CN104406953A - Large-area uniform raman detection chip for porous membrane sensitivity enhancing and preparation method for large-area uniform raman detection chip - Google Patents
Large-area uniform raman detection chip for porous membrane sensitivity enhancing and preparation method for large-area uniform raman detection chip Download PDFInfo
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Abstract
The invention provides a large-area uniform raman detection chip for porous membrane sensitivity enhancing and a preparation method for the large-area uniform raman detection chip. The raman detection chip comprises a substrate, a gold-based enhanced structural membrane which is formed on the substrate and is used as an electromagnetic enhancement layer of the raman detection chip, and a nano porous membrane which is formed on the outer surface of the gold-based enhanced structural membrane so as to enrich molecules to be detected. According to the large-area uniform raman detection chip for porous membrane sensitivity enhancing, the nano porous membrane serving as a molecule enriching layer can obviously increase the quantity of the molecules to be detected within a local enhanced electric field working range, so that the raman detection sensitivity of the chip is improved; the large-area uniform raman detection chip is particularly suitable for detection on small-molecular substances with ultralow concentration. The raman detection chip disclosed by the invention has the advantages of low preparation cost, high large-area uniformity and the like, and can suppress interference on a raman fingerprint diagram of the molecules to be detected due to metals.
Description
Technical field
The present invention relates to technical field of optical detection, Large-Area-Uniform Raman detection chip particularly relating to a kind of perforated membrane enhanced sensitivity and preparation method thereof.
Background technology
Raman scattering is a kind of inelastic scattering.Because between incident light and molecular vibration mode, portion of energy shifts, make scattered light compare incident light frequency and change, this frequency shifts is called Raman shift, and it and molecular structure are closely related, just can deduce out molecular structure by measuring Raman shift.
Method for measuring Raman spectrum is widely used in the fields such as environmental monitoring, food safety detection, judicial expertise, material analysis, bio-science research.But the raman scattering cross section of most of molecule is very little, make Raman diffused light very faint, especially when test substance concentration is lower, Raman diffused light is often flooded by noise, is difficult to detect.Therefore, Raman spectrum detects often needs by the effect of various Enhancement Method competence exertion.These Enhancement Method comprise: the enhancing of Electromagnetic enhancement, electron resonance, Chemical enhancement, target enrichment enhancing etc.
In reality, most popular technology is Surface enhanced raman spectroscopy (SERS) technology, and SERS is mainly based on the surperficial electromagnetism enhancement effect of metal Nano structure, and its enhancer reaches as high as 10
9, there are Single Molecule Detection potentiality.But, because the dimensional uniformity of metal Nano structure is poor, skewness, poor controllability, the making of the SERS substrate of SERS chip, especially Large-Area-Uniform is made to be difficult to have repeatability, therefore the repeatability that strengthens of Raman signal is bad, and makes structurally ordered metal nano array and require technology condition very harsh; When test substance concentration is very low, the molecule of Electromagnetic enhancement body structure surface absorption is little, needs to use the SERS substrate with complicated Electromagnetic enhancement structure the Raman signal of testing molecule just can be detected.Such SERS substrate complicated process of preparation, testing conditions is harsh; And the interaction of testing molecule and metal surface also can bring the movement of molecular fingerprint Raman signal.
Nano-porous materials is often referred to even pore distribution, porosity higher (>=0.4) and aperture are less than the functional material of 100nm, have that cost is low, method for making is simple, pore structure and porosity are controlled flexibly, thermodynamics and chemical stability good, physical strength is high, and specific surface area is large, the advantages such as specific inductive capacity is little, and fluid permeability is strong.Nano-porous materials is allowed inside surface chemical modification and produces three-dimensional high-density avtive spot, high in Visible-to-Near InfaRed wave band transparency.Molecular templating techniques prepares one of porosint main method, the molecular mixing of organic molecule and formation porosint that its preparation process mainly forms template is dissolved and is formed colloidal solution, and organic molecule be combined with each other and forms figurate micella or liquid crystal (template) under certain electrochemical conditions; The molecule forming porosint is afterwards piled up in organic formwork mixed gel film template, condensation; Finally adopt the way such as high-temperature heat treatment, extraction removal organic molecule polymer template to obtain hole profile to fix, the porosint that composition is pure.Preparing one deck perforated membrane at SERS substrate surface can effective enrichment testing molecule, the sensitivity that further raising SERS detects, be particularly useful for the Raman detection of super low concentration material, and perforated membrane can intercept testing molecule and contact with the direct of metal surface, thus effectively can suppress the impact of the fingerprint Raman signal of metal pair testing molecule.
Realizing in process of the present invention, applicant finds complex process needed for the SERS chip with better repeatability, higher sensitivity prepared by prior art, cost intensive, be difficult to avoid the metal Nano structure and the testing molecule that produce Electromagnetic enhancement, particularly with direct contact of biomolecule to be measured and the interference to molecular fingerprint Raman signal to be measured that causes.
Summary of the invention
(1) technical matters that will solve
In view of above-mentioned technical matters, Large-Area-Uniform Raman detection chip that the invention provides a kind of perforated membrane enhanced sensitivity and preparation method thereof, with Simplified flowsheet, reduce costs, farthest avoid producing the metal Nano structure of Electromagnetic enhancement and testing molecule, particularly with direct contact of biomolecule to be measured and the interference to molecular fingerprint Raman signal to be measured that causes.
(2) technical scheme
According to an aspect of the present invention, a kind of Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity is provided.This Raman detection chip comprises: substrate; Auri strengthens structural membrane, is formed on substrate, as the Electromagnetic enhancement layer of Raman detection chip; And nano-porous films, be formed at the outside surface that auri strengthens structural membrane, with enrichment testing molecule.
According to another aspect of the present invention, a kind of preparation method of Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity is additionally provided.This preparation method comprises: steps A: on substrate, form gold-base alloy film; Step B: the inorganic medium gel mould comprising organic molecular template in described gold-base alloy film outer surface preparation, in this inorganic medium gel mould, inorganic medium composition forms three-dimensional net structure around organic molecule template; And step C: high-temperature heat treatment, to impel in described gold-base alloy film composition in addition to gold to external diffusion, realize the nanoscale roughening of this gold-base alloy film, form auri and strengthen structural membrane; Eliminate the organic molecule template in inorganic medium gel mould simultaneously, and change inorganic medium composition into inorganic oxide, thus obtain inorganic oxide perforated membrane.
(3) beneficial effect
As can be seen from technique scheme, Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity of the present invention and preparation method thereof has following beneficial effect:
(1) nano-porous films is added in the outside of metal reinforcg structure film, this nano-porous films significantly can increase the testing molecule quantity within the scope of local enhancing electric field action as molecule enriched layer, thus improve the Raman detection sensitivity of chip, the small-molecule substance being specially adapted to super low concentration detects, and has the advantage that preparation cost is low;
(2) in addition, this nano-porous films effectively can be isolated testing molecule and be contacted with the direct of metal, thus can effectively suppress metal reinforcg structure film to the interference of molecular fingerprint Raman signal to be measured, the inactivation after there is bioactive molecule and Metal Contact can also be avoided;
(3) nano-porous films can also serve as the protective seam of metal reinforcg structure film, delays the chemical reaction between the complicated gas componant in metal reinforcg structure film and surrounding environment, strengthens the stability of chip;
(4) also add metal nano decorative layer in the outside of nano-porous films, by the local plasmon resonance of metal Nano structure, strengthen the Raman scattering of testing molecule further;
(5) add golden film in the inner side of electrum film, this golden film, by reflected excitation light and Raman light, can not only promote that the field of Electromagnetic enhancement layer strengthens, and can improve the collection efficiency to Raman light.In addition, discontinuous electrum film can also be strengthened at on-chip adhesion.
(6) the organic molecule kind being used as template in the process preparing nano-porous films is many, and concentration adjustment scope is large, makes the porosity of perforated membrane, pore structure and hole dimension can flexible according to requirements;
(7) chip is being carried out in the process of high-temperature heat treatment, the silver atoms of electrum film is to external diffusion, film continuity is destroyed, thus achieve the large area roughening of film, and surface structure is even, it can be used as the Electromagnetic enhancement layer of Raman detection chip, higher Raman scattering enhancer and reproducible Raman spectrum can be obtained.
Accompanying drawing explanation
Figure 1A is the diagrammatic cross-section of the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity according to a first embodiment of the present invention;
Figure 1B is the diagrammatic cross-section of the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity according to a second embodiment of the present invention;
Preparation method's process flow diagram that Fig. 2 is the Large-Area-Uniform Raman detection chip of the enhanced sensitivity of perforated membrane shown in Figure 1B according to a third embodiment of the present invention;
Fig. 3 A is the Nile blue Molecular Raman spectrum be adsorbed onto from 50nM aqueous solution on chip utilizing the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity to record.In order to compare, give utilization in figure not containing the Large-Area-Uniform Raman detection chip of electrum film and not containing the Nile blue Molecular Raman spectrum be adsorbed onto from 50nM aqueous solution on chip that the Large-Area-Uniform Raman detection chip of mesoporous silica films records;
Fig. 3 B utilizes the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity, respectively not containing the Large-Area-Uniform Raman detection chip of electrum film and not containing the crystal violet Molecular Raman spectrum be adsorbed onto from 50nM aqueous solution on chip that the Large-Area-Uniform Raman detection chip of mesoporous silica films records;
Fig. 4 A is for utilizing the Large-Area-Uniform Raman detection chip of the perforated membrane enhanced sensitivity shown in Figure 1A to the sxemiquantitative test result of variable concentrations Nile blue aqueous solution;
Fig. 4 B is for utilizing the Large-Area-Uniform Raman detection chip of the perforated membrane enhanced sensitivity shown in Figure 1A to the sxemiquantitative test result of variable concentrations crystal violet aqueous solution.
[main element symbol description of the present invention]
1-substrate; 10-transition film;
11-gold film; 2-auri strengthens structural membrane;
3-mesoporous silica films; 4-metal nanoparticle;
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.It should be noted that, in accompanying drawing or instructions describe, similar or identical part all uses identical figure number.The implementation not illustrating in accompanying drawing or describe is form known to a person of ordinary skill in the art in art.In addition, although herein can providing package containing the demonstration of the parameter of particular value, should be appreciated that, parameter without the need to definitely equaling corresponding value, but can be similar to corresponding value in acceptable error margin or design constraint.The direction term mentioned in embodiment, such as " on ", D score, "front", "rear", "left", "right" etc., be only the direction with reference to accompanying drawing.Therefore, the direction term of use is used to illustrate and is not used for limiting the scope of the invention.
Large-Area-Uniform Raman detection chip that the invention provides a kind of perforated membrane enhanced sensitivity of low cost and preparation method thereof, farthest to avoid the testing molecule particularly impact on molecule intrinsic Raman signal that causes with direct contact of metal of biomolecule to be measured.
One, the first embodiment
In first exemplary embodiment of the present invention, propose a kind of Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity.Figure 1A is the diagrammatic cross-section of the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity according to a first embodiment of the present invention.As shown in Figure 1A, the Large-Area-Uniform Raman detection chip of this perforated membrane enhanced sensitivity comprises: substrate 1; Transition film 10, is formed at the upper surface of substrate 1; Gold film 11, is formed at the upper surface of transition film 10; Auri strengthens structural membrane 2, and be formed at the outside surface of golden film 11, it is as the Electromagnetic enhancement layer of the present embodiment Raman detection chip; Nano-porous films 3, is formed at the outside surface that auri strengthens 2 of structural membrane, with enrichment testing molecule, increases the testing molecule quantity in local enhanced field reach, improves the sensitivity of Raman detection chip.
In the present embodiment, substrate 1 is sheet glass, but the present invention is not as limit.In other embodiments of the invention, substrate 1 can also be the one in silicon chip, potsherd, sheet metal.
In the present embodiment, auri strengthens the Electromagnetic enhancement layer of structural membrane as Raman detection chip, and it only formed by high-temperature heat treatment by electrum film.The thickness of this electrum film is 50nm, and golden constituent mass number percent is 50%, but the present invention is not as limit.In other embodiments of the invention, auri strengthens structural membrane also can be not less than 20nm for thickness, other the gold-base alloy film of gold constituent mass number percent between 20% to 80%, such as: formed via high-temperature heat treatment process by gold copper, gold-tin alloy, golden nickel alloy, golden titanium alloy, golden evanohm, rhotanium, gold and silver palldium alloy, yellow gold, golden copper and indium alloy etc.Wherein, the temperature of this high-temperature heat treatment process is between 200 DEG C to 500 DEG C, and the time is no less than 30 minutes.
In the present embodiment, transition film 10 is the chromium thin film that 3nm is thick, and it act as the adhesion strengthening substrate 1 and subsequent structural.Further, in other embodiments of the invention, the material of transition film 10 can also be chromium, titanium, nickel or tantalum, and thickness is not less than 3nm, and even when the adhesion of substrate and subsequent structural is enough strong, then this transition film can omit.
In the present embodiment, the thickness of golden film 11 is 20nm.In other embodiments of the invention, golden film 11 also can be not less than the auri enhancing structural membrane replacement of 10nm by thickness, now deposit one deck electrum film or other gold-base alloy film at transition film surface, its thickness is not less than 10nm.This golden film, by reflected excitation light and Raman light, not only promotes that the field of upper strata sensitive membrane strengthens, and improves the collection efficiency to Raman light, thus strengthen testing molecule Raman signal.This golden film can increase discontinuous gold and silver and strengthen structural membrane at on-chip adhesion simultaneously;
In the present embodiment, nano-porous films is mesoporous silica films, and its thickness is 40nm, and the aperture in hole is between 2nm to 5nm, but the present invention is not as limit.In other embodiments of the invention, this nano-porous films can also be not less than 10nm for thickness, and the aperture in hole is less than other nano-porous films of 50nm.
Wherein, in the present embodiment Raman detection chip, this nano-porous films has following beneficial effect:
1) nano-porous films is added in the outside of metal reinforcg structure film, this nano-porous films significantly can increase the testing molecule quantity within the scope of local enhancing electric field action as molecule enriched layer, thus improve the Raman detection sensitivity of chip, the small-molecule substance being specially adapted to super low concentration detects, meanwhile, the preparation of this nano-porous films has the advantage of low cost;
(2) in addition, this nano-porous films effectively can be isolated testing molecule and be contacted with the direct of metal, thus can effectively suppress metal reinforcg structure film to the interference of molecular fingerprint Raman signal to be measured, the inactivation after there is bioactive molecule and Metal Contact can also be avoided;
(3) nano-porous films can also serve as the protective seam of metal reinforcg structure film, delays the chemical reaction between the complicated gas componant in metal film and surrounding environment, strengthens the stability of chip;
Below provide above-mentioned gold and silver and strengthen structural membrane and mesoporous silica films respectively to the active test result contributed of the Large-Area-Uniform Raman detection chip SERS of perforated membrane enhanced sensitivity.In the present embodiment, mesoporous silica films is that high-temperature heat treatment obtains for 4 hours at the temperature of 450 DEG C; Other chip being used for contrasting makes corresponding simplification respectively on the basis of this structure.
In test process, chip to the sampling method of test substance is: be immersed in by chip in test substance solution, after 30 minutes, chip slowly shifted out solution evenly, in atmosphere natural drying.Experimental technique is: 532nm monochromatic light lasing light emitter (emergent power is 50mW) vertical irradiation also focuses on chip surface; Adopt business-like Raman spectrometer Received signal strength, spectrometer integral time is 20s, and integral number of times is 1 time.The spectrum obtained in chip surface random selecting 20 test points does average to make comparisons.
Fig. 3 A is the SERS spectrum detecting 50nM Nile blue aqueous solution, and the molecule SERS signal intensity that the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity detects is better than situation when not having mesoporous silica films far away; Compared to the chip of glass/golden film/mesoporous silica films, it is fairly obvious that gold and silver strengthens the enhancing effect of structural membrane, and the molecule SERS signal intensity that the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity detects is better than 6 ~ 7 times when not having gold and silver to strengthen structural membrane.Fig. 3 B gives an identical core assembly sheet to the test result of 50nM crystal violet aqueous solution, and the conclusion obtained when its conclusion and test 50nM Nile blue aqueous solution is similar: the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity strengthens effect to testing molecule SERS spectrum and will be better than the two effect strengthened separately far away.
The Large-Area-Uniform Raman detection chip below providing the enhanced sensitivity of perforated membrane shown in Figure 1A is to the sxemiquantitative test result of variable concentrations Nile blue aqueous solution (Fig. 4 A) and variable concentrations crystal violet aqueous solution (Fig. 4 B).
In test process, chip to the sampling method of test substance is: be immersed in by chip in detection material solution, after 30 minutes, chip slowly shifted out solution evenly, in atmosphere natural drying.Experimental technique in the present embodiment is: 532nm monochromatic light lasing light emitter (emergent power is 50mW) vertical irradiation also focuses on chip surface; Adopt business-like Raman spectrometer Received signal strength, spectrometer integral time is 20s, and integral number of times is 1 time.The spectrum obtained in chip surface random selecting 20 test points does average to make comparisons.
Experimental result display raises along with solution concentration, and the SERS signal intensity detecting molecule increases.In Fig. 4 A, to the Large-Area-Uniform Raman detection chip of the test result of Nile blue aqueous solution display perforated membrane enhanced sensitivity, there is very high sensitivity, the SERS signal of the testing molecule of 1nM can be low to moderate by concentrations; In Fig. 4 B, to the SERS signal intensity also stable enhancing gradually that the test result display of crystal violet aqueous solution detects along with chip when testing molecule concentration raises gradually with the amplification of 20nM, illustrate that the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity has good resolution and stability thus.
Visible, the present embodiment is by increasing perforated membrane in the outside of electrum Electromagnetic enhancement layer, effectively can improve the sensitivity of SERS chip, farthest avoid the direct impact contacted molecule intrinsic Raman signal of metal and test substance molecule particularly biomolecule to be measured, have that cost is low, the simple advantage of technique, this is described in detail in preparation embodiment hereafter simultaneously.
Two, the second embodiment
In second exemplary embodiment of the present invention, propose the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity as shown in Figure 1B.Shown in this chip and Figure 1A, the difference of chip is: in the outside of perforated membrane, is also formed with metal nanoparticle layer 5.
Wherein metal nanoparticle comprises golden nanometer particle, Nano silver grain, gold-silver alloy nanoparticles, the golden nanometer particle wrapped up by dielectric layer, the Nano silver grain wrapped up by dielectric layer, the gold-silver alloy nanoparticles etc. of being wrapped up by dielectric layer.In addition, this metal nanoparticle also can replace with metal nanometer line, metal nano-rod, metal nano-tube, or the combination of above-mentioned multiple nano material.
In preparation process, metal nanoparticle adopts the technology such as electrostatic self-assembled to be fixed on nano-porous films surface.The local plasmon resonance of incident light activated metal nanoparticle, can strengthen the Raman scattering of testing molecule further.
Three, the 3rd embodiment
In the 3rd exemplary embodiment of the present invention, additionally provide the preparation method of the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity described in the second embodiment.Fig. 2 is the process flow diagram of the Large-Area-Uniform Raman detection chip preparation method of perforated membrane enhanced sensitivity according to a third embodiment of the present invention.
Please refer to Fig. 1 and Fig. 2, this preparation method comprises:
Step S202: prepare transition film 10 at substrate 1;
Wherein, substrate can select the one in sheet glass, silicon chip, potsherd, sheet metal.Before preparation transition film, need to clean substrate.The process of cleaning is according to normal process.
Vacuum deposition technique is adopted to prepare transition film at the upper surface of the substrate cleaned up.The material of this transition film is chromium, titanium, nickel or tantalum, and its thickness is not less than 3nm, and its function is used to the adhesion increasing substrate and subsequent structural.
Step S204: prepare golden film 11 on transition film;
In the present embodiment, golden film thickness is 20nm, but the present invention is not as limit.In the present invention, as long as the thickness of golden film is not less than 10nm can realize the present invention.
Wherein, golden film 11 also can be replaced by electrum or other gold-base alloy film.This golden film, by reflected excitation light and Raman light, not only promotes that the field of upper strata sensitive membrane strengthens, and improves the collection efficiency to Raman light, thus strengthen testing molecule Raman signal.This golden film can increase discontinuous gold and silver and strengthen structural membrane at on-chip adhesion simultaneously.
Step S206: prepare electrum film 2 on golden film 11;
In the present embodiment, the thickness of electrum film 2 is 50nm, but the present invention is not as limit.In the present invention, as long as the thickness of electrum film 2 is not less than 20nm can realize the present invention.
Golden film in step S204 also can be replaced by electrum or other gold-base alloy film, in the case, step S204 and step S206 just merges into same step, thus only on the basis of step 1, deposit need be not less than electrum or other gold-base alloy film of 30nm.
In above-mentioned steps S202, S204 and S206, the technology preparing film can be vacuum sputtering technique, vacuum evaporation technology etc.
Step S208: adopt the preparation of sol-gel chemistry film technique to include the silicon-based gel film of organic molecule template at electrum film outer surface, silica-based composition forms three-dimensional net structure around organic molecule template in this silicon-based gel film;
Wherein, organic molecule template can be ionic surfactant or non-ionic block polymers or liquid crystal.
Step S210: the chip that before high-temperature heat treatment, four steps obtain, this high-temperature heat treatment removes the organic molecule template in silicon-based gel film, and change silica-based composition into silicon dioxide, thus obtain mesoporous silica films, make silver atoms in electrum film to external diffusion simultaneously, achieve roughening and the homogenising of electrum film, form gold and silver and strengthen structural membrane;
Wherein, the temperature of high-temperature heat treatment is between 200 DEG C to 500 DEG C, and the time is no less than 30 minutes.
After carrying out high-temperature heat treatment to electrum film, hot conditions can be more wide in range to meet the demand preparing different materials, different parameters perforated membrane, effectively simplifies the manufacture craft of SERS chip, reduce cost.In addition, carrying out in high-temperature heat treatment process to chip, the continuity of electrum film is destroyed, achieve the roughening of metallic film, and the metal film surfaces even structure of roughening, it can be used as the Electromagnetic enhancement layer of the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity, can obtain higher Raman scattering enhancer and reproducible Raman spectrum, auri supports film, Stability Analysis of Structures.
Inorganic oxide perforated membrane is prepared on electrum film basis, this inorganic oxide perforated membrane facilitates the enrichment of testing molecule, effectively increase the testing molecule quantity in local enhanced field reach, thus improve the Raman detection sensitivity of chip, the small-molecule substance being specially adapted to super low concentration detects.Inorganic oxide perforated membrane is effectively isolated testing molecule and is contacted with the direct of metal, thus can effectively suppress metal reinforcg structure film to the interference of molecular fingerprint Raman signal to be measured, can also avoid the inactivation after having bioactive molecule and Metal Contact.In addition, inorganic oxide perforated membrane can also serve as the protective seam of Electromagnetic enhancement layer, delays the chemical reaction between the complicated gas componant in metal reinforcg structure film and surrounding environment, strengthens the stability of chip.
When the mesoporous silica films in chip is other inorganic oxide perforated membrane, the corresponding change of high-temperature heat treatment temperature in step S210;
Step S212: modify one or more layers metal nanoparticle 4 at mesoporous silica films outside surface, improves the local Electromagnetic enhancement effect of chip further.
Wherein, this metal nanoparticle comprises: at least two kinds of molecular stuff and other stuff of grain etc. in golden nanometer particle, Nano silver grain, gold-silver alloy nanoparticles, golden contracted payment nano particle, silver-colored gold-covered nano particle, medium gold-covered nano particle, medium contracted payment nano particle and these particles.This one or more layers metal nanoparticle adopts the technology such as electrostatic self-assembled to modify in porous film surface.
So far, by reference to the accompanying drawings the present invention's three embodiments have been described in detail.Describe according to above, those skilled in the art should have Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity of the present invention and preparation method thereof and have clearly been familiar with.
In addition, the above-mentioned definition to each element and method is not limited in various concrete structures, shape or the mode mentioned in embodiment, those of ordinary skill in the art can change simply it or replace, such as: the glass substrate as supporter can be square or circular or even glass bar-shaped.
In sum, the manufacture craft of the Large-Area-Uniform Raman detection chip of perforated membrane enhanced sensitivity of the present invention is controlled, stability and reproducible, Raman enhancer is high, Monitoring lower-cut is low, testing molecule can be avoided directly to contact with noble metal, thus noble metal can be avoided the interference of Molecular Raman dactylogram to be measured.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. a Raman detection chip for perforated membrane enhanced sensitivity, is characterized in that, comprising:
Substrate;
Auri strengthens structural membrane, is formed on described substrate, as the Electromagnetic enhancement layer of described Raman detection chip; And
Nano-porous films, is formed at the outside surface that described auri strengthens structural membrane, with enrichment testing molecule.
2. Raman detection chip according to claim 1, is characterized in that, described nano-porous films is inorganic oxide perforated membrane, and its thickness is not less than 10nm, and the aperture in hole is less than 50nm.
3. Raman detection chip according to claim 2, is characterized in that, described inorganic oxide perforated membrane is mesoporous silica films, and its thickness is between 20nm to 100nm, and mesoporous pore size is between 2nm to 10nm.
4. Raman detection chip according to claim 1, is characterized in that, also comprise:
Metal nano decorative layer, is formed at the outside of described nano-porous films.
5. Raman detection chip according to claim 4, is characterized in that, described metal nano decorative layer is made up of one or more in metal nanoparticle, metal nanometer line, metal nano-rod, metal nano-tube.
6. Raman detection chip according to claim 5, it is characterized in that, described metal nanoparticle is the one in following structure: golden nanometer particle, Nano silver grain, gold-silver alloy nanoparticles, the golden nanometer particle wrapped up by dielectric layer, the Nano silver grain wrapped up by dielectric layer, the gold-silver alloy nanoparticles of being wrapped up by dielectric layer.
7. Raman detection chip according to any one of claim 1 to 6, is characterized in that, the thickness that described auri strengthens structural membrane is not less than 20nm, and wherein the mass percent of golden component is between 20% to 80%.
8. Raman detection chip according to claim 7, it is characterized in that, it is that the film of a kind of material in following material is formed via high-temperature heat treatment: electrum, gold copper, gold-tin alloy, golden nickel alloy, golden titanium alloy, golden evanohm, yellow gold and golden copper and indium alloy that described auri strengthens structural membrane.
9. Raman detection chip according to claim 8, is characterized in that, described auri strengthen structural membrane be electrum film via temperature between 200 DEG C to 500 DEG C, the Technology for Heating Processing that the time is no less than 30 minutes is formed.
10. Raman detection chip according to any one of claim 1 to 6, is characterized in that, also comprise:
Gold film, its thickness is not less than 10nm, is formed between described substrate and auri enhancing structural membrane; And
Transition film, its thickness is not less than 3nm, is formed between described golden film and substrate, for strengthening the adhesion of described golden film and substrate.
The preparation method of Raman detection chip according to any one of 11. 1 kinds of claims 1 to 6, is characterized in that, comprising:
Steps A: form gold-base alloy film on substrate;
Step B: the inorganic medium gel mould comprising organic molecular template in described gold-base alloy film outer surface preparation, in this inorganic medium gel mould, inorganic medium composition forms three-dimensional net structure around organic molecule template; And
Step C: high-temperature heat treatment, to impel in described gold-base alloy film composition in addition to gold to external diffusion, realizes the nanoscale roughening of this gold-base alloy film, form auri and strengthen structural membrane; Eliminate the organic molecule template in inorganic medium gel mould simultaneously, and change inorganic medium composition into inorganic oxide, thus obtain inorganic oxide perforated membrane.
12. preparation methods according to claim 11, is characterized in that, described inorganic oxide perforated membrane is mesoporous silica films, and described gold-base alloy film is electrum film.
13. preparation methods according to claim 12, is characterized in that, in the step of described high-temperature heat treatment, the temperature of described high-temperature heat treatment is between 200 DEG C to 500 DEG C, and the time is no less than 30 minutes.
14. preparation methods according to claim 11, is characterized in that, described in comprise organic molecular template inorganic medium gel mould adopt the preparation of sol-gel chemistry film build method; Described organic molecule template is ionic surfactant or non-ionic block polymers or liquid crystal.
15. preparation methods according to claim 11, is characterized in that, also comprise:
Described inorganic oxide perforated membrane outside surface is coated with metal nano decorative layer, to improve the local Electromagnetic enhancement effect of Raman detection chip further.
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| CN107121423A (en) * | 2017-05-08 | 2017-09-01 | 中国科学院重庆绿色智能技术研究院 | A kind of porous array Electromagnetic enhancement SERS devices, preparation method and detection method detected for trace Microcystin |
| CN108982474A (en) * | 2018-09-07 | 2018-12-11 | 江西师范大学 | A kind of surface reinforced Raman active substrate and preparation method thereof based on the compound plasmon resonance structure of metal-dielectric |
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