CN102910576A - Method for producing high-sensitivity surface reinforcement Raman sensor chip - Google Patents
Method for producing high-sensitivity surface reinforcement Raman sensor chip Download PDFInfo
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- CN102910576A CN102910576A CN2012104627287A CN201210462728A CN102910576A CN 102910576 A CN102910576 A CN 102910576A CN 2012104627287 A CN2012104627287 A CN 2012104627287A CN 201210462728 A CN201210462728 A CN 201210462728A CN 102910576 A CN102910576 A CN 102910576A
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Abstract
The invention discloses a method for producing a high-sensitivity surface reinforcement Raman sensor chip. The method comprises the following steps: (1) carrying out hydrophilic treatment on a substrate; (2) selecting uniform medium nanosphere latex solution, and a self-assembling a single layer of densely arranged medium nanosphere array on the substrate subjected to the hydrophilic treatment by using a spin coating method or a puling method; (3) utilizing a reactive ion etching technology to etch the medium nanosphere array which is obtained in the step 2; and (4) coating a metal film on the etched medium nanosphere array which is obtained in the step 3, thus obtaining the high-sensitivity surface reinforcement Raman sensor chip, wherein the thickness of the coating film is smaller than the etching thickness in the step 3,. The method is used for solving the contradiction among repeatability, uniformity and sensitivity of the conventional surface reinforcement Raman sensor chips which are produced through a physical etching method and a chemical synthesizing method, and the produced surface reinforcement Raman sensor chip has high sensitivity and good repeatability and uniformity.
Description
Technical field
The present invention relates to a kind of optical sensing chip technology of preparing, be specifically related to a kind of high-sensitive surface-enhanced Raman sensing chip preparation method.
Background technology
The Raman spectrum of material is a kind of fingerprint characteristic spectrum, so high specificity, can be unmarked, in real time material is surveyed.Yet the Raman scattering signal of material very a little less than, than the low several orders of magnitude of incident light, so sensitivity is low.The local of nanometer metal structure strengthens the several orders of magnitude of Electromagnetic enhancement that characteristic can make metal structure surface, correspondingly can significantly promote Raman signal, and this is referred to as SERS.
People have studied the preparation method of SERS enhancing structure by several different methods, mainly be divided at present two large classes, be respectively physics photoetching and chemical synthesis, the characteristics of physics photoetching are that the homogeneity of preparation structure is good, repeatability is high, but limited by diffraction limit, and the physics photoetching can't prepare the structure of tens nanometers even several nanometers, this causes its Electromagnetic enhancement performance not strong, so the sensitivity of the sensing chip of the method preparation is not high; Therefore on the contrary, chemical synthesis then is easy to prepare the structure of small scale, can obtain the chip of higher sensitivity, but chemical synthesis is generally random structure, do not have periodically, so its homogeneity, poor repeatability.
Summary of the invention
In view of this, the invention provides a kind of high-sensitive surface-enhanced Raman sensing chip preparation method, solve the contradiction that can not get both between repeatability, homogeneity and the sensitivity of the chip that has the physics photoetching of surface-enhanced Raman sensing chip and chemical synthesis and preparation method acquisition now, prepare the surface-enhanced Raman chip highly sensitive and repeated, that homogeneity is good.
High-sensitive surface-enhanced Raman sensing chip preparation method of the present invention comprises the steps:
1) substrate is carried out hydrophilic treated;
2) select uniform medium nanosphere latex solution, utilize spin-coating method or the czochralski method compact arranged medium nanosphere of self-assembled monolayer array on the substrate after the hydrophilic treated;
3) utilizing reactive ion etching technology to step 2) resulting medium nanosphere array carries out etching;
4) on the medium nanosphere array after the resulting etching of step 3), plate metal film, coating film thickness namely obtains high-sensitive surface-enhanced Raman sensing chip less than the etch thicknesses in the step 3).
Further, in the described step 1), substrate is quartz substrate or K9 glass substrate.
Further, in the described step 1), the step of hydrophilic treated is: the solution that places the concentrated sulfuric acid and hydrogen peroxide to be made into mass ratio 3:1 substrate, and then 80 ℃ of heating baths 1 hour are taken out substrate and are repeatedly washed with deionized water, and with sonic oscillation 2 ~ 3 minutes; The solution that places ammoniacal liquor, hydrogen peroxide and deionized water to be made into mass ratio 1:1:5 substrate again, then sonic oscillation 1 hour takes out substrate deionized water rinsing 2 ~ 3 times, and saves backup with deionized water.
Further, described step 2) in, the medium nanosphere is polystyrene spheres.
Further, in the described step 3), the etching gas that reactive ion etching is used is oxygen.
Further, in the described step 4), metal film is golden film or silverskin, and the plated film mode is evaporation, sputter coating or plating.
Further, in the described step 3), etch thicknesses is 50nm ~ 220nm; In the described step 4), coating film thickness is 40nm ~ 200nm.
Beneficial effect of the present invention is:
The present invention at first obtains single-layer medium nanosphere array structure by medium nanosphere self-assembling technique, but be close-packed arrays between the medium nanosphere of its formation, if directly be made into the surface-enhanced Raman sensing chip, the characteristics of slit coupling enhancing will do not had, sensitivity is not high, therefore the present invention carves the medium nanosphere little by etching technics again, carve between the medium nanosphere after little and produced the gap, then plate metal film, and coating film thickness is less than etch thicknesses, medium nanosphere after at once little is after metal film forms the metal spherical shell in the covering, still have the gap of a few nanometer to tens nanometers between the two metal spherical shells, the strong coupling humidification of this gap can form high-intensity local electromagnetic field, makes Raman signal obtain the enhancing of several orders of magnitude, has namely obtained high-sensitive surface-enhanced Raman sensing chip.
Therefore, the present invention's advantage compared with prior art is:
(1) compares with existing physics photoetching method, the present invention is not limited by diffraction limit, the coupling that prepared chip structure has a few nanometer to tens nanometers that the physics photoetching method can't realize strengthens the gap, therefore the highly sensitive of surface-enhanced Raman sensing chip that obtain;
(2) compare with existing chemical synthesis random structure, the prepared chip structure of the present invention is the large tracts of land period profile, this has guaranteed the homogeneity of chip diverse location sensitivity, simultaneously, the self assembly of medium nanosphere is controlled, etching is controlled, plated film is controlled, therefore the prepared chip of the present invention has good repeatability, and the accuracy that strengthens the Raman spectrum Quantitative Comparison for material surface provides assurance.
In sum, the invention solves the contradiction that can not get both between repeatability, homogeneity and the sensitivity of the chip that has the physics photoetching of surface-enhanced Raman sensing chip and chemical synthesis and preparation method acquisition now, prepared the surface-enhanced Raman chip highly sensitive and repeated, that homogeneity is good.
Description of drawings
In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in further detail below in conjunction with accompanying drawing, wherein:
Fig. 1 is process chart of the present invention;
Fig. 2 is the structural representation of the medium nanosphere array after the self assembly;
Fig. 3 is the structural representation of the medium nanosphere array after the etching;
Fig. 4 is the structural representation of the medium nanosphere array behind the plated film.
The specific embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
Fig. 1 is process chart of the present invention, and as shown in the figure, high-sensitive surface-enhanced Raman sensing chip preparation method of the present invention comprises the steps:
1) substrate is carried out hydrophilic treated; Described substrate is quartz substrate, and the step of hydrophilic treated is: the solution that places the concentrated sulfuric acid and hydrogen peroxide to be made into mass ratio 3:1 substrate, and then 80 ℃ of heating baths 1 hour are taken out substrate and are repeatedly washed with deionized water, and with sonic oscillation 2 ~ 3 minutes; The solution that places ammoniacal liquor, hydrogen peroxide and deionized water to be made into mass ratio 1:1:5 substrate again, then sonic oscillation 1 hour takes out substrate deionized water rinsing 2 ~ 3 times, and saves backup with deionized water;
2) the polystyrene spheres latex solution of selection diameter 520nm, utilize the spin-coating method compact arranged medium nanosphere of self-assembled monolayer array on the substrate after the hydrophilic treated, medium nanosphere array structure after the self assembly as shown in Figure 2, medium nanosphere 2 is the individual layer close-packed arrays on substrate 1;
3) utilizing reactive ion etching technology to step 2) resulting medium nanosphere array carries out etching, etching gas is oxygen, and etch thicknesses is 65nm, and the medium nanosphere array structure after the etching as shown in Figure 3, after medium nanosphere 2 is little by quarter, produced the gap between the medium nanosphere 2;
4) on the medium nanosphere array after the resulting etching of step 3), mode plated with gold film by evaporation, coating film thickness is 50nm, medium nanosphere array structure behind the plated film as shown in Figure 4, after carving medium nanosphere 2 after little metal film 3 forming the metal spherical shells on covering, still have the gap of tens nanometers between the two metal spherical shells, namely obtained high-sensitive surface-enhanced Raman sensing chip.
Among the present invention, substrate can be the conventional substrates such as quartz substrate or K9 glass substrate; Can utilize spin-coating method or czochralski method to carry out self assembly; The active high metal material of the preferred Electromagnetic enhancement of metal film, such as golden film or silverskin, the plated film mode can be evaporation, sputter coating or plating etc.; Preferred 50nm ~ the 220nm of etch thicknesses, the preferred 40nm ~ 200nm of coating film thickness, coating film thickness must be less than etch thicknesses, to guarantee having the nanoscale spacing between the metal spherical shell.Among the present invention, the known technology of technical field under the methods such as the method for hydrophilic treated, spin-coating method, czochralski method, reactive ion etching technology, evaporation, sputter coating, plating all can adopt.
The present invention at first obtains single-layer medium nanosphere array structure by medium nanosphere self-assembling technique, but be close-packed arrays between the medium nanosphere of its formation, if directly be made into the surface-enhanced Raman sensing chip, the characteristics of slit coupling enhancing will do not had, sensitivity is not high, therefore the present invention carves the medium nanosphere little by etching technics again, carve between the medium nanosphere after little and produced the gap, then plate metal film, and coating film thickness is less than etch thicknesses, medium nanosphere after at once little is after metal film forms the metal spherical shell in the covering, still have the gap of a few nanometer to tens nanometers between the two metal spherical shells, the strong coupling humidification of this gap can form high-intensity local electromagnetic field, makes Raman signal obtain the enhancing of several orders of magnitude, has namely obtained high-sensitive surface-enhanced Raman sensing chip.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (7)
1. a high-sensitive surface-enhanced Raman sensing chip preparation method is characterized in that: comprise the steps:
1) substrate is carried out hydrophilic treated;
2) select uniform medium nanosphere latex solution, utilize spin-coating method or the czochralski method compact arranged medium nanosphere of self-assembled monolayer array on the substrate after the hydrophilic treated;
3) utilizing reactive ion etching technology to step 2) resulting medium nanosphere array carries out etching;
4) on the medium nanosphere array after the resulting etching of step 3), plate metal film, coating film thickness namely obtains high-sensitive surface-enhanced Raman sensing chip less than the etch thicknesses in the step 3).
2. high-sensitive surface-enhanced Raman sensing chip preparation method according to claim 1, it is characterized in that: in the described step 1), substrate is quartz substrate or K9 glass substrate.
3. high-sensitive surface-enhanced Raman sensing chip preparation method according to claim 1, it is characterized in that: in the described step 1), the step of hydrophilic treated is: the solution that places the concentrated sulfuric acid and hydrogen peroxide to be made into mass ratio 3:1 substrate, 80 ℃ of heating baths 1 hour, then take out substrate and repeatedly wash with deionized water, and with sonic oscillation 2 ~ 3 minutes; The solution that places ammoniacal liquor, hydrogen peroxide and deionized water to be made into mass ratio 1:1:5 substrate again, then sonic oscillation 1 hour takes out substrate deionized water rinsing 2 ~ 3 times, and saves backup with deionized water.
4. high-sensitive surface-enhanced Raman sensing chip preparation method according to claim 1, it is characterized in that: described step 2), the medium nanosphere is polystyrene spheres.
5. high-sensitive surface-enhanced Raman sensing chip preparation method according to claim 1, it is characterized in that: in the described step 3), the etching gas that reactive ion etching is used is oxygen.
6. high-sensitive surface-enhanced Raman sensing chip preparation method according to claim 1, it is characterized in that: in the described step 4), metal film is golden film or silverskin, and the plated film mode is evaporation, sputter coating or plating.
7. according to claim 1 to the described high-sensitive surface-enhanced Raman sensing chip preparation method of 6 any one, it is characterized in that: in the described step 3), etch thicknesses is 50nm ~ 220nm; In the described step 4), coating film thickness is 40nm ~ 200nm.
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| CN103145095A (en) * | 2013-03-26 | 2013-06-12 | 吉林大学 | Preparation method of panchromatic structural color or color variation pattern array |
| CN103512869A (en) * | 2013-10-11 | 2014-01-15 | 华东理工大学 | Preparation method of nanopore chip with plasmon resonance scattering response function |
| CN103626119A (en) * | 2013-12-08 | 2014-03-12 | 中国科学院光电技术研究所 | Preparation method for nano metal ball bowl array structure |
| CN105206175A (en) * | 2015-10-23 | 2015-12-30 | 浙江大学 | Anti-counterfeit label based on patterned metal nanocomposite and production method of anti-counterfeit label |
| CN107607516A (en) * | 2017-09-11 | 2018-01-19 | 电子科技大学 | A kind of chemical sensor of Raman enhancing and preparation method thereof |
| CN108181296A (en) * | 2018-03-14 | 2018-06-19 | 南京信息工程大学 | Optical fiber surface enhancing Raman microprobe based on surface phasmon effect and preparation method thereof |
| CN110668396A (en) * | 2019-09-16 | 2020-01-10 | 吉林师范大学 | Preparation method of periodic wavy nanopore structure array |
| CN111933520A (en) * | 2020-10-09 | 2020-11-13 | 晶芯成(北京)科技有限公司 | Wafer surface treatment method and surface treatment device |
| CN112921276A (en) * | 2021-01-22 | 2021-06-08 | 电子科技大学 | Preparation method of SERS substrate based on 2D noble metal nanostructure |
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| CN103512869A (en) * | 2013-10-11 | 2014-01-15 | 华东理工大学 | Preparation method of nanopore chip with plasmon resonance scattering response function |
| CN103626119A (en) * | 2013-12-08 | 2014-03-12 | 中国科学院光电技术研究所 | Preparation method for nano metal ball bowl array structure |
| CN105206175B (en) * | 2015-10-23 | 2018-06-29 | 浙江大学 | Anti-counterfeiting mark based on pattern metal nanocomposite and preparation method thereof |
| CN105206175A (en) * | 2015-10-23 | 2015-12-30 | 浙江大学 | Anti-counterfeit label based on patterned metal nanocomposite and production method of anti-counterfeit label |
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| CN108181296A (en) * | 2018-03-14 | 2018-06-19 | 南京信息工程大学 | Optical fiber surface enhancing Raman microprobe based on surface phasmon effect and preparation method thereof |
| CN108181296B (en) * | 2018-03-14 | 2024-03-19 | 南京信息工程大学 | Optical fiber surface enhanced Raman probe based on surface plasmon effect |
| CN110668396A (en) * | 2019-09-16 | 2020-01-10 | 吉林师范大学 | Preparation method of periodic wavy nanopore structure array |
| CN111933520A (en) * | 2020-10-09 | 2020-11-13 | 晶芯成(北京)科技有限公司 | Wafer surface treatment method and surface treatment device |
| CN112921276A (en) * | 2021-01-22 | 2021-06-08 | 电子科技大学 | Preparation method of SERS substrate based on 2D noble metal nanostructure |
| CN112921276B (en) * | 2021-01-22 | 2022-03-15 | 电子科技大学 | Preparation method of SERS substrate based on 2D noble metal nanostructure |
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