CN102692405B - Rice-grain-shaped fluoride/silver composite nanometer material and preparation method and application thereof - Google Patents
Rice-grain-shaped fluoride/silver composite nanometer material and preparation method and application thereof Download PDFInfo
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- CN102692405B CN102692405B CN201210186065.0A CN201210186065A CN102692405B CN 102692405 B CN102692405 B CN 102692405B CN 201210186065 A CN201210186065 A CN 201210186065A CN 102692405 B CN102692405 B CN 102692405B
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Abstract
The invention discloses a rice-grain-shaped fluoride/silver composite nanometer material. The material consists of rice-grain-shaped fluoride cores and a silver nano-particle layer, wherein silver nano-particles are gathered on the surfaces of the rice-grain-shaped cores. The invention also discloses a preparation method for the rice-grain-shaped fluoride/silver composite nanometer material and application of the rice-grain-shaped fluoride/silver composite nanometer material. Rice-grain-shaped fluoride is prepared by a hydrothermal method, and conditions are mild and controllable; the source of the rice-grain-shaped fluoride is wide, and multiple kinds of fluorides can be obtained; the silver nano-particles are sputtered in a magnetron sputtering mode, so that the method is convenient, quick, time-saving and low in cost; the product has high morphological reproducibility and can be massively produced; organic molecules and surfactant molecules are not contained in the product, so that the fluorescence interference is avoided; and according to the fluoride/silver composite nanostructure system, the fluoride absorbs the energy and transfers the energy to silver, so that the Raman scattering effect is effectively strengthened, and the single-molecule detection level can be reached on the detection of analytes.
Description
Technical field
The present invention relates to a kind of grain of rice shape fluoride/silver-colored composite nanostructure and the preparation method with surface reinforced Raman active substrate.
Background technology
The quick detection of explosive TNT/DNT is significant in national security, public place and environmental monitoring and protection.The current examination criteria method to TNT/DNT liquid phase has chromatography of ions, high performance liquid chromatography.Because the steam of TNT/DNT under room temperature forces down (< 100ppb), direct-detection explosive gas difficulty.Gas chromatography/mass spectrometry technology (GC/MS) is that gas phase TNT/DNT detects the most frequently used method.But these methods exist the defects such as testing cost is high, instrument is huge, consuming time, sensitivity is low, and public place and field must without the need to completing in preparation of samples and fast response time to the testing requirement of explosive.Current detection technology can not meet the requirement of the quick explosive detection of on-the-spot high sensitivity, therefore, country and society be badly in need of a kind of simple, reliably method carry out that scene is quick, these explosives of the accurate detection and Identification of high sensitivity.Surface enhanced raman spectroscopy (SERS) technology owing to can realize fast, high sensitivity, harmless in situ detection and be subject to extensive concern, be applied to chemistry and biology sensor, biomedical detection and the field such as trace detection and analysis.The feature of SERS technology is that the detection and Identification of trace TNT/DNT gas provide a kind of Site Detection new tool reliably.
In fact, the application of SERS technology depends on how to obtain signal evenly and have higher SERS active-substrate to a great extent.Research shows that the rice-granule nano particle had compared with big L/D ratio has desirable enhancement effect, can excite maximum LSPR when the polarization direction of incident light is mated with the dimension of nano material, produces strong SERS effect thus.The nearest researcher Fe that utilized distinct methods to synthesize
2o
3au or Fe
2o
3ag composite structure, as utilized triamido propyl trimethoxy silicane (APTMS) by grain of rice shape Fe
2o
3after showing functionalization, adhere to Au seed and finally form Fe
2o
3au nucleocapsid structure; At grain of rice shape Fe
2o
3surface coating skim SiO
2as middle layer, then show deposition layer of Au or Ag at it, form rice grain structure.Although but existing method obtains comparatively ideal SERS performance, but introduce couplant in building-up process, as alkyl, biomolecule etc., these may cause extra signal disturbing, especially analyte molecule Raman signal and coupling group signal similar time interference larger.In addition, some method also exist time-consuming, program is loaded down with trivial details, cost is high, needs the defects such as special post-processed.
Summary of the invention
The object of the invention is to, for the deficiency in existing detection technique, provide a kind of grain of rice shape fluoride/silver-colored composite nanostructure with surface reinforced Raman active substrate and preparation method thereof.
Grain of rice shape fluoride/silver-colored composite nano materials of the present invention, be made up of the fluoride kernel of grain of rice shape and Silver nano-particle layer, described silver nano-grain is gathered in the surface of grain of rice shape kernel.
The preparation method of grain of rice shape fluoride/silver-colored composite nano materials of the present invention, comprises the steps:
(1) by volumetric molar concentration 0.1-2 molL
-1eDTA solution, slowly join volumetric molar concentration 0.1-3 molL
-1rare-earth chloride solution in, the mol ratio of EDTA and rare earth-iron-boron is 1:1, stirring reaction 10-60 minute;
(2) in above-mentioned solution, volumetric molar concentration 0.1-3 molL is added
-1sodium fluoride or potassium fluoride solution, after stirring, be transferred in the autoclave containing polytetrafluoroethylliner liner, set temperature 60-180 DEG C, continue reaction after 1-72 hour, naturally cool to room temperature, use supercentrifuge centrifuging, wash respectively with water and absolute ethyl alcohol, obtain grain of rice shape fluoride nano material;
(3) grain of rice shape fluoride nano material is distributed in absolute ethyl alcohol and obtains suspension, get suspension and drop on monocrystalline silicon piece, dry;
(4) monocrystalline silicon piece is put into the vacuum chamber of magnetron sputtering apparatus, regulate magnetron sputtering power 1-300 watt, sputtering time 1-30 minute, magnetron sputtering silver nano-grain, obtains grain of rice shape fluoride/silver-colored composite nano materials.
In step (1) and step (2), the mol ratio of described sodium fluoride or potassium fluoride and rare earth-iron-boron is 1-20.
In step (1), described rare earth-iron-boron is neodymium, the chloride of samarium, europium, terbium or holmium.
In step (2), described washing first carries out using deionized water as cleansing solution and then using absolute ethyl alcohol as cleansing solution.
In step (4), described magnetron sputtering power 10-200 watt, sputtering time 5-200 second.
Grain of rice shape fluoride/silver-colored composite nano materials of the present invention, is applied to the trace detection of surface enhanced Raman scattering effect.
On the grain of rice shape fluoride that the present invention utilizes physical sputtering method to be directly splashed to by argent nano particle on monocrystalline silicon piece, fluoride nano particles, as excellent luminous host material, after surface is modified by Au or Ag, has good luminescence enhancement ability.Fluoride is transferred to metal after absorbing excitation energy as energy donor, produces huge local surface plasma resonance, can predict, also will produce strong SERS effect.
In preparation method of the present invention, do not need to add any surfactant, organism and coupling agent, eliminate the interference that in product, other group may cause product Raman signal from source, this method cost is low, simple to operate, the used time is short.Particularly, sputter procedure firmly can be fixed on Nano silver grain on silicon chip, in reality detects, this silicon chip directly can be placed in analysis thing and carry out SERS test, convenient, fast, without the need to post-processed.The senser element that the present invention analyzes based on SERS for development, the optical chemical senser element of Development of Novel is used for trace detection provides important technical support.
Do not add surfactant and organic molecule in grain of rice shape fluoride/silver-colored composite nano materials of the present invention, eliminate the interference of unknown group to Raman signal from source, improve sensitivity for analysis.This fluoride/silver-colored composite nanostructure system, Absorption of Fluoride energy, and be transferred to silver, effectively enhance Raman scattering effect, Single Molecule Detection level can be reached to the detection analyzing thing.By the factor such as sputtering time, power that choice for use is different in using, the architectural feature of product is changed, thus make pattern, size, the surface structure of product, and the surface plasma body resonant vibration caused thus and SERS performance etc. have Modulatory character.This method is easy, efficient, cost is low, simple to operate, be applicable to large-scale production.This compound substance is easy to the substrate being made into certain size, meets the demand of field and public place Site Detection.
Beneficial effect of the present invention is:
(1) grain of rice shape fluoride adopts hydro-thermal method preparation, and mild condition is controlled;
(2) grain of rice shape fluoride source is extensive, available fluoride NaLnF
4(Ln=neodymium Nd, samarium Sm, europium Eu, terbium Tb, holmium Ho);
(3) by magnetron sputtering mode sputtering silver nano particle, convenient and swift, save time, cost is low;
(4) product morphology favorable reproducibility, can large-scale production;
(5) product is not containing any organic molecule and surfactant molecule, avoids fluorescence interference;
(6) fluoride/silver-colored composite nanostructure system, Absorption of Fluoride energy, and be transferred to silver, effectively enhance Raman scattering effect, Single Molecule Detection level can be reached to the detection analyzing thing.
Accompanying drawing explanation
Fig. 1 .1 is grain of rice shape NaNdF
4the high power scanning electron microscope diagram sheet (SEM) of nano particle, grain of rice shape NaNdF
4length about 190 nm, diameter about 60 nm, size uniformity, presents good monodispersity.
Fig. 1 .2 is grain of rice shape NaSmF
4the high power scanning electron microscope diagram sheet (SEM) of nano particle, grain of rice shape NaSmF
4length about 190 nm, diameter about 60 nm, size uniformity, presents good monodispersity.
Fig. 2 .1 is with NaSmF
4as substrate template, the SEM figure of fixing magnetron sputtering power 50 W, sputtering time 10 s gained grain of rice shape fluoride/silver-colored composite nano materials;
Fig. 2 .2 is with NaSmF
4as substrate template, the SEM figure of fixing magnetron sputtering power 50 W, sputtering time 30 s gained grain of rice shape fluoride/silver-colored composite nano materials;
Fig. 2 .3 is with NaSmF
4as substrate template, the SEM figure of fixing magnetron sputtering power 50 W, sputtering time 150 s gained grain of rice shape fluoride/silver-colored composite nano materials;
Fig. 3 .1 is with NaSmF
4as substrate template, the SEM figure of fixing magnetron sputtering time 30 s, sputtering power 30 W gained grain of rice shape fluoride/silver-colored composite nano materials;
Fig. 3 .2 is with NaSmF
4as substrate template, the SEM figure of fixing magnetron sputtering time 30 s, sputtering power 50 W gained grain of rice shape fluoride/silver-colored composite nano materials;
Fig. 3 .3 is with NaSmF
4as substrate template, the SEM figure of fixing magnetron sputtering time 30 s, sputtering power 150 W gained grain of rice shape fluoride/silver-colored composite nano materials;
Fig. 4 is the Surface enhanced raman spectroscopy figure of grain of rice shape fluoride/Ag composite nanostructure of the present invention;
Embodiment
The following examples are the further descriptions to content of the present invention; its object is to the explanation technology contents of the present invention of more detailed tool; but this description does not form any restriction to connotation of the present invention; therefore, any distortion based on connotation of the present invention or change all should be worked as and belonged within the present invention's scope required for protection.
embodiment 1(solwution method synthesis grain of rice shape NaNdF under room temperature
4nano particle)
Get 1 mL volumetric molar concentration 0.2 molL
-1neodymium trichloride solution in 100 mL beakers, add 30 mL deionized waters and mix, then in beaker, add 1mL volumetric molar concentration 0.2 molL
-1ethylenediamine tetraacetic acid (EDTA), magnetic agitation, after 30 minutes, adds 10 mL volumetric molar concentration 0.2 molL in the most backward above solution
-1fluorinse, after stirring, be transferred in the autoclave containing polytetrafluoroethylliner liner, set temperature 120 DEG C, constant temperature, after 24 hours, naturally cools to room temperature.Use supercentrifuge centrifuging, obtain solid and with deionized water cyclic washing 3 times, then with absolute ethanol washing once, be then distributed in 5 mL absolute ethyl alcohols, grain of rice shape NaNdF can be obtained
4nano particle suspension, grain of rice shape NaNdF
4appearance structure as shown in Fig. 1 .1.
embodiment 2(solwution method synthesis grain of rice shape NaSmF under room temperature
4nano particle)
Get 1 mL volumetric molar concentration 1 molL
-1samarium trichloride solution in 100 mL beakers, add 30 mL deionized waters and mix, then in beaker, add 1mL volumetric molar concentration 1 molL
-1eDTA, magnetic agitation, after 30 minutes, adds 10 mL volumetric molar concentration 1 molL in the most backward above solution
-1fluorinse, after stirring, be transferred in the autoclave containing polytetrafluoroethylliner liner, set temperature 120 DEG C, constant temperature, after 24 hours, naturally cools to room temperature.Use supercentrifuge centrifuging, with deionized water cyclic washing 3 times, then with absolute ethanol washing once, be distributed in 5 mL absolute ethyl alcohols, grain of rice shape NaSmF can be obtained
4nano particle suspension, grain of rice shape NaSmF
4structure as are shown in figure 1.2.
embodiment 3(solwution method synthesis grain of rice shape NaEuF under room temperature
4nano particle)
Get 1 mL volumetric molar concentration 2 molL
-1europium chloride solution in 100 mL beakers, add 30 mL deionized waters and mix, then in beaker, add 1mL volumetric molar concentration 2 molL
-1eDTA, magnetic agitation, after 30 minutes, adds 10 mL volumetric molar concentration 3 molL in the most backward above solution
-1fluorinse, after stirring, be transferred in the autoclave containing polytetrafluoroethylliner liner, set temperature 140 DEG C, constant temperature is after 36 hours, naturally cool to room temperature, use supercentrifuge centrifuging, with deionized water cyclic washing 3 times, then with absolute ethanol washing once, be distributed in 5 mL absolute ethyl alcohols, grain of rice shape NaEuF can be obtained
4nano particle suspension.
embodiment 4(solwution method synthesis grain of rice shape NaTbF under room temperature
4nano particle)
Get 1 mL volumetric molar concentration 0.5 molL
-1terbium trichloride solution in 100 mL beakers, add 30 mL deionized waters and mix, then in beaker, add 1mL volumetric molar concentration 0.5 molL
-1eDTA, magnetic agitation, after 30 minutes, adds 10 mL volumetric molar concentration 0.5 molL in the most backward above solution
-1fluorinse, after stirring, be transferred in the autoclave containing polytetrafluoroethylliner liner, put into baking oven, set temperature 150 DEG C, constant temperature, after 48 hours, naturally cools to room temperature, uses supercentrifuge centrifuging, with deionized water cyclic washing 3 times, again with absolute ethanol washing once, be distributed in 5 mL absolute ethyl alcohols, grain of rice shape NaTbF can be obtained
4nano particle suspension.
embodiment 5(solwution method synthesis grain of rice shape NaHoF under room temperature
4nano particle)
Get 1 mL volumetric molar concentration 1 molL
-1tri-chlorination holmium solution in 100 mL beakers, add 30 mL deionized waters and mix, then add 1mL volumetric molar concentration 1molL in beaker
-1eDTA, magnetic agitation, after 30 minutes, adds 10 mL volumetric molar concentration 2 molL in the most backward above solution
-1fluorinse, after stirring, be transferred in the autoclave containing polytetrafluoroethylliner liner, put into baking oven, set temperature 160 DEG C, constant temperature, after 24 hours, naturally cools to room temperature., use supercentrifuge centrifuging, with deionized water cyclic washing 3 times, then with absolute ethanol washing once, be distributed in 5 mL absolute ethyl alcohols, grain of rice shape NaHoF can be obtained
4nano particle suspension.
embodiment 6(with embodiment 2 gained grain of rice shape NaSmF
4nanoparticle is as substrate template, and fixing magnetron sputtering power 50 W, changes sputtering time)
Example 2 gained NaSmF
4suspension drops on 2 cm × 2 cm monocrystalline silicon pieces, dry.Silicon chip is put into the vacuum chamber of magnetron sputtering apparatus, airtight, magnetron sputtering silver nano-grain.Arrange instrument parameter, open mechanical pump, run molecular pump, take out low vacuum, vacuum tightness reaches 10
-4pa, regulates heater current to be 5 A.Logical argon gas, makes sputtering chamber air pressure about 5 Pa.Open radio-frequency power supply, power 50 W of fixing magnetron sputtering, first pre-sputtering 5 s, opens baffle plate and timing, and sputtering time is 10-150 s, closes overhead gage.Instrument is cooled to room temperature, takes out silicon chip, can obtain the grain of rice shape fluoride/silver-colored composite nanostructure of different shell thickness and diameter.As shown in the photo that Fig. 2 .1-2.3 provides, fix other reaction conditions, under different sputtering time, the surface structure of products therefrom is obviously different, and during 10 s, a small amount of silver nano-grain is only assembled on fluoride surface.During 30 s, fluoride surface substantially cover by silver nano-grain.Continue to extend sputtering time, the diameter of grain of rice shape fluoride/Ag composite structure becomes large, and length increases, and surface is roughening.And during 150 s, the mutual adhesion of Nano silver grain, unclear boundaries between the grain of rice and the grain of rice, makes grain of rice length shorten a little.
embodiment 7(with embodiment 2 gained grain of rice shape NaSmF
4nanoparticle is as substrate template, and fixing magnetron sputtering time 30 s, changes sputtering power)
Example 2 gained NaSmF
4suspension drops on 2 cm × 2 cm monocrystalline silicon pieces, dry.Silicon chip is put into the vacuum chamber of magnetron sputtering apparatus, airtight, magnetron sputtering silver nano-grain.Setting instrument parameter, adjust sputtering power 30 W respectively to 150 W, pre-sputtering 5 s, opens baffle plate and timing, after sputtering 30 s, closes overhead gage.Instrument is cooled to room temperature, takes out silicon chip, can obtain the grain of rice shape fluoride/silver-colored composite nanostructure of different shell thickness and diameter.As shown in the photo that Fig. 3 .1-3.3 provides.Example illustrates, fixes other reaction conditions, also obtains the grain of rice shape fluoride/Ag composite structure of different surfaces structure under different sputtering power.Its forming process is similar to sputtering time, and namely during 30 W, a small amount of silver nano-grain is splashed to grain of rice shape fluoride surface.During 50 W, silver nano-grain continues to assemble formation skim silver and covers fluoride surface.Continue to increase sputtering power, the diameter of grain of rice shape fluoride/Ag composite structure becomes large, and length increases, and surface is roughening.During power 150 W, obtain fluoride/silver composite structure that diameter is larger, but mutual adhesion between the grain of rice, unclear boundaries, makes grain of rice length shorten.
Can be drawn by above embodiment 6,7: the power and the time that control magnetron sputtering, the effective control to its surface pattern, fine structure and size can be realized, thus realize the surface plasma body resonant vibration of product and the regulation and control of surface-enhanced Raman performance.
embodiment 8: Performance Detection is done to embodiment product
Example 2 gained NaSmF
4suspension drops on 2 cm × 2 cm monocrystalline silicon pieces, dry.Silicon chip is put into the vacuum chamber of magnetron sputtering apparatus, airtight, magnetron sputtering silver nano-grain.Arrange instrument parameter, power 50 W of fixing magnetron sputtering, first pre-sputtering 5 s, opens baffle plate and timing, sputters 120 s, closes overhead gage.Instrument is cooled to room temperature, takes out silicon chip, can obtain shaggy grain of rice shape fluoride/silver-colored composite nanostructure.
The fluoride obtained under this condition/silver-colored composite nanostructure is as surface-enhanced Raman spectrum active substrate, soak in the rhodamine 6G (R6G) of different low concentration respectively after 12 hours, take out dry, then its Raman signal is surveyed, obtain Surface enhanced raman spectroscopy figure, as shown in Figure 4, using grain of rice shape fluoride/silver-colored composite nanostructure as substrate, R6G is the Raman spectrogram of probe molecule, and the minimal detectable concentration recorded is 1 × 10
-17m, highest detection concentration 1 × 10
-11m, enhancer reaches 10
14doubly, reach Single Molecule Detection level, in spectrogram, the signal of R6G is detailed, and resolution is high.Grain of rice shape fluoride/silver-colored composite nanostructure that the present embodiment obtains is as SERS substrate, and signal is even, and favorable repeatability, detection sensitivity is high, can be used for the detection of ultratrace organic molecule and biomolecule.
Claims (4)
1. the preparation method of grain of rice shape fluoride/silver-colored composite nano materials, comprises the steps:
(1) by volumetric molar concentration 0.1-2 molL
-1eDTA solution, slowly join volumetric molar concentration 0.1-3 molL
-1rare-earth chloride solution in, the mol ratio of EDTA and rare earth-iron-boron is 1:1, stirring reaction 10-60 minute;
(2) in above-mentioned solution, volumetric molar concentration 0.1-3 molL is added
-1sodium fluoride or potassium fluoride solution, after stirring, be transferred in the autoclave containing polytetrafluoroethylliner liner, set temperature 60-180 DEG C, continue reaction after 1-72 hour, naturally cool to room temperature, use supercentrifuge centrifuging, wash respectively with water and absolute ethyl alcohol, obtain grain of rice shape fluoride nano material;
(3) grain of rice shape fluoride nano material is distributed in absolute ethyl alcohol and obtains suspension, get suspension and drop on monocrystalline silicon piece, dry;
(4) monocrystalline silicon piece is put into the vacuum chamber of magnetron sputtering apparatus, regulate magnetron sputtering power 10-200 watt, sputtering time 5-200 second, magnetron sputtering silver nano-grain, obtain grain of rice shape fluoride/silver-colored composite nano materials, this composite nano materials has the effect of surface reinforced Raman active substrate, and it is made up of the fluoride kernel of grain of rice shape and Silver nano-particle layer, and described silver nano-grain is gathered in the surface of grain of rice shape kernel.
2. the preparation method of grain of rice shape fluoride/silver-colored composite nano materials as claimed in claim 1, is characterized in that: in step (1) and step (2), the mol ratio of described sodium fluoride or potassium fluoride and rare earth-iron-boron is 1-20:1.
3. the preparation method of grain of rice shape fluoride/silver-colored composite nano materials as claimed in claim 1, it is characterized in that: in step (1), described rare earth-iron-boron is the chloride of neodymium, samarium, europium, terbium or holmium.
4. the preparation method of grain of rice shape fluoride/silver-colored composite nano materials as claimed in claim 1, is characterized in that: in step (2), and described washing first carries out using deionized water as cleansing solution and then using absolute ethyl alcohol as cleansing solution.
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| CN101475223A (en) * | 2009-01-16 | 2009-07-08 | 北京工业大学 | Preparation of nanostructured alpha type ferric oxide hollow submicrosphere |
| US7985539B2 (en) * | 2002-05-07 | 2011-07-26 | Northwestern University | Nanoparticle probes with raman spectroscopic fingerprints for analyte detection |
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| CN1745291A (en) * | 2003-02-18 | 2006-03-08 | 英特尔公司 | Metal coated nanocrystalline silicon as an active surface enhanced raman spectroscopy (SERS) substrate |
| CN101475223A (en) * | 2009-01-16 | 2009-07-08 | 北京工业大学 | Preparation of nanostructured alpha type ferric oxide hollow submicrosphere |
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