CN101140234B - Preparation method of surface reinforced Raman diffuse transmission substrate - Google Patents
Preparation method of surface reinforced Raman diffuse transmission substrate Download PDFInfo
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- CN101140234B CN101140234B CN200710042776XA CN200710042776A CN101140234B CN 101140234 B CN101140234 B CN 101140234B CN 200710042776X A CN200710042776X A CN 200710042776XA CN 200710042776 A CN200710042776 A CN 200710042776A CN 101140234 B CN101140234 B CN 101140234B
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- silex glass
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Abstract
A method to produce surface enhanced Raman substrate (SERS) focalizes a laser beam with pulse width of 10 swung dash 500femtosecond, power of 1 swung dash 100milliwatt and peak power of 2 is multiplied by 10<SUP>9</SUP> swung dash 5 is multiplied by 10<SUP>12</SUP>W to form a light spot with a diameter of several microns, thus projecting the focalized light spot of the femtosecond laser beam ontoa silicon glass surface mixed with precious metals, synchronously scanning the focalized light spot and forming a silicon glass substrate with nanometer roughness precious metal grains on its surface. And then the substrate is positioned to silver nitrate or aurum chlorate for steeping to form a precious metal film layer with nanometer roughness and obtaining a SERS. Relevant experiments indicatethat the SERS produced according to the present invention is provided with a remarkably enhanced surface Raman scattering effect.
Description
Technical field
The present invention relates to a plurality of fields such as optics, material and biology, particularly a kind of method of utilizing the femtosecond laser parallel micromachining technology to prepare the Surface enhanced raman spectroscopy substrate.
Background technology
Development of life science has entered into the detection on unicellular and the single molecules level and has controlled the epoch.But because the optical means direct imaging, and the object of being studied is disturbed minimum, have advantages such as harmless, in site measurement, become the research means of life science first-selection.Raman spectrum can obtain the vibrational energy level information of molecule, is called " the fingerprint spectrum " of molecule, and the detailed structure information of molecule can be provided, as the type of chemical bond, intensity, angle, the variation of structure picture etc.But common Raman scattering efficient is very low, and the raman scattering cross section of molecule is difficult to biological sample is directly surveyed than low tens magnitudes in fluorescent scattering cross section generally speaking, improves excitation light intensity and then may produce spinoffs such as the optical damage of sample and photobleaching.Discover the seventies in 20th century, when pyridine molecule during near coarse electrode surface, the local electric field that the metal surface plasma resonance body produces strengthens can greatly strengthen the received electric field of molecule, and then strengthen the Raman signal that the far field receives, Surface enhanced raman spectroscopy that Here it is (surface-enhanced Raman scattering,, abbreviate SERS as).The SERS method can improve the raman scattering cross section of molecule greatly, and the ratio of the Raman signal intensity after strengthening and normal Raman signal intensity is called as the SERS enhancer.The multiple materials such as metal film of the electrode of electronation, metal-sol, evaporation, cold deposition or sputter can be realized SERS, and the gold of hundred nanoscales and the money kind metal Raman that can offer the best strengthens effect.The SERS spectroscopy can be low to moderate 10 to the concentration detectability of fluid sample
-1310
-14M (mol/L).This is very suitable for research price height, quantity is few, concentration is low biological sample.In conjunction with the resolution characteristic of its Non-Destructive Testing characteristic and finger-print type, special advantage and good prospects for application are arranged aspect the medical applications such as the SERS spectroscopy detects at live body, the early diagnosis of disease, immunoassay.The preparation of SERS substrate is the target that researchers pursue for many years, also is this field focus of research at present.
In generation nineteen fifty, Stookey etc. have invented the fotoceram (noble metal-doped silicateglass) of mixing noble metal.Gold in the fotoceram or silver ion can be under the situation of UV-irradiation trapped electrons, thereby be reduced to atom.It is that the center is grown to nanocluster with these atoms that suitable high annealing can impel the metallic ion in the glass.Discovering in recent years, the superelevation instantaneous power of femtosecond laser also can be induced the metallic reducing in the glass.When a branch of pulse width is 100fs, single pulse energy is after the femtosecond laser of 1 μ J is focused, and the instantaneous electric field intensity at its focus place can reach 100TW/cm
2, be enough to and the material production nonlinear interaction, be modulated at the focus place mutually by self-alignment and produce the white light super continuous spectrums.Femtosecond laser itself and the super continuous spectrums that produces thereof will be induced the multi-photon absorption process of glass, thereby with the metallic ion reduction, the size and the position of condition control silver nano-grains such as position that also can be by changing femtosecond laser scanning and intensity.But the silver nano-grain that this method forms is positioned at the inside of glass, needs high annealing, and the nanoparticle size of preparation limited (the best size of the silver nano-grain in the SERS substrate is about 100nm), can not directly apply to SERS.In femtosecond photoinduction silver recovery, factors such as the concentration that the silver in the wavelength of femtosecond laser, energy, pulse width, repetition frequency and the glass mixes, the kind that the reduction electronic elements is provided and concentration all can influence size, efficient and the space distribution of the silver nano-grain of separating out.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of preparation method of Surface enhanced raman spectroscopy substrate is provided.
Technical solution of the present invention is as follows:
A kind of preparation method of Surface enhanced raman spectroscopy substrate is characterised in that to comprise the following steps:
The first, the preparation of femtosecond laser: with pulse width is 10～500 femtoseconds, and power is 1～100 milliwatt, and peak power is that the femtosecond laser light beam of 2x109～5x1012W focuses on, and the formation diameter is several microns a hot spot;
The second, a silex glass of mixing noble metal is fixed, make described femtosecond laser beams focusing hot spot be radiated at described surface of mixing the silex glass of noble metal;
The 3rd, at hot spot that moves laser beam perpendicular to optical axis direction or the described silex glass of mixing noble metal, make and laser beam is assembled and scanned the surface that this mixes the silex glass of noble metal, form the silex glass substrate that the surface has the noble metal granule of nanometer roughness;
The 4th, the silex glass substrate that the 3rd step was prepared places silver nitrate or chloric acid gold solution to soak, and forms the precious metal film layer with nanometer roughness, obtains the Surface enhanced raman spectroscopy substrate;
Described noble metal is a gold or silver-colored.
Technique effect of the present invention
Utilize the Surface enhanced raman spectroscopy substrate of the inventive method preparation, test shows: be on the sensing unit of the glycocoll of the 1 mol Surface enhanced raman spectroscopy substrate that drops in the inventive method preparation with concentration, measure its Raman spectrum 2500 times when not adding substrate.
Description of drawings
Fig. 1 is the Surface enhanced raman spectroscopy substrate of the inventive method preparation and the contrast that does not add the Raman spectrum of substrate
Embodiment
The invention will be further described below in conjunction with embodiment, but should not limit protection scope of the present invention with this.
With pulse width is 10～500 femtoseconds, and power is that (peak power is 2x10 to 1～100 milliwatt
9～5x10
12W) laser beam focuses on, and the formation diameter is several microns a hot spot; It is radiated at mixes noble metal (gold or silver etc.) silex glass surface.By the gated sweep platform focal beam spot is scanned at glass surface, place in the hot spot irradiation, the superelevation instantaneous power of femtosecond laser is reduced to atom with the precious metal ion of glass inside, and accumulates in glass surface, forms the noble metal granule with nanoscale roughness.The glass of aforementioned preparation is placed silver nitrate (AgNO
3) or chloric acid gold (HAuCl
44H
2O) in the solution, soak the some time, grow into precious metal film layer, form Surface enhanced raman spectroscopy substrate relatively uniformly with nanoscale roughness by the electroless plating mode.Available machined parameters is as shown in the table.
Embodiment 1
Present embodiment choose for to mix silver-colored silex glass (content of silver ion is 0.1mol%), the peak power of femtosecond laser is 2x10
11W focuses on glass surface through microcobjective, and scans with three-dimensional mobile platform, and obtaining width is 50 microns, and length is 300 microns sensing unit.The glass of preparation places liquor argenti nitratis ophthalmicus, soaks the some time, is grown to the precious metal film layer with nanometer roughness, forms the Surface enhanced raman spectroscopy substrate.With concentration is that the glycocoll of 1 mol drops on the sensing unit, measures its Raman spectrum 2500 times when not adding substrate, has realized the enhancing to the sample Raman spectrum, and the result as shown in Figure 1.The Surface enhanced raman spectroscopy of (a) glycine molecule among the figure, measurement concentration is 1mol/L, be 20 seconds integral time.(b) the normal Raman spectrum of glycine molecule, measurement concentration is 10mol/L, be 300 seconds integral time.
Embodiment 2
Present embodiment choose for to mix silver-colored silex glass (content of silver ion is 0.1mol%), utilizing pulsewidth is 400 femtoseconds, 100 hertz of repetition frequencys, centre wavelength 780 nanometers, power is that (peak power is 2x10 to 8 milliwatts
10W) laser focuses on glass surface through microcobjective, and scans with three-dimensional mobile platform, and obtaining width is 50 microns, and length is 300 microns sensing unit.The glass of preparation places liquor argenti nitratis ophthalmicus, soaks the some time, is grown to the precious metal film layer with nanometer roughness, forms the Surface enhanced raman spectroscopy substrate.
Embodiment 3
Present embodiment choose for to mix silver-colored silex glass (content of silver ion is 0.1mol%), utilizing pulsewidth is 10 femtoseconds, 10 hertz of repetition frequencys, centre wavelength 830 nanometers, power is that (peak power is 2x10 to 20 milliwatts
12W) laser focuses on glass surface through microcobjective, and scans with three-dimensional mobile platform, and obtaining width is 50 microns, and length is 300 microns sensing unit.The glass of preparation places the chloric acid gold solution, soaks the some time, is grown to the precious metal film layer with nanometer roughness, forms the Surface enhanced raman spectroscopy substrate.
Embodiment 4
Present embodiment choose for to mix silver-colored silex glass (content of silver ion is 0.1mol%), utilizing pulsewidth is 40 femtoseconds, 1000 hertz of repetition frequencys, centre wavelength 800 nanometers, power is that (peak power is 2x10 to 8 milliwatts
11W) laser focuses on glass surface through microcobjective, and scans with three-dimensional mobile platform, and obtaining width is 50 microns, and length is 300 microns sensing unit.The glass of preparation places the chloric acid gold solution, soaks the some time, is grown to the precious metal film layer with nanometer roughness, forms the Surface enhanced raman spectroscopy substrate.
Embodiment 5
Present embodiment choose for to mix silver-colored silex glass (content of silver ion is 0.1mol%), utilizing pulsewidth is 400 femtoseconds, 100 hertz of repetition frequencys, centre wavelength 780 nanometers, power is that (peak power is 2x10 to 8 milliwatts
10W) laser focuses on glass surface through microcobjective, and scans with three-dimensional mobile platform, and obtaining width is 50 microns, and length is 300 microns sensing unit.The glass of preparation places liquor argenti nitratis ophthalmicus, soaks the some time, is grown to the precious metal film layer with nanometer roughness, forms the Surface enhanced raman spectroscopy substrate.
Embodiment 6
Present embodiment choose for to mix silver-colored silex glass (content of silver ion is 0.1mol%), utilizing pulsewidth is 10 femtoseconds, 10 hertz of repetition frequencys, centre wavelength 830 nanometers, power is that (peak power is 2x10 to 20 milliwatts
12W) laser focuses on glass surface through microcobjective, and scans with three-dimensional mobile platform, and obtaining width is 50 microns, and length is 300 microns sensing unit.The glass of preparation places the chloric acid gold solution, soaks the some time, is grown to the precious metal film layer with nanometer roughness, forms the Surface enhanced raman spectroscopy substrate.
Claims (2)
1. the preparation method of a Surface enhanced raman spectroscopy substrate is characterised in that to comprise the following steps:
The first, the preparation of femtosecond laser: with pulse width is 10～500 femtoseconds, and power is 1～100 milliwatt, and peak power is 2 * 10
9～5 * 10
12The laser beam of W focuses on, and the formation diameter is several microns a hot spot;
The second, a silex glass of mixing noble metal is fixed, make described femtosecond laser beams focusing hot spot be radiated at described surface of mixing the silex glass of noble metal;
The 3rd, at hot spot that moves laser beam perpendicular to optical axis direction or the described silex glass of mixing noble metal, make laser beam assemble and scan the surface of the silex glass of this noble metal, form the silex glass substrate that the surface has the noble metal granule of nanometer roughness;
The 4th, the silex glass substrate that the 3rd step was prepared places silver nitrate or chloric acid gold solution to soak, and forms the precious metal film layer with nanometer roughness, obtains the Surface enhanced raman spectroscopy substrate.
2. the preparation method of Surface enhanced raman spectroscopy substrate according to claim 1 is characterized in that described noble metal is gold or silver-colored.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102269706A (en) * | 2011-06-13 | 2011-12-07 | 青岛农业大学 | Simple method for manufacturing plasma resonance controlled surface-enhanced Raman substrate |
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| CN102020231B (en) * | 2010-10-25 | 2012-12-26 | 中国科学院理化技术研究所 | Enhanced Raman scattering substrates of silicon semiconductor and a manufacturing method and application for the same |
| CN102262083A (en) * | 2011-01-29 | 2011-11-30 | 中国科学院合肥物质科学研究院 | Dynamic surface enhanced Raman spectroscopy detection method |
| CN102285629B (en) * | 2011-05-05 | 2014-03-26 | 厦门大学 | Preparation method for surface-enhanced Raman spectrum active substrate |
| CN103364390A (en) * | 2012-04-10 | 2013-10-23 | 国家纳米科学中心 | Surface-enhanced Raman substrate, preparation method and application thereof |
| CN102916257B (en) * | 2012-10-23 | 2015-02-04 | 中国科学技术大学 | Low-cost coating with self-cleaning and infrared broadband hiding functions, preparation method and application of coating |
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| CN104028777B (en) * | 2014-06-23 | 2016-02-10 | 北京理工大学 | The method of surface enhanced Raman substrate is prepared based on femtosecond laser dynamic control |
| CN104230183A (en) * | 2014-09-15 | 2014-12-24 | 上海理工大学 | Preparation method of tunable surface enhanced Raman scattering substrate |
| CN104773957B (en) * | 2015-04-07 | 2018-07-06 | 中国原子能科学研究院 | A kind of glass for adulterating gold nano grain and preparation method thereof and Gold Films Irradiated by Femtosecond Laser system |
| CN105158227B (en) * | 2015-06-05 | 2018-03-06 | 中物院成都科学技术发展中心 | A kind of method for preparing SERS substrates |
| CN107037032B (en) * | 2017-05-31 | 2020-03-31 | 厦门大学 | Method for rapidly preparing large-area graphene/metal composite structure SERS substrate |
| CN108226123B (en) * | 2017-12-12 | 2021-02-23 | 华南师范大学 | Method for preparing surface enhanced Raman scattering substrate by femtosecond laser |
| CN110455775B (en) * | 2019-09-11 | 2023-12-01 | 重庆大学 | Super-hydrophobic surface-enhanced substrate for surface-enhanced Raman spectrum detection |
| CN112666147A (en) * | 2020-11-23 | 2021-04-16 | 广西电网有限责任公司电力科学研究院 | Preparation method of nano-silver SERS substrate based on coordination network polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102269706A (en) * | 2011-06-13 | 2011-12-07 | 青岛农业大学 | Simple method for manufacturing plasma resonance controlled surface-enhanced Raman substrate |
| CN102269706B (en) * | 2011-06-13 | 2014-04-09 | 青岛农业大学 | Simple method for manufacturing plasma resonance controlled surface-enhanced Raman substrate |
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