CN110484918A - Surface-enhanced Raman substrate and preparation method thereof based on hanging Au nanometers of finger closed array - Google Patents

Surface-enhanced Raman substrate and preparation method thereof based on hanging Au nanometers of finger closed array Download PDF

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CN110484918A
CN110484918A CN201910666854.6A CN201910666854A CN110484918A CN 110484918 A CN110484918 A CN 110484918A CN 201910666854 A CN201910666854 A CN 201910666854A CN 110484918 A CN110484918 A CN 110484918A
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finger
film
hanging
nanometers
substrate
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CN110484918B (en
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刘凡新
王振林
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Nanjing University
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Nanjing University
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    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • G—PHYSICS
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    • G01N21/65—Raman scattering
    • G01N2021/653—Coherent methods [CARS]
    • G01N2021/655—Stimulated Raman

Abstract

The invention discloses a kind of surface-enhanced Raman substrates and preparation method thereof based on hanging Au nanometers of finger closed array, it is made of the substrate of Au nanometers of finger array structures with the dielectric film being deposited in nanometer finger closed array structured substrate, the Au finger is hanging structure；The dielectric film is tetrahedron carbon film, silica membrane, aluminum oxide film, silicon thin film, titanium deoxid film.The present invention passes through nano impression combination oxygen plasma selective etch, form hanging Au nanometer finger array structure, compared to not hanging metal structure, the phasmon electric field of Au nanometers of finger the upper surface and the lower surfaces may serve to the Raman signal of enhancing molecule.

Description

Surface-enhanced Raman substrate and its preparation based on hanging Au nanometers of finger closed array Method
Technical field
The present invention relates to a kind of metal Nano structure and preparation method thereof, specially hanging Au nanometer finger closed array Structure is as surface-enhanced Raman substrate and preparation method thereof
Background technique
Surface enhanced Raman spectroscopy (Surface-Enhanced Raman Spectroscopy, SERS) technology molecule Fingerprint recognition detection is suffered from fields such as the national security such as environmental monitoring, monitoring for food hygiene, drugs monitorings and is widely applied. It enhances the resonant excitation that principle is the surface phasmon effect based on metal Nano structure, in metallic nanostructured surface shape At the electromagnetic field of enhancing, so that the Raman signal for being located at molecule near metal surface enhancing electromagnetic field is greatly enhanced, generally The enhancement factor of Raman signal is directly proportional to the enhancing biquadratic of electromagnetic field intensity.Relative to other measurement means, Raman detection With molecular recognition and fingerprint property, and it is insensitive to aqueous solution, it is particularly useful to the detection of biomolecule.But Raman spectrum The disadvantage is that signal is very weak, and using surface enhanced Raman technique this problem is resolved.Therefore, surface-enhanced Raman Spectral technique can really be applied to the trace detection field of biomolecule.
For surface enhanced Raman technique, it is most important that effective enhancing substrate of the exploitation based on metal Nano structure, And has the features such as enhancement factor is high, at low cost, reproducibility is good.It is current studies have shown that in numerous metal nano array junctions In structure, the coupled structure system of two structural unit formation close to each other is widely studied, this is because relative to single nanometer Structural system, two nanostructures electric field obtained that intercouples in lesser gap is the maximum predicted so far Enhance electric field, can reach Single Molecule Detection level.For metal Coupling structure, the intensity of coupled electromagnetic field needs in gap Consider classical electromagnetic theory and quantum effect, for classical electromagnetic theory, gap is smaller, and couple electromagnetic field intensity is exponential Increase；And when considering quantum effect, when gap is smaller, tunneling effect of the electronics in quantum mechanics in gap is more obvious, because And couple electromagnetic field intensity is caused to substantially reduce；Therefore, because the joint effect of classical electromagnetic theory and quantum effect, it will necessarily The gap size optimized there are one, so that coupling enhancing electric field reaches most strong.Theoretical research shows to metal/air/metal Coupled structure, this optimal the air gap size are 0.6nm or so；For metal/dielectric/metal Coupling structure, due to dielectric Property it is adjustable, optimal media gap can be adjustable within the scope of several nanometers to several angstroms.
It is main in the world at present to be prepared using technologies such as electron beam exposure combination physical chemistry etchings with minimum clearance Metal Coupling structure, but due to caused by the electronic wave in quantum effect beam spot size limit, metal Coupling structure In gap minimum be about 5nm or so, according to existing processing conditions, further decrease relatively difficult.And this gap is big It is small to be much larger than optimal gap size.
On the other hand, metal Nano structure substrate is also faced with the influence of body effect at present, is increased according to metal Nano structure The symmetrical feature of strong-electromagnetic field, in addition to upper surface formed enhancing electromagnetic field other than, due to substrate dielectric constant be greater than sky Gas, so that the enhancing electromagnetic field couples that lower surface is formed enter inside high dielectric substrate, since detection molecules are to cannot be introduced into lining Inside bottom, therefore, this part electromagnetic field is to be unable to get utilization.
Summary of the invention
Goal of the invention: It is an object of the present invention to solve the deficiency of the existing technology and provide a kind of new preparation method, systems The standby hanging Au nanometer coupling array structure with extra small (1-2 nanometers) gap, gap size controllable precise, utilizes this knot Structure realizes surface-enhanced Raman detection as surface-enhanced Raman substrate.
Technical solution: in order to achieve the goal above, The technical solution adopted by the invention is as follows:
Based on the surface-enhanced Raman substrate of hanging Au nanometers of finger closed array, by the lining of Au nanometers of finger array structures Bottom and the dielectric film being deposited in nanometer finger closed array structured substrate form, which is characterized in that the Au finger is Hanging structure；The dielectric film is tetrahedron carbon film, silica membrane, aluminum oxide film, silicon thin film, titanium dioxide Titanium film.
To prepare above-mentioned surface-enhanced Raman substrate, used the technical scheme comprises the following steps:
1) on the substrate of the Au nanometer finger array structure of nano impression preparation, by oxygen plasma to support Au's Polymeric columns progress chemical etching, and the size constancy of Au nanometers of fingers, to form hanging Au nanometer finger array junctions Structure, it is spare；
2) by deposition medium film on the hanging Au nanometers of finger array structure substrates that step 1) obtains, dielectric film can To deposit tetrahedron carbon film by filtering cathode vacuum arc process, dielectric film can be the titanium dioxide of Atomic layer deposition method preparation Silicon thin film, aluminum oxide film, silicon thin film, titanium deoxid film；
3) high straight alcohol then is titrated on the hanging Au nanometer finger array structure substrate that step 2) obtains, utilizes second Capillary force in alcohol volatilization process promotes Au nanometers of fingers to collapse between each other, after Au finger closure, there is model between each other Moral wals force, to form hanging Au nanometers of stable finger closed array structures.
Nanometer finger between gap size mainly determined by the thickness of twice of the dielectric film deposited, and and nano impression The size of nanometer finger is unrelated in the process, and then gap size is controllable precise.
The above-described surface-enhanced Raman substrate based on hanging Au nanometer finger closed array structure, Jie Matter film is tetrahedron carbon film, titanium deoxid film, silica membrane, aluminum oxide film, silicon thin film.
The above-described surface-enhanced Raman substrate based on hanging Au nanometer finger closed array structure, as excellent Choosing, the dielectric film are tetrahedron carbon film (ta-C:Tetrahedral amorphous carbon).
The present invention is for metal Nano structure substrate since the gap in the presence of the preparation of micro Process means is too big and substrate The shortcomings that effect, the present invention are solved by preparing the method for hanging Au nanometer finger closed array structure.Firstly, by receiving Au nanometers of finger array structures of duplication that rice imprints can be inexpensive can form class flexible since supporter is polymer material Like the array of structures of finger.Then, hanging Au nanometer can be formed to polymer material selective etch by oxygen plasma Finger closed array structure for oxygen plasma, can carry out to eliminate the influence of body effect with the carbon in polymer Chemical reaction, and Au is inert, is that can not be reacted with oxygen plasma, to only etch support polymer, is formed outstanding Empty Au structure, in this way, the enhancing electromagnetic field symmetrical above and below of Au structure can all be utilized the signal of enhancing Raman detection molecule, To provide surface-enhanced Raman monitoring sensitivity.Third, in deposited dielectric films above, since the semiconductor of dielectric film is special Property is different with material, and therefore, different dielectric materials corresponds to different optimal gaps, to realize the big model of gap size Enclose adjusting.Finally, by titrating high-purity ethanol solution on the hanging Au nanometer finger array structure that dielectric film coats, by It is flexible polymer material in the pillar that ethanol solution is very easy to below volatilization and Au, will lead to adjacent close Au hand two-by-two Refer to mutually to collapse under the action of capillary force and be close together, since the Van der Waals between Au finger acts on, after closure Au finger it is no longer separated, form stable hanging Au nanometer finger closed array structure.Experiment and theory show that surface increases Haling graceful enhancement factor can reach 109Times.
Above-described hanging Au nanometer finger array structure provided by the invention is as surface-enhanced Raman substrate Method, specifically includes the following steps:
(1) on the substrate of glass, silicon wafer or other materials, orderly Au nanometers of column is obtained by the method for nano impression Array structure, cylindrical material are flexible polymer, and the height of pillar is 400 nanometers, and the diameter of pillar is 70 nanometers, the thickness of Au It is 50 nanometers；
(2) then on the Au nanometer column array structure that step (1) obtains, by oxygen plasma selective etch, The diameter of polymer pillar is become 55 nanometers, and the diameter of Au disk above be maintained at 70 nanometers it is constant.Polymer pillar The size of diameter can be adjusted according to etch period；
(3) 1 nanometer of tetrahedron carbon film is then deposited on the hanging Au nanometer finger array structure that step (2) obtains；
(4) it is then titrated on the hanging Au nanometer finger array structure for the tetrahedron carbon film coated that step (3) obtains High-purity ethanol solution volatilizees naturally under air conditions, to ultimately form hanging Au nanometer finger closed array structure.
The method of the above-described surface-enhanced Raman substrate based on hanging Au nanometer finger closed array structure, institute The dielectric material stated be tetrahedron carbon film, titanium deoxid film, silica membrane, aluminum oxide film, silicon thin film or its His dielectric material.
The utility model has the advantages that the surface-enhanced Raman lining of the present invention based on hanging Au nanometer finger closed array structure Compared to the prior art bottom has the advantage that
1, by nano impression combination oxygen plasma selective etch, hanging Au nanometer finger array junctions are formd Structure, compared to not hanging metal structure, the phasmon electric field of Au nanometers of finger the upper surface and the lower surfaces may serve to increase The Raman signal of strong molecule；
2, by the effect of dielectric film deposition and capillary power, hanging Au nanometer finger closed array knot is formd Structure, gap size are determined by twice of dielectric film thickness, this is breached in current physics micro Process caused by electronic diffraction The low defect of machining resolution, and the dielectric material of different surfaces characteristic can be selected, this is significantly according to the needs of surface modification The needs of different biological molecules monitoring are expanded；
3, the nanometer embossing as involved in preparation method, oxygen plasma selective etch technology and medium are thin The equal comparative maturity of film deposition technique is, it can be achieved that prepare low-cost, high-volumely.
Detailed description of the invention
It is described in further detail below in conjunction with attached drawing and embodiments of the present invention
Fig. 1 is the scanning electron microscopic picture of hanging Au nanometer finger array structure of the present invention；
Fig. 2 is the scanning electron microscopic picture that hanging Au nanometer of the present invention is closed finger array structure；
Fig. 3 is cross-section structure transmission electron microscope schematic diagram of the Fig. 2 along adjacent closure finger two-by-two；
Fig. 4, which is hanging Au nanometer finger array structure as the Raman of enhancing substrate, enhances result figure:
Curve S1 is hanging Au nanometer finger, and curve S2 is non-hanging Au nanometer finger；
Fig. 5 is that hanging Au nanometer finger array structure directly detects in plasticiser poisoning children's urine as enhancing substrate Plasticiser；
Curve P1 is MBP, and curve P2 is MBP-Glu, and curve P3 is children's urine.
Specific embodiment
Embodiment 1
The preparation side of surface-enhanced Raman substrate based on hanging Au nanometer finger array structure described in the present embodiment Method, comprising the following steps:
1) nano-imprinting method combination Au sputter deposition is used, the substrate of Au nanometers of finger array structures is prepared.
2) oxygen plasma selective etch is used, the diameter of polymer pillar is become 55 nanometers, and Au circle above It is constant that the diameter of disk is maintained at 70 nanometers, to form hanging Au nanometer finger array structure.The diameter of polymer pillar Size can be adjusted according to etch period.It is specifically shown in shown in Fig. 1 scanning electron microscopic picture.
3) the hanging Au nanometer finger array structure that is prepared using filtering cathode vacuum arc process in step 2) The tetrahedron carbon film of 1 nano thickness is deposited on substrate.Filtering cathode vacuum arc process mainly uses Singapore in specific this example (referring to Chinese patent ZL97198178.7) completed in the source the FCVA system of Na Feng Science and Technology Ltd. production.Filtering cathode is true Empty arc technology forms certain potential difference, then lead to mainly by applying certain electric current in anode on cathode graphite target The method that extra pulse machinery taps lights striking, so that cathodic vacuum arc discharges, thus graphite evaporate and ionized, formation etc. from Daughter filters out neutral big particle by tangent bend axial passage under the action of electric and magnetic fields, and by accelerating deposition Onto substrate.In the whole process, preferably, anode current is 2.5 amperes, and striking electric current is 30 amperes, filters line Loop current is 10 amperes, and substrate bias is 0 volt.
4) the then titration point on the hanging Au nanometer finger array structure for the tetrahedron carbon film coated that step 3) obtains Straight alcohol solvent is analysed, is volatilized naturally under air conditions to get hanging Au nanometer finger closed array of the present invention is arrived Structure.It is specifically shown in shown in Fig. 2 scanning electron microscopic picture.
The high resolution electron microscopy in the section of minimum clearance detects and increases as surface in hanging Au nanometer finger array structure Hale the reinforcing effect detection of graceful substrate:
(1) it is carried out first with ion beam etching (FIB) along the middle section for the adjacent nano finger being close together two-by-two Cutting sample is divided after obtaining the sample that high-resolution-ration transmission electric-lens (HR-TEM) can be detected using high-resolution-ration transmission electric-lens Analysis, specific experiment result is as shown in figure 3, the experimental results showed that there are twice among the nanometer finger being close together between adjacent The minimum clearance of tetrahedral carbon film thickness, gap size is 2 nanometers, consistent with involved in experiment.
(2) using rhodamine molecule (R6G) as molecular detection, its surface-enhanced Raman characteristic is detected.Specific experiment mistake Journey are as follows: it is 10 that 1. substrates prepared, which are put into concentration,-8It is impregnated 30 minutes in the rhodamine ethanol solution of mol/L；2. then Substrate is taken out from rhodamine ethanol solution, is first rinsed with ethanol solution, then with being dried with nitrogen, can be used to Raman inspection It surveys.Specific experiment result is as shown in Figure 4.In addition, enhancement factor calculating (reference Applied Physics Letter 88, 143121, select peak position 1650cm-1To calculate), specifically it is shown in Table 1.
The Raman enhancement effect testing result of the hanging Au nanometer finger array closing structure of table 1
Metal material Gold
Raman enhancement factor 9.69E+09
Embodiment 2
It is realized in plasticiser based on hanging Au nanometer finger array closing structure as surface-enhanced Raman substrate The detection example of plasticiser in malicious children's urine.The following steps are included:
(1) prepare first based on hanging Au nanometer finger array closing structure as surface-enhanced Raman substrate, it is spare.
(2) this example uses the modeling being poisoned in children's urine by the plasticiser that gas-chromatography-spectrum joint technology confirmed The surface-enhanced Raman of agent metabolin monitors.Children inevitably contact plastic products in daily life, including Plastic file bag, plastic bottle, plastics tablecloth.During plastics-production, usually using the organic compounds such as plasticiser, including neighbour Rutgers (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP) and phthalic acid two (2- ethylhexyl) ester (DEHP) improves its flexibility.Plastic products are according to viewpoint of Chinese food safety standard (referring to GB9685- 2016), the content of plasticiser is strictly limited in 5% or less in plastic products.Plasticiser can be by directly contacting into human body. By metabolic process complicated in human body, PAEs translates into phthalic acid mono-n-butylester (MBP).Finally, MBP will be with glucose In conjunction with formation phthalic acid mono-n-butylester didextrose aldehydic acid ester (MBP-Glu).Above-mentioned metabolic process has obtained successful clarification. MBP is a kind of incretion interferent, can destroy the endocrine function of human normal, and the incidence of asthma and allergy is caused to increase, Toxicity of thyroid, hepatotoxicity wind agitation and acute irritation effect, it is particularly hazardous to 12 years old or less children.Currently, many because plasticiser causes Accident usually still occur in China.Although GC-MS can detecte MBP-Glu, due to the complicated preprocessing process of urine, it Can not carry out fast slowdown monitoring.Surface enhanced Raman technique may be a kind of up-and-coming tool, can be quick by urine The intracorporal MBP-Glu of children is detected without any treatment process.
Use hanging Au nanometer finger array closing structure as surface-enhanced Raman substrate to having passed through gas phase color The MBP-Glu in children's urine that spectrum-spectrum joint technology confirmed is detected, specifically as shown in Figure 5.The surface enhanced of urine Raman spectrum shows and the MBP and MBP-Glu of sterling comparison, finds to contain MBP-Glu really in urine.GC-MS is demonstrate,proved in this example The content of MBP-Glu is 100ng/ml in real children's urine, this is the limit gauge that medicine concludes plasticiser poisoning.Result above Show that SERS can be suggested to the quick and pre- diagnosis judgement of children's health monitoring.
Therefore, the surface-enhanced Raman substrate based on hanging Au nanometer finger array closed array structure has enhancing The high feature of the factor.

Claims (3)

1. based on the surface-enhanced Raman substrate of hanging Au nanometers of finger closed array, by the substrate of Au nanometers of finger array structures With the dielectric film composition being deposited in nanometer finger closed array structured substrate, it is characterised in that: the Au finger is outstanding Hollow structure；The dielectric film is tetrahedron carbon film, silica membrane, aluminum oxide film, silicon thin film, titanium dioxide Film.
2. the preparation method based on hanging Au nanometers of finger closed array body structure surface enhancing Raman substrate described in claim 1, It is characterized by comprising following steps:
1) polymerization on the substrate of the Au nanometer finger array structure of nano impression preparation, by oxygen plasma to support Au Object cylinder progress chemical etching, and the size constancy of Au nanometers of fingers, so that hanging Au nanometer finger array structure is formed, it is standby With；
2) by deposition medium film on the hanging Au nanometers of finger array structure substrates that step 1) obtains, dielectric film can be logical Filtering cathode vacuum arc process deposition tetrahedron carbon film is crossed, dielectric film can be thin for the silica of Atomic layer deposition method preparation Film, aluminum oxide film, silicon thin film, titanium deoxid film；
3) high straight alcohol then is titrated on the hanging Au nanometer finger array structure substrate that step 2) obtains, is waved using ethyl alcohol Capillary force during hair promotes Au nanometers of fingers to collapse between each other, after Au finger closure, there is Fan Dewa between each other Er Sili, to form hanging Au nanometers of stable finger closed array structures.
3. the system of the surface-enhanced Raman substrate as claimed in claim 2 based on hanging Au nanometer finger closed array structure Preparation Method, it is characterised in that: the gap in step 2) between metal finger determines that medium is thin by the thickness of twice of dielectric film Film includes tetrahedron carbon film, silica membrane, aluminum oxide film, silicon thin film, titanium deoxid film.
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