CN104931480A - SERS substrate and manufacturing method thereof - Google Patents
SERS substrate and manufacturing method thereof Download PDFInfo
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- CN104931480A CN104931480A CN201510338662.4A CN201510338662A CN104931480A CN 104931480 A CN104931480 A CN 104931480A CN 201510338662 A CN201510338662 A CN 201510338662A CN 104931480 A CN104931480 A CN 104931480A
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Abstract
The invention discloses an SERS substrate and a manufacturing method thereof. The method includes the steps that a substrate body is provided; a polymer layer is formed on the substrate body; the polymer layer is directly bombarded through plasma so that a columnar nano-structure can be formed; the columnar nano-structure is covered with a metal layer. The SERS substrate formed through the method can effectively enhance Raman scattering signals, the technology is simple, and the SERS substrate is high in controllability and suitable for being commercially produced on a large scale.
Description
Technical field
The invention belongs to field of nanometer technology, particularly relate to a kind of SERS substrate and preparation method thereof.
Background technology
The detection technique of raman scattering spectrum is a kind of structure of matter analysis means not needing to mark detected sample, has non-destructive, without the need to features such as contacts.Along with the development of laser technology and infant laser signal detection reception technique, as a kind of means realizing structure of matter molecular level and detect, raman scattering spectrum detection technique is expected to obtain actual in fields such as biological detection, medical diagnosis on disease, food safety detection, environmental monitoring, chemical analyses and apply widely.
Surface enhanced raman spectroscopy (SERS) refers to and use noble metal nano structure to strengthen local electromagnetic intensity under laser action, the raman scattering spectrum signal intensity of accompanying molecule near noble metal nano body structure surface is amplified, thus realizes a kind of technology to the detection of trace molecules.
At present, the SERS substrate adopted based on nanometer rough surface or nanostructured, to strengthen the intensity of Raman scattering signal more.The preparation method of the SERS substrate reported mainly contains sol particle method, the galvanochemistry wet etch techniques of metal electrode, metal nano bead etching technique, self-catalysis VLS chemosynthesis growing technology, beamwriter lithography, focused-ion-beam lithography and other physical chemistry etching method etc., these technology more or less all have problems in process complexity or process controllability etc., are difficult to realize commercially producing on a large scale.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, provide a kind of SERS substrate and preparation method thereof, technique is simple and controllability is strong, is applicable to commercially produce on a large scale.
For achieving the above object, technical scheme of the present invention is:
A preparation method for SERS substrate, is characterized in that, comprising:
Substrate is provided;
Form polymeric layer over the substrate;
Using plasma bombards polymeric layer, to form columnar nano-structure;
Covering metal layer.
Optionally, described polymeric layer comprises: positive photoresist, negative photoresist, polyimide, dimethyl silicone polymer or Parylene.
Optionally, described plasma comprises argon plasma, oxygen plasma or nitrogen plasma.
Optionally, described metal level is gold, silver, copper or platinum.
Optionally, the thickness of described polymeric layer is 0.2um-5um.
Optionally, the flow of plasma source of the gas is 50-400sccm, and chamber pressure is 0.2Pa, and radio-frequency power is 50-350W, and the processing time is 2-120min.
Optionally, described columnar nano-structure forms Cluster Structures, there is nanoaperture between the columnar nano-structure in Cluster Structures.
In addition, present invention also offers a kind of SERS substrate, comprising:
Substrate;
Columnar nano-structure on substrate, described columnar nano-structure is formed by after plasma bombardment polymeric material;
Cover the metal level of columnar nano-structure.
Optionally, described columnar nano-structure is Cluster Structures, there is nanoaperture between the columnar nano-structure in Cluster Structures.
Optionally, described polymeric material comprises: positive photoresist, negative photoresist, polyimide, dimethyl silicone polymer or Parylene.
SERS substrate that the embodiment of the present invention provides and preparation method thereof, using plasma technology, bombards polymeric layer, and in bombardment process, the portion of product that bombardment polymkeric substance produces can be polymerized again, forms columnar nano-structure.The SERS substrate that the method utilizes traditional micro fabrication just can realize based on nanostructured, effectively can strengthen Raman scattering signal, and technique is simple and controllability is strong, is applicable to commercially produce on a large scale.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the invention process, be briefly described to the accompanying drawing used required in embodiment below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 shows the process flow diagram of the preparation method of the SERS substrate according to the embodiment of the present invention;
Fig. 2-5 shows the cross section structure schematic diagram that preparation method according to an embodiment of the invention forms SERS substrate in the process of SERS substrate;
Fig. 6-8 shows the cross section structure schematic diagram that preparation method according to another embodiment of the present invention forms SERS substrate in the process of SERS substrate;
Fig. 9 is the stereoscan photograph after adopting the preparation method of the SERS substrate of the embodiment of the present invention to form columnar nano-structure;
Figure 10 is the stereoscan photograph after the preparation method of the SERS substrate of the employing embodiment of the present invention forms metal level.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention, therefore the present invention is by the restriction of following public specific embodiment.
Secondly, the present invention is described in detail in conjunction with schematic diagram, when describing the embodiment of the present invention in detail; for ease of explanation; represent that the sectional view of device architecture can be disobeyed general ratio and be made partial enlargement, and described schematic diagram is example, it should not limit the scope of protection of the invention at this.In addition, the three-dimensional space of length, width and the degree of depth should be comprised in actual fabrication.
The invention provides a kind of preparation method of SERS substrate, shown in figure 1, comprising: substrate is provided; Form polymeric layer over the substrate; Using plasma directly bombards polymeric layer, to form columnar nano-structure; Covering metal layer.
In the present invention, using plasma technology, bombard polymeric layer, in bombardment process, the portion of product that bombardment polymkeric substance produces can be polymerized again, form columnar nano-structure, in the method, utilize the SERS substrate that traditional micro fabrication just can realize based on nanostructured, effectively can strengthen Raman scattering signal, technique is simple and controllability is strong, is applicable to commercially produce on a large scale.
In order to understand technical scheme of the present invention and technique effect better, be described in detail below with reference to specific embodiment.
First, in step S01, provide substrate 101, as shown in Figure 2.
In an embodiment of the present invention, this substrate 101 is support substrates, for subsequent technique provides support, can be the arbitrary substrate in micro fabrication, such as, can be monocrystalline substrate, glass substrate or the silicon substrate etc. being formed with monox.
Then, in step S02, described substrate 101 forms polymeric layer 201, shown in figure 3 or Fig. 6.
In embodiments of the present invention, the material of described polymeric layer 201 can be positive photoresist, negative photoresist, polyimide, dimethyl silicone polymer (PDMS) or Parylene (Parylene) etc., the polymeric material that can also be etched by plasma bombardment for other, the thickness of polymeric layer can be 0.2um-5um.
In certain embodiments, as shown in Figure 3, can overlying polymer layer 201 on the substrate 101, form polymeric layer, in a specific embodiment, the material of described polymeric layer 201 can be polyimide, this polymeric layer 201 is covered by spin coating proceeding, when spin coating, rotating speed can be 1500rpm, spin-coating time can be 40s, carry out baking process after the spin-coating, the above-mentioned substrate 101 being formed with polymeric layer 201 can be positioned on hot plate and toast, the temperature of baking is 100 DEG C, the time of baking is 10min, obtain the polymeric layer that thickness is 2um.
In further embodiments, after overlying polymer layer 201, patterning can be carried out further, only on the substrate in required region, form polymeric layer 201, as shown in Figure 6.In specific embodiment, first, the method in above-described embodiment can be adopted, first overlying polymer layer 201 on the substrate 101, thickness can be 2um, as shown in Figure 3, then, patterning is carried out to polymeric layer 201, only on the substrate of subregion, forms polymeric layer 201, can first mask film covering layer (scheming not shown), then, under the covering of mask layer, polymeric layer 201 is etched, and remove mask layer, thus form the polymeric layer 201 of patterning, as shown in Figure 6.
In some other embodiment, for positive photoresist, negative photoresist or photosensitive polymeric material, can directly adopt photoetching, development method to form the polymeric layer 201 of patterning.
Then, in step S03, using plasma directly bombards polymeric layer 201, to form columnar nano-structure 301, shown in figure 4 or Fig. 7.
In embodiments of the present invention, the plasma processing tools in semiconductor technology can be adopted to carry out the technique of this plasma bombardment, plasma can be argon plasma, oxygen plasma or nitrogen plasma etc., can also be other any plasmas that can bombard polymeric layer, in plasma bombardment technique, the flow of plasma source of the gas is 50-400sccm, and chamber pressure is 0.2Pa, radio-frequency power is 150-350W, and the processing time is 2-120min.After the bombardment carrying out plasma, polymeric layer 201 can be polymerized again by the portion of product after bombarding, the region that initially there is polymeric layer is formed columnar nano-structure 301, this columnar nano-structure 301 is the structure of nano-scale, namely the diameter of columnar nano-structure 301 is about 20nm-200nm, highly be about 100nm-2um, distance between nanostructured is also nano-scale, columnar nano-structure 301 can for bending or inclination, can be close to each other between certain part of columnar nano-structure 301, thus a large amount of nanoaperture is formed between columnar nano-structure 301.Shown in figure 9, for the preparation method of the SERS substrate adopting the embodiment of the present invention forms the stereoscan photograph after columnar nano-structure 301, can see, the columnar nano-structure 301 formed forms columnar nanometer forest structure, namely columnar nano-structure 301 presents large-area distribution, is the Cluster Structures be made up of columnar nano-structure 301, there is nanoaperture between the columnar nano-structure 301 in Cluster Structures, the head of some columnar nano-structure 301 is close to each other, forms a large amount of nano gap.The Cluster Structures that this columnar nano-structure 301 is formed, can provide more " focus " for SERS effect, and then can produce stronger SERS enhancing effect, reaches the object detecting trace materials.
In this specific embodiment, plasma source of the gas is argon gas, the radio-frequency power of the cavity of plasma process is 270W, and chamber pressure is 0.2Pa, and the flow of argon gas is 200sccm, the time of process is 60min, remove after polymeric layer 201 completely in bombardment, on original polymeric layer region, define columnar nano-structure 301, the height of the columnar nano-structure 301 of formation is lower than the elemental height of polymeric layer 201, be approximately 1.4um, shown in figure 4 or Fig. 7.
Then, in step S04, covering metal layer 401, shown in figure 5 or Fig. 8.
This metal level 401 is the metal level strengthening Raman scattering effect, and being generally noble metal film, such as, can be gold, silver, copper or platinum etc.In this specific embodiment, the method for physical sputtering can be adopted to cover the metal level 401 of one deck silver, the thickness of Ag films can be 30 nanometers, makes covering metal layer 401 in columnar nano-structure 301.As shown in Figure 10, preparation method for the SERS substrate adopting the embodiment of the present invention forms the stereoscan photograph after metal level 401, can see, the sidewall of the columnar nano-structure 301 after metal level 401 covers contains a large amount of nanometer coarse structures, and also there is a large amount of nanoaperture in the Cluster Structures inside that columnar nano-structure 301 forms, thus, high performance SERS substrate can be obtained.
So far, the SERS substrate of the embodiment of the present invention is defined.
This SERS substrate can be mutually integrated with micro-channel structure further, forms micro-fluidic SERS detection means.
In addition, present invention also offers the SERS substrate formed by said method, shown in figure 5 or Fig. 8, comprising: substrate 101; Columnar nano-structure 301 on substrate 101, described columnar nano-structure 301 is formed by after plasma bombardment polymeric material; Cover the metal level 401 of columnar nano-structure 301.
Wherein, described polymeric material can comprise: positive photoresist, negative photoresist, polyimide, dimethyl silicone polymer or Parylene.
Described plasma can comprise argon plasma, oxygen plasma or nitrogen plasma.
, between the columnar nano-structure in Cluster Structures, there is nanoaperture in described columnar nano-structure composition Cluster Structures.
Metal level is generally noble metal film, such as, can be gold, silver, copper or platinum etc.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.
Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Any those of ordinary skill in the art, do not departing under technical solution of the present invention ambit, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (10)
1. a preparation method for SERS substrate, is characterized in that, comprising:
Substrate is provided;
Form polymeric layer over the substrate;
Using plasma bombards polymeric layer, to form columnar nano-structure;
Covering metal layer.
2. preparation method according to claim 1, is characterized in that, described polymeric layer comprises: positive photoresist, negative photoresist, polyimide, dimethyl silicone polymer or Parylene.
3. preparation method according to claim 2, is characterized in that, described plasma comprises argon plasma, oxygen plasma or nitrogen plasma.
4. preparation method according to claim 1, is characterized in that, described metal level is gold, silver, copper or platinum.
5. preparation method according to claim 1, is characterized in that, the thickness of described polymeric layer is 0.2um-5um.
6. preparation method according to claim 5, is characterized in that, the flow of plasma source of the gas is 50-400sccm, and chamber pressure is 0.2Pa, and radio-frequency power is 50-350W, and the processing time is 2-120min.
7. preparation method according to claim 1, is characterized in that, described columnar nano-structure forms Cluster Structures, there is nanoaperture between the columnar nano-structure in Cluster Structures.
8. a SERS substrate, is characterized in that, comprising:
Substrate;
Columnar nano-structure on substrate, described columnar nano-structure is formed by after plasma bombardment polymeric material;
Cover the metal level of columnar nano-structure.
9. SERS substrate according to claim 8, is characterized in that, described columnar nano-structure forms Cluster Structures, there is nanoaperture between the columnar nano-structure in Cluster Structures.
10. SERS substrate according to claim 8, is characterized in that, described polymeric material comprises: positive photoresist, negative photoresist, polyimide, dimethyl silicone polymer or Parylene.
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| CN106970068A (en) * | 2017-05-31 | 2017-07-21 | 厦门大学 | A kind of quick preparation wide area surface strengthens the method for Raman scattering substrate |
| CN107313046A (en) * | 2017-05-12 | 2017-11-03 | 北京邮电大学 | A kind of SERS substrates and preparation method thereof |
| CN109650325A (en) * | 2019-02-02 | 2019-04-19 | 中国科学院微电子研究所 | Surface enhanced Raman scattering substrate, preparation method and 3D enrichment and detection method |
| CN110940656A (en) * | 2018-09-25 | 2020-03-31 | 中国科学院微电子研究所 | SERS active substrate, preparation method thereof and trace tested agent molecule enrichment method |
| CN111118450A (en) * | 2019-12-23 | 2020-05-08 | 无锡物联网创新中心有限公司 | ZnO thin film structure and preparation method thereof |
| CN111999279A (en) * | 2020-07-21 | 2020-11-27 | 北京邮电大学 | Flexible SERS substrate based on small ball array and preparation method thereof |
| CN112533468A (en) * | 2020-12-08 | 2021-03-19 | 江苏创芯海微科技有限公司 | Anti-reflection electromagnetic shielding structure and preparation method thereof |
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| CN106970068A (en) * | 2017-05-31 | 2017-07-21 | 厦门大学 | A kind of quick preparation wide area surface strengthens the method for Raman scattering substrate |
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| CN109650325B (en) * | 2019-02-02 | 2020-10-30 | 中国科学院微电子研究所 | Surface-enhanced Raman scattering substrate, preparation method and 3D enrichment and detection method |
| CN111118450A (en) * | 2019-12-23 | 2020-05-08 | 无锡物联网创新中心有限公司 | ZnO thin film structure and preparation method thereof |
| CN111999279A (en) * | 2020-07-21 | 2020-11-27 | 北京邮电大学 | Flexible SERS substrate based on small ball array and preparation method thereof |
| CN111999279B (en) * | 2020-07-21 | 2021-09-21 | 北京邮电大学 | Flexible SERS substrate based on small ball array and preparation method thereof |
| CN112533468A (en) * | 2020-12-08 | 2021-03-19 | 江苏创芯海微科技有限公司 | Anti-reflection electromagnetic shielding structure and preparation method thereof |
| CN112533468B (en) * | 2020-12-08 | 2021-11-30 | 江苏创芯海微科技有限公司 | Anti-reflection electromagnetic shielding structure and preparation method thereof |
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Application publication date: 20150923 |