高灵敏度光谱分析技术。 与拉曼光谱一样， SERS可以用于准确定性 鉴别样品。 SERS 具有超高的分析灵敏度， 较普通拉曼分析灵敏度提高约 6-10 个数量级， 可分析小到单分子， 大到细胞水平的研究对象。 现有技术中， SERS 检测一般有三种方式： ①在样品溶液中添加纳米材料， 并诱导纳米粒子聚集以 形成 SERS热点； ②在表面增强拉曼基底上直接滴加样品溶液， 让其铺展、干燥 并进行分析； ③将 SERS光极插入样品溶液采集信号等。
现有技术中， 表面增强拉曼基底上直接滴加样品溶液属于较为普遍采用的 方式， 该方式中， 表面增强拉曼基底一般采用硬质载玻片、 硅片等固体基础物 质， 表面生长具有一定粗糙度的物质， 再通过蒸镀贵金属形成基底； 或直接在 硬质载体上附着贵金属纳米材料， 能够达到较好的增强效果。 但是现有技术的 上述结构需要在固体基础物质表面刻蚀而形成基础层， 其后生长基质， 具有成 本高， 制作周期长， 难以适应批量生产的缺点； 并且固体基础物质较硬且脆， 易于损坏， 使用时不具有根据环境条件适应方位的特点。
现有技术中，在制作 SERS基底上的增强层较多的使用生长纳米银颗粒的方 式， 成本以及增强效果综合性价比较高。 但是生长了纳米银颗粒的基底长期保 存后会在纳米银表面产生氧化膜， 而被氧化后的纳米银颗粒其表面性质发生变 化，使得 SERS基底增强效果衰减较为明显，一般在两天左右即达不到期望的增 强效果； 导致银金属以及基底材料的浪费。
现有技术的拉曼光谱仪， 激发光射至样品后对样品激发， 并采集样品反射 光及分子振动产生的散射光， 对光谱进行分析， 得到含量及成分等定性、 定量 数据。
由于激发光只对样品激发一次， 因而激发光的利用效率较低， 激发能量利 用不够充分， 对于超痕量成分的分析检测达不到所期望的效果。
为解决现有技术中拉曼效应在检测分析领域灵敏度不高的问题， 出现 了表面增强拉曼光谱分析技术。 表面增强拉曼光谱（SERS )是一种在 20世纪 90年代随着纳米技术发展而发展起来的高灵敏度光谱分析技术。与拉曼光谱一 样， SERS可以用于准确定性鉴别样品。 SERS具有超高的分析灵敏度， 较普通拉 曼分析灵敏度提高约 6-10个数量级，可分析小到单分子，大到细胞水平的研究 对象。
实际应用中， SERS基底上直接滴加样品溶液属于较为普遍采用的方式， 该 方式中， SERS基底一般采用硬质载玻片、 硅片等固体基础物质， 表面生长具有 一定粗糙度的物质， 再通过蒸镀贵金属形成基底； 或直接在硬质载体上附着贵 金属纳米材料， 能够达到较好的增强效果。 但是现有技术的上述结构需要在固 体基础物质表面刻蚀而形成基础层， 其后生长基质， 具有成本高， 制作周期长， 难以适应批量生产的缺点； 并且固体基础物质较硬且脆， 易于损坏， 使用时不 具有根据环境条件适应方位的特点。
为解决上述问题， 出现了一种 SERS 基底， 采用在具有微米数量级粗糙度 的磨砂玻璃、 砂纸或者滤纸等表面上直接形成贵金属表面增强层， 不需要在基 础层上形成刻蚀表面， 且不需将贵金属层粗糙化， 形成的基底同样具有极好的 增强效果和超高的分析灵敏度， 适用于超痕量样品的检测； 该结构的 SERS 基底的制作简单、 生产周期短、 成本较低， 适用于批量化生产。 但是， 由于 该基底的基础层具有粗糙度， SERS照射并反射后会出现在一定范围内的不规则 突变， 因而在进行检测时具有一定的离散性， 重现性较差， 导致检测结果重复 精度不高， 影响了该基底的应用。
因此， 需要一种表面增强拉曼基底以及制备方法、 光谱仪、 检测方法、 微 调装置， 不但具有超高的分析灵敏度， 适用于超痕量样品的检测， 而且制作 简单、 生产周期短、 成本低， 适于批量生产， 为进一歩促进 SERS技术在国土 安全， 环境监测， 食品安全及医疗卫生等领域得到更广泛的应用提供条件； 该 基底的制备使得 SERS基底进行长时间保存依然具有较好的增强效果； 采用该 基底的拉曼光谱仪增加激发光的利用效率， 充分利用激发能量， 使其适用于 超痕量样品的检测， 并得到期望的效果； 并采用的检测方法不但具有超高的 分析灵敏度， 适用于超痕量样品的检测， 还具有高重现性， 准确的获得检测 结果， 而且操作简单、 检测周期短， 适用于该方法的微调装置结构简单， 成 本较低。
发明内容
有鉴于此， 本发明的目的是提供一种高性能和廉价的表面增强拉曼基底、 制备方法、 拉曼光谱仪及检测方法和微调装置， 不但具有超高的分析灵敏度， 适用于超痕量样品的检测， 而且制作简单、 生产周期短、 成本低， 适于批量 生产， 为进一歩促进 SERS技术在国土安全， 环境监测， 食品安全及医疗卫生 等领域得到更广泛的应用提供条件； 该基底的制备使得 SERS基底进行长时间 保存依然具有较好的增强效果； 采用该基底的拉曼光谱仪增加激发光的利用 效率， 充分利用激发能量， 使其适用于超痕量样品的检测， 并得到期望的效 果； 并采用的检测方法不但具有超高的分析灵敏度， 适用于超痕量样品的检 测， 还具有高重现性， 准确的获得检测结果， 而且操作简单、 检测周期短， 适用于该方法的微调装置结构简单， 成本较低。 本发明的磨砂玻璃表面增强拉曼基底， 包括基础层和表面增强层， 所述基 础层为磨砂玻璃， 表面增强层附着在磨砂玻璃的磨砂表面。
进一歩， 所述表面增强层为贵金属层； 所述贵金属层附着有贵金属纳米材 料层；
进一歩，所述磨砂玻璃的磨砂表面的粗糙度相当于 180到 5000目的金相砂 纸表面粗糙度， 所述贵金属层厚度为 20-400nm; 所述贵金属层为金、 银、 铜中 的任意一种， 所述贵金属纳米材料层为金、 银、 铜中的一种或两种以上的纳米 材料层； 所述磨砂玻璃为弧形凹槽形结构， 所述磨砂表面为弧形凹槽形结构的 内表面。
本发明还公开了一种表面增强拉曼基底的制备方法， 包括下列歩骤： a. 在基础层表面附着表面增强层形成表面增强拉曼基底；
b.将歩骤 a中形成的表面增强拉曼基底置于惰性气体内保存。
5.根据权利要求 4所述的表面增强拉曼基底的制备方法， 其特征在于： 歩骤 a中， 首先在基础层表面形成超疏水结构， 所述贵金属纳米材料层附 着于超疏水结构表面； 所述基础层为平滑凹槽形结构， 所述超疏水结构位于平 滑凹槽内表面。
进一歩， 歩骤 a中， 纳米银颗粒表面增强层形成过程包括下列歩骤： I . 将基础层置于液体粘合剂中浸泡 10-40分钟后取出；
II .用二次去离子水清洗， 并置于银纳米材料水混液中浸泡 60-180分钟；
III.重复歩骤 I和 II 2-8次后以去离子水清洗并吹干；
IV.在氮气氛或真空中 80-160°C干燥 30-80分钟。
本发明还公开了一种拉曼光谱仪， 包括拉曼光谱仪本体和检测头组件， 所 述检测头组件包括外壳和设置在外壳内的双光路组件， 双光路组件至少包括沿 激发光方向设置的一个凸透镜和一个凹面镜， 所述凸透镜与凹面镜共焦， 待检 测样品位于凸透镜与凹面镜共焦点。
进一歩所述壳体设有用于取放样品的取放口， 取放口以可开合的方式设有 用于遮光的密封盖； 所述密封盖以铰接的方式设置于壳体形成门形结构， 密封盖的封盖尺寸大 于取放口且与取放口的边缘径向外表面之间设有遮光垫； 所述壳体内设有用于 放置待检测样品并使待检测样品位于凸透镜与凹面镜共焦点的托架或托盘， 所 述托架或托盘至少在凸透镜与凹面镜共焦点透光； 所述托架或托盘固定连接于 密封盖可随密封盖开合而移出或放入； 或者， 所述托架或托盘固定设置于壳体 内。
进一歩， 所述托盘或托架为平滑凹槽形托盘， 平滑凹槽形托盘的开口向上 且其底部最低点位于凸透镜与凹面镜共焦点； 所述平滑凹槽形托盘内表面为超 疏水结构； 所述超疏水结构表面生长有用于表面增强的自组装纳米材料； 激发 光内引入用于使待检测样品溶剂挥发的热光； 所述壳体内设有用于引入激发光 并将拉曼信号光引出的二向色镜。
本发明还公开了一种表面增强拉曼光谱的检测方法， 包括下列歩骤： a. SERS基底上均匀涂敷待检测样品；
b. 利用光源经照明系统照射 SERS基底上其中一点待检测样品并获取其拉 曼光谱；
c在 SERS基底上具有样品的范围内对的样品进行多点检测并重复歩骤 b; d. 利用获取的多点待测样品的光谱信息， 去背景后求平均值， 根据该平均 值将测得的多点待测样品的光谱信息去除最小值和最大值， 将去除最小值和最 大值的多点待测样品的光谱信息再求平均值， 获取被测样品的拉曼光谱信息， 对照已有拉曼光谱数据库， 定性或 /和定量的得出被测样品的信息。
进一歩，歩骤 a中，所述待检测样品在 SERS基底上呈面状均匀分布于 SERS 基底表面；歩骤 c中，在 SERS基底上具有样品的范围内对样品进行多点检测通 过在同一平面内移动 SERS基底实现;所述 SERS基底包括基础层和表面增强层， 所述基础层为磨砂玻璃、 砂纸、 滤纸或镜头纸， 所述表面增强附着在磨砂玻璃 的磨砂表面、 砂纸的工作表面或滤纸的表面。
本发明还公开了一种用于表面增强拉曼光谱的微调装置， 包括用于放置 SERS基底的 SERS基底架和用于驱动 SERS基底架使基底在检测平面内移动的驱 动组件。
进一歩， SERS基底架包括基座组件和位于基座组件上的基底托盘， 所述基 底托盘上放置有 SERS基底， 所述 SERS基底包括基础层和表面增强层， 所述基 础层为磨砂玻璃、 砂纸、 滤纸或镜头纸； 所述基座组件包括拖板和基座， 所述 基底托盘以可绕自身轴线转动的方式设置于拖板， 所述拖板以可在检测平面往 复运动的方式设置于基座； 所述驱动组件包括用于驱动基底托盘绕自身轴线转 动的转动驱动组件和用于驱动拖板在检测平面往复运动的往复驱动组件； 进一歩， 所述转动驱动组件包括安装于拖板的转动驱动电机、 由转动驱动 电机驱动的转动主动齿轮和位于基底托盘外圆并与转动主动齿轮啮合传动的转 动从动齿轮； 往复驱动组件包括安装于基座的往复驱动电机、 由往复驱动电机 驱动的滚珠丝杠和与滚珠丝杠驱动配合并设置于拖板的螺母； 所述微调装置还 包括壳体， 所述壳体设有用于取放样品的取放口， 取放口以可开合的方式设有 用于遮光的密封盖； 所述基座固定设置于密封盖内， 并使基底托盘位于拉曼光 谱仪的检测平面内； 或者， 所述基座固定设置于壳体内， 并使基底托盘位于拉 曼光谱仪的检测平面内； 所述基座为框形， 且框形其中相对应的两边形成两条 并列的轨道， 拖板形成两条与轨道对应且与其滑动配合的拖板分支， 所述螺母 横向延伸且分别固定连接于两个拖板分支； 所述基底托盘底部与其同轴设有圆 形凸起且两个拖板分支上分别设有用于与圆形凸起转动配合的滑槽；
进一歩， SERS基底架包括基座组件和位于基座组件上的基底托盘， 所述基 底托盘上放置有 SERS基底， 所述 SERS基底包括基础层和表面增强层， 所述基 础层为磨砂玻璃、 砂纸、 滤纸或镜头纸； 所述基座组件包括 y轴拖板和基座， 所述基底托盘以可在检测平面内沿 X轴往复运动的方式设置于 y轴拖板， 所述 y轴拖板以可在检测平面内沿 y轴往复运动的方式设置于基座； 所述驱动组件 包括用于驱动基底托盘沿 X轴往复运动的 X轴驱动组件和用于驱动拖板沿 y轴 往复运动的的 y轴驱动组件。
本发明的有益效果： 本发明的表面增强拉曼基底、 制备方法、 拉曼光谱仪 及检测方法和微调装置； 基底采用在具有微米数量级粗糙度的磨砂玻璃上直接 形成贵金属表面增强层， 不需要在基础层上形成刻蚀表面， 且不需将贵金属层 粗糙化， 形成的基底同样具有极好的增强效果和超高的分析灵敏度， 适用于 超痕量样品的检测， 最为突出的是， 表面增强拉曼基底的制作简单、 生产周 期短、 成本较低， 适用于批量化生产， 这是现有技术的表面增强拉曼基底制 备方法所不能达到的。
基底的生产方法中， 纳米颗粒的基底采用惰性气体保护保存的方式， 保证 长周期保存后其表面不被氧化， 使得基底进行长时间保存用于 SERS基底依然 具有较好的增强效果， 使得基底具有超高的分析灵敏度， 适用于超痕量样品 的检测， 而且制作简单、 生产周期短、 成本低， 适于批量生产， 特别针对纳 米银颗粒， 从而节约成本；
拉曼光谱仪采用凸透镜与凹面镜相结合的结构， 且待检测样品位于其共焦 点， 将激发过样品的激发光反射后再次激发样品， 实现单光源双光程激发， 同 时， 也能在聚焦透镜 （凸透镜） 有效接收立体角内收集到激光激发的样品前向 散射的拉曼光谱， 在不改变现有拉曼光谱仪光源的前提下， 增加激发光的利 用效率， 充分利用激发能量， 使其适用于超痕量样品的检测， 可在现场分析 中实现超高灵敏度即测即显示分析， 可对超痕量样品给出定性定量结果， 并得 到期望的效果， 具有较低的成本。
采用多次检测取平均值的检测方法， 避免现有技术的检测方法离散性较高 的问题， 具有高重现性和超高的分析灵敏度， 适用于超痕量样品的检测， 还 能够准确的获得检测结果， 而且操作简单、 检测周期短； 本方法采用微调装 置实现基底的移动而进行多点检测， 该装置结构简单， 成本较低， 操作简单 方便； 上述方法及装置为进一歩促进 SERS技术在国土安全， 环境监测， 食品安 全及医疗卫生等领域得到更广泛的应用提供条件。 附图说明
下面结合附图和实施例对本发明作进一歩描述。
图 1为本发明基底第一种实施例结构示意图； 图 2为本发明基底第二种实施例结构示意图（附着有贵金属纳米材料层）； 图 3为 5 L 1 ppm的三唑磷 (5 ng) ,与 1200目金相砂纸粗糙度相同的磨砂 玻璃为基础层形成的表面增强拉曼基底， 通过 785 nm激发光的便携式拉曼光 谱仪进行测试获得的光谱图；
图 4为 SxlO^ mol /1奈尔蓝，以 3000目金相砂纸粗糙度相同的磨砂玻璃 为基础层形成的表面增强拉曼基底，通过 632.8 nm激发光的便携式拉曼光谱仪 进行测试获得的光谱图；
图 5为 400 目金相砂纸粗糙度相同的磨砂玻璃为基础层蒸镀 120nm银的 SEM照片；
图 6为 3000目金相砂纸粗糙度相同的磨砂玻璃为基础层蒸镀 120nm银的 SEM照片；
图 7为 5000目金相砂纸粗糙度相同的磨砂玻璃为基础层蒸镀 120nm银的 SEM照片；
图 8为本发明拉曼光谱仪的原理示意图；
图 9为拉曼光谱仪共焦点的样品处放大图；
图 10为拉曼光谱仪检测头组件纵向截面图；
图 11为图 10沿 A向截面图；
图 12为图 11B处放大图；
图 13为本发明微调装置的结构示意图；
图 14为图 13的俯视图；
图 15为带有壳体的微调装置；
图 16为图 15沿 C-C向剖视图；
图 17为图 16D处放大图；
图 18为本发明微调装置另一结构示意图。
具体实施方式
图 1为本发明基底第一种实施例结构示意图， 图 2为本发明基底第二种实 施例结构示意图（附着有贵金属纳米材料层），图 3为 5 L 1 ppm的三唑磷 (5 ng) , 与 1200目金相砂纸粗糙度相同的磨砂玻璃为基础层形成的表面增强拉曼基底， 通过 785 nm激发光的便携式拉曼光谱仪进行测试获得的光谱图；图 4为 5xl0—1Q mol 1奈尔蓝， 以 3000 目金相砂纸粗糙度相同的磨砂玻璃为基础层形成的表 面增强拉曼基底，通过 632.8 nm激发光的便携式拉曼光谱仪进行测试获得的光 谱图； 图 5为 400目金相砂纸粗糙度相同的磨砂玻璃为基础层蒸镀 120nm银的 SEM照片； 图 6为 3000目金相砂纸粗糙度相同的磨砂玻璃为基础层蒸镀 120nm 银的 SEM照片； 图 7为 5000 目金相砂纸粗糙度相同的磨砂玻璃为基础层蒸镀 120nm银的 SEM照片； 如图所示： 本实施例的磨砂玻璃表面增强拉曼基底， 包 括基础层和表面增强层， 所述基础层为磨砂玻璃， 表面增强附着在磨砂玻璃的 磨砂表面； 磨砂玻璃即毛玻璃， 为现有技术的一面平滑， 另一面为类似于金相 砂纸砂纸一样粗糙的玻璃； 本发明中， 该磨砂玻璃为玻璃片。
本实施例中， 所述表面增强为贵金属层。
本实施例中， 所述贵金属层附着有贵金属纳米材料层。
所述贵金属层为金、 银、 铜中的任意一种， 所述贵金属纳米材料层为金、 银、 铜中的一种或两种以上的纳米材料层。
本实施例中，所述磨砂玻璃的磨砂表面的粗糙度相当于 180到 5000目的金 相砂纸表面粗糙度， 本实施例的范围优选为 3000目的粗糙度； 通过图 4、 图 5 和图 6的 SEM照片对比可得出， 3000目的粗糙度最优；本实施例的上述方案中， 独立形成磨砂玻璃表面增强拉曼基底的完整结构， 利用磨砂玻璃制成， 具有成 本低、 重现性好， 使用性能较强和可批量生产的特点， 这是其它表面增强拉曼 基底难以实现的。
本发明基底的另一实施例， 即是在上述实施例的所述贵金属层 2上附着有 贵金属纳米材料层 3， 如图 2所示； 与磨砂玻璃的表面粗糙度相结合， 具有双 向增强效果， 进一歩增强表面增强效果， 与现有技术相比， 进一歩提高分析灵 敏度。 结果如图 3所示。
本实施例中， 所述贵金属层 2厚度为 20-400nm， 优选为 120nm; 该厚度能 够充分发挥纳米材料层和金相砂纸表面的双向增强功能。 本实施例中， 所述贵金属纳米材料层 3可以为金或银的纳米材料层， 本实 施例采用银材料； 可采用贵金属金银的不同纳米粒子形状， 如纳米棒， 纳米球 及其它不规则形体， 均能实现发明目的。
本实施例中， 所述磨砂玻璃为弧形凹槽形结构， 所述磨砂表面为弧形凹槽 形结构的内表面； 使用时， 被检测样品利用重力作用直接位于底部最低点， 具 有自动定位的效果，并使样品具有集中性，提高检测灵敏度从而提高工作效率。
本发明的基底采用下列方法进行制备：
本发明基底制备方法实施例一， 表面增强拉曼基底的制备方法，包括下列 歩骤：
a.将磨砂玻璃 1在有机溶剂中清洗， 使其磨砂表面清洁， 有机溶剂为乙醇 或丙酮，本实施例采用乙醇；磨砂表面的粗糙度与 3000目的金相砂纸粗糙度相 同， 本实施例中同时也采用 180目、 400目和 5000目的粗糙度进行试验， 所得 结果与 3000目比效果稍差；
b.在磨砂玻璃 1的磨砂表面蒸发镀贵金属层 2 ; 本实施例中， 贵金属为银， 蒸镀厚度为 20-400nm， 最优为 120nm， 节约材料并能达到既定的目的；
本发明制备方法实施例一， 表面增强拉曼基底的制备方法，包括下列歩骤： a. 将磨砂玻璃 1在有机溶剂中清洗，使其磨砂表面清洁；本实施例的有机 溶剂为乙醇或丙酮，本实施例采用乙醇；磨砂表面的粗糙度与 3000目的金相砂 纸粗糙度相同， 本实施例中同时也采用 180目、 400目和 5000目的粗糙度进行 试验， 所得结果与 3000目比效果稍差；
b.将磨砂玻璃 1置于旋涂仪上， 本实施例中， 磨砂玻璃 1为片状且裁剪成 1 X 1英寸大小， 设置旋涂仪转速 500-3000转之间， 本转速范围能够适应于在 磨砂玻璃 1的磨砂表面上涂布贵金属层， 过高过低均无法均匀涂布； 本实施例 采用 1000转，并且在 500和 3000转均进行试验，所得结果与 1000转相比稍差； c.在旋涂仪内滴加贵金属盐溶液等待 20s以上； 本实施例中， 贵金属盐溶 液配置如下： 15 mL 0. 1M AgN03中， 添加 7. 5 mLO. 8M腿， 逐滴滴加浓氨水至 溶液澄清； 各组分添加比例可根据需要按比例减少或增加； d.在旋涂仪内滴加还原液， 等待 30s以上； 与贵金属盐溶液相对应， 还原 液为 0. 5M的葡萄糖；
e.将贵金属盐溶液以及还原液按总量分成 8-13份并重复歩骤 c和 d进行分 次滴加， 本实施例中， 将贵金属盐溶液以及还原液按总量分成 10份， 分 10次 重复歩骤 c和 d进行滴加， 同时， 分成 8份和 13份进行试验， 所得结果并无明 显差别； 在磨砂玻璃 1的磨砂表面上形成贵金属层 2;
f.在旋涂仪内滴加用于清洗贵金属层表面的贵金属氧化物的清洗液， 等待 30s; 本实施例中， 清洗液与 AgN03对应为 0. 5 mL按 1 : 1稀释的氨水；
g. 在旋涂仪内滴加二次蒸馏水， 清洗 3-5次， 本实施例为 4次， 清洗次数 可根据需要进行改变。
本方法中， 采用银形成贵金属层 2， 该方法同样适用金和铜， 只是采用的 还原及清洗介质不同， 在此不再赘述。
本发明制备方法实施例一， 表面增强拉曼基底的制备方法，包括下列歩骤： a. 将磨砂玻璃 1在有机溶剂中清洗，使其磨砂表面清洁；本实施例的有机 溶剂为乙醇或丙酮，本实施例采用乙醇；磨砂表面的粗糙度与 3000目的金相砂 纸粗糙度相同， 本实施例中同时也采用 180目、 400目和 5000目的粗糙度进行 试验， 所得结果与 3000目比效果稍差；
b.在基础层具有类似金相砂纸的表面粗糙度的表面 （金相砂纸表面） 上喷 洒贵金属盐溶液， 并喷洒还原液， 等待 l-5min， 等待时间分别为 lmin、 3min 和 5min， 实验结果并无明显差别； 本实施例中， 贵金属盐溶液配置如下： 15 mL 0. 1M AgN03中， 添加 7. 5 mLO. 8M ΚΟΗ, 逐滴滴加浓氨水至溶液澄清， 各组分添 加比例可根据需要按比例减少或增加； 还原液为 0. 5Μ的葡萄糖；
c.将贵金属盐溶液以及还原液按总量分成 8-13份并重复歩骤 b进行分次喷 洒并还原， 本实施例为分成 10份， 同时， 分成 8份和 13份进行试验， 所得结 果并无明显差别； 在磨砂玻璃 1的磨砂表面上形成贵金属层；
e.喷洒用于清洗贵金属层表面的贵金属氧化物的清洗液， 等待 30s以上； 本实施例中， 清洗液与 AgN03对应为 0. 5 mL按 1： 1稀释的氨水； g.用二次蒸馏水清洗 3-5次， 本实施例为 4次， 本实施例为 4次， 清洗次 数可根据需要进行改变。
本方法中， 采用银形成贵金属层 2， 该方法同样适用金和铜， 只是采用的 还原及清洗介质不同， 在此不再赘述。
本发明制备方法实施例一， 表面增强拉曼基底的制备方法，包括下列歩骤： a. 将磨砂玻璃 1在有机溶剂中清洗，使其磨砂表面清洁，有机溶剂为乙醇 或丙酮， 本实施例采用乙醇； 金相砂纸采用 3000 目； 本实施例中同时也采用 180目、 400目和 5000目砂纸进行试验， 所得结果与 3000目比效果稍差； b.将贵金属盐溶液和还原液按比例混合； 本实施例中， 贵金属盐溶液配置 如下： 15 mL 0. 1M AgN03中， 添加 7. 5 mLO. 8M ΚΟΗ, 逐滴滴加浓氨水至溶液澄 清， 各组分添加比例可根据需要按比例减少或增加； 还原液为 0. 5Μ的葡萄糖; c立即将磨砂玻璃 1放入混合液中， 恒温 30-70摄氏度等待 5-30min， 本 实施例恒温 60摄氏度等待 15min， 温度和等待时间之间应该具有良好的匹配， 本实施例中， 还进行恒温 30摄氏度等待 30min， 恒温， 70摄氏度等待 5min， 所 得结果并无明显差别， 在磨砂玻璃 1的磨砂表面上形成贵金属层；
d.将形成贵金属层的磨砂玻璃 1浸入二次蒸馏水， 清洗 3-5次， 本实施例 为 4次， 本实施例为 4次， 清洗次数可根据需要进行改变。
本方法中， 采用银形成贵金属层 2， 该方法同样适用金和铜， 只是采用的 还原及清洗介质不同， 在此不再赘述。
本实施例中， 还包括在贵金属层 2上附着贵金属纳米材料层 3的方法， 该 方法适用于上述两种方法形成的贵金属层， 具体包括下列歩骤：
I .将附着有贵金属层 2的磨砂玻璃 1置于液体粘合剂中浸泡 10-40分钟后 取出， 本实施例采用 20分钟， 本实施例中， 还进行浸泡 10分钟和浸泡 40分钟 实验， 所得结果并无明显差别； 粘合剂采用二硫醇， 巯基及氨基硅垸的水解产 物中的任意一种， 本实施例采用氨基硅垸的水解产物；
Π .用二次去离子水清洗， 并置于贵金属纳米材料水混液中浸泡 60-180分 钟， 本实施例采用 100分钟， 本实施例中， 还进行浸泡 60分钟和浸泡 80分钟 实验， 所得结果并无明显差别； 本实施例中， 贵金属纳米材料为银纳米颗粒， 贵金属纳米材料水混液是指硝酸银溶液加柠檬酸三钠反应后还原银的纳米粒子 在该溶液中形成的水混液；
III.重复歩骤 I和 II 2-8 次后以去离子水清洗并采用氮气吹干， 本实施例 重复歩骤 I和 Π 6次；
IV.在氮气氛或真空中 80-160°C干燥 30-80分钟，本实施例采用氮气氛围 下在 110°C条件下干燥 30分钟， 本实施例中， 还进行在 80°C条件下干燥 80分 钟和在 160°C条件下干燥 30分钟， 所得结果并无明显差别； 干燥的时间和温度 可以根据烘干情况互相补充长短和高低。
由上述结构和制备方法可以得出，磨砂玻璃 1的磨砂表面的表面粗糙度较 为重要， 采用类似于 3000目金相 砂纸的表面粗糙度为最优， 过高或过低均会 使效果变差。 这是因为过高或过低都会使 SERS热点的数目降低。
当然， 在磨砂玻璃表面形成增强拉曼基底还可以采用镀膜机镀膜形成， 包 括离子束溅射镀膜机、 热蒸发镀膜机或电子束蒸镀镀膜机， 一般镀膜 10-50分 钟，形成 20-400nm的贵金属膜层；镀膜还可以是镀两层贵金属层，第一层为银， 第二层为金， 银层厚， 金层薄； 均能够实现发明目的。
以下为本发明的基底采用惰性气体保护的制备方法：
本发明的的表面增强拉曼基底的制备方法， 包括下列歩骤：
a. 在基础层 1表面附着纳米银颗粒表面增强层 3形成表面增强拉曼基底; 基础层即为用于形成基底的基础层， 基础层 1可采用现有技术中的任何已经公 开的基础层， 包括有机材料等等；
b.将歩骤 a中形成的表面增强拉曼基底置于惰性气体内保存。
当然， 在进行歩骤 a时， 需要对基础层 1进行必要的清洗， 以保证附着效 果。
本实施例中， 歩骤 a中， 首先在基础层 1表面形成超疏水结构 2， 所述纳 米银颗粒表面增强层 3附着于超疏水结构表面； 可以是直接表面处理形成还可 以是增加超疏水膜； 采用超疏水结构， 使水溶液类样品形成近似球状， 增大暴 露于空气中的表面积， 不但使溶剂易于挥发， 实现提纯； 并且较为集中的位于 底部， 样品中的成分集中， 利于提高对痕量和超痕量成分的检测精确度； 超疏 水结构与纳米 Ag的增强效应较佳； 最外层的自组装纳米材料层外表面还可修 饰有用于分离富集及识别样品自组装分子膜； 制作时， 使其兼有分离富集和内 参比功能， 形成配套高灵敏度和高可靠性的 SERS基底。
本实施例中， 所述基础层 1用于形成超疏水结构 2的表面的粗糙度相当于 180到 5000目的金相砂纸表面粗糙度； 具有较好的结合强度， 并且能够自身形 成超疏水结构， 节约制造成本并节省制造工序； 本实施例中， 采用磨砂玻璃或 者金相砂纸； 可避免采用现有技术中刻蚀形成， 也就避免了现有技术的上述结 构需要在固体基础物质表面刻蚀而形成基础层， 其后生长基质， 具有成本高， 制作周期长， 难以适应批量生产的缺点； 并且固体基础物质较硬且脆， 易于损 坏， 使用时不具有根据环境条件适应方位的特点等等缺点。
采用在磨砂玻璃或者金相砂纸上直接形成超疏水结构， 不需要在基础层上 形成刻蚀表面， 形成的基底同样具有极好的增强效果和超高的分析灵敏度， 适用于超痕量样品的检测， 最为突出的是， SERS基底的制作简单、 生产周期 短、 成本较低， 适用于批量化生产， 由于不具有刻蚀表面， 应用中不会对拉 曼增强以及分析过程形成干扰，这是现有技术的 SERS基底制备方法所不能达到 的。
如图 2所示： 本实施例中， 所述基础层 1为平滑凹槽形结构， 所述超疏水 结构 2位于平滑凹槽内表面； 使用时， 被检测样品利用重力作用直接位于底部 最低点， 具有自动定位的效果， 提高工作效率。
本实施例中， 所述惰性气体为氮气， 成本低， 容易获得。
本实施例中， 歩骤 a中， 纳米银颗粒表面增强层形成过程包括下列歩骤： I .将基础层置于液体粘合剂中浸泡 10-40分钟后取出； 本实施例采用 20 分钟， 本实施例中， 还进行浸泡 10分钟和浸泡 40分钟实验， 所得结果并无明 显差别； 粘合剂采用二硫醇， 巯基及氨基硅垸的水解产物中的任意一种， 本实 II . 用二次去离子水清洗， 并置于银纳米材料水混液中浸泡 60-180分钟； 本实施例采用 100分钟，本实施例中，还进行浸泡 60分钟和浸泡 80分钟实验， 所得结果并无明显差别； 本实施例中， 银纳米材料水混液是指硝酸银溶液加柠 檬酸三钠反应后还原银的纳米粒子在该溶液中形成的水混液；
III.重复歩骤 I和 II 2-8次后以去离子水清洗并吹干；本实施例重复歩骤 I 和 Π 6次；
IV.在氮气氛或真空中 80-160°C干燥 30-80分钟；本实施例采用氮气氛围 下在 110°C条件下干燥 30分钟， 本实施例中， 还进行在 80°C条件下干燥 80分 钟和在 160°C条件下干燥 30分钟， 所得结果并无明显差别； 干燥的时间和温度 可以根据烘干情况互相补充长短和高低。
由上述结构和制备方法可以得出， 基础层的磨砂表面的表面粗糙度较为重 要，采用类似于 3000目金相砂纸的表面粗糙度为最优，过高或过低均会使效果 变差。 这是因为过高或过低都会使 SERS热点的数目降低。
图 8为本发明光谱仪的原理示意图，图 9为光谱仪共焦点的样品处放大图， 图 10为光谱仪检测头组件纵向截面图， 图 11为图 10沿 A向截面图， 图 12为 图 11B处放大图， 如图所示： 本实施例的双光程拉曼光谱仪， 包括拉曼光谱仪 本体 6和检测头组件， 所述检测头组件包括外壳 12和设置在外壳 12内的双光 路组件，双光路组件至少包括沿激发光方向设置的一个凸透镜 17和一个凹面镜 19， 当然凸透镜 17可以是几个， 并不影响本发明目的的实现； 所述凸透镜 17 与凹面镜 19共焦， 待检测样品 9位于凸透镜 17与凹面镜 19共焦点， 光源 7 发射的激发光入射后经过凸透镜 17聚光后对待检测样品 9进行激发，通过凹面 镜 19反射聚焦后再次对待检测样品 9进行激发，实现激发光的二次利用， 同时 增强待测样品 9内成分的拉曼效应的信号光强。
本实施例中， 所述壳体 12设有用于取放样品的取放口 12a， 取放口 12a以 可开合的方式设有用于遮光的密封盖 15; 方便样品的放入， 使用方便简单。
本实施例中， 所述密封盖 15以铰接的方式设置于壳体 12形成门形结构， 如图所示， 密封盖 15—侧端部铰接于壳体 12， 灵一侧端部通过卡扣 14扣接， 形成遮光密封;密封盖 15的封盖尺寸大于取放口 12a且与取放口 12a的边缘径 向外表面之间设有遮光垫 16， 如图所示， 遮光垫 16可采用橡胶等柔性材料； 结构简单， 操作容易， 并且易于定位， 且通过遮光垫与外界遮光隔绝， 利于检 测结果的的精确性。
本实施例中，所述壳体 12内设有用于放置待检测样品 9并使待检测样品 9 位于凸透镜 17与凹面镜 19共焦点的托架或托盘， 所述托架或托盘至少在凸透 镜 17与凹面镜 19共焦点透光； 本实施例中， 可使托架或托盘整体透明， 以减 小对激发光的干扰。
本实施例中， 所述托架或托盘固定连接于密封盖 15可随密封盖 15开合而 移出或放入， 如图所示， 托架或托盘通过连接架 13固定连接于密封盖 15; 方 便样品的取出和放入， 操作简单， 同时， 利用密封盖 15的方位实现托盘或托架 的固定定位， 将待检测样品 9放置于共焦处实现双光程激发；
或者， 所述托架或托盘固定设置于壳体内； 具有较稳定的定位效果， 并且 不会随着设备的长周期使用而影响定位精度。
本实施例中， 所述托盘或托架为平滑凹槽形托盘 18 (即为本发明的基底）， 平滑凹槽形托盘 18的开口向上且其底部最低点位于凸透镜 17与凹面镜 19共焦 点， 本实施例采用半球形结构托盘， 类似于碗形； 将被检测样品 9置于平滑凹 槽形托盘后利用重力作用直接位于底部最低点， 具有自动定位的效果， 提高工 作效率。
本实施例中，所述平滑凹槽形托盘 18内表面为超疏水结构，可以是直接表 面处理形成还可以是增加超疏水膜； 采用超疏水结构， 使水溶液类样品形成近 似球状， 增大暴露于空气中的表面积， 不但使溶剂易于挥发， 实现提纯； 并且 较为集中的位于底部， 样品中的成分集中， 利于提高对痕量和超痕量成分的检 测精确度。
本实施例中， 所述超疏水结构表面生长有用于表面增强的自组装纳米材料 10， 如本实施例中， 自组装有金、 银、 铜纳米材料等能产生表面增强拉曼散射 ( SERS ) 的金属， 均位于超疏水膜以 Ag的增强效应为最佳； 最外层的自组装 纳米材料层外表面还可修饰有用于分离富集及识别样品自组装分子膜;制作时， 使其兼有分离富集和内参比功能，形成配套高灵敏度和高可靠性的 SERS基底。
本实施例中， 光源 7发射的激发光内引入用于使待检测样品 9溶剂挥发的 热光， 热光即能加热使水溶剂蒸发的光； 本实施例中采用红外光作为热光， 利 用红外光使待检测样品挥发从而使成分提高相对含量， 利于检测的进行并使结 果精确。
本实施例中，所述壳体 12内设有用于引入激发光并将拉曼信号光引出的二 向色镜 4， 简化结构， 进一歩利于携带； 如图所示二向色镜 4反射的拉曼光信 号通过一个凸透镜 5进入拉曼光谱仪本体， 进行光谱分析； 如图所示， 位于二 向色镜 4和凸透镜 5之间设有陷波滤波器， 其目的是消除激发光源对拉曼信号 的影响。
本发明的检测方法具有高灵敏、 高重现性， 该高灵敏、 高重现性表面增强 拉曼光谱的检测方法， 包括下列歩骤：
a. SERS 基底上均匀涂敷待检测样品； 涂覆方式可呈点状多点分布或呈面 状分布；
b . 利用光源经照明系统照射 SERS基底上其中一点待检测样品并获取其拉 曼光谱； 利用表面增强拉曼光谱获取样品的含量， 属于现有技术中， 在此不再 赘述；
c .在 SERS基底上具有样品的范围内对的样品进行多点检测并重复歩骤 b; d. 利用获取的多点待测样品的光谱信息， 去背景后求平均值， 根据该平均 值将测得的多点待测样品的光谱信息去除最小值和最大值， 将去除最小值和最 大值的多点待测样品的光谱信息再求平均值， 获取被测样品的拉曼光谱信息， 对照已有拉曼光谱数据库，定性或 /和定量的得出被测样品的信息；平均值根据 所得数据进行计算获得。
本实施例中，歩骤 a中，所述待检测样品在 SERS基底上呈面状分布于 SERS 基底表面； 该结构溶液分布形式利于随机选择监测点， 操作相对方便。
本实施例中，歩骤 c中，在 SERS基底上具有样品的范围内对的样品进行多 点检测通过在同一平面内移动 SERS基底实现； 操作方便简单， 避免重新对焦， 提高工作效率。
本实施例中，所述 SERS基底包括基础层和表面增强层，所述基础层为磨砂 玻璃、 砂纸或滤纸， 所述表面增强附着在磨砂玻璃的磨砂表面、 砂纸的工作表 面、 滤纸的表面或镜头纸等； 本实施例采用磨砂玻璃基底层。
图 13为本发明微调装置的结构示意图，图 14为图 13的俯视图，图 15为带 有壳体的微调装置，图 16为图 15沿 C-C向剖视图，图 17为图 16D处放大图； 本发明还公开了一种用于高灵敏、 高重现性表面增强拉曼光谱的微调装置， 包 括用于放置 SERS基底的 SERS基底架和用于驱动 SERS基底架使基底在检测平面 内移动的驱动组件，检测平面指的是 SERS光极聚焦点所在的平面，通过该点的 平面有较多个， 只是驱动 SERS基底架使基底在其中任意一个平面内移动即可。
本实施例中， SERS基底架包括基座组件和位于基座组件上的基底托盘 3c， 所述基底托盘 3c用于放置基底； 所述基座组件包括拖板 2c和基座 lc， 所述基 底托盘 3c以可绕自身轴线转动的方式设置于拖板 2c，所述拖板 2c以可在检测 平面往复运动的方式设置于基座 lc ; 所述驱动组件包括用于驱动基底托盘 3c 绕自身轴线转动的转动驱动组件和用于驱动拖板 2c 在检测平面往复运动的往 复驱动组件； 利用基座组件以及驱动组件驱动基底托盘 3c 实现转动和往复运 动， 使整个基底无检测盲点。
本实施例中，所述转动驱动组件包括安装于拖板 2c的转动驱动电机、由转 动驱动电机 6c驱动的转动主动齿轮 5c和位于基底托盘 3c外圆并与转动主动齿 轮 5c啮合传动的转动从动齿轮 4c， 本实施例中， 基底托盘 3c和转动从动齿轮 4c一体成形， 结构简单， 制作容易；
往复驱动组件包括安装于基座 lc的往复驱动电机 9c、 由往复驱动电机 9c 驱动的滚珠丝杠 8c和与滚珠丝杠 8c驱动配合并设置于拖板 2c的螺母 7c ; 采用齿轮啮合副以及滚珠丝杠的驱动结构， 精密且可控， 配合以驱动过程 设定刻度的方式， 使得检测点可控。
本实施例中， 所述微调装置还包括壳体 10c， 所述壳体 10c设有用于取放 样品的取放口 10ca， 取放口 10ca以可开合的方式设有用于遮光的密封盖 12c; 所述基座 lc固定设置于密封盖 12c， 实际上， 基座 lc固定于密封盖 12c且密 封盖 12c关闭后， SERS基底架 a整体都位于壳体 10c内， 并使基底托盘 3c位 于拉曼光谱仪的检测平面内；所述基底托盘 3c固定连接于密封盖 12c可随密封 盖 12c开合而移出或放入， 如图所示， 基底托盘 3c通过连接架 14固定连接于 密封盖 12c ; 方便样品的取出和放入， 操作简单， 同时， 利用密封盖 12c的方 位实现托盘或托架的固定定位；
当然， 所述基座 lc也可以固定设置于壳体 10c内并与壳体 10c固定连接， 同时， 使基底托盘 3c位于拉曼光谱仪的检测平面内， 也能实现发明目的。
本实施例中，所述密封盖 12c以铰接的方式设置于壳体 10c形成门形结构， 如图所示，密封盖 12c—侧端部铰接于壳体 10c，灵一侧端部通过卡扣 11扣接， 形成遮光密封； 密封盖 12c的封盖尺寸大于取放口 10ca且与取放口 10ca的边 缘径向外表面之间设有遮光垫 13c， 如图所示， 遮光垫 13c可采用橡胶等柔性 材料； 结构简单， 操作容易， 并且易于定位， 且通过遮光垫与外界遮光隔绝， 利于检测结果的的精确性。
本实施例中，所述基座 lc为框形，且框形其中相对应的两边形成两条并列 的轨道， 拖板 2c形成两条与轨道对应且与其滑动配合的拖板分支， 如图所示， 两个拖板分支分别形成滑槽并通过该滑槽直接与轨道滑动配合； 所述螺母横向 延伸形成延长段且分别固定连接于两个拖板分支； 采用框形结构， 利于激光的 通过， 特别适用于双光程的拉曼光谱仪， 进一歩提高灵敏度， 以适应于痕量样 品的检测； 如图所示， 往复驱动电机 9c以及滚珠丝杠 8c位于两个轨道之间用 于驱动螺母 7c以及两个拖板分支;所述基底托盘底部与其同轴设有圆形凸起且 两个拖板分支上分别设有用于与圆形凸起转动配合的滑槽， 也就是基底托盘底 部形成类似于轴状的圆形凸起， 而该圆形凸起担在两个拖板分支上， 拖板分支 设有容纳该圆形凸起的滑槽， 形成滑动配合并能限制基底托盘的径向位移； 使 基底托盘只能相对于拖板转动， 以保证检测点的可控性； 如图所示， 转动驱动 电机固定于其中一个拖板分支， 结构简单紧凑； 如图所示， 基座 lc通过沿其纵 向的两个连接架 14连接于密封盖 12c。
本实施例中，所述基底托盘 3c透明或中部托空； 以适应双光程拉曼光谱仪 (申请号： 201210358471 )， 以获得更高灵敏度的检测结果。
本发明的微调装置在使用时， 通过驱动转动驱动电机以及往复驱动电机带 动基底托盘进行往复运动、 转动及其结合， 实现基底托盘以及基底的微调， 实 现对分布于基底上的样品进行检测； 往复驱动电机和转动驱动电机均采用伺服 电机， 通过自动控制系统根据输入的外部命令进行自动控制并驱动转动， 已获 得设定的位置的样品检测， 在此不再赘述。
图 18为本发明微调装置另一结构示意图，如图所示，本机构与上述实施例 的结构区别仅在于对基底托盘的驱动方式不同， 基底托盘不再转动， 而是在 X 轴和 y轴上往复运动， 实现微调， 而满足本发明的需要， 具体区别如下：
SERS 基底架包括基座组件和位于基座组件上的基底托盘， 所述基底托盘 上放置有 SERS基底， 所述 SERS基底包括基础层和表面增强层， 所述基础层为 磨砂玻璃、 砂纸、 滤纸或镜头纸； 所述基座组件包括 y轴拖板和基座， y轴拖 板和基座的结构与上述实施例的拖板和基座相同； 所述基底托盘以可在检测平 面内沿 X轴往复运动的方式设置于 y轴拖板， 所述 y轴拖板以可在检测平面内 沿 y轴往复运动的方式设置于基座； 所述驱动组件包括用于驱动基底托盘沿 X 轴往复运动的 X轴驱动组件和用于驱动拖板沿 y轴往复运动的的 y轴驱动组件， y轴驱动组件与上述实施例的往复驱动组件完全相同， 也就是 y轴拖板的驱动 完全与上述实施例的拖板驱动相同， 在此不再赘述； y轴拖板上设有两条 X轴 轨道 15c， 基底托盘与两条 X轴轨道 15c配合沿两条 X轴轨道 15c在 x轴上往 复运动，且 y轴拖板上设有 X轴驱动电机 6ca， x轴驱动电机 6ca驱动 x轴滚珠 丝杠 5ca转动， 带动基底托盘上的 X轴螺母 4ca沿 X轴往复运动， 从而带动基 底托盘沿 X轴往复运动。
最后说明的是， 以上实施例仅用以说明本发明的技术方案而非限制， 尽管 参照较佳实施例对本发明进行了详细说明， 本领域的普通技术人员应当理解， 可以对本发明的技术方案进行修改或者等同替换， 而不脱离本发明技术方案的 旨和范围， 其均应涵盖在本发明的权利要求范围当中。

Claims

权 利 要 求 书
1.一种表面增强拉曼基底， 其特征在于： 包括基础层和表面增强层， 所述 基础层为磨砂玻璃， 表面增强层附着在磨砂玻璃的磨砂表面。
2.根据权利要求 1所述的磨砂玻璃表面增强拉曼基底， 其特征在于： 所述 表面增强层为贵金属层； 所述贵金属层附着有贵金属纳米材料层。
3.根据权利要求 2所述的磨砂玻璃表面增强拉曼基底， 其特征在于： 所述 磨砂玻璃的磨砂表面的粗糙度相当于 180到 5000目的金相砂纸表面粗糙度，所 述贵金属层厚度为 20-400mn; 所述贵金属层为金、 银、 铜中的任意一种， 所述 贵金属纳米材料层为金、 银、 铜中的一种或两种以上的纳米材料层： 所述磨砂 玻璃为弧形凹槽形结构， 所述磨砂表面为弧形凹槽形结构的内表面。
4一种表面增强拉曼基底的制备方法， 其特征在于： 包括下列步骤： a. 在基础层表面附着表面增强层形成表面增强拉曼基底；
b.将步骤 a中形成的表面增强拉曼基底置于惰性气体内保存。
5.根据权利要求 4所述的表面增强拉曼基底的制备方法， 其特征在于： 步骤 a中， 首先在基础层表面形成超疏水结构， 所述贵金属纳米材料层附 着于超疏水结构表面； 所述基础层为平滑凹槽形结构， 所述超疏水结构位于平 滑凹槽内表面。
6.根据权利要求 5所述的表面增强拉曼基底的制备方法， 其特征在于： 步骤 a中， 纳米银颗粒表面增强层形成过程包括下列步骤：
I . 将基础层置于液体粘合剂中浸泡 10-40分钟后取出；
II .用二次去离子水清洗， 并置于银纳米材料水混液中浸泡 60-180分钟；
III.重复步骤 I和 II 2-8次后以去离子水清洗并吹干；
IV.在氮气氛或真空中 80-160°C干燥 30-80分钟。
7.—种拉曼光谱仪， 其特征在于： 包括拉曼光谱仪本体和检测头组件， 所 述检测头组件包括外壳和设置在外壳内的双光路组件， 双光路组件至少包括沿 激发光方向设置的一个凸透镜和一个凹面镜， 所述凸透镜与凹面镜共焦， 待检 测样品位于凸透镜与凹面镜共焦点。
8.根据权利要求 7所述的拉曼光谱仪， 其特征在于： 所述壳体设有用于取 放样品的取放口， 取放口以可开合的方式设有用于遮光的密封盖；
所述密封盖以铰接的方式设置于壳体形成门形结构， 密封盖的封盖尺寸大 于取放口且与取放口的边缘径向外表面之间设有遮光垫； 所述壳体内设有用于 放置待检测样品并使待检测样品位于凸透镜与凹面镜共焦点的托架或托盘， 所 述托架或托盘至少在凸透镜与凹面镜共焦点透光； 所述托架或托盘固定连接于 密封盖可随密封盖开合而移出或放入； 或者， 所述托架或托盘固定设置于壳体 内。
9.根据权利要求 8所述的拉曼光谱仪， 其特征在于： 所述托盘或托架为平 滑凹槽形托盘， 平滑凹槽形托盘的开口向上且其底部最低点位于凸透镜与凹面 镜共焦点； 所述平滑凹槽形托盘内表面为超疏水结构； 所述超疏水结构表面生 长有用于表面增强的自组装纳米材料； 激发光内引入用于使待检测样品溶剂挥 发的热光； 所述壳体内设有用于引入激发光并将拉曼信号光引出的二向色镜。
10.一种表面增强拉曼光谱的检测方法， 其特征在于： 包括下列步骤： a . SERS基底上均匀涂敷待检测样品；
b . 利用光源经照明系统照射 SERS基底上其中一点待检测样品并获取其拉 曼光谱；
c 在 SERS基底上具有样品的范围内对的样品进行多点检测并重复步骤 b ; d . 利用获取的多点待测样品的光谱信息， 去背景后求平均值， 根据该平均 值将测得的多点待测样品的光谱信息去除最小值和最大值， 将去除最小值和最 大值的多点待测样品的光谱信息再求平均值， 获取被测样品的拉曼光谱信息， 对照已有拉曼光谱数据库， 定性或 /和定量的得出被测样品的信息。
1 1.根据权利要求 10所述的表面增强拉曼光谱的检测方法， 其特征在于： 步骤 a中， 所述待检测样品在 SERS基底上呈面状均匀分布于 SERS基底表面； 步骤 c中，在 SERS基底上具有样品的范围内对样品进行多点检测通过在同一平 面内移动 SERS基底实现； 所述 SERS基底包括基础层和表面增强层， 所述基础 层为磨砂玻璃、 砂纸、 滤纸或镜头纸， 所述表面增强附着在磨砂玻璃的磨砂表 面、 砂纸的工作表面或滤纸的表面。
12.—种用于表面增强拉曼光谱的微调装置， 其特征在于： 包括用于放置 SERS基底的 SERS基底架和用于驱动 SERS基底架使基底在检测平面内移动的驱 动组件。
13. 根据权利要求 12所述的微调装置， 其特征在于： SERS基底架包括基 座组件和位于基座组件上的基底托盘， 所述基底托盘上放置有 SERS基底，所述 SERS基底包括基础层和表面增强层， 所述基础层为磨砂玻璃、 砂纸、 滤纸或镜 头纸； 所述基座组件包括拖板和基座， 所述基底托盘以可绕自身轴线转动的方 式设置于拖板， 所述拖板以可在检测平面往复运动的方式设置于基座； 所述驱 动组件包括用于驱动基底托盘绕自身轴线转动的转动驱动组件和用于驱动拖板 在检测平面往复运动的往复驱动组件。
14. 根据权利要求 13所述的微调装置， 其特征在于： 所述转动驱动组件包 括安装于拖板的转动驱动电机、 由转动驱动电机驱动的转动主动齿轮和位于基 底托盘外圆并与转动主动齿轮啮合传动的转动从动齿轮； 往复驱动组件包括安 装于基座的往复驱动电机、 由往复驱动电机驱动的滚珠丝杠和与滚珠丝杠驱动 配合并设置于拖板的螺母； 所述微调装置还包括売体， 所述壳体设有用于取放 样品的取放口， 取放口以可开合的方式设有用于遮光的密封盖； 所述基座固定 设置于密封盖内， 并使基底托盘位于拉曼光谱仪的检测平面内； 或者， 所述基 座固定设置于壳体内， 并使基底托盘位于拉曼光谱仪的检测平面内； 所述基座 为框形， 且框形其中相对应的两边形成两条并列的轨道， 拖板形成两条与轨道 对应且与其滑动配合的拖板分支， 所述螺母横向延伸且分别固定连接于两个拖 板分支； 所述基底托盘底部与其同轴设有圆形凸起且两个拖板分支上分别设有 用于与圆形凸起转动配合的滑槽。
15. 根据权利要求 12所述的微调装置， 其特征在于： SERS基底架包括基 座组件和位于基座组件上的基底托盘， 所述基底托盘上放置有 SERS基底，所述 SERS基底包括基础层和表面增强层， 所述基础层为磨砂玻璃、 砂纸、 滤纸或镜 头纸； 所述基座组件包括 y轴拖板和基座， 所述基底托盘以可在检测平面内沿 X轴往复运动的方式设置于 y轴拖板， 所述 y轴拖板以可在检测平面内沿 y轴 往复运动的方式设置于基座； 所述驱动组件包括用于驱动基底托盘沿 X轴往复 运动的 X轴驱动组件和用于驱动拖板沿 y轴往复运动的的 y轴驱动组件。
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