CN102408094B - Preparation method for highly repetitive surface enhanced Raman spectrum (SERS) active substrate - Google Patents
Preparation method for highly repetitive surface enhanced Raman spectrum (SERS) active substrate Download PDFInfo
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- CN102408094B CN102408094B CN201110355896.1A CN201110355896A CN102408094B CN 102408094 B CN102408094 B CN 102408094B CN 201110355896 A CN201110355896 A CN 201110355896A CN 102408094 B CN102408094 B CN 102408094B
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Abstract
The invention relates to a surface enhanced Raman spectrum technology or the technical field of chemical analysis and provides a preparation method for a highly repetitive surface enhanced Raman spectrum (SERS) active substrate. The preparation method comprises the following steps: (1) preparing a precious metal nano particle colloid; (2) obtaining a high-concentrated metal nano particle; (3) synthesizing metal nano particle printing ink; (4) preparing a screen printing plate; (5) printing an SERS active substrate; and (6) preparing the highly repetitive SERS active substrate and tailoring the dried SERS active substrate to different sizes according to design specifications and sealing for later use. The preparation method has the following beneficial effects: the preparation process is simple and practicable without expensive instruments and equipment; and the prepared SERS active substrate is good in synergy effect, high in stability, excellent in uniformity and low in price, is convenient to save and carry, can avoid cross contamination in the detection process and can be beneficial to rapid analysis of mass samples in laboratories and the outdoor site SERS detection.
Description
Technical field
The present invention relates to SERS technology or chemical analysis technology field, specifically, be a kind of preparation method of surface-enhanced Raman spectrum active substrate, especially utilize screen printing technique to prepare in enormous quantities the simple and easy method of high duplication surface-enhanced Raman spectrum active substrate.
Technical background
SERS (SERS) technology can provide the information of the molecular level that other analysis and detection technology is difficult to obtain, have detection time short, water disturb little, can direct in-situ analysis, the advantage such as highly sensitive, detection range is wide, and do not need the conditions such as complicated pre-treatment or highly purified carrier gas, in many fields such as bioanalysis, criminal investigation discriminating, food and environment pollution detections, all have wide practical use.
Research shows, with the nano particle of the first subgroup metals such as Ag, Au and part transition metal, prepare SERS (SERS) active substrate material, make between metallic effectively reinforcement metal surface plasma body resonant vibration of appropriate gathering, thereby the electric charge that strengthens substrate surface regional area field coupling or absorption molecule shifts, and then strengthens the Raman response signal of tester.Therefore, SERS is detected to analytical technology, the good SERS active substrate of processability is a very important research contents, is also the key factor that this technology can be applied and develop.
At present, by technology such as electrochemical activation, chemical synthesis, molecule assembling, vacuum evaporation, nanometer offset printing, beamwriter lithography methods, scholars after deliberation and prepare polytype SERS active substrate material.But SERS active substrate repeatability prepared by the short-cut methods such as electrochemical activation, chemical synthesis and molecule assembling is poor, affect uniformity and the validity of testing result; And SERS active substrate prepared by the technology such as vacuum evaporation, nanometer offset printing, beamwriter lithography method needs advanced expensive instrument and equipment and preparation process time and effort consuming conventionally.The problem that these SERS active substrate technologies of preparing exist has hindered SERS and has detected the rapid conversion of analytical technology from scientific research to practical application.
Summary of the invention
Problem to be solved by this invention is, overcoming on the basis of prior art deficiency, provide a kind of preparation method of high duplication surface-enhanced Raman spectrum active substrate: be a kind of silver (Ag), precious metal colloid nano particle such as gold (Au) etc. to be processed into screen printing ink, recycling screen printing technique is prepared the method for high duplication SERS (SERS) active substrate in enormous quantities.
That screen printing technique has is easy and simple to handle, applied widely, process controllability is good, wire mark product uniformity and easily miniaturization and the advantage such as large-scale production expense is comparatively cheap.Screen printing technique has been widely used in the fields such as preparation of throwing type electrochemistry in Electroanalytical Chemistry or biology sensor at present.Utilize screen printing technique that the printing-ink that contains the noble metal nano particles such as Ag or Au is prepared into throwing type SERS active substrate, can be by regulating the method for silk screen pore size to control coherent condition and the uniformity coefficient of metallic, thereby prepare Raman signal strengthen effective, stability is high and there is good uniformity, be easy to preserve carry, relatively inexpensive SERS base material, can meet the rapid analysis needs of laboratory batch samples, also the disposable use of SERS detection is carried out at the scene beyond facilitating in laboratory, avoids cross pollution.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for high duplication surface-enhanced Raman spectrum active substrate, is characterized in that, its step comprises:
(1) prepare noble metal nano particles colloid
Get silver nitrate (AgNO
3) be dissolved in pure water, the preparation mass ratio liquor argenti nitratis ophthalmicus that is 0.01～0.02%, is heated to 85～95 ℃, and dropwise adding mass ratio is 1～2% sodium citrate aqueous solution, continue to boil and stir after 30～50 minutes and be cooled to room temperature, obtain the Ag nano particle colloid of grey;
(2) obtain high concentration metal nanoparticle
The Ag nano particle colloid that 10 mL steps (1) are obtained is put into centrifuge tube high speed centrifugation 8～10 minutes, removes 98%～99% supernatant liquor, takes off floor height concentration metal nanoparticle with standby;
(3) synthetic metal nanoparticle printing-ink
The sodium carboxymethyl cellulose solution that preparation mass ratio is 8～10%, it is mixed with the high concentration metal nanoparticle that step (2) obtains, the volume that described sodium carboxymethyl cellulose solution mixes with described high concentration metal nanoparticle, for than 1:2～4, synthesizes the high concentration metal nanoparticle printing-ink with appropriate viscosity;
(4) make screen printing screens
The screen printing screens that making consists of hollow out round dot pattern of the same size, the diameter of described round dot is 3～10mm, and the mode being listed as with 10 row * 10 is uniformly distributed, and the grid aperture of the half tone of made is 1～100 μ m;
(5) print SERS (SERS) active substrate
The screen printing screens that step (4) is made is overlying on loading material, in described half tone one end, add the synthetic high concentration metal nanoparticle printing-ink with appropriate viscosity of step (3), adopt screen printing apparatus manually or automatically to print SERS active substrate;
(6) prepare high duplication surface-enhanced Raman spectrum active substrate
The SERS active substrate that step (5) is printed is dried 10～30 minutes in the air dry oven of 30～40 ℃, obtains high duplication surface-enhanced Raman spectrum active substrate; Dried SERS active substrate can be cut into different size and seal according to design specification and preserve with standby.
Further, with method step (1) Suo Shu, prepare Au nano particle colloid or electrum nano particle colloid.
Further, the described loading material of step (5) is glass mat, silicon chip, sheet glass, filter paper, printing paper or potsherd.
The application process of high duplication surface-enhanced Raman spectrum active substrate prepared by the present invention is: the testing sample point of 5～20 μ L is added drop-wise on SERS active substrate, adopts Raman spectroscopy instrument to detect, obtain the SERS spectrogram of testing sample.
Good effect of the present invention is:
(1) preparation process is simple, without expensive advanced instrument equipment;
(2) prepared SERS active substrate synergy is good, stability is high, have good uniformity and cheap, can disposable use and preservation and easy to carry, can avoid the cross pollution in testing process, be conducive to the rapid analysis of laboratory batch samples and carry out SERS detection at outdoor scene;
(3) application of SERS detection analytical technology is had to certain positive effect with development.
Accompanying drawing explanation
The preparation method's that accompanying drawing 1 is high duplication surface-enhanced Raman spectrum active substrate of the present invention FB(flow block);
Accompanying drawing 2 is Ag nano particle colloid uv absorption spectra;
Accompanying drawing 3 is the photo of Ag nano particle screen printing ink;
Accompanying drawing 4 is the photo of high duplication surface-enhanced Raman spectrum active substrate;
Accompanying drawing 5 is the scanning electron microscope (SEM) photograph of high duplication surface-enhanced Raman spectrum active substrate;
Accompanying drawing 6 is the SERS spectrogram of high duplication surface-enhanced Raman spectrum active substrate to rhodamine 6G;
Accompanying drawing 7 is that the repeatability of high duplication surface-enhanced Raman spectrum active substrate detection signal is investigated result collection of illustrative plates.
The specific embodiment
Below in conjunction with accompanying drawing, provide the preparation method's of the high duplication surface-enhanced Raman spectrum active substrate of the present invention specific embodiment, so that method of the present invention is described in detail, still, be noted that preparation method of the present invention is not limited to following introduction.
embodiment 1
Referring to accompanying drawing 1.A preparation method for high duplication surface-enhanced Raman spectrum active substrate, its step comprises:
(1) prepare Ag nano particle colloid
Get silver nitrate (AgNO
3) being dissolved in pure water, preparation 100mL mass ratio is 0.02% AgNO
3solution, is heated to 95 ℃, and dropwise adding mass ratio is 1% sodium citrate aqueous solution 2mL, continues to boil and stir after 50 minutes to be cooled to room temperature, obtains the Ag nano particle colloid (referring to accompanying drawing 2) of stable grey.
(2) obtain high concentration Ag nano particle
The Ag nano particle colloid that the step of 10 mL (1) is obtained is put into centrifuge tube high speed centrifugation 10 minutes, removes 99% supernatant liquor, takes off floor height concentration Ag nano particle with standby.
(3) synthetic Ag nano particle printing-ink
The sodium carboxymethyl cellulose solution that preparation mass ratio is 10%, mixes with the high concentration Ag nano particle that step (2) obtains it with volume ratio 1:4, the synthetic high concentration Ag nano particle printing-ink (referring to accompanying drawing 3) with appropriate viscosity.
(4) make screen printing screens
The round dot that design is 3mm by diameter is uniformly distributed with the arrangement mode of 10 row * 10 row the pierced pattern being formed, and with this design producing screen printing screens, the grid aperture of the screen printing screens of made is 10 μ m.
(5) print SERS (SERS) active substrate
The screen printing screens that step (4) is made is overlying on glass mat, adds the synthetic Ag nano particle printing-ink of step (3) in one end of this half tone, adopts automatic screen printing machine to print SERS active substrate;
Described glass mat can substitute with silicon chip or sheet glass or filter paper or printing paper or potsherd.
(6) prepare high duplication surface-enhanced Raman spectrum active substrate
The SERS active substrate that step (5) is printed is dried 10 minutes in the air dry oven of 40 ℃, obtains high duplication surface-enhanced Raman spectrum active substrate;
The specification sealing that dried SERS active substrate is cut into 5 row * 5 row is preserved, with standby (referring to attached Figure 4 and 5).
embodiment 2
(1) prepare Ag nano particle colloid
Get silver nitrate (AgNO
3) being dissolved in pure water, preparation 100mL mass ratio is 0.01% AgNO
3solution, is heated to 85 ℃, and dropwise adding mass ratio is 2% sodium citrate aqueous solution 2mL, continues to boil and stir after 30 minutes to be cooled to room temperature, obtains the Ag nano particle colloid of stable grey.
(2) obtain high concentration Ag nano particle
The Ag nano particle colloid that the step of 10 mL (1) is obtained is put into centrifuge tube high speed centrifugation 8 minutes, removes 98% supernatant liquor, takes off floor height concentration Ag nano particle with standby.
(3) synthetic Ag nano particle printing-ink
The sodium carboxymethyl cellulose solution that preparation mass ratio is 8%, mixes with the high concentration Ag nano particle that step (2) obtains it with volume ratio 1:2, the synthetic high concentration Ag nano particle printing-ink with appropriate viscosity.
(4) make screen printing screens
The round dot that design is 10mm by diameter is uniformly distributed with the arrangement mode of 10 row * 10 row the pierced pattern being formed, and with this design producing screen printing screens, the grid aperture of the screen printing screens of made is 100 μ m.
(5) print SERS (SERS) active substrate
The screen printing screens that step (4) is made is overlying on glass mat, adds the synthetic Ag nano particle printing-ink of step (3) in one end of this half tone, adopts automatic screen printing machine to print SERS active substrate;
(6) prepare high duplication surface-enhanced Raman spectrum active substrate
The SERS active substrate that step (5) is printed is dried 30 minutes in the air dry oven of 30 ℃, obtains high duplication surface-enhanced Raman spectrum active substrate;
The specification sealing that dried SERS active substrate is cut into 5 row * 5 row is preserved, with standby.
embodiment 3
A preparation method for high duplication surface-enhanced Raman spectrum active substrate, its basic step is with embodiment 1, but as different from Example 1: with method step (1) Suo Shu, prepare Au nano particle colloid.
embodiment 4
A preparation method for high duplication surface-enhanced Raman spectrum active substrate, its basic step is with embodiment 1, but as different from Example 1:
With method step (1) Suo Shu, prepare electrum nano particle colloid;
The grid aperture of the screen printing screens of step (4) made is 1.0 μ m.
One of concrete application process of high duplication surface-enhanced Raman spectrum active substrate prepared by the present invention is: the rhodamine 6G solution point of 10 μ L is added drop-wise on high duplication surface-enhanced Raman spectrum active substrate, adopt Portable Raman spectrometer to detect, obtain that rhodamine is highly sensitive, the rhodamine 6G SERS spectrogram of high duplication (referring to accompanying drawing 6 and 7).
The foregoing is only preferred implementation method of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the inventive method; can also make variation or the accommodation of some equivalences, the variation of these equivalences or accommodation also should be considered as protection category of the present invention.
Claims (2)
1. a preparation method for high duplication surface-enhanced Raman spectrum active substrate, is characterized in that, its step comprises:
(1) prepare noble metal nano particles colloid
Get silver nitrate (AgNO
3) be dissolved in pure water, the preparation mass ratio liquor argenti nitratis ophthalmicus that is 0.01～0.02%, is heated to 85～95 ℃, and dropwise adding mass ratio is 1～2% sodium citrate aqueous solution, continue to boil and stir after 30～50 minutes and be cooled to room temperature, obtain the Ag nano particle colloid of grey;
(2) obtain high concentration metal nanoparticle
The Ag nano particle colloid that 10 mL steps (1) are obtained is put into centrifuge tube high speed centrifugation 8～10 minutes, removes 98%～99% supernatant liquor, takes off floor height concentration metal nanoparticle with standby;
(3) synthetic metal nanoparticle printing-ink
The sodium carboxymethyl cellulose solution that preparation mass ratio is 8～10%, it is mixed with the high concentration metal nanoparticle that step (2) obtains, the volume ratio that described sodium carboxymethyl cellulose solution mixes with described high concentration metal nanoparticle is 1:2～4, the synthetic high concentration metal nanoparticle printing-ink with appropriate viscosity;
(4) make screen printing screens
The screen printing screens that making consists of hollow out round dot pattern of the same size, the diameter of described round dot is 3～10mm, and the mode being listed as with 10 row * 10 is uniformly distributed, and the grid aperture of the half tone of made is 1～100 μ m;
(5) print surface-enhanced Raman spectrum active substrate
The screen printing screens that step (4) is made is overlying on loading material, in described half tone one end, add the synthetic high concentration metal nanoparticle printing-ink with appropriate viscosity of step (3), adopt screen printing apparatus manually or automatically to print SERS active substrate;
(6) prepare high duplication surface-enhanced Raman spectrum active substrate
The SERS active substrate that step (5) is printed is dried 10～30 minutes in the air dry oven of 30～40 ℃, obtains high duplication surface-enhanced Raman spectrum active substrate; Dried SERS active substrate is cut into different size and seals according to design specification and preserve with standby.
2. the preparation method of high duplication surface-enhanced Raman spectrum active substrate according to claim 1, is characterized in that, the described loading material of step (5) is glass mat, silicon chip, sheet glass, filter paper, printing paper or potsherd.
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| CN102183502B (en) * | 2011-01-14 | 2012-12-12 | 楚雄师范学院 | Method for preparing nano silver film with enhanced Raman scattering substrate based on microwave technique |
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