CN105174194A - Gold micro-nano structure array and preparation method as well as application thereof - Google Patents
Gold micro-nano structure array and preparation method as well as application thereof Download PDFInfo
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- CN105174194A CN105174194A CN201510477676.4A CN201510477676A CN105174194A CN 105174194 A CN105174194 A CN 105174194A CN 201510477676 A CN201510477676 A CN 201510477676A CN 105174194 A CN105174194 A CN 105174194A
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Abstract
The invention discloses a gold micro-nano structure array and preparation method as well as application thereof. The array comprises a substrate coated with a gold film, a gold microprism array is arranged on the gold film, tops of gold microprisms forming the gold microprism array are hemispheric; each gold microprism with the hemispheric top has the prismdiameter of 200nm-3[mu]m and the prism height of 300nm-6[mu]m, and is composed of gold nano particles; and the particle size of the gold nano particles is 3-30nm. The method comprises the following steps of: firstly, forming the gold film on the substrate through sputtering, then, adding the substrate coated with the gold film into a gold electrolyte as a cathode, performing electrodeposition for 8-20 hours with 30-500[mu]A/cm<2> direct current, wherein, the gold electrolyte is a mixed solution of 0.2-5g/L chloroauric acid solution and 2-50g/L polyvinyl pyrrolidone solution, thereby obtaining the target product. The gold micro-nano structure array can be used as an SERS (Surface Enhanced Raman Scattering) active substrate, and the content of rhodamine or methyl parathion attached on the gold micro-nano structure array is measured through a laser Raman spectrometer.
Description
Technical field
The present invention relates to a kind of micro-nano structure array and preparation method and purposes, especially be a kind of golden micro-nano structure array and its production and use.
Background technology
SERS (SERS) spectrum has advantages such as identifying molecular fingerprint feature, high sensitivity and quick response, has a wide range of applications in fields such as chemical analysis, biological medicine, environmental monitorings.For this reason, people have prepared a large amount of noble metal nano structure SERS substrates, as being entitled as " Agnanosheet-assembledmicro-hemispheresaseffectiveSERSsub strates " of applicant, ChemicalCommunications, 2011,47,2709-2711 (" the micron hemisphere of Nano silver piece assembling is as effective SERS substrate ", " chemical communication ", the 47th phase in 2011 2709th ~ 2711 pages) article described in.The Nano silver piece that the product mentioned in this article is 10 ~ 20 nanometers by thickness is assembled into hemisphere, and its preparation method is adopt electrochemical deposition method obtained diameter on indium oxide tin glass to be the hemisphere of 2 ~ 7 microns, to be used as SERS substrate.Though it is active that this product has higher SERS, there is shortcoming part also, first, silver nanostructured easily oxidation and sulfuration in atmosphere, seriously have impact on the stability of SERS substrate; Secondly, preparation method can not obtain the SERS substrate of good stability.
Summary of the invention
The technical problem to be solved in the present invention, for overcoming shortcoming part of the prior art, provides a kind of rational in infrastructure, the golden micro-nano structure array of good stability.
Another technical problem that the present invention will solve is for providing a kind of preparation method of above-mentioned golden micro-nano structure array.
Another technical problem that the present invention will solve is for providing a kind of purposes of above-mentioned golden micro-nano structure array.
For solving technical problem of the present invention, the technical scheme adopted is: golden micro-nano structure array comprises substrate, particularly,
Described substrate is covered with golden film, described golden film is equipped with golden micron post array, the top of the golden micron post of described composition gold micron post array is hemispherical;
The column diameter of the golden micron post on described hemispherical top is 200nm ~ 3 μm, post height is 300nm ~ 6 μm, and it is made up of gold nano grain;
The particle diameter of described gold nano grain is 3 ~ 30nm.
Further improvement as golden micro-nano structure array:
Preferably, the thickness of golden film is 10 ~ 50nm.
Preferably, substrate is conductor, or semiconductor, or insulator.
For solving another technical problem of the present invention, another technical scheme adopted is: the preparation method of above-mentioned golden micro-nano structure array comprises electrochemical deposition method, and particularly key step is as follows:
Prior to substrate sputtering golden film, then the substrate it being covered with golden film is placed in Gold electrolysis liquid as negative electrode, in 30 ~ 500 μ A/cm
2dC current under electro-deposition 8 ~ 20h, wherein, Gold electrolysis liquid is the mixed liquor of the chlorauric acid solution of 0.2 ~ 5g/L and the polyvinylpyrrolidonesolution solution of 2 ~ 50g/L, obtained golden micro-nano structure array.
Further improvement as the preparation method of golden micro-nano structure array:
Preferably, substrate is conductor, or semiconductor, or insulator.
Preferably, the thickness of golden film is 10 ~ 50nm.
Preferably, anode during electro-deposition is graphite.
Preferably, washed with de-ionized water gold micro-nano structure array 1 ~ 3 time is used.
For solving another technical problem of the present invention, another technical scheme adopted is: the purposes of above-mentioned golden micro-nano structure array is,
Using the active substrate of golden micro-nano structure array as SERS, laser Raman spectrometer is used to measure the rhodamine (6G) of attachment or the content of parathion-methyl on it.
Further improvement as the purposes of golden micro-nano structure array:
Preferably, the excitation wavelength of laser Raman spectrometer is 532nm, power output is 0.03 ~ 1mW, the time of integration is 1 ~ 30s.
Relative to the beneficial effect of prior art be:
One, use ESEM to characterize to obtained object product, from its result, object product is be overlying on the golden film on substrate to be equipped with golden micron post array; Wherein, the top forming the golden micron post of golden micron post array is hemispherical, and the column diameter of the golden micron post on hemispherical top is 200nm ~ 3 μm, post height is 300nm ~ 6 μm, and it is made up of gold nano grain, and the particle diameter of gold nano grain is 3 ~ 30nm.This object product by being assembled into based on gold nano grain, both the stability of object product had been ensure that due to the aerial stability of gold, because of golden micron post array, the specific area of object product is guaranteed again, also because the golden micron post on the hemispherical top forming golden micron post array is made up of gold nano grain, and ensure that object product has the larger specific area of catching testing molecule and a large amount of SERS focuses strengthened that generates an electromagnetic field further.
Its two, using obtained object product as SERS active-substrate, through carrying out the tests of the repeatedly many batches under variable concentrations respectively to rhodamine and parathion-methyl, when the concentration of measured object rhodamine is low to moderate 10
-12the concentration of mol/L, parathion-methyl is low to moderate 10
-8during mol/L, still it can be detected effectively, and its uniformity detected and the multiple spot of repeatability on object product and any point all very good.
Its three, preparation method is simple, science, efficient.Not only obtain rational in infrastructure, the object product of good stability---golden micro-nano structure array; After also making the object product obtained coordinate with laser Raman spectrometer, possessed organophosphorus pesticide parathion-methyl in environmental toxic pollutant rhodamine and water is carried out fast, the function of trace detection; More there is preparation process simple and convenient, the feature that cost is low; And then make object product very easily in the quick detection being widely used for the fields such as environment, chemistry, biology.
Accompanying drawing explanation
Fig. 1 is to one of result that obtained object product uses ESEM (SEM) to characterize.Wherein, the SEM image of product for the purpose of Fig. 1 a, the high magnification SEM image that Fig. 1 b is object product shown in Fig. 1 a.
Fig. 2 is to one of result that the object product containing variable concentrations rhodamine uses laser Raman spectrometer to characterize.Curve I in figure is for containing 10
-6the SERS spectral line of the object product of mol/L rhodamine, curve II is for containing 10
-8the SERS spectral line of the object product of mol/L rhodamine, curve III is for containing 10
-10the SERS spectral line of the object product of mol/L rhodamine, curve IV is for containing 10
-12the SERS spectral line of the object product of mol/L rhodamine; Which confirms using object product as SERS active-substrate, the trace rhodamine of attachment on it can be detected.
Fig. 3 is to one of result that the object product containing variable concentrations parathion-methyl uses laser Raman spectrometer to characterize.Curve I in figure is for containing 10
-6the SERS spectral line of the object product of mol/L parathion-methyl, curve II is for containing 10
-7the SERS spectral line of the object product of mol/L parathion-methyl, curve III is for containing 10
-8the SERS spectral line of the object product of mol/L parathion-methyl; Which confirms using object product as SERS active-substrate, the trace parathion-methyl of attachment on it can be detected.
Detailed description of the invention
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
First buy from market or obtain voluntarily:
As the conductor of substrate, semiconductor and insulator; Deionized water.
Then,
Embodiment 1
The concrete steps of preparation are:
Prior to substrate sputtering golden film; Wherein, substrate is the monocrystalline silicon piece in semiconductor, and the thickness of golden film is 10nm.Again graphite is placed in Gold electrolysis liquid as negative electrode, in 30 μ A/cm together as anode, the substrate that it is covered with golden film
2dC current under electro-deposition 20h; Wherein, Gold electrolysis liquid is the mixed liquor of the chlorauric acid solution of 0.2g/L and the polyvinylpyrrolidonesolution solution of 50g/L, obtains and is similar to the golden micro-nano structure array shown in Fig. 1.Afterwards, washed with de-ionized water gold micro-nano structure array 1 time is used.
Embodiment 2
The concrete steps of preparation are:
Prior to substrate sputtering golden film; Wherein, substrate is the monocrystalline silicon piece in semiconductor, and the thickness of golden film is 20nm.Again graphite is placed in Gold electrolysis liquid as negative electrode, in 130 μ A/cm together as anode, the substrate that it is covered with golden film
2dC current under electro-deposition 17h; Wherein, Gold electrolysis liquid is the mixed liquor of the chlorauric acid solution of 1.2g/L and the polyvinylpyrrolidonesolution solution of 38g/L, obtains and is similar to the golden micro-nano structure array shown in Fig. 1.Afterwards, washed with de-ionized water gold micro-nano structure array 2 times are used.
Embodiment 3
The concrete steps of preparation are:
Prior to substrate sputtering golden film; Wherein, substrate is the monocrystalline silicon piece in semiconductor, and the thickness of golden film is 30nm.Again graphite is placed in Gold electrolysis liquid as negative electrode, in 250 μ A/cm together as anode, the substrate that it is covered with golden film
2dC current under electro-deposition 14h; Wherein, Gold electrolysis liquid is the mixed liquor of the chlorauric acid solution of 2.5g/L and the polyvinylpyrrolidonesolution solution of 25g/L, obtained golden micro-nano structure array as shown in Figure 1.Afterwards, washed with de-ionized water gold micro-nano structure array 2 times are used.
Embodiment 4
The concrete steps of preparation are:
Prior to substrate sputtering golden film; Wherein, substrate is the monocrystalline silicon piece in semiconductor, and the thickness of golden film is 40nm.Again graphite is placed in Gold electrolysis liquid as negative electrode, in 375 μ A/cm together as anode, the substrate that it is covered with golden film
2dC current under electro-deposition 11h; Wherein, Gold electrolysis liquid is the mixed liquor of the chlorauric acid solution of 3.75g/L and the polyvinylpyrrolidonesolution solution of 12g/L, obtains and is similar to the golden micro-nano structure array shown in Fig. 1.Afterwards, washed with de-ionized water gold micro-nano structure array 3 times are used.
Embodiment 5
The concrete steps of preparation are:
Prior to substrate sputtering golden film; Wherein, substrate is the monocrystalline silicon piece in semiconductor, and the thickness of golden film is 50nm.Again graphite is placed in Gold electrolysis liquid as negative electrode, in 500 μ A/cm together as anode, the substrate that it is covered with golden film
2dC current under electro-deposition 8h; Wherein, Gold electrolysis liquid is the mixed liquor of the chlorauric acid solution of 5g/L and the polyvinylpyrrolidonesolution solution of 2g/L, obtains and is similar to the golden micro-nano structure array shown in Fig. 1.Afterwards, washed with de-ionized water gold micro-nano structure array 3 times are used.
Select respectively again as the conductor of substrate or semiconductor or insulator, repeat above-described embodiment 1 ~ 5, obtained as or be similar to the golden micro-nano structure array shown in Fig. 1 equally.
The purposes of gold micro-nano structure array is,
Using the active substrate of golden micro-nano structure array as SERS, use laser Raman spectrometer to measure the rhodamine of attachment or the content of parathion-methyl on it, obtain as or be similar to the result shown in Fig. 2 or Fig. 3; Wherein, the excitation wavelength of laser Raman spectrometer is 532nm, power output is 0.03 ~ 1mW, the time of integration is 1 ~ 30s.
Obviously, those skilled in the art can carry out various change and modification to golden micro-nano structure array of the present invention and its production and use and not depart from the spirit and scope of the present invention.Like this, if belong within the scope of the claims in the present invention and equivalent technologies thereof to these amendments of the present invention and modification, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. a golden micro-nano structure array, comprises substrate, it is characterized in that:
Described substrate is covered with golden film, described golden film is equipped with golden micron post array, the top of the golden micron post of described composition gold micron post array is hemispherical;
The column diameter of the golden micron post on described hemispherical top is 200nm ~ 3 μm, post height is 300nm ~ 6 μm, and it is made up of gold nano grain;
The particle diameter of described gold nano grain is 3 ~ 30nm.
2. golden micro-nano structure array according to claim 1, is characterized in that the thickness of golden film is 10 ~ 50nm.
3. golden micro-nano structure array according to claim 1, is characterized in that substrate is conductor, or semiconductor, or insulator.
4. a preparation method for golden micro-nano structure array described in claim 1, comprises electrochemical deposition method, it is characterized in that key step is as follows:
Prior to substrate sputtering golden film, then the substrate it being covered with golden film is placed in Gold electrolysis liquid as negative electrode, in 30 ~ 500 μ A/cm
2dC current under electro-deposition 8 ~ 20h, wherein, Gold electrolysis liquid is the mixed liquor of the chlorauric acid solution of 0.2 ~ 5g/L and the polyvinylpyrrolidonesolution solution of 2 ~ 50g/L, obtained golden micro-nano structure array.
5. the preparation method of golden micro-nano structure array according to claim 4, is characterized in that substrate is conductor, or semiconductor, or insulator.
6. the preparation method of golden micro-nano structure array according to claim 4, is characterized in that the thickness of golden film is 10 ~ 50nm.
7. the preparation method of golden micro-nano structure array according to claim 4, anode when it is characterized in that electro-deposition is graphite.
8. the preparation method of golden micro-nano structure array according to claim 4, is characterized in that using washed with de-ionized water gold micro-nano structure array 1 ~ 3 time.
9. a purposes for golden micro-nano structure array described in claim 1, is characterized in that:
Using the active substrate of golden micro-nano structure array as SERS, laser Raman spectrometer is used to measure the rhodamine of attachment or the content of parathion-methyl on it.
10. the purposes of golden micro-nano structure array according to claim 9, is characterized in that the excitation wavelength of laser Raman spectrometer is 532nm, power output is 0.03 ~ 1mW, the time of integration is 1 ~ 30s.
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| CN106967978A (en) * | 2017-05-03 | 2017-07-21 | 中国科学院合肥物质科学研究院 | Film of gold nano grain assembling and its production and use |
| CN107151807A (en) * | 2017-04-28 | 2017-09-12 | 中国科学院合肥物质科学研究院 | Porous golden micro-nano structure of hemispherical shell and its production and use |
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Application publication date: 20151223 |