CN106596503A - Raman reflection substrate with three-dimensional sequential periodical macroporous structure and preparation method of Raman reflection substrate - Google Patents
Raman reflection substrate with three-dimensional sequential periodical macroporous structure and preparation method of Raman reflection substrate Download PDFInfo
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The invention relates to the technical field of Raman analysis and detection, in particular to Raman reflection substrate with a three-dimensional sequential periodical macroporous structure, and a preparation method of the Raman reflection substrate. The Raman reflection substrate comprises the following components: 1, a main component, namely a semiconductor three-dimensional sequential periodical macroporous structure of ZnO or TiO2, wherein the specific surface area is 50 to 200 m<2>/g, the porosity is 0.2 to 1 cm<3>/g, and the weight proportion is 98 to 99.9 percent; 2, metal nanoparticles, wherein the weigh proportion is 0.1 to 2 percent. The metal nanoparticles and the semiconductor three-dimensional structure form a heterojunction; the semiconductor three-dimensional sequential periodical macroporous structure is prepared by a colloidal crystal template plate; the metal nanoparticles grow in a pore channel structure of the semiconductor three-dimensional sequential periodical macroporous structure in a limited range; the Raman reflection substrate can effectively amplify a Raman spectrum signal of the substrate, improves the reproductivity of a Raman scattered signal, can effectively adsorb and enrich molecules and improves the detection sensitivity; the preparation method is simple, quick and practical in process and high in controllability, and large-area preparation and large-scale production are easily realized.
Description
Technical field
The present invention relates to Raman analysis detection technique field, and in particular to one kind has three-dimensional order periodicity macroporous structure
Raman reflective substrate and preparation method thereof.
Background technology
Raman scattering spectrum becomes the powerful molecule of One function because it is to molecule and the specificity at chemical bond oscillations peak
Detection technique.Due to the very little scattering cross section of Raman scattering, Raman scattering is a very weak process, and is unfavorable for micro
The qualitative analysis of material.Surface Raman enhancement scattering (SERS) effect refer to adsorb roughening metal surfaces compound due to
Surface local plasmon excimer is excited caused Electromagnetic enhancement, and on rough surface binding molecule to constitute Raman enhanced
The Chemical enhancement that active site causes, the Raman scattering signal for causing binding molecule increases than normal Raman scattering (NRS) signal
Strong phenomenon.Surface Raman enhancement has high sensitivity, the ability of quick detection because of it, it is possible to obtain normal Raman spectrum institute is not
Facile structural information, is widely used in the fields such as study of surfaces, biological surface science, food security.Surface Raman increases
Strong spectral has been widely used in biochemistry, chemical molecular detection, iconography, environment prison because of the high sensitivity of its detection property
Survey and sensor application aspect.Not only there is high sensitivity as the substrate of preferable effectively surface Raman enhancement spectrum, also
Need to ensure good signal reproducibility.
Surface Raman enhancement active substrate can pass through：(1) ordered 3 D structure is built；(2) metal nanoparticle is utilized
Plasma resonance effect is realizing.The existing ordered 3 D structure of current report improves Raman detection signal as substrate.In structure
Ordered 3 D structure aspect is built, the ordered 3 D structure having been reported is the photon crystal film of two dimension, three-dimensional photonic crystal
Film and optical fiber etc..However, photon crystal film easily comes off from substrate, is difficult large area preparation, most of research institute's reports
Photon crystal film as application during substrate, its structure is unstable and sensitivity is not high, test limit model in detection
Limit is with, it is crucial that the reappearance of its signal can not be protected.The high activity substrate of three-dimensional order is fallen over each other research, and
Three-dimensional photonic crystal fiber due to complex manufacturing technology, high cost and can not be widely used.
In terms of using metal nanoparticle plasma resonance effect, the noble metals such as silver, gold, copper are generally used as coarse
Metal surface.SERS effects are mainly derived from " focus " of Electromagnetic enhancement in roughened metal surface (hotspot).Close at present
In active substrate preparation method document report a lot, these methods mainly including metal colloid particles self assembly, instead
Answer ion etching (RIE), electron beam lithography (EBL) and nanosphere etching etc..For commercialization, practical SERS active groups
For bottom, the repeatability of substrate, the uniformity of Raman signal, the sensitivity of detection and the cost of preparation are all to need to consider
Factor.But, the SERS active-substrate prepared with above-mentioned preparation method has some limitation.For example, metallic colloid grain
Son is inevitably reunited in self assembling process, the poor reproducibility of SERS signal, is prepared so as to limit large area；And
Based on lithographic technique (EBL and RIE) although there is control well to underlying structure, preparation cost is high, time-consuming, and is difficult system
It is standby go out centimetres SERS substrates, therefore be difficult in practical application.In addition, based on lithographic technique, it is difficult to prepare
Go out spacing in 10 nanometers and following nanostructured.In general, when the gap in noble metal substrate between nano unit is less than
When 10 nanometers, electromagnetic wave can occur very strong local coupling in the gap, so as to produce obvious SERS effects.Anodised aluminium
(AA0) template auxiliary assembling metal Nano structure, although controllable (10 receive there is provided gap is prepared under the conditions of a kind of relatively low cost
Rice), reproducible, the method for hypersensitive SERS substrates.But, the method preparation process is loaded down with trivial details, and technological means has high demands, it is difficult to
Prepare large area, the array of long-range order.PS (polystyrene) bead of one layer of densification of single dispersing in smooth substrates, with reference to
Ion etching and metal plating, are also one of feasible method of preparation SERS active-substrate.The method prepares simple, low cost
It is honest and clean, but sensitivity is relatively low, and PS beads are combined loosely with substrate, are easy to come off under ultrasound condition.
The content of the invention
Present invention aims to the defect and deficiency of prior art, there is provided one kind has three-dimensional order periodically big
Raman reflective substrate of pore structure and preparation method thereof, its Raman reflective substrate composition is：1st, Main Ingredients and Appearance be ZnO or
TiO2Semiconductor three-dimensional order periodicity macroporous structure, its specific surface area be 50-200m2 g-1, porosity is 0.2-1cm3 g-1, weight proportion is 98%-99.9%；2nd, metal nanoparticle, weight proportion is 0.1%-2%；The metal nanoparticle is led with partly
Body three-dimensional structure forms hetero-junctions.
The present invention has the beneficial effect that：
（1）It promotes electricity using the synergistic effects between semiconductor three-dimensional order periodicity macroporous structure and metal nanoparticle
Son is directly transmitted in ordered 3 D structure and metal nanoparticle：In plasma enhancing Raman reflective substrate, the gold of load
Metal nano-particle forms hetero-junctions with semiconductor three-dimensional structure；The formation of hetero-junctions promotes electronics in ordered 3 D structure and gold
Metal nano-particle is directly transmitted, and effectively amplifies the raman spectral signal of substrate.
（2）It utilizes semiconductor three-dimensional order periodicity macroporous structure, confinement growth metal nanoparticle effectively to suppress gold
The reunion of metal nano-particle, so as to improve the reappearance of plasma enhancing Raman scattering signal.
（3）The preparation of substrate is tied by the way that metal nanoparticle to be incorporated into the connection of three-dimensional order periodicity macroporous structure
Realize in structure, with load without the need for special installation and harsh conditions, preparation method is simple, technique for the reduction of metal nanoparticle
Quick easy, controllability is strong, easily realizes that large area is prepared and large-scale production.
（4）Three-dimensional order periodic structure has bigger serface and porosity, can effectively adsorb and be enriched with detected material
Molecule, improves detection sensitivity.
Description of the drawings
Accompanying drawing described herein be for providing a further understanding of the present invention, constituting the part of the application, but
Inappropriate limitation of the present invention is not constituted, in the accompanying drawings：
Fig. 1 is three-dimensional order periodicity macroporous structure substrate of the present invention（3DOM TiO2@Ag）SEM figure；
Fig. 2 is three-dimensional order periodicity macroporous structure substrate of the present invention（3DOM TiO2@Ag）TEM figure；
Fig. 3 is three-dimensional order periodicity macroporous structure substrate of the present invention（3DOM TiO2@Ag）Plasma to dye molecule eosin
Body strengthens Raman reflectogram；
Fig. 4 is three-dimensional order periodicity macroporous structure substrate of the present invention（3DOM ZnO@Pt）SEM figure；
Fig. 5 is three-dimensional order periodicity macroporous structure substrate of the present invention（3DOM ZnO @Pt）TEM figure；
Fig. 6 is three-dimensional order periodicity macroporous structure substrate of the present invention（3DOM TiO2@Pt）TEM figure；
Fig. 7 is three-dimensional order periodicity macroporous structure substrate（3DOM TiO2@Pt）TEM figure.
Specific embodiment
Describe the present invention in detail below in conjunction with accompanying drawing and specific embodiment, illustrative examples therein and say
It is bright to be only used for explaining the present invention but not as a limitation of the invention.
A kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure described in this specific embodiment and its
Preparation method, its drawing diffusing reflection base composition is：1st, Main Ingredients and Appearance is ZnO or TiO2Semiconductor three-dimensional order it is periodically big
Pore structure, its specific surface area is 50-200m2 g-1, porosity is 0.2-1cm3 g-1, weight proportion is 98%-99.9%；2nd, gold
Metal nano-particle, weight proportion is 0.1%-2%；The metal nanoparticle forms hetero-junctions with semiconductor three-dimensional structure.
A kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure and preparation method thereof, its method is concrete
For：1st, using colloidal crystal template method, semiconductor three-dimensional order periodicity macroporous structure is prepared；2nd, have in above-mentioned semiconductor three-dimensional
In the pore passage structure of sequence periodicity macroporous structure, using local reduction way or ultraviolet lighting reducing process, in semiconductor three-dimensional order
Carried metal nano particle in the duct of macroporous structure, forms metal nanoparticle and loads with the hetero-junctions of semiconductor three-dimensional structure
Metal nanoparticle, obtains the Raman reflective substrate with three-dimensional order periodicity macroporous structure.
Further：Described colloidal crystal template method is specially：1st, using styrene photonic crystal glue crystalline substance as template,
Metal oxide precursor is filled in die clearance, by heating rate control, by template 550oRemove under C, obtain half
Conductor three-dimensional ordered macroporous structure.
Further：Semiconductor three-dimensional order periodicity macroporous structure inside connection；The semiconductor three-dimensional order cycle
Property macroporous structure aperture be 100-200nm；Specific surface area is more than 50m2 g-1；Porosity is more than 0.2cm3 g-1。
Further：The local reduction way is specially：Semiconductor three-dimensional ordered macroporous structure is immersed in into metallic solution
In, 50W power ultrasonic half an hour makes metallic solution be fully infiltrated in the duct of semiconductor three-dimensional macroporous structure；Continue with 50W work(
Rate ultrasound, while adding sodium borohydride reduction metal ion, makes metal nanoparticle be supported on semiconductor three-dimensional macroporous structure
On duct, the hetero-junctions of metal nanoparticle and semiconductor three-dimensional structure is formed.
Further：The ultraviolet lighting reducing process is specially：Semiconductor three-dimensional ordered macroporous structure is immersed in into metal
In solution, 50W power ultrasonic half an hour makes metallic solution be fully infiltrated in the duct of semiconductor three-dimensional macroporous structure；Continue with
50W power ultrasonics, while solution is placed in into illumination under 100W uviol lamps, make metal nanoparticle be supported on semiconductor three-dimensional macropore
On the duct of structure, the hetero-junctions of metal nanoparticle and semiconductor three-dimensional structure is formed.
Further：The metal oxide precursor is in butyl titanate, TiO 2 sol, zinc acetate colloidal sol
Plant or several.
Further：The heating rate control is specially with 5oThe programming rate of C/min, by heating-up temperature from room temperature
It is increased to 550oC, and 550o3 hours are incubated under C；Subsequently cooling, with 5oThe cooling rate of C/min, by temperature from 550oC drops
As little as room temperature.
Further：The metallic solution is that silver nitrate solution, potassium chloroplatinate solution, tetra chlorauric acid solution, copper nitrate are molten
One or more in liquid, copper-bath, solution concentration is 1mol/L.
In embodiment 1：
Using styrene photonic crystal glue crystalline substance as colloidal crystal template, butyl titanate presoma is filled in die clearance, it is quiet
After putting one day, by heating rate control, by template 550oRemove under C, obtain TiO2Three-dimensional ordered macroporous structure.Heat up speed
Rate is：With 5oThe programming rate of C/min, 550 are increased to by heating-up temperature from room temperatureoC, and 550o3 hours are incubated under C；With
After lower the temperature, with 5oThe cooling rate of C/min, by temperature from 550oC is reduced to room temperature.
Using ultraviolet lighting reducing process in TiO2Loaded Ag nano particle in the duct of three-dimensional ordered macroporous structure, forms Ag
The hetero-junctions of nano particle and semiconductor three-dimensional structure.Detailed process is：By TiO2Three-dimensional ordered macroporous structure is immersed in 1mol/
In the silver nitrate solution of L, 50W power ultrasonic half an hour makes metallic solution be fully infiltrated into the duct of semiconductor three-dimensional macroporous structure
In；；Continue with 50W power ultrasonics, using 100W ultraviolet source irradiation reaction solution, Ag nano particles is restored from solution
Carry out and be supported on TiO2On the duct of three-dimensional macroporous structure, Ag nano particles and TiO are formed2The hetero-junctions of three-dimensional structure.This three
Pattern, structure and the size of orderly periodicity macroporous structure substrate are tieed up referring to Fig. 1, size, the pattern of the Ag nano particles of load
And crystal face is referring to Fig. 2.
Fig. 3 shows this three-dimensional order periodicity macroporous structure substrate（3DOM TiO2@Ag）To dye molecule plasma
Body strengthens Raman reflection.With the nano-TiO without three-dimensional order periodicity macroporous structure2Compare, 3DOM TiO2@Ag substrates are to daybreak
The Raman detection intensity of red molecule is significantly increased.
In example 2：
Using styrene photonic crystal glue crystalline substance as colloidal crystal template, zinc acetate Gel Precursor is filled in die clearance,
After standing one day, by heating rate control, by template 550oRemove under C, obtain ZnO three-dimensional ordered macroporous structures.Heat up
Speed is：With 5oThe programming rate of C/min, 550 are increased to by heating-up temperature from room temperatureoC, and 550o3 hours are incubated under C；
Subsequently cooling, with 5oThe cooling rate of C/min, by temperature from 550oC is reduced to room temperature.
Using local reduction way in the duct of ZnO three-dimensional ordered macroporous structures supporting Pt nano particle, formed Pt nanometers
The hetero-junctions of particle and semiconductor three-dimensional structure.Detailed process is：ZnO three-dimensional ordered macroporous structures are immersed in into the chlorine of 1mol/L
In platinic acid potassium solution, 50W power ultrasonic half an hour makes metallic solution be fully infiltrated in the duct of ZnO three-dimensional macroporous structures；Continue
With 50W power ultrasonics, while adding sodium borohydride reduction Pt4+Ion, makes Pt nano particles be supported on ZnO three-dimensional macroporous structures
On duct, the hetero-junctions of Pt nano particles and ZnO three-dimensional structures is formed.The shape of this three-dimensional order periodicity macroporous structure substrate
Referring to Fig. 4, the size of the Pt nano particles of load, pattern and crystal face are referring to Fig. 5 for looks, structure and size.With no three-dimensional order
The nano-ZnO of periodicity macroporous structure is compared, and Raman detection intensity of the agricultural chemicals Dyfonate in 3DOM ZnO@Pt substrates is enhanced
3 times.
In embodiment 3：
Using styrene photonic crystal glue crystalline substance as colloidal crystal template, zinc acetate Gel Precursor is filled in die clearance,
After standing one day, by heating rate control, by template 550oRemove under C, obtain TiO2Three-dimensional ordered macroporous structure.Heat up
Speed is：With 5oThe programming rate of C/min, 550 are increased to by heating-up temperature from room temperatureoC, and 550o3 hours are incubated under C；
Subsequently cooling, with 5oThe cooling rate of C/min, by temperature from 550oC is reduced to room temperature.
Using local reduction way in TiO2Supporting Pt nano particle in the duct of three-dimensional ordered macroporous structure, forms Pt nanometers
The hetero-junctions of particle and semiconductor three-dimensional structure.Detailed process is：By TiO2Three-dimensional ordered macroporous structure is immersed in 1mol/L's
In potassium chloroplatinate solution, 50W power ultrasonic half an hour makes metallic solution be fully infiltrated into TiO2In the duct of three-dimensional macroporous structure；After
Continue with 50W power ultrasonics, while adding sodium borohydride reduction Pt4+Ion, makes Pt4Nano particle is supported on semiconductor three-dimensional macropore
On the duct of structure, Pt is formed4Nano particle and TiO2The hetero-junctions of three-dimensional structure.This three-dimensional order periodicity macroporous structure
Referring to Fig. 6, the size of the Pt nano particles of load, pattern and crystal face are referring to Fig. 7 for the pattern of substrate, structure and size.With do not have
The nano-TiO of three-dimensional order periodicity macroporous structure2Compare, agricultural chemicals Rogor is in 3DOM TiO2Raman detection in@Pt substrates is strong
Degree has been enhanced 4 times.
A kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure of the present invention and preparation method thereof,
It applies colloidal crystal template method, prepares semiconductor three-dimensional order periodicity macroporous structure；In above-mentioned semiconductor three-dimensional order week
In the pore passage structure of phase property macroporous structure, carried metal nano particle；It can effectively amplify the raman spectral signal of substrate, can carry
High beta plasma strengthens the reappearance of Raman scattering signal, can effectively adsorb and be enriched with detected material molecule, improves detection sensitive
Degree, its preparation method is simple, technique is quickly easy, and controllability is strong, easily realizes that large area is prepared and large-scale production.
The present invention has the beneficial effect that：
（1）It promotes electricity using the synergistic effects between semiconductor three-dimensional order periodicity macroporous structure and metal nanoparticle
Son is directly transmitted in ordered 3 D structure and metal nanoparticle：In plasma enhancing Raman reflective substrate, the gold of load
Metal nano-particle forms hetero-junctions with semiconductor three-dimensional structure；The formation of hetero-junctions promotes electronics in ordered 3 D structure and gold
Metal nano-particle is directly transmitted, and effectively amplifies the raman spectral signal of substrate.
（2）It utilizes semiconductor three-dimensional order periodicity macroporous structure, confinement growth metal nanoparticle effectively to suppress gold
The reunion of the deflocculation metal nanoparticle of metal nano-particle, so as to improve the reproduction of plasma enhancing Raman scattering signal
Property.
（3）The preparation of substrate is tied by the way that metal nanoparticle to be incorporated into the connection of three-dimensional order periodicity macroporous structure
Realize in structure, with load without the need for special installation and harsh conditions, preparation method is simple, technique for the reduction of metal nanoparticle
Quick easy, controllability is strong, easily realizes that large area is prepared and large-scale production.
（4）Three-dimensional order periodic structure has bigger serface and porosity, can effectively adsorb and be enriched with detected material
Molecule, improves detection sensitivity.
The above is only the better embodiment of the present invention, therefore all constructions according to described in present patent application scope,
Equivalence changes or modification that feature and principle are done, are included in the range of present patent application.
Claims (9)
1. a kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure, it is characterised in that its Raman reflective substrate
Composition is：1st, Main Ingredients and Appearance is ZnO or TiO2Semiconductor three-dimensional order periodicity macroporous structure, its specific surface area be 50-
200m2 g-1, porosity is 0.2-1cm3 g-1, weight proportion is 98%-99.9%；2nd, metal nanoparticle, weight proportion is
0.1%-2%；The metal nanoparticle forms hetero-junctions with semiconductor three-dimensional structure.
2. a kind of preparation method of the Raman reflective substrate with three-dimensional order periodicity macroporous structure, it is characterised in that its side
Method is specially：1st, using colloidal crystal template method, semiconductor three-dimensional order periodicity macroporous structure is prepared；2nd, in above-mentioned semiconductor
In the pore passage structure of three-dimensional order periodicity macroporous structure, using local reduction way or ultraviolet lighting reducing process, in semiconductor three
Carried metal nano particle in the duct of dimension ordered big hole structure, forms metal nanoparticle heterogeneous with semiconductor three-dimensional structure
Knot carried metal nano particle, obtains the Raman reflective substrate with three-dimensional order periodicity macroporous structure.
3. a kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure according to claim 2 and its preparation
Method, it is characterised in that described colloidal crystal template method is specially：1st, it is brilliant as template using styrene photonic crystal glue, to
Metal oxide precursor is filled in die clearance, by heating rate control, by template 550oRemove under C, partly led
Body three-dimensional ordered macroporous structure.
4. a kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure according to claim 2 and its preparation
Method, it is characterised in that：Semiconductor three-dimensional order periodicity macroporous structure inside connection；Semiconductor three-dimensional order is periodically
The aperture of macroporous structure is 100-200nm；Specific surface area is more than 50m2 g-1；Porosity is more than 0.2cm3 g-1。
5. a kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure according to claim 2 and its preparation
Method, it is characterised in that the local reduction way is specially：Semiconductor three-dimensional ordered macroporous structure is immersed in metallic solution,
50W power ultrasonic half an hour makes metallic solution be fully infiltrated in the duct of semiconductor three-dimensional macroporous structure；Continue super with 50W power
Sound, while adding sodium borohydride reduction metal ion, makes metal nanoparticle be supported on the duct of semiconductor three-dimensional macroporous structure
On, metal nanoparticle is grown using the confinement of three-dimensional order periodicity macroporous structure, effectively suppress the reunion of metal nanoparticle
Suppress the reunion of metal nanoparticle, form the hetero-junctions of metal nanoparticle and semiconductor three-dimensional structure.
6. a kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure according to claim 2 and its preparation
Method, it is characterised in that the ultraviolet lighting reducing process is specially：Semiconductor three-dimensional ordered macroporous structure is immersed in into metal molten
In liquid, 50W power ultrasonic half an hour makes metallic solution be fully infiltrated in the duct of semiconductor three-dimensional macroporous structure；Continue with 50W
Power ultrasonic, while solution is placed in into illumination under 100W uviol lamps, makes metal nanoparticle be supported on semiconductor three-dimensional macropore knot
On the duct of structure, the hetero-junctions of metal nanoparticle and semiconductor three-dimensional structure is formed.
7. a kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure according to claim 3 and its preparation
Method, it is characterised in that：The metal oxide precursor is in butyl titanate, TiO 2 sol, zinc acetate colloidal sol
Plant or several.
8. a kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure according to claim 3 and its preparation
Method, it is characterised in that the heating rate control is specially with 5oThe programming rate of C/min, by heating-up temperature from room temperature liter
Up to 550oC, and 550o3 hours are incubated under C；Subsequently cooling, with 5oThe cooling rate of C/min, by temperature from 550oC is reduced
To room temperature.
9. a kind of Raman reflective substrate with three-dimensional order periodicity macroporous structure according to claim 5 or 6 and its
Preparation method, it is characterised in that：The metallic solution is silver nitrate solution, potassium chloroplatinate solution, tetra chlorauric acid solution, copper nitrate
One or more in solution, copper-bath, solution concentration is 1mol/L.
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| CN107064263A (en) * | 2017-05-09 | 2017-08-18 | 同济大学 | Aptamer photoelectric sensor for detecting Atrazine and preparation method thereof |
| WO2020113706A1 (en) * | 2018-12-06 | 2020-06-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Application of semiconductor compound in benzaldehyde specificity detection and detection method therefor |
| CN113567414A (en) * | 2021-07-02 | 2021-10-29 | 合肥工业大学 | ZIF 8-derived semiconductor heterojunction-silver SERS substrate and preparation method and application thereof |
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| CN113567414A (en) * | 2021-07-02 | 2021-10-29 | 合肥工业大学 | ZIF 8-derived semiconductor heterojunction-silver SERS substrate and preparation method and application thereof |
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