CN101324528A - Thin film with local field enhancement function and preparing method thereof - Google Patents
Thin film with local field enhancement function and preparing method thereof Download PDFInfo
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- CN101324528A CN101324528A CNA2008101167586A CN200810116758A CN101324528A CN 101324528 A CN101324528 A CN 101324528A CN A2008101167586 A CNA2008101167586 A CN A2008101167586A CN 200810116758 A CN200810116758 A CN 200810116758A CN 101324528 A CN101324528 A CN 101324528A
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Abstract
The invention discloses a film with the function of local field enhancement. The film is characterized in that the film is composed of metal particles and dielectric particles in a combined arrangement, wherein the size of the particles is submicron-scaled or nano-scaled; and the film has a particle thickness of single layer to double layer. The invention further discloses a method for preparing the film with the function of local field enhancement and a Raman scattering substrate. The film serves a function of the local field enhancement by adopting the combined arrangement of the metal particles and the dielectric particles; and when the film is applied to the surface-enhanced Raman scattering substrate, the detection sensitivity and the signal to noise ratio of small Raman scattering signals can be improved.
Description
Technical field
The present invention relates to nanocomposite optical and faint spectrum Detection Techniques field, particularly relate to a kind of film and preparation method thereof with local field enhancement function.
Background technology
SERS (Surface Enhanced Raman Spectroscopy, surface enhanced Raman spectroscopy) has developed into technical method relatively more commonly used.Usually adopt the metal particle that is coated with rough surface metal film, stochastic distribution on the dielectric substrate, nano metal island etc. to have the surface structure of nanometer or sub-wavelength yardstick.Sample is placed on the substrate with such metal surface coarse structure, when excitation light irradiation is to substrate, will interact with sample and metal coarse structure, motivates the surface plasma vibration, thereby produces surperficial enhancement effect.This effect can improve the intensity of raman spectral signal effectively, improves detection sensitivity and signal to noise ratio (S/N ratio), realizes trace analysis and single molecule analysis.
Active metal nanoparticle and sub-wavelength yardstick structural substrates are the key factors of decision SERS enhancer, and the metal particle of suitable diameter and colloidal sol thereof are a kind of SERS substrate membrane layer materials commonly used.
In realizing process of the present invention, the inventor finds that the surperficial enhancement effect that method produced of prior art also can be further improved, thereby obtains the detection sensitivity and the signal to noise ratio (S/N ratio) of higher Raman scattering signal.
Summary of the invention
The problem that the embodiment of the invention will solve provides a kind of film with local field enhancement function and preparation method thereof, to obtain the detection sensitivity and the signal to noise ratio (S/N ratio) of the faint Raman scattering signal higher than prior art.
For achieving the above object; the technical scheme of the embodiment of the invention provides a kind of film with local field enhancement function; described film mixes arrangement by metal particle and media particles and constitutes; described metal particle and media particles are of a size of sub-micron or nanoscale, and the thickness of described film is that individual layer is to double-deck particle thickness.
Wherein, the material of described metal particle is that the real part of specific inductive capacity is the bigger negative value of absolute value and imaginary part is the material of smaller value.
Wherein, the material of described media particles is generally quartz, glass, polymeric material.
The technical scheme of the embodiment of the invention also provides a kind of preparation method with film of local field enhancement function, said method comprising the steps of: the metal particle and the media particles that will be of a size of sub-micron or nanoscale are mixed; In described mixed metal particle and media particles, add solvent, and stir, form the colloid material; Described colloid material evenly is coated with invests substrate surface; The described colloid material that invests substrate surface that is coated with is got rid of through the high speed rotating hydro-extractor and is coated with, form the film of individual layer to double-deck particle thickness; Drying or other package technique are solidified described film.
Wherein, in the described step that metal particle and media particles are mixed, the ratio of described metal particle and media particles is 1: 1.
Wherein, described solvent is a water.
Wherein, described whipping process is to be stirred by the ultrasonic oscillator vibration.
Wherein, described substrate is glass or quartz material.
Wherein, described other package technique is L B film technology, chemisorption self-assembling technique or Electrostatic Absorption self-assembling technique.
The technical scheme of the embodiment of the invention also provides a kind of Raman scattering substrate, and described Raman scattering substrate comprises: substrate; Preparation is at described suprabasil film with local field enhancement function; described film mixes arrangement by metal particle and media particles and constitutes; described metal particle and media particles are of a size of sub-micron or nanoscale, and the thickness of described film is that individual layer is to double-deck particle thickness.
Technique scheme only is an optimal technical scheme of the present invention; have following advantage: the embodiment of the invention is mixed the film that arrangement constitutes by adopting by metal particle and media particles; this film has local field enhancement function; when described film is used for the Surface enhanced raman spectroscopy substrate, can improve the detection sensitivity and the signal to noise ratio (S/N ratio) of faint Raman scattering signal.
Description of drawings
Fig. 1 is the preparation method's of film with local field enhancement function of the embodiment of the invention an a kind of process flow diagram;
Fig. 2 is a kind of computation model synoptic diagram of the embodiment of the invention;
Fig. 3 a is the electric-field intensity distribution figure of two media particles of the embodiment of the invention;
Fig. 3 b～3c is a media particles of the embodiment of the invention and the electric-field intensity distribution figure of a metal particle;
Fig. 3 d is the electric-field intensity distribution figure of two metal particles of the embodiment of the invention;
Fig. 4 is the change calculations curve maps of two microgranular textures of the embodiment of the invention along field enhancement factor in the x direction different distance plane of vision;
Fig. 5 a is two metal particles of the embodiment of the invention and the electric-field intensity distribution figure of a media particles;
Fig. 5 b is two media particles of the embodiment of the invention and the electric-field intensity distribution figure of a metal particle;
Fig. 5 c is a metal particle of the embodiment of the invention and the electric-field intensity distribution figure of three media particles;
Fig. 6 is the change calculations curve map of the multiparticulates structure of the embodiment of the invention along field enhancement factor in the x direction different distance plane of vision;
Fig. 7 is that the metal particle and the media particles of the embodiment of the invention mixed the principle of work synoptic diagram that strengthens the Raman scattering substrate.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
A kind of film with local field enhancement function of the embodiment of the invention mixes arrangement by metal particle and media particles and constitutes, and described metal particle and media particles are of a size of sub-micron or nanoscale, and thickness is that individual layer is to double-deck particle thickness.Described metal particle can be gold, silver etc. can produce the surface plasma resonance enhancement effect not with the various materials of testing sample generation chemical reaction, described media particles can be quartz, various glass, polymeric material or the like not with the dielectric material of testing sample generation chemical reaction.Described film is a metal particle with after media particles is evenly mixed, be prepared in transparent or the opaque medium substrate on form the hybrid fine particles film.
The embodiment of the invention a kind of have local field enhancement function film the preparation method as shown in Figure 1, may further comprise the steps:
S101 mixes the metal particle and the media particles of sub-micron or nanoscale.In the present embodiment, metal particle is gold or silver-colored particulate, and media particles is a silicon dioxide microparticle, and the ratio of metal particle and media particles is 1: 1.
S102 adds an amount of hydrosolvent in mixed metal particle and media particles, through the long-time mixing that stirs of vibrating of ultrasonic oscillator, form the colloid material.
S103 evenly is coated with this colloid material and invests optical glass or other substrate surface.
S104 gets rid of through the high speed rotating hydro-extractor and is coated with being coated with the colloid material that invests substrate surface, forms the film of individual layer to double-deck particle thickness.
S105, drying or other package technique are solidified described film.Described other package technique is L B film technology, chemisorption self-assembling technique or Electrostatic Absorption self-assembling technique etc.
Film with local field enhancement function of the present invention is based on light and nanostructured interacts and the local surface plasma resonance excites generation enhancing local fields between metal particle and media particles.For the near field of light field distribution, can adopt computation model shown in Figure 2, utilize the Finite Difference-Time Domain separating method to carry out simulation calculation.Light beam 3 is from a right-angle side vertical incidence of right angle glass (ε=2.25) prism 1, with greater than the angular illumination of critical angle to hypotenuse, total reflection takes place at glass 1-air 2 interfaces, produce evanescent wave.Be positioned at metal particle and/or media particles 5,6 and evanescent wave interaction on the glass prism inclined-plane, produce local and strengthen electromagnetic field.If incident light 3 is a uniform plane wave, vacuum wavelength is 470nm.The diameter of all metal particles and media particles is 50nm, and the material of metal particle is silver-colored Ag (ε
Ag=-8.23+0.29i), the DIELECTRIC CONSTANT of media particles
d=6.25.Based on three-dimensional Finite Difference-Time Domain separating method, the local electromagnetic field enhancing of two or more metal particles and/or media particles different distributions structure is calculated and analyzed.
When two particulate homeotropic alignments, if the TM polarized incident light with 45 ° of incidents, then its electric-field intensity distribution is shown in Fig. 3 a～3d.When two particulates were media particles (being labeled as D among the figure), shown in Fig. 3 a, respectively local was between the inclined-plane of media particles and glass prism and between two media particles for electric field, and field enhancement factor is about 181.When two particulates were metal particle (being labeled as M among the figure), shown in Fig. 3 d, the main local of electric field was between two particulates, and field enhancement factor is about 3837.When two particulates were respectively a media particles and a metal particle, between two particulates, the field enhancement factor that Fig. 3 b and Fig. 3 c arrange was respectively 1.5353 * 10 to electric field by the height local
4With 1.9765 * 10
4Fig. 4 provides along the variation (centre of sphere of particulate is positioned at the x=0nm plane) of field enhancement factor in the x direction different distance plane of vision.Can find out obviously that from result of calculation right for media particles-metal particle, not only to having improved about 5 times, and the local degree of electric field is higher than metal particle-metal particle for field enhancement factor, thereby resolution will be higher.The right resolution of media particles-metal particle is about 15nm, and the right resolution of metal particle-metal particle is about 35nm.
When a plurality of particulate random alignment, have the situation of a plurality of media particles or metal particle on the inclined-plane for glass prism 1, if the TM polarized incident light with 45 ° of incidents, then its electric-field intensity distribution is shown in Fig. 5 a～5c.When there was a media particles on the next door of two metal particles arranging along prism inclined-plane vertical direction among Fig. 5 a, the existence of media particles was little to the influence of electric-field intensity distribution, and field enhancement factor is about 4196.When there was a media particles on the next door of a metal particle of arranging along prism inclined-plane vertical direction among Fig. 5 b and a media particles, the existence of media particles was little equally to the influence of Electric Field Distribution, and field enhancement factor is about 2.6977 * 10
4When there are two media particles on the next door of a metal particle of arranging along prism inclined-plane vertical direction among Fig. 5 c and a media particles, the existence of media particles produces comparatively significantly influence to electric-field intensity distribution, field enhancement factor is about 2148, about order of magnitude that descended, but still strengthened about one times than the situation of single metal particulate (field enhancement factor is about 1160).Fig. 6 provides along the variation (centre of sphere of particulate is positioned at the x=0nm plane) of field enhancement factor in the x direction different distance plane of vision.
For the hybrid fine particles of media particles and metal particle coexistence, the existence of media particles can not reduce the local degree and the field enhancement factor of electromagnetic field, and when formation media particles-metal particle to the time, will bring higher electromagnetic field local and field enhancement factor.Medium and metal particle mixed structure film have than the stronger enhancement effect of simple metal particle membrane structure.
The film of making through process shown in Figure 1 mixes enhancing Raman scattering substrate with substrate formation metal particle with the medium nanoparticle.Described Raman scattering substrate comprises substrate and prepares at described suprabasil film with local field enhancement function; described film mixes arrangement by metal particle and media particles and constitutes; described metal particle and media particles are of a size of sub-micron or nanoscale, and the thickness of described film is that individual layer is to double-deck particle thickness.Testing sample placed carry out raman scattering spectrum on this substrate and detect, promptly the SERS method is surveyed.The principle of work synoptic diagram as shown in Figure 7.The film that preparation metal particle 8 and media particles 9 are mixed in substrate 7 forms and strengthens substrate, testing sample 10 is coated on this enhancing substrate again.When incident laser 11 exciting irradiations are to hybrid fine particles, because the local fields enhancement effect of hybrid fine particles, can obtain stronger electric field and excite testing sample, thereby obtain the stronger Raman diffused light spectrum signal 12 of testing sample, have higher signal to noise ratio (S/N ratio) and the spatial resolution of Geng Gao simultaneously.Its performance will be better than the performance of the SERS substrate of common simple metal particulate and rough surface structure.
The present invention equally also is applicable among other application that needs the local fields enhancement effect, as can be used for fields such as near-field nanometer light source, the storage of super-high density near field optic, nano-photoetching and near field optic operation.
The embodiment of the invention is mixed the film that arrangement constitutes by adopting by metal particle and media particles; this film has local field enhancement function; when described film is used for the Surface enhanced raman spectroscopy substrate, can improve the detection sensitivity and the signal to noise ratio (S/N ratio) of faint Raman scattering signal.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1, a kind of film with local field enhancement function; it is characterized in that; described film mixes arrangement by metal particle and media particles and constitutes, and described metal particle and media particles are sub-micron or nanoscale, and the thickness of described film is that individual layer is to double-deck particle thickness.
2, have the film of local field enhancement function according to claim 1, it is characterized in that, the material of described metal particle is that the real part of specific inductive capacity is the bigger negative value of absolute value and imaginary part is the material of smaller value.
3, have the film of local field enhancement function according to claim 1, it is characterized in that, the material of described media particles is quartz, glass, polymeric material.
4, a kind of preparation method with film of local field enhancement function is characterized in that, said method comprising the steps of:
The metal particle and the media particles of sub-micron or nanoscale are mixed;
In described mixed metal particle and media particles, add solvent, and stir, form the colloid material;
Described colloid material evenly is coated with invests substrate surface;
The described colloid material that invests substrate surface that is coated with is got rid of through the high speed rotating hydro-extractor and is coated with, form the film of individual layer to double-deck particle thickness;
Drying or other package technique are solidified described film.
As having the preparation method of the film of local field enhancement function as described in the claim 4, it is characterized in that 5, in the described step that metal particle and media particles are mixed, the ratio of described metal particle and media particles is 1: 1.
6, as having the preparation method of the film of local field enhancement function as described in the claim 4, it is characterized in that described solvent is a water.
As having the preparation method of the film of local field enhancement function as described in the claim 4, it is characterized in that 7, described whipping process is to be stirred by the ultrasonic oscillator vibration.
8, as having the preparation method of the film of local field enhancement function as described in the claim 4, it is characterized in that described substrate is glass or quartz material.
9, as having the preparation method of the film of local field enhancement function as described in the claim 4, it is characterized in that described other package technique is L B film technology, chemisorption self-assembling technique or Electrostatic Absorption self-assembling technique.
10, a kind of Raman scattering substrate is characterized in that, described Raman scattering substrate comprises:
Substrate;
Preparation is at described suprabasil film with local field enhancement function; described film mixes arrangement by metal particle and media particles and constitutes; described metal particle and media particles are sub-micron or nanoscale, and the thickness of described film is that individual layer is to double-deck particle thickness.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102483355A (en) * | 2010-01-29 | 2012-05-30 | 惠普发展公司，有限责任合伙企业 | Self-collecting SERS substrate |
| CN102706857A (en) * | 2012-07-02 | 2012-10-03 | 中国科学院合肥物质科学研究院 | Preparation method of multifunctional surface enhanced raman scattering (SERS) substrate |
| CN103901231A (en) * | 2014-04-08 | 2014-07-02 | 东南大学 | Preparation method for asphalt sample suitable for atomic force microscope observation |
| CN103969241A (en) * | 2014-05-20 | 2014-08-06 | 中国科学技术大学 | Raman base |
| CN104246480A (en) * | 2012-04-27 | 2014-12-24 | 精工爱普生株式会社 | Optical device and detection apparatus |
| CN113328325A (en) * | 2021-04-22 | 2021-08-31 | 江苏度微光学科技有限公司 | Flexible polymer random laser and preparation method thereof |
Families Citing this family (1)
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| CN105702851B (en) * | 2014-11-28 | 2018-09-25 | 中国科学院深圳先进技术研究院 | 2-2 type piezo-electricity composite materials and preparation method thereof |
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2008
- 2008-07-16 CN CN2008101167586A patent/CN101324528B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102483355A (en) * | 2010-01-29 | 2012-05-30 | 惠普发展公司，有限责任合伙企业 | Self-collecting SERS substrate |
| CN104246480A (en) * | 2012-04-27 | 2014-12-24 | 精工爱普生株式会社 | Optical device and detection apparatus |
| CN102706857A (en) * | 2012-07-02 | 2012-10-03 | 中国科学院合肥物质科学研究院 | Preparation method of multifunctional surface enhanced raman scattering (SERS) substrate |
| CN102706857B (en) * | 2012-07-02 | 2014-03-19 | 中国科学院合肥物质科学研究院 | Preparation method of multifunctional surface enhanced raman scattering (SERS) substrate |
| CN103901231A (en) * | 2014-04-08 | 2014-07-02 | 东南大学 | Preparation method for asphalt sample suitable for atomic force microscope observation |
| CN103969241A (en) * | 2014-05-20 | 2014-08-06 | 中国科学技术大学 | Raman base |
| CN113328325A (en) * | 2021-04-22 | 2021-08-31 | 江苏度微光学科技有限公司 | Flexible polymer random laser and preparation method thereof |
| CN113328325B (en) * | 2021-04-22 | 2023-10-31 | 江苏度微光学科技有限公司 | Flexible polymer random laser and preparation method thereof |
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