CN103257132B - Silver nanoparticle cap array surface-enhanced Raman activity substrate and preparation method thereof - Google Patents
Silver nanoparticle cap array surface-enhanced Raman activity substrate and preparation method thereof Download PDFInfo
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- CN103257132B CN103257132B CN201310131120.0A CN201310131120A CN103257132B CN 103257132 B CN103257132 B CN 103257132B CN 201310131120 A CN201310131120 A CN 201310131120A CN 103257132 B CN103257132 B CN 103257132B
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Abstract
The invention discloses a silver nanoparticle cap array surface-enhanced raman activity substrate and a preparation method thereof. The substrate is formed in a way that a silver film with an order nanoparticle cap array structure adhered to a silicon single crystal underlayer, the thickness of the silver film is 80-150mm, silver nanoparticle caps are in raised foam-shaped structures the centers of which are provided with holes, the diameters of the silver nanoparticle caps are 30-95nm, and center distance of the adjacent two adjacent nanometer caps is 100-110nm. The silver nanoparticle cap array surface-enhanced raman activity substrate provided by the invention has the advantages that the morphology is uniform, the structure is controlled, the prominent surface raman enhancing effects can be realized on analytes with different densities, the enhancing factor can achieve 109, and an enhancing signal is uniform and stable. A method provided by the invention has the advantages that structure parameters and morphologies of the silver nanoparticle caps are adjusted according to structure parameters of an ultrathin alumina template and a metal sedimentation process, and parameters of the silver nanoparticle cap array substrate can adjust and control the surface raman enhancing effect, the operation is simple, the cost is low, the volume production is easy, and the repeatability of products among different batches is high.
Description
Technical field
The present invention relates to a kind of surface reinforced Raman active substrate and preparation method thereof, particularly a kind of silver nanocaps array surface strengthens Raman active substrate and preparation method thereof.
Background technology
Since SERS (Surface-enhanced Raman Scattering, SERS) after being found in 1974, to be widely used in fields such as surface interface science, analysis science and biomedicines very soon, the information on molecular level is provided for the structure of the various surface/interface of deep sign and process.Through constantly development and research, it shows great potentiality in life science and nano science field, because it has very high sensitivity, the molecule of monolayer and the sub-monolayer being adsorbed on metal surface can be detected, the structural information of surface molecular can be provided again, be considered to the instrument of a kind of very effective detection interfacial characteristics and intermolecular interaction, characterizing surface molecular absorption behavior and molecular structure.
In view of SERS technology has a wide range of applications, prepare a kind of stability high, strengthen effective, that reappearance is strong SERS active-substrate and become key component.Traditional SERS active-substrate conventional is at present a lot, as: Electrochemical roughening noble metal active electrode basement, noble metal colloidal sol active substrate, the active substrate of the film activity substrate of vacuum evaporation noble metal island, the substrate of noble metal dendrite and chemical etching and chemical deposition noble metal, but the surface roughness that these self assembly active substrates provide is difficult to the stability, homogeneity and the repeatability that control thus to have impact on binding molecule spectrum.The method of the orderly surface nano-structure of preparation that Recent study is more has the shortcomings and limitations on some Synthesis and applications, such as: very little with the area of beamwriter lithography and the surface nano-structure prepared by scan-probe method, productive rate is low, apparatus expensive; For self-organizing growth method and nano-imprint method, the structural parameters of more difficult adjustment surface nano-structure usually.And due to its preparation procedure loaded down with trivial details, the reasons such as the high and preparation efficiency of preparation cost is low limit its development.Therefore be badly in need of exploitation a kind of efficient, flexibly, low cost, high sensitivity can be prepared, can repeat, the method for the surface nano-structure SERS substrate of stable homogeneous.
Film substrate is a kind of stable SERS substrate, refers to cover nanoscale, rough surface at solid carrier surface, meet the metallic diaphragm that surface plasma excites.In solid-state SERS substrate, by being, the surface geometry form of metal film determines that analyte Raman signal strengthens the key of effect.Novel UTAM(Ultra-Thin Alumina Mask, ultrathin alumina template) nano surface technology of preparing provides the method for the surface nano-structure of a kind of effective preparation large area and structure-controllable.UTAM nano surface technology of preparing has lot of advantages, comprise that structural parameters are adjustable, large area preparation, performance be controlled, high density, fast and high production, equipment investment low, these advantages make UTAM nano surface technology of preparing become a very promising research direction in Surface Nano-Patterning research field and receive and pay close attention to widely.
Summary of the invention
An object of the present invention is to provide a kind of silver nanocaps array surface to strengthen Raman active substrate.
Two of object of the present invention is to provide a kind of based on UTAM(Ultra-Thin Alumina Mask, ultrathin alumina template) the silver nanocaps array surface of nano surface technology of preparing strengthens the preparation method of Raman active substrate, for trace compound and biomolecule being carried out to detections analysis.
For achieving the above object, the present invention is by the following technical solutions:
A kind of silver nanocaps array surface strengthens Raman active substrate, it is characterized in that this substrate is stained with in silicon monocrystalline substrate the Ag films that one deck has orderly silver nanocaps array structure: the thickness of this Ag films is 80 ~ 150 nm, described silver nanocaps is the center balloon-shaped structure with holes of protuberance, diameter is 30 ~ 95 nm, and adjacent two nanometer cap centre-to-centre spacing are 100 ~ 110 nm.
Prepare the method that above-mentioned silver nanocaps array surface strengthens Raman active substrate, it is characterized in that the concrete steps of the method are,
A. prepared by ultrathin alumina template UTAM;
B. step a gained UTAM is carried out aperture adjustment;
C. step b gained UTAM is transferred on Si substrate;
D. by step c gained UTAM/Si sample, be 8 × 10 in vacuum
-4under Pa, evaporation rate 0.3 ~ 0.5 nm/s condition, evaporation silver powder 200 ~ 300 s; Then remove UTAM and Si substrate, the surface with orderly silver nanocaps array is transferred in deionized water upward and cleans, gone to again in acetone after cleaning and stick on single crystal Si substrate, after solidification, namely obtain the substrate of silver nanocaps surface reinforced Raman active.
The concrete steps of above-mentioned ultrathin alumina template UTAM are:
A_1. the pretreatment of aluminium flake: by high-purity aluminium flake of thick for 0.2 mm 99.999% ultrasonic cleaning 30 min in acetone, 450 ~ 550 DEG C of annealing under nitrogen protection, then, in the ethanol of temperature 0 DEG C and the mixed liquor of perchloric acid, under 750 mA constant current conditions, electrochemical polish is carried out;
A_2. anodic oxidation: by the aluminium flake after step a_1 process with 0.3 M oxalic acid solution for electrolyte, carry out first time anodized under 40 V constant voltages after, the time is 7 ~ 12 h; Then under temperature 60 C condition, in the mixed liquor of mass fraction 6% phosphoric acid and 1.8% chromic acid, soak 10 h, then with 0.3 M oxalic acid solution for electrolyte, under 40 V constant voltages, carry out second time anodic oxidation 3 ~ 5 min;
A_3. the removal of unreacted aluminium substrate: step a_2 gained alumina formwork is immersed in CuCl
2with in the mixed liquor of HCl, unoxidized aluminium substrate is dissolved away completely, to obtain pure ultrathin alumina template.
Above-mentioned UTAM aperture adjustment concrete steps are: the barrier layer of alumina formwork is swum in 30 DEG C down, and mass percent is in the dilute phosphoric acid solution of 5%, and pore-enlargement 45 ~ 60 min, obtains the UTAM of different pore size.
The concrete steps that above-mentioned UTAM transfers on Si substrate are: by after reaming and surface swims in acetone soln with the UTAM sample of photoresist, after the photoresist on surface all dissolves, transferred to by UTAM on clean Si substrate.
The concrete steps that above-mentioned UTAM removes are: be immersed in the NaOH solution of 0.1M by the UTAM/Si sample of evaporation certain thickness Ag films, now silicon base is separated with UTAM, continue immersion 20 min, UTAM is completely dissolved, the Ag films of individualism is forwarded in deionized water and cleans, gone to again in acetone after cleaning on the single crystal Si substrate sticking to and be coated with UV glue, after solidification, namely obtained the substrate of silver nanocaps surface reinforced Raman active.
Advantage of the present invention and effect are: the present invention compared with prior art, has the following advantages:
1) it is homogeneous that the silver nanocaps array surface that UTAM legal system provided by the invention is standby strengthens Raman active substrate pattern, structure-controllable, and the analysis thing for variable concentrations has significant surface Raman enhancement effect, and strengthen signal stable homogeneous.
2) the silver nanocaps array surface of large area high-sequential provided by the invention, structure-controllable strengthens the preparation method of Raman active substrate, structural parameters and the pattern of porous order thin film can be regulated according to the structural parameters of ultrathin alumina template, realize silver nanocaps array substrate strengthens effect Different Effects to Raman surface.
3) preparation method of the surface reinforced Raman active substrate of large area high-sequential provided by the invention, structure-controllable silver nanocaps array, can realize the surface nano-structure prepared based on different substrates and metal material large area high-sequential.
4) the present invention adopts the method using UTAM as mask thermal evaporation physical vapour deposition (PVD) noble metal nano cap, and have simple to operate, cost is low, is easy to batch production, repeatable high advantage between different batches.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the UTAM adopting two-step penetration method to prepare.
Fig. 2 is the SEM figure of the part UTAM sample that deposited Ag film.
Fig. 3 is the SEM figure of the silver nanocaps array utilizing UTAM to prepare, and wherein illustration is the SEM figure of the silver nanocaps array of partial enlargement.
Fig. 4 is the Raman spectrogram according to depositing gained silver nanocaps arrays SERS-active substrate in the obtained UTAM of different pore-enlargement (being followed successively by 45,50,55 and 60 min from bottom to top), with concentration for 1 × 10
-6rhodamine 6G (R6G) solution of M is probe molecule.
Fig. 5 is the homogeneity for test sample SERS signal, and adopt 10 some test gained SERS spectrograms at random at sample surfaces, probe molecule is concentration 1 × 10
-6the R6G solution of M.
Detailed description of the invention
Embodiment 1: the present embodiment is at UTAM upper surface, and deposition prepares large-area ordered, homogeneous Ag nanometer cap array structure.And with 1 × 10
-6the rhodamine (rhodamine 6G, R6G) of M is probe molecule, carries out the test of Surface Raman Spectra.First by aluminium flake acetone ultrasonic cleaning 30 min of thick for 0.2 mm 99.999%; under nitrogen protection after 450 ~ 550 DEG C of annealing; in the ethanol of temperature 0 DEG C and the mixed liquor (volume ratio 1:9) of perchloric acid, electrochemical polish under constant current (750 mA) condition, obtained aluminium flake for subsequent use.By pretreated aluminium flake for subsequent use in 0.3 M oxalic acid 40 V voltages, be oxidized 12 h at 4 DEG C, take out, put into the mixed solution that volume ratio is the 1.8w% chromic acid of 1:1 and the phosphoric acid of 6w%, at the temperature of 60 DEG C, corrode 10 h; After repeatedly rinsing by deionized water, then put into electrolytic cell, adopt and carry out secondary oxidation 5 min with once oxidation the same terms.After taking-up, surface coating photoresist, immerses CuCl after baking molding
2with in the mixed liquor of HCl, dissolve unoxidized aluminium substrate, to obtain purer UTAM sample.The UTAM sample barrier layer removing aluminium substrate is swum in constant temperature 30 DEG C of 5% dilute phosphoric acid solution down, to remove the thicker barrier layer in bottom and adjustment aperture size.Experimentally need to regulate pore-enlargement, obtain the bilateral UTAM of different pore size, the pore-enlargement adopted in this example is 45 ~ 60 min, and corresponding aperture is 45 ~ 60 nm.Finally UTAM is dipped in acetone soln and dissolves photoresist, transfer on Si substrate, dry, for subsequent use, as shown in Figure 1.UTAM/Si sample is placed in evaporating and coating equipment, and vacuum is 8 × 10
-4under Pa, evaporation rate 0.3 ~ 0.5 nm/s condition, nm is thick for evaporation silver powder 100, obtain structure as shown in Figure 2, then UTAM is removed by the NaOH solution of 0.1M, and gained silverskin upset transfer is fixed on substrate, the silver nanocaps array that in obtained silicon base as shown in Figure 3, arrangement is orderly, structure and morphology is homogeneous.Structural parameters according to UTAM regulate, and the metal silver nanocaps array surface can preparing a series of different parameters (hole diameter at silver nanoparticle center is 12 ~ 35 nm) strengthens Raman active substrate.It is 1 × 10 that the above-mentioned sample obtained is dipped in concentration
-6take out after 30 min in the solution of M rhodamine 6G, nitrogen dries up, and tests with laser capture microdissection Raman spectrometer.Fig. 4 is the Raman spectrogram depositing gained silver nanocaps arrays SERS-active substrate in the obtained UTAM of different pore-enlargement (being followed successively by 45,50,55 and 60 min from bottom to top).Can see that the SERS signal of different pore-enlargement silver nanocaps array active substrate strengthens effect all fine, especially strengthen the most remarkable with the active substrate Raman of the gained of pore-enlargement 60 min, enhancer can reach 0.98 × 10
9.For investigating the homogeneity of active substrate of preparation, getting 10 points at random at sample surfaces and surveying its SERS, acquired results as shown in Figure 5, three principal character peak 1362cm
-1, 1509cm
-1, 1650cm
-1relative standard deviation be respectively 6.2%, 6.5%, 6.6%, according to bibliographical information, as SERS active-substrate, the relative standard deviation at its characteristic peak place wants < 20 %, the Raman signal relative standard deviation < 7% of the silver nanocaps array prepared by UTAM in this example, the surface enhanced Raman substrate signal stable homogeneous that the method is obtained is described, favorable repeatability, may be used for the detection of trace compound or biomolecule.
Claims (6)
1. silver nanocaps array surface strengthens a Raman active substrate, it is characterized in that this substrate is stained with in silicon monocrystalline substrate the Ag films that one deck has orderly silver nanocaps array structure; The thickness of this Ag films is: 80 ~ 150 nm; Described silver nanocaps is the center balloon-shaped structure with holes of protuberance, and diameter is 30 ~ 95 nm, and adjacent two nanometer cap centre-to-centre spacing are 100 ~ 110 nm.
2. prepare the method that silver nanocaps array surface according to claim 1 strengthens Raman active substrate, it is characterized in that the concrete steps of the method are,
A. prepared by ultrathin alumina template UTAM;
B. step a gained UTAM is carried out aperture adjustment;
C. step b gained UTAM is transferred on Si substrate;
D. by step c gained UTAM/Si sample, be 8 × 10 in vacuum
-4under Pa, evaporation rate 0.3 ~ 0.5 nm/s condition, evaporation silver powder 200 ~ 300 s; Then remove UTAM and Si substrate, the surface with orderly silver nanocaps array is transferred in deionized water upward and cleans, gone to again in acetone after cleaning and stick on single crystal Si substrate, after solidification, namely obtain the substrate of silver nanocaps surface reinforced Raman active.
3. method according to claim 2, is characterized in that the concrete steps of the ultrathin alumina template UTAM described in preparing are:
A_1. the pretreatment of aluminium flake: by high-purity aluminium flake of thick for 0.2 mm 99.999% ultrasonic cleaning 30 min in acetone, 450 ~ 550 DEG C of annealing under nitrogen protection, then, in the ethanol of temperature 0 DEG C and the mixed liquor of perchloric acid, under 750 mA constant current conditions, electrochemical polish is carried out;
A_2. anodic oxidation: by the aluminium flake after step a_1 process with 0.3 M oxalic acid solution for electrolyte, under 40 V constant voltages, carry out first time anodized, the time is 7 ~ 12 h; Then under temperature 60 C condition, in the mixed liquor of mass fraction 6% phosphoric acid and 1.8% chromic acid, soak 10 h, then with 0.3 M oxalic acid solution for electrolyte, under 40 V constant voltages, carry out second time anodic oxidation 3 ~ 5 min;
A_3. the removal of unreacted aluminium substrate: step a_2 gained alumina formwork is immersed in CuCl
2with in the mixed liquor of HCl, unoxidized aluminium substrate is dissolved away completely, to obtain pure ultrathin alumina template.
4. method according to claim 2, it is characterized in that described UTAM aperture adjustment concrete steps are: the barrier layer of alumina formwork is swum in 30 DEG C down, mass percent is in the dilute phosphoric acid solution of 5%, and pore-enlargement 45 ~ 60 min, obtains the UTAM of different pore size.
5. method according to claim 2, it is characterized in that the concrete steps that described UTAM transfers on Si substrate are: by after reaming and surface swims in acetone soln with the UTAM sample of photoresist, after the photoresist on surface all dissolves, UTAM is transferred on clean Si substrate.
6. method according to claim 2, it is characterized in that the concrete steps that described UTAM removes are: be immersed in the NaOH solution of 0.1M by the UTAM/Si sample of evaporation certain thickness Ag films, now silicon base is separated with UTAM, continue immersion 20 min, UTAM is completely dissolved, the Ag films of individualism is forwarded in deionized water and cleans, gone to again in acetone after cleaning on the single crystal Si substrate sticking to and be coated with UV glue, after solidification, namely obtained the substrate of silver nanocaps surface reinforced Raman active.
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CN106645077B (en) * | 2015-10-28 | 2019-06-25 | 上海大学 | The preparation method of SERS active-substrate of the spot size less than 5nm |
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CN108374153B (en) * | 2018-01-17 | 2021-06-15 | 南京大学 | Method for growing large-area and highly-ordered nanoparticles through magnetron sputtering |
CN113185144B (en) * | 2021-04-29 | 2022-06-21 | 安徽师范大学 | Preparation method of echinoid ordered micro-nano array structure |
CN114018897B (en) * | 2021-10-21 | 2023-04-07 | 云南省产品质量监督检验研究院 | Preparation method of silicon-based SERS substrate based on double-layer silver nanostructure |
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