CN103604795B - A kind of across yardstick thermometal collaborative enhancing Raman scattering chip and preparation method thereof - Google Patents
A kind of across yardstick thermometal collaborative enhancing Raman scattering chip and preparation method thereof Download PDFInfo
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- CN103604795B CN103604795B CN201310618273.8A CN201310618273A CN103604795B CN 103604795 B CN103604795 B CN 103604795B CN 201310618273 A CN201310618273 A CN 201310618273A CN 103604795 B CN103604795 B CN 103604795B
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Abstract
The invention discloses a kind of across yardstick thermometal collaborative enhancing Raman scattering chip, comprise chip base, described chip base is processed with micro structure array, described micro structure array surface is coated with double layer of metal film; The invention also discloses and work in coordination with across yardstick thermometal the method strengthening Raman scattering chip a kind of preparation, first applicable chip base material is chosen, then at selected substrate material surface processing micro structure array, finally double layer of metal film is plated successively on micro structure array surface.Of the present invention have across yardstick multilevel hierarchy across the collaborative Raman scattering chip that strengthens of yardstick thermometal, synergy between the micron scale construction of chip base and metal nano level island membrane structure and the thermometal of double layer of metal film act synergistically, make the multiple Raman enhancer of this chipset, there is the sensitivity for analysis of superelevation; The method that the present invention prepares Raman chip is simple, and repeatability is high, is easy to accomplish scale production.
Description
Technical field
The present invention relates to a kind of Raman chip and preparation method thereof, particularly one strengthens Raman scattering chip and preparation method thereof across yardstick thermometal is collaborative.
Background technology
Incident light and material molecule cause molecule to do forced vibration when interacting thus produce scattered light, and the spectral line that wherein frequency of scattered light is identical with the frequency of incident light is Rayleigh scattering, and the spectral line that the frequency of scattered light is different with the frequency of incident light is Raman scattering.Raman scattering spectrum is characteristic fingerprint spectrum, and relevant with the vibration of material molecule, rotational energy level, can reflect molecular composition and the structural form of measured matter, be the powerful of amalyzing substances structure; But because the signal intensity of Raman spectrum is very weak, thus its detection sensitivity is low, causes Raman spectrum well not applied within a very long time.
The appearance of Surface enhanced raman spectroscopy technology, significantly improves this situation.When material molecule is adsorbed on coarse metal surface, surface local plasmon excimer is excited the Electromagnetic enhancement (i.e. physics enhancing) caused, and cluster on rough surface and the absorption molecule on it forms the active site (i.e. Chemical enhancement) that Raman strengthens, the effect of both makes the Raman scattering of measured object produce great enhancement effect, and its enhancer can reach 10
3~ 10
7.Research shows, thermometal composite nanostructure is compared with one-component metal Nano structure, and electronics and the optical property with uniqueness can strengthen Raman spectrum Detection results.At present; thermometal composite nano materials mainly adopts chemical synthesis to prepare; the shape and size defect more rambunctious of metal nano material is there is in the method in preparation process; thus be difficult to accomplish scale production; the demand of a large amount of analytical test cannot be met, thus limit its industrialization and the application in every field.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of Raman chip with high detection sensitivity, the present invention also provides a kind of method can preparing Raman chip on a large scale.
For achieving the above object, the invention provides following technical scheme: of the present invention across yardstick thermometal collaborative enhancing Raman scattering chip, comprise chip base, described chip base is processed with micro structure array, described micro structure array surface is coated with double layer of metal film successively.
Of the present invention have across yardstick multilevel hierarchy across the collaborative Raman scattering chip that strengthens of yardstick thermometal, synergy between the micron scale construction of chip base and metal nano level island membrane structure and the thermometal of double layer of metal film act synergistically, make the multiple Raman enhancer of this chipset, there is more significant Raman scattering and strengthen ability.
Further, described chip base material is silicon, glass, quartz, dimethyl silicone polymer or polymethylmethacrylate.
Further, the microstructure of described micro structure array is cylindricality, taper, spherical, triangle, pyramid or reverse pyramid.
Further, the microstructure size of described micro structure array is 0.5 ~ 100 μm, and array period is 0.5 ~ 100 μm.
Further, described metal is Au, Ag, Cu or Pt.
Further, in described double layer of metal film, first layer metal film thickness is 100 ~ 500nm, and second layer metal film thickness is 5 ~ 100nm.
The invention also discloses and work in coordination with across yardstick thermometal the method strengthening Raman scattering chip a kind of preparation, comprise the following steps:
Step one: choose silicon, glass, quartz, dimethyl silicone polymer or polymethylmethacrylate as chip base material;
Step 2: at selected substrate material surface processing micro structure array, the microstructure of the micro structure array processed is cylindricality, taper, spherical, triangle, pyramid or reverse pyramid;
Step 3: plate double layer of metal film successively on micro structure array surface.
Further, the microstructure size of described micro structure array is 0.5 ~ 100 μm, and array period is 0.5 ~ 100 μm.
Further, in described double layer of metal film, first layer metal film thickness is 100 ~ 500nm, and second layer metal film thickness is 5 ~ 100nm.
The method that the present invention's preparation works in coordination with enhancing Raman scattering chip across yardstick thermometal is simple, and repeatability is high, is easy to accomplish scale production.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, the invention provides following accompanying drawing and being described:
Fig. 1 is the cross-sectional view of working in coordination with enhancing Raman scattering chip across yardstick thermometal that embodiment 1 obtains;
Fig. 2 is the electron scanning micrograph of working in coordination with enhancing Raman scattering chip across yardstick thermometal that embodiment 1 obtains;
Fig. 3 is that working in coordination with across yardstick thermometal of utilizing embodiment 1 obtained strengthens Raman scattering chip, by the Raman spectrogram of the RenishawinVia micro-Raman spectroscopy test 10nM rhodamine B of 532nm exciting light.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
Following examples will disclose a kind of across yardstick thermometal collaborative enhancing Raman scattering (Trans-scaleBimetallicSynergisticEnhancedRamanScattering, TBSERS) chip, comprise chip base 1, described chip base 1 is processed with micro structure array, and described micro structure array surface is coated with double layer of metal film 2 and 3 successively.
Wherein, described chip base 1 material is silicon, glass, quartz, dimethyl silicone polymer (PDMS) or polymethylmethacrylate (PMMA).
The microstructure of described micro structure array is cylindricality, taper, spherical, triangle, pyramid or reverse pyramid.
The microstructure size of described micro structure array is 0.5 ~ 100 μm, and array period is 0.5 ~ 100 μm.
Described metal is Au, Ag, Cu or Pt.
Embodiment 1:
The present embodiment prepares the method for TBSERS chip, comprises the following steps:
Step one: choose chip base 1 material;
Step 2: at selected substrate material surface processing micro structure array;
Step 3: plate double layer of metal film successively on micro structure array surface.
Prepare the improvement of the method for TBSERS chip as the present embodiment, described step one chip base 1 starting material are silicon.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure of the micro structure array that described step 2 is processed is reverse pyramid.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure size of described micro structure array is 1.5 μm, and array period is 2.0 μm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, institute's metal-coated membrane is two-layer.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film thickness is 300nm, and second layer metal film thickness is 10nm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film is Au film, and described second layer metal film is Ag film.
TBSERS chip obtained by the present embodiment as shown in Figure 1, comprises chip base 1 from the bottom up successively, the second layer metal film 3 being attached to the first layer metal film 2 in chip base 1 and being attached on first layer metal film 2.
Embodiment 2:
The present embodiment prepares the method for TBSERS chip, comprises the following steps:
Step one: choose chip base 1 material;
Step 2: at selected substrate material surface processing micro structure array;
Step 3: plate double layer of metal film successively on micro structure array surface.
Prepare the improvement of the method for TBSERS chip as the present embodiment, described step one chip base 1 starting material are glass.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure of the micro structure array that described step 2 is processed is tapered.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure size of described micro structure array is 2 μm, and array period is 2 μm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, institute's metal-coated membrane is two-layer.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film thickness is 120nm, and second layer metal film thickness is 20nm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film is Ag film, and described second layer metal film is Au film.
Embodiment 3:
The present embodiment prepares the method for TBSERS chip, comprises the following steps:
Step one: choose chip base 1 material;
Step 2: at selected substrate material surface processing micro structure array;
Step 3: plate double layer of metal film successively on micro structure array surface.
Prepare the improvement of the method for TBSERS chip as the present embodiment, described step one chip base 1 starting material are quartz.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure of the micro structure array that described step 2 is processed is spherical in shape.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure size of described micro structure array is 30 μm, and array period is 30 μm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, institute's metal-coated membrane is two-layer.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film thickness is 180nm, and second layer metal film thickness is 30nm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film is Au film, and described second layer metal film is Pt film.
Embodiment 4:
The present embodiment prepares the method for TBSERS chip, comprises the following steps:
Step one: choose chip base 1 material;
Step 2: at selected substrate material surface processing micro structure array;
Step 3: plate double layer of metal film successively on micro structure array surface.
Prepare the improvement of the method for TBSERS chip as the present embodiment, described step one chip base 1 starting material are PDMS.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure of the micro structure array that described step 2 is processed is triangular in shape.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure size of described micro structure array is 60 μm, and array period is 60 μm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, institute's metal-coated membrane is two-layer.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film thickness is 220nm, and second layer metal film thickness is 30nm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film is Cu film, and described second layer metal film is Ag film.
Embodiment 5:
The present embodiment prepares the method for TBSERS chip, comprises the following steps:
Step one: choose chip base 1 material;
Step 2: at selected substrate material surface processing micro structure array;
Step 3: plate double layer of metal film successively on micro structure array surface.
Prepare the improvement of the method for TBSERS chip as the present embodiment, described step one chip base 1 starting material are PMMA.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure of the micro structure array that described step 2 is processed is pyramid.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure size of described micro structure array is 80 μm, and array period is 80 μm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, institute's metal-coated membrane is two-layer.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film thickness is 270nm, and second layer metal film thickness is 40nm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film is Ag film, and described second layer metal film is Au film.
Embodiment 6:
The present embodiment prepares the method for TBSERS chip, comprises the following steps:
Step one: choose chip base 1 material;
Step 2: at selected substrate material surface processing micro structure array;
Step 3: plate double layer of metal film successively on micro structure array surface.
Prepare the improvement of the method for TBSERS chip as the present embodiment, described step one chip base 1 starting material are PDMS.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure of the micro structure array that described step 2 is processed is cylindricality.
Prepare the improvement of the method for TBSERS chip as the present embodiment, the microstructure size of described micro structure array is 100 μm, and array period is 100 μm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, institute's metal-coated membrane is two-layer.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film thickness is 300nm, and second layer metal film thickness is 50nm.
Prepare the improvement of the method for TBSERS chip as the present embodiment, in described double layer of metal film, first layer metal film is Au film, and described second layer metal film is Ag film.
Fig. 2 is the electron scanning micrograph of TBSERS chip prepared by embodiment 1, the as can be seen from the figure multilevel hierarchy of chip surface.
Fig. 3 is the TBSERS chip utilizing embodiment 1, by the Raman spectrogram of the RenishawinVia micro-Raman spectroscopy test 10nM rhodamine B of 532nm exciting light.As can be seen from the figure: the Raman signal that low concentration material can be detected by TBSERS chip, its raman characteristic peak can obviously be distinguished.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (6)
1. one kind strengthens Raman scattering chip across yardstick thermometal is collaborative, comprise chip base (1), it is characterized in that: (1) is processed with micro structure array to described chip base, described micro structure array surface is coated with double layer of metal film (2) and (3) successively, the microstructure of described micro structure array is cylindricality, taper, spherical, triangle, pyramid or reverse pyramid, in described double layer of metal film, first layer metal film thickness is 120 ~ 300nm, and second layer metal film thickness is 5 ~ 50nm.
2. strengthen Raman scattering chip across yardstick thermometal is collaborative according to claim 1, it is characterized in that: described chip base (1) material is silicon, glass, quartz, dimethyl silicone polymer or polymethylmethacrylate.
3. strengthen Raman scattering chip across yardstick thermometal is collaborative according to claim 1, it is characterized in that: the microstructure size of described micro structure array is 0.5 ~ 100 μm, and array period is 0.5 ~ 100 μm.
4. strengthen Raman scattering chip across yardstick thermometal is collaborative according to claim 1, it is characterized in that: described metal is Au, Ag, Cu or Pt.
5. prepare and work in coordination with across yardstick thermometal the method strengthening Raman scattering chip as claimed in claim 1, it is characterized in that, comprise the following steps:
Step one: choose silicon, glass, quartz, dimethyl silicone polymer or polymethylmethacrylate as chip base (1) material;
Step 2: at selected substrate material surface processing micro structure array, the microstructure of the micro structure array processed is cylindricality, taper, spherical, triangle, pyramid or reverse pyramid;
Step 3: plate double layer of metal film successively on micro structure array surface;
In described double layer of metal film, first layer metal film thickness is 120 ~ 300nm, and second layer metal film thickness is 10 ~ 50nm.
6. prepare according to claim 5 and work in coordination with across yardstick thermometal the method strengthening Raman scattering chip, it is characterized in that: the microstructure size of described micro structure array is 0.5 ~ 100 μm, and array period is 0.5 ~ 100 μm.
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| CN106018379B (en) * | 2016-05-16 | 2019-04-16 | 华南师范大学 | A kind of wide area surface enhancing Raman scattering substrate and preparation method thereof |
| CN106645089A (en) * | 2016-12-30 | 2017-05-10 | 中国科学院重庆绿色智能技术研究院 | Surface enhanced Raman scattering chip capable of regulating hot spots and preparation method and application thereof |
| CN107119252B (en) * | 2017-05-26 | 2019-02-05 | 云南师范大学 | A kind of preparation method of silicon substrate surface enhancing Raman substrate |
| CN109856116B (en) * | 2019-02-28 | 2021-06-29 | 吉林大学 | Hierarchical nanocone array for in-situ monitoring of chemical reaction by using surface enhanced Raman scattering and preparation method thereof |
| CN109929905A (en) * | 2019-04-01 | 2019-06-25 | 天津国科医工科技发展有限公司 | Three-dimensional Raman for bacterium Rapid identification enhances film and its method and system |
| CN114411152B (en) * | 2022-01-10 | 2023-08-29 | 哈尔滨工业大学 | AFM nano milling and chemical corrosion processing-based surface enhanced Raman substrate preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0309491D0 (en) * | 2003-04-25 | 2003-06-04 | E2V Technologics Ltd | Molecular detector arrangement |
| JP2005195441A (en) * | 2004-01-07 | 2005-07-21 | Fuji Photo Film Co Ltd | Raman spectroscopy, and device for raman spectroscopy |
| CN101566570A (en) * | 2009-05-27 | 2009-10-28 | 东南大学 | Orderly controllable surface-reinforced Raman scattering active substrate and preparation method thereof |
| CN101776604A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Production method of basement for enhancing raman scattering of molecule |
| CN101776603A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Enhancement method for raman scattering by using artificial metal micro-nano structure |
-
2013
- 2013-11-27 CN CN201310618273.8A patent/CN103604795B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0309491D0 (en) * | 2003-04-25 | 2003-06-04 | E2V Technologics Ltd | Molecular detector arrangement |
| JP2005195441A (en) * | 2004-01-07 | 2005-07-21 | Fuji Photo Film Co Ltd | Raman spectroscopy, and device for raman spectroscopy |
| CN101566570A (en) * | 2009-05-27 | 2009-10-28 | 东南大学 | Orderly controllable surface-reinforced Raman scattering active substrate and preparation method thereof |
| CN101776604A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Production method of basement for enhancing raman scattering of molecule |
| CN101776603A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Enhancement method for raman scattering by using artificial metal micro-nano structure |
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