CN101726480A - Surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure and preparation method thereof - Google Patents
Surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a surface-enhanced Raman substrate based on a diamond-like carbon film modified metal nano structure and a preparation method thereof. The surface-enhanced Raman substrate consists of a substrate in a metal nano structure and a diamond-like carbon film deposited on the substrate in a metal nano structure. In the invention, when nano metal Ag is used as the substrate material and after the diamond-like carbon film is deposited, the nano material metal Ag can not be oxidized, thereby enhancing the chemical stability of the nano structure substrate which takes Ag as the material, and enhancing the Raman effect of the substrate; the preparation method for the surface-enhanced Raman substrate based on the diamond-like carbon film modified metal nano structure, which is provided by the invention, has mature super-thin ta-C film technology and low cost, thereby being capable of realizing industrialized production.
Description
Technical field
The present invention designs a kind of nano film material and preparation method thereof, is specifically related to a kind of surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure and preparation method thereof.
Background technology
Surface enhanced raman spectroscopy (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; With respect to other measurement means, Raman detection has molecular recognition and fingerprint character, and insensitive to aqueous solution, and the detection of biomolecule is particularly useful.But the shortcoming of Raman spectrum be signal very a little less than, and adopt surface enhanced Raman technique to make the solution of this difficult problem that new breakthrough 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, silver (Ag) and the gold nano-structure array of (Au) and its colloidal solid solution all are widely used, and nano-structure array is with respect to colloidal solution, have stability by force, advantage such as can repeat, thereby in Raman detection, be used widely.Wherein Ag is for Au, because enhancer exceeds two orders of magnitude, and can be operated in visible wavelength (for Raman spectrum, the biquadratic of its signal and excitation wavelength is inversely proportional to) and is used widely.But, Ag nanostructured substrate also has many shortcomings, and is as poor chemical stability in air or solution, easily oxidized and cause the substrate enhancer to reduce, next is that the compatibility of metal A g substrate and detection of biological molecule is poor, and the silver ion that decomposes in the solution can make biomolecule be damaged.
In order to solve the problem based on the surface-enhanced Raman substrate existence of Ag, the method for mainly taking is an Ag substrate for preparing to be placed in the nitrogen preserve, and increased use cost like this, and the substrate life-span is shorter, can not be repeatedly used at present.For biomolecule detection, generally select for use the lower Au of enhancer to prepare substrate for this reason.In addition, because Au is better to the compatibility of biomolecule, stable chemical performance is also taked to solve the problems referred to above by synthetic Ag nuclear @Au shell method in the world, the enhancing effect of system improves to some extent than simple Au substrate, but the affiliation sacrifice part that adds of Au is strengthened the property.
Summary of the invention
Goal of the invention: the objective of the invention is in order to solve the deficiencies in the prior art, a kind of chemical stability and good biocompatibility are provided, and can strengthen the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure of Ramam effect, another object of the present invention provides this preparation method based on the surface-enhanced Raman substrate of diamond-like carbon film modified metal nano structure.
Technical scheme, in order to realize above purpose, the technical solution used in the present invention is:
A kind of surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, it is made up of the substrate of metal Nano structure and the diamond like carbon film that is deposited on the metal Nano structure substrate.
Above-described surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, the substrate of described metal Nano structure are the nanostructured substrate of silver, gold, copper or other metal material.
Above-described surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, as preferably, described diamond like carbon film is tetrahedral structure amorphous carbon-film (ta-C:Tetrahedral amorphouscarbon) or is the film of the deriving (ta-C:H of the tetrahedral structure amorphous carbon-film of hydrogeneous, nitrogen, fluorine and/or oxygen, ta-C:N, ta-C:H:N), as preferred version, the thickness that is deposited on the diamond like carbon film on the metal Nano structure substrate is 1 to 2 nanometer.
The present invention is directed to that Ag nanostructured substrate exists in surface-enhanced Raman detects, as the character instability, shortcomings such as Bc difference, the present invention adopts the method in the surface deposition diamond like carbon film of metal Nano structure substrate to solve.Diamond like carbon film is a kind of amorphous carbon-film, has many and diamond thin confers similar advantages, as high rigidity, high-wearing feature, high resistivity, good chemical stability and resistance to corrosion.Wherein hydrogeneous amorphous carbon-film (a-C:H) and contain higher sp
3The tetrahedral structure amorphous carbon-film (ta-C) of linkage content is most widely used in different types of diamond like carbon film.Especially ta-C film when even thickness is reduced to 1～2nm, still has advantages such as continuous densification, metachemistry stability.In addition, the ta-C film also has some other excellent performances: 1, have excellent biological compatibility, thermal stability and visible and the infrared band optical radiation is transparent; 2, with respect to diamond thin, the ta-C film can at room temperature just can deposit on the different substrates; 3, the ta-C film surface is super level and smooth, can keep the surfaceness of deposition substrate substantially, and is especially helpful to optics and biomedical applications.Therefore, the present invention deposits the ultra-thin ta-C film of one deck on the nanostructured substrate of Ag, Au or other metal, comprises the film of deriving of the tetrahedral structure amorphous carbon-film of hydrogeneous, nitrogen, fluorine, oxygen element, as the surface-enhanced Raman substrate.
The ultra-thin ta-C film of deposition one deck can solve the problem that the Ag nanostructured is faced as the surface-enhanced Raman substrate on the nanostructured substrate of metal.At first can solve shortcomings such as Ag poor chemical stability, easy oxidation, can also avoid Ag in effects of ionization, thereby destroy biomolecule.Secondly, because it is the strongest in the surface that surface plasmon resonance strengthens the characteristics of electric field, leave the surface then and be index like decay, and the compatibility of ta-C film (comprising that its hydrogen, nitrogen, fluorine, oxygen element mix) itself and biomolecule is good, by hydrogen bond can be to make biomolecule in the solution be adsorbed on the surface of substrate at an easy rate, strengthens very beneficial for surperficial Raman signal.At last, the most important thing is that the ta-C film not only can not reduce the local electric field enhancer of simple Ag nanostructured, also can improve its enhancer.Discover that its principle mainly contains three aspects: the one, the ta-C film has very high refractive index (～2.5) as high dielectric thin film, can play the effect of constraint light, makes Raman absorbing light efficient improve, thereby strengthens Raman signal; The 2nd, from ta-C layer inside surface and outside surface scattering interference of light, will reduce the optical electric field of dielectric layer inside, because energy conservation, the optical electric field of dielectric layer outside surface increases; The 3rd, in the multiple scattering process back and forth of two end faces of dielectric layer, make in the chamber, to form a bigger enhancer.
But studies show that, thickening along with the ta-C film, be index like decay because the loss of scattering-in light and surface plasmon resonance electric field leave the surface, the surface field of the feasible substrate of modifying with respect to the substrate of unmodified reduced, reduce thereby cause Raman to strengthen; The present invention draws with Theoretical Calculation by experiment: when the thickness of ta-C film greater than
And less than
The time, can protect the Ag surface can be not oxidized, and demonstrate stronger Raman than the substrate of unmodified and strengthen.Therefore, to be deposited on the thickness of the diamond like carbon film on the metal Nano structure substrate be that 1 to 2 nanometer is as optimal case in the present invention.
Certainly, strengthen effect,,, can realize that also its Raman strengthens by the ta-C film of depositing ultrathin for the substrate of other metal nano materials such as Au and Cu from the surface.
The method of above-described surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure provided by the invention specifically may further comprise the steps:
(1) on the substrate of metal Nano structure, by argon plasma etch method remove surface contaminant on the metal Nano structure substrate, standby;
(2) depositing diamond-like film on the metal Nano structure substrate that step (1) obtains then.
The method of above-described surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, described metal Nano structure substrate are silver, gold, copper or other nanostructured substrate.
The diamond like carbon film of deposition is preferably the film of deriving of the tetrahedral structure amorphous carbon-film of tetrahedral structure amorphous carbon-film or hydrogeneous, nitrogen, fluorine and/or oxygen element in the method for above-described surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, step (2).
The method of above-described surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, in order to increase the adhesion of film and nano metal substrate, carrying out step (2) operation, promptly carrying out on the metal Nano structure substrate before the depositing diamond-like film step, on the metal Nano structure substrate, deposit one deck silicon layer, wherein silicon layer amorphous si film earlier.
The method of the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure of the present invention, wherein diamond like carbon film utilizes the filtered cathodic vacuum arc method to be deposited on the metal Nano structure substrate.
A kind of Raman detection device, it comprises excitation source, surveys detection of scattering light device and the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure of the present invention.
Beneficial effect: the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure of the present invention is compared with prior art and is had the following advantages:
1, with nano metal Ag during as backing material, behind the depositing diamond-like film, metal A g nano material can be not oxidized, and can strengthen Ag is the chemical stability of the nanostructured substrate of material, and can strengthen the Ramam effect of substrate; Especially diamond like carbon film itself has the permeability of good biocompatibility and visible waveband, so the Ag nanostructured substrate that the tetrahedral structure amorphous carbon-film is modified can be used in surface-enhanced Raman.
2, the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure of the present invention, applied widely, to other metal,, behind the depositing diamond-like film, can improve the enhancing effect as surface-enhanced Ramans such as gold, silver and copper nanostructured substrate.
3, the Raman detection that can be widely used in chemical pollutant trace detection and biomolecule based on the surface-enhanced Raman substrate of diamond-like carbon film modified metal nano structure of the present invention.
4, the preparation method of the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure provided by the invention, wherein ultra-thin ta-C thin film technique maturation, production cost are low, can realize industrialized production.
Description of drawings
Fig. 1 is the structural representation of Nano Silver triarray structured substrate of the present invention.
Fig. 2 is the cross-sectional view of Fig. 1 along the A-A direction.
Fig. 3 is the chemical stability testing result figure of the amorphous carbon film nanometer Ag material substrate of different-thickness.
Fig. 4 is that the Raman of Ag nanostructured substrate of the amorphous carbon film of different-thickness strengthens figure as a result.
Embodiment
1, a kind of surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, it is made up of the substrate of metal A g nanostructured and the tetrahedral structure amorphous carbon-film that is deposited on the metal A g nanostructured substrate.Wherein the thickness of tetrahedral structure amorphous carbon-film is 1 nanometer.
1, a kind of surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, it is made up of with the film of deriving that is deposited on the hydrogeneous tetrahedral structure amorphous carbon-film on the metal A u nanostructured substrate the substrate of metal A u nanostructured.The thickness of the film of deriving of wherein hydrogeneous tetrahedral structure amorphous carbon-film is 2 nanometers.
1, a kind of surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, it is made up of with the film of deriving that is deposited on the nitrogenous tetrahedral structure amorphous carbon-film on the metal Cu nanostructured substrate the substrate of metal Cu nanostructured.The thickness of the film of deriving of wherein nitrogenous tetrahedral structure amorphous carbon-film is 2 nanometers.
Embodiment 4
1, a kind of surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure, it is by the substrate of metal A g nanostructured, and the amorphous si film that is deposited on the metal A g nanostructured substrate is formed with the tetrahedral structure amorphous carbon-film that is deposited on the amorphous si film.Wherein the thickness of tetrahedral structure amorphous carbon-film is 2 nanometers.
Embodiment 5
A kind of preparation method of the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure specifically may further comprise the steps:
(1) adopt the nanosphere imprint lithography in conjunction with metal sputter deposition (with reference to Chinese patent ZL03131989.0 and ZL 200410041939.9), the substrate of preparation Nano Silver triarray structure, substrat structure is as shown in Figure 1.
(2) adopt filtered cathodic vacuum arc method deposit thickness tetrahedral structure amorphous carbon film on the substrate of the Nano Silver triarray structure that step (1) prepares, promptly obtain the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure of the present invention from 5 dusts to 40 dust different-thickness.In concrete this example, the filtered cathodic vacuum arc method mainly is to finish on the FCVA origin system that adopts Singapore Nanofilm Technologies Internat to produce.The filtered cathodic vacuum arc technology is mainly by applying certain electric current at anode, on the negative electrode graphite target, form certain potential difference (PD), the way of knocking by pulse machine is lighted striking again, make cathodic vacuum arc discharge, thereby graphite evaporation and ionization, form plasma, by the tangent bend axial passage, under the effect in electric field and magnetic field, filter out neutral macroparticle, and deposit on the substrate through quickening.In whole process, as preferred version, anode current is 2.5 amperes, and the striking electric current is 30 amperes, and filtering coil current is 10 amperes, and substrate bias is 0 volt.
Embodiment 6
Detect the tetrahedral structure amorphous carbon film strengthens Raman active to the substrate surface of Nano Silver triarray structure influence.
(1) (adopt U.S. PHI680 type auger electron spectroscopy, projectile energy is 5 kilovolts and 6 and receives peace to utilize auger electron spectroscopy (AES); Etching condition comes etched substrate for using 0.5 dried volt to produce argon plasma, and the etching area is 1mm
2To the etch rate of amorphous tetrahedron film be 5 dusts/minute; average every etching is got once spectrum 6 seconds) and x-ray photoelectron spectroscopy (employing Tianjin, the island ESCA3600 of company type energy spectrometer; with Mg Ka (1253.6 electron-volts) is x-ray source; binding energy by Au 4f2/7 comes the corrective system error for 84.0 electron-volts) detect the surface protection situation of tetrahedral structure amorphous carbon film to Nano Silver triarray structured substrate; concrete experimental result as shown in Figure 3, experimental result shows that the thickness when film exists
The time, the Ag substrate does not have oxidized, and experimental result shows, when the thickness of tetrahedral structure amorphous carbon film more than or equal to
The time, just can protect chemical stability based on the nanometer Ag material substrate, when the thickness of tetrahedral structure amorphous carbon film less than
The time, relatively poor based on nanometer Ag material substrate chemical stability, the thickness of the metal A g of the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure therefore provided by the invention be greater than
(2) utilize rhodamine molecule (R6G) as molecular detection, detect its surface-enhanced Raman characteristic.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 4, experimental result show that Raman strengthens thickness with film and increases to strengthen afterwards earlier and reduce, when the thickness of film less than
The time, the substrate that tetrahedral structure amorphous carbon film (ta-C) is modified strengthens high than the substrate Raman of unmodified.When the thickness of film greater than
The time, as be
With
Constantly, the substrate of tetrahedral structure amorphous carbon film (ta-C) modification weakens than the substrate Raman enhancing of unmodified.In addition, enhancer calculating (with reference to Applied Physics Letter 88,143121) shows that the thickness when film exists
The time, it is the twice (shown in Fig. 4 (B)) of unmodified that the Raman of the substrate of modification strengthens.
Raman enhancement effect testing result on table 1 substrate behind the deposition different-thickness silver
| The thickness of ta- |
0 dust | 5 |
10 |
20 |
40 dusts |
| The Raman enhancer | ??5.30E+05 | ??2.61E+06 | ??1.13E+06 | ??3.88E+05 | ??1.48E+05 |
Therefore, the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure provided by the invention, deposit thickness is on nanometer metallic silver
Extremely
Tetrahedral structure amorphous carbon film (ta-C) after, not only can make substrate have chemical stability, can also strengthen the Raman signal of substrate.
Claims (10)
1. the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure is characterized in that, it is made up of the substrate of metal Nano structure and the diamond like carbon film that is deposited on the metal Nano structure substrate.
2. the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure according to claim 1 is characterized in that, the substrate of described metal Nano structure is the nanostructured substrate of silver, gold or copper.
3. the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure according to claim 1, it is characterized in that described diamond like carbon film is the tetrahedral structure amorphous carbon-film or is the film of deriving of the tetrahedral structure amorphous carbon-film of hydrogeneous, nitrogen, fluorine and/or oxygen.
4. the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure according to claim 1 is characterized in that, the thickness that is deposited on the diamond like carbon film on the metal Nano structure substrate is 1 to 2 nanometer.
5. method for preparing the described surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure of claim 1 is characterized in that may further comprise the steps:
(1) on the substrate of metal Nano structure, by argon plasma etch method remove surface contaminant on the metal Nano structure substrate, standby;
(2) depositing diamond-like film on the metal Nano structure substrate that step (1) obtains then.
6. the method for the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure according to claim 5 is characterized in that, described metal Nano structure substrate is silver, gold or copper nanostructured substrate.
7. the method for the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure according to claim 5, it is characterized in that the diamond like carbon film of deposition is the film of deriving of the tetrahedral structure amorphous carbon-film of tetrahedral structure amorphous carbon-film or hydrogeneous, nitrogen, fluorine and/or oxygen element in the step (2).
8. the method for the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure according to claim 5, it is characterized in that, carrying out step (2), promptly before depositing diamond-like film on the metal Nano structure substrate, on the metal Nano structure substrate, deposit one deck amorphous si film earlier.
9. the method for the surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure according to claim 5 is characterized in that diamond like carbon film is to utilize the filtered cathodic vacuum arc method to be deposited on the metal Nano structure substrate.
10. a Raman detection device is characterized in that it comprises excitation source, surveys detection of scattering light device and the described surface-enhanced Raman substrate based on diamond-like carbon film modified metal nano structure of claim 1.
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| CN102886933A (en) * | 2011-07-21 | 2013-01-23 | 中国科学院上海硅酸盐研究所 | High-sensitivity SERS (surface enhanced Raman scattering) sensor active-substrate for drug detection and preparation method thereof |
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