CN101716839A - Large-area metal nano-structural substrate for surface-enhanced Raman and preparation method thereof - Google Patents
Large-area metal nano-structural substrate for surface-enhanced Raman and preparation method thereof Download PDFInfo
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- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 18
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- 239000007769 metal material Substances 0.000 claims abstract description 9
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000005530 etching Methods 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 13
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Abstract
The invention discloses a large-area metal nano-structural substrate for surface-enhanced Raman and a preparation method thereof. The large-area metal nano-structural substrate for the surface-enhanced Raman consists of a nano-scale structural substrate consisting of different phase alloy materials and a nano-thickness metal material deposited on the substrate. The metal nano-structural substrate provided by the invention has good Raman enhancing effect, and can be widely applied in the fields of physics, chemistry, materials science, biomedicine and the like. The preparation method for the large-area metal nano-structural substrate for the surface-enhanced Raman uses an alloy material consisting of different phases as a primary template, adopts a selective plasma etching method to etch the nano-structural substrate, and then adopts an ion beam sputtering method to deposit the nano-thickness metal material on the nano-structural substrate so as to form the surface-enhanced Raman substrate based on different phase metal materials; and the preparation method has mature industrial technology and low production cost, and can implement industrialized mass production.
Description
Technical field
The present invention designs a kind of nano structural material, a kind of surface-enhanced Raman of specific design large-area metal nano-structural substrate and preparation method thereof.
Background technology
SERS (SERS) technology all has a wide range of applications in fields such as physics, chemistry, materialogy, biomedicines.The principle of its enhancing is based on plasmon resonance makes the metal surface electric field be enhanced, and with respect to other measurement means, Raman detection has molecular recognition and fingerprint character, and insensitive to the aqueous solution, and the detection of biomolecule is particularly useful.But its shortcoming be signal very a little less than, and adopt surface enhanced Raman technique can make the solution of this difficult problem that new breakthrough has been arranged.
Concerning the surface strengthens Raman detection, the most important thing is to develop effective enhancing substrate based on metal Nano structure, realize that Raman signal farthest strengthens.At present, nano-structure array and its colloidal solid solution of silver (Ag) and gold (Au) all are widely used, and nano-structure array is with respect to colloidal solution, have stability strong, can repeat, characteristics such as simple to operate, thereby in Raman detection, be used widely, produce the method for preparing the metal structure substrate at present and mainly contain methods such as nanosphere imprint lithography, ion beam focusing etching, mask lithography, nano impression and electron beam lithography, but these methods, with high costs, complex process, preparation speed are slow, can not realize industrialized production.
Summary of the invention
Goal of the invention: the objective of the invention is in order to solve the deficiencies in the prior art, providing a kind of has wide range of applications, can effectively strengthen the surface-enhanced Raman large-area metal nano-structural substrate of Raman signal, another object of the present invention provide a kind of technology simple, be convenient to the preparation method of the low surface-enhanced Raman of suitability for industrialized production and production cost with the large-area metal nano-structural substrate.
Technical scheme: in order to realize above purpose, a kind of surface-enhanced Raman large-area metal nano-structural substrate of the present invention, it is made up of with the metal material that is deposited on the nanometer grade thickness on the substrate the substrate of the nanoscale structures that different phase alloy materials are formed.
Above-described surface-enhanced Raman large-area metal nano-structural substrate, wherein said different phase alloy materials are aluminium titanium carbon alloy.As preferred version, described aluminium titanium carbon alloy is made up of the alundum (Al of 64at% and the titanium carbide of 36at%, and this aluminium titanium carbon alloy nanoscale structures substrate is by alundum (Al (Al
2O
3) and the nano-scale particle of titanium carbide (TiC) form at 1500 ℃ of sintering.As other scheme, the template substrate of different phase alloy materials of the present invention also comprises the material of other similar alloy phases except aluminium titanium carbon alloy.
Alundum (Al (Al in the above-described nano aluminum titanium carbon alloy
2O
3) and titanium carbide (TiC) particle grain size size about 300 nanometers or less than this size.
Above-described surface-enhanced Raman large-area metal nano-structural substrate, the metal material that wherein is deposited on the nanometer grade thickness on the substrate is silver or golden.As preferred version, the silver or the golden thickness that are deposited on the substrate are 10 to 100 nanometers.
A kind of method for preparing surface-enhanced Raman with the large-area metal nano-structural substrate specifically may further comprise the steps:
(1) select the alloy material of different phase compositions as primary template;
(2) according to the hardness difference of alloy material, utilize selectivity plasma etching method, etch the substrate of nanoscale structures, standby;
(3) get the substrate of the nanoscale structures that step (2) prepares, by the method for ion beam sputtering, the metal material of depositing nano level thickness on the substrate of nanoscale structures promptly obtains surface-enhanced Raman large-area metal nano-structural substrate.
The above-described surface-enhanced Raman preparation method of large-area metal nano-structural substrate, wherein the primary template selected for use of step (1) is formed aluminium titanium carbon alloy by alundum (Al and titanium carbide and is made, certainly except that alundum (Al and titanium carbide phase alloy, can also select other similar alloy materials for use.Alundum (Al (Al in the alloy of this different phase compositions
2O
3) and titanium carbide (TiC) particle grain size size about 300 nanometers or less than this size.
The above-described surface-enhanced Raman preparation method of large-area metal nano-structural substrate, its physical property of different component in the alloy material that step (2) is different wherein, as the hardness difference, cause different sputter rates, by selectivity plasma etching method, out of phase material is had different etch rates, and wherein the hardness of titanium carbide (TiC) is greater than alundum (Al (Al
2O
3), so the selectivity plasma is to alundum (Al (Al
2O
3) etching speed faster than the etching speed of titanium carbide (TiC).
In the actual mechanical process, the aluminium titanium carbon alloy template of being made up of alundum (Al and titanium carbide is put into ion beam etching (IBE:Ion beam etching) chamber, feed argon gas (Ar) and ethene (C then
2H
4) mist, as preferred version, the volume flow ratio of argon gas and ethene is 2: 1, the substrate tilting angle is 65 ° in the etching process, utilize radio frequency glow discharge to produce plasma and come the etched substrate surface, because the hardness ratio alundum (Al of titanium carbide is big in the alloy phase of substrate, carrying out along with sputter procedure, alundum (Al phase etching very fast, by the control sputtering time, obtain the surface that differing heights rises and falls at original smooth aluminium titanium carbon alloy template surface, highly can be from tens nanometers to the hundreds of nanometer.
The above-described surface-enhanced Raman preparation method of large-area metal nano-structural substrate, step (3) wherein, by the method for ion beam sputtering, deposit thickness is the silver-colored or golden of 10 to 100 nanometers on the substrate of nanoscale structures on the substrate of nanoscale structures.
A kind of Raman detection device, it comprises an excitation source, surveys detection of scattering light device and a surface-enhanced Raman of the present invention large-area metal nano-structural substrate for one.
Beneficial effect: the present invention compared with prior art has following outstanding advantage:
1, surface-enhanced Raman provided by the invention large-area metal nano-structural substrate, metal Nano structure substrate pattern homogeneous, analyte for variable concentrations has repeatably surface reinforced Raman active, and the scope of application is extensive, can effectively strengthen Raman signal.
2, the surface-enhanced Raman provided by the invention preparation method of large-area metal nano-structural substrate can be according to the size of particle in the substrate alloy phase, and the size of regulating nanometer metal structure is adjustable continuously from the nanoscale to the micron order; The present invention adopts the selective plasma etching method to etch the substrate of nanoscale structures, and selective plasma etching technics technology maturation in industry be convenient to operation than complex technologys such as electron beam lithography and photoetching, and cost is low.
3, the surface-enhanced Raman provided by the invention preparation method of large-area metal nano-structural substrate, can be according to the needs of surface-enhanced Raman, preparation is based on the metal Nano structure substrate of different materials, and preparation technology is simple, convenient, easily once prepare large-area surface-enhanced Raman substrate, can realize industrialized production.
Description of drawings
Fig. 1 is a smooth aluminium titanium carbon alloy substrate template structural representation of the present invention.
Fig. 2 is the aluminium titanium carbon alloy substrat structure schematic diagram that selective etch of the present invention is crossed.
Fig. 3 is the surface-enhanced Raman substrat structure schematic diagram behind plated metal on the substrate of the present invention.
Fig. 4 is the AFM figure of differing heights fluctuating of the present invention peak shape substrate, and wherein (A) is smooth substrate; (B) be height relief 50 nanometers; (C) be height relief 70 nanometers; (D) be height relief 100 nanometers.
Fig. 5 is the Raman enhancement effect curve map of the substrate that obtains behind deposition different-thickness metal on the aluminium titanium carbon alloy template of the present invention.
The specific embodiment
Below in conjunction with specific embodiment, further illustrate the present invention, should understand these embodiment only is used to the present invention is described and is not used in and limit the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims institute restricted portion to the modification of the various equivalent form of values of the present invention.
A kind of surface-enhanced Raman large-area metal nano-structural substrate, it is made up of with the gold that is deposited on 10 nano thickness on the aluminium titanium carbon alloy nano material substrate the substrate of the nanoscale structures that aluminium titanium carbon alloy material is formed.Wherein aluminium titanium carbon alloy is made up of the alundum (Al of 64at% and the titanium carbide of 36at%, and the particle diameter of aluminium titanium carbon alloy is 300 nanometers.
A kind of surface-enhanced Raman large-area metal nano-structural substrate, it is made up of with the gold that is deposited on 100 nano thickness on the aluminium titanium carbon alloy nano material substrate the substrate of the nanoscale structures that aluminium titanium carbon alloy material is formed.Wherein aluminium titanium carbon alloy is made up of the alundum (Al of 64at% and the titanium carbide of 36at%, and the particle diameter of aluminium titanium carbon alloy is 280 nanometers.
A kind of surface-enhanced Raman large-area metal nano-structural substrate, it is made up of with the gold that is deposited on 30 nano thickness on the aluminium titanium carbon alloy nano material substrate the substrate of the nanoscale structures that aluminium titanium carbon alloy material is formed.Wherein aluminium titanium carbon alloy is made up of the alundum (Al of 64at% and the titanium carbide of 36at%, and the particle diameter of aluminium titanium carbon alloy is 300 nanometers.
Embodiment 4
A kind of surface-enhanced Raman large-area metal nano-structural substrate, it is made up of with the ag material that is deposited on 50 nano thickness on the aluminium titanium carbon alloy nano material substrate the substrate of the nanoscale structures that aluminium titanium carbon alloy material is formed.Wherein aluminium titanium carbon alloy is made up of the alundum (Al of 64at% and the titanium carbide of 36at%, and the particle diameter of aluminium titanium carbon alloy is 200 nanometers.
A kind of surface-enhanced Raman preparation method of large-area metal nano-structural substrate specifically may further comprise the steps:
(1) select aluminium titanium carbon alloy material as primary template, the structure of aluminium titanium carbon alloy material as shown in Figure 1, wherein the size of alundum (Al and titanium carbide granule is 300 nanometers;
(2) the aluminium titanium carbon alloy template of being made up of alundum (Al and titanium carbide is put into ion beam etching (IBE:Ion beam etching) chamber, feed flow rate ratio then and be 2: 1 argon gas (Ar) and ethene (C
2H
4) mist, the substrate tilting angle is 65 ° in the etching process, utilizes radio frequency glow discharge to produce argon gas (Ar) and ethene (C
2H
4) hybrid plasma come the etched substrate surface, because the hardness ratio alundum (Al of titanium carbide is big in the alloy phase of substrate, carrying out along with sputter procedure, alundum (Al phase etching very fast, by the control sputtering time, obtain the rise and fall surface of peak shape of height at original smooth aluminium titanium carbon alloy template surface, wherein the height at top is 150 nanometers, concrete structure such as Fig. 2 and shown in Figure 4;
(3) get the substrate of the nanoscale structures that step (2) prepares, (concrete experiment condition is for using 682 type plated film instrument of U.S. Gatan company for method by ion beam sputtering, by glow discharge ionization argon gas, produce the argon ion plasma, etching Ag metal targets then, deposit Ag, wherein operating voltage and electric current are 7 kilovolts and 300 microamperes), deposition 10 nanometers are to the Ag material of 100 nano thickness on the substrate of nanoscale structures, promptly obtain surface-enhanced Raman large-area metal nano-structural substrate, concrete structure as shown in Figure 3.
Embodiment 6
A kind of surface-enhanced Raman preparation method of large-area metal nano-structural substrate specifically may further comprise the steps:
(1) select aluminium titanium carbon alloy material as primary template, wherein aluminium titanium carbon alloy is made up of the alundum (Al of 64at% and the titanium carbide of 36at%, and the size of alundum (Al and titanium carbide granule is 250 nanometers;
(2) the aluminium titanium carbon alloy template of being made up of alundum (Al and titanium carbide is put into ion beam etching (IBE:Ion beam etching) chamber, feed flow rate ratio then and be 2: 1 argon gas (Ar) and ethene (C
2H
4) mist, the substrate tilting angle is 65 ° in the etching process, utilizes radio frequency glow discharge to produce argon gas (Ar) and ethene (C
2H
4) hybrid plasma come the etched substrate surface, because the hardness ratio alundum (Al of titanium carbide is big in the alloy phase of substrate, carrying out along with sputter procedure, alundum (Al phase etching very fast, by the control sputtering time, obtain the rise and fall surface of peak shape of height at original smooth aluminium titanium carbon alloy template surface, wherein the height at top is 100 nanometers, and is standby;
(3) get the substrate of the nanoscale structures that step (2) prepares, (concrete experiment condition is for using 682 type plated film instrument of U.S. Gatan company for method by ion beam sputtering, by glow discharge ionization argon gas, produce the argon ion plasma, etching Au metal targets then, deposit Au, wherein operating voltage and electric current are 7 kilovolts and 300 microamperes), deposition 10 nanometers promptly obtain surface-enhanced Raman large-area metal nano-structural substrate to the Au material of 100 nano thickness on the substrate of nanoscale structures.
Embodiment 7
The surface-enhanced Raman that detection obtains behind deposition different-thickness metal on the aluminium titanium carbon alloy template Raman enhancement effect of large-area nano structured substrate.
Utilize rhodamine molecule (R6G) as molecular detection, the surface-enhanced Raman after depositing 10nm, 30nm, 50nm, 70nm and 100nm thickness silver on the aluminium titanium carbon alloy template that research the present invention the prepares Raman enhancement effect of large-area nano structured substrate.
Concrete experimentation is: 1. the substrate for preparing being put into concentration is 10
-6Dipping is 24 hours in the rhodamine aqueous solution of mol; 2. then substrate is taken out from the rhodamine aqueous solution, with the ethanolic solution flushing, dry up with nitrogen then earlier, promptly can be used for Raman detection.Concrete experimental result such as table 1 and shown in Figure 5, experimental result show that behind the silver more than the deposition 10nm on the aluminium titanium carbon alloy template, the Raman enhancement effect of substrate strengthens gradually, and enhancer is from 10
4To 10
6The order of magnitude changes, and wherein when the thickness of silver was 30 nanometers, the Raman enhancement effect was the strongest, reaches 10
6The order of magnitude, when the thickness of silver during greater than 30 nanometers the Raman enhancement effect reduce gradually, the Raman enhancement effect of the substrate of deposition 50nm, 70nm and 100nm thickness silver is respectively 1.2E+06,6.0E+05 and 2.0E+05.
Raman enhancement effect testing result on table 1 substrate behind the deposition different-thickness silver
| The thickness of silver on the substrate | ??10nm | ??30nm | ??50nm | ??70nm | ??100nm |
| The Raman enhancer | ??0.5E+05 | ??1.7E+06 | ??1.2E+06 | ??6.0E+05 | ??2.0E+05 |
Show that by above experimental result surface-enhanced Raman provided by the invention has good Raman enhancement effect with the large-area nano structured substrate, can be widely used in physics, chemistry, materialogy and biomedical sector.And strengthen substrate by the Raman that preparation method provided by the invention prepares, show that after testing the Raman enhancement effect of substrate strengthens behind the silver of deposition 30nm thickness on the carbon alloy template.
Claims (10)
1. a surface-enhanced Raman large-area metal nano-structural substrate is characterized in that, it is made up of with the metal material that is deposited on the nanometer grade thickness on the substrate the substrate of the nanoscale structures that different phase alloy materials are formed.
2. surface-enhanced Raman large-area metal nano-structural substrate according to claim 1 is characterized in that, described different phase alloy materials are aluminium titanium carbon alloy.
3. surface-enhanced Raman large-area metal nano-structural substrate according to claim 2 is characterized in that, described aluminium titanium carbon alloy is made up of the alundum (Al of 64at% (atomic percent) and the titanium carbide of 36at% (atomic percent).
4. surface-enhanced Raman large-area metal nano-structural substrate according to claim 2 is characterized in that, the particle diameter of described nano aluminum titanium carbon alloy is the aluminium titanium carbon alloy less than 300 nanometers.
5. surface-enhanced Raman large-area metal nano-structural substrate according to claim 1 is characterized in that, the described metal material that is deposited on the nanometer grade thickness on the substrate is silver or golden.
6. surface-enhanced Raman large-area metal nano-structural substrate according to claim 5 is characterized in that, the silver or the golden thickness that are deposited on the substrate are 10 to 100 nanometers.
7. one kind prepares the method that claim 1 described surface-enhanced Raman is used the large-area metal nano-structural substrate, it is characterized in that may further comprise the steps:
(1) select the alloy material of different phase compositions as primary template;
(2) according to the hardness difference of alloy material, utilize selectivity plasma etching method, etch the substrate of nanoscale structures, standby;
(3) get the substrate of the nanoscale structures that step (2) prepares, by the method for ion beam sputtering, the metal material of depositing nano level thickness on the substrate of nanoscale structures promptly obtains surface-enhanced Raman large-area metal nano-structural substrate.
8. surface-enhanced Raman according to claim 7 is characterized in that with the method for large-area metal nano-structural substrate, the aluminium titanium carbon alloy that used primary template is made up of the titanium carbide of the alundum (Al of 64at% and 36at% in the step (1).
9. the surface-enhanced Raman according to claim 7 method of large-area metal nano-structural substrate, it is characterized in that, the described selectivity plasma etching of step (2) method, feeding flow rate ratio is 2: 1 the argon gas and the mist of ethene, utilize radio frequency glow discharge to produce plasma, the substrate tilting angle is 65 ° in the etching process, comes the etched substrate surface.
10. Raman detection device, it comprises an excitation source, surveys detection of scattering light device and the described surface-enhanced Raman of claim 1 a large-area metal nano-structural substrate for one.
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| CN103313950B (en) * | 2010-10-15 | 2015-09-30 | 葛迪恩实业公司 | The method of process soda lime silica glass baseplate surface, surface-treated glass substrate and use its device |
| CN103842785A (en) * | 2011-05-13 | 2014-06-04 | 李�浩 | Sers substrates |
| CN103276355A (en) * | 2013-05-20 | 2013-09-04 | 杭州电子科技大学 | Preparation method of novel film-coated needle tip for needle tip enhanced Raman measurement |
| CN107421940A (en) * | 2017-05-26 | 2017-12-01 | 云南师范大学 | The method that borax corrosion monocrystalline silicon makes surface enhanced Raman substrate |
| CN107643278B (en) * | 2017-09-14 | 2020-04-21 | 浙江工业大学 | Preparation method of surface-enhanced Raman substrate |
| CN107643278A (en) * | 2017-09-14 | 2018-01-30 | 浙江工业大学 | A kind of preparation method of surface-enhanced Raman substrate |
| CN108535234A (en) * | 2018-01-17 | 2018-09-14 | 天津大学 | Human body IgG Protein Detection SERS substrates based on modified by silver nanoparticles |
| CN109612975A (en) * | 2018-12-07 | 2019-04-12 | 国家纳米科学中心 | A kind of surface enhanced Raman substrate and preparation method thereof |
| CN109612975B (en) * | 2018-12-07 | 2021-11-02 | 国家纳米科学中心 | Surface-enhanced Raman substrate and preparation method thereof |
| CN109827945A (en) * | 2019-02-28 | 2019-05-31 | 合肥工业大学 | A kind of preparation method of high SERS activity Ag/MXene-Ti3C2 composite material |
| CN109827945B (en) * | 2019-02-28 | 2021-09-21 | 合肥工业大学 | Preparation method of Ag/MXene-Ti3C2 composite material with high SERS activity |
| WO2022267229A1 (en) * | 2021-06-24 | 2022-12-29 | 浙江大学 | Packaging material for nondestructive testing of quality of agricultural products and food products, and preparation and testing method |
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