CN107177874B - A kind of superhigh-density ordered silver nanoparticle ball array and its application - Google Patents
A kind of superhigh-density ordered silver nanoparticle ball array and its application Download PDFInfo
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- CN107177874B CN107177874B CN201710188407.5A CN201710188407A CN107177874B CN 107177874 B CN107177874 B CN 107177874B CN 201710188407 A CN201710188407 A CN 201710188407A CN 107177874 B CN107177874 B CN 107177874B
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/12—Anodising more than once, e.g. in different baths
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- 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
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention discloses a kind of superhigh-density ordered silver nanoparticle ball arrays, are prepared with the following method: S1. prepares superhigh-density ordered aluminium nanometer hole AAO array mould plate sample；S2. in the silverskin of the surface hot evaporation 10nm thickness of the AAO array mould plate sample；S3. the sample after hot dip silverskin is annealed 3h in 150 DEG C of nitrogen atmospheres, obtains superhigh-density ordered silver nanoparticle ball array.The present invention is not necessarily to AAO template being transferred to other substrates, without removing extra metallic aluminium, therefore can large area prepare orderly Ag nanometer ball array, and preparation process is simple.Prepared superhigh-density ordered silver nanoparticle ball array can be used as active (SERS) base material of surface Raman enhancement, and for detecting phenolic comp ' ds pollution, detection sensitivity is high.Preparation process temperature is low simultaneously, and energy consumption is small, and application prospect is good.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, more particularly, to a kind of superhigh-density ordered silver nanoparticle ball
Array and its application.
Background technique
Raman scattering spectrum becomes a powerful molecule due to its specificity to molecule and chemical bond oscillations peak
Detection technique.Surface enhanced Raman scattering (SERS, Surface Enhanced Raman Scattering) is because it is with sensitive
Degree is high, quickly detects, can obtain the structural information that normal Raman spectrum is difficult to obtain, be widely used in study of surfaces,
Biological surface science, the fields such as food safety.SERS effect is primarily present in the gap between metal Nano structure, i.e. " hot spot "
(hot spot), due to metal surface plasma resonance effects, the electromagnetic field of " hot spot " nearby is greatly enhanced.Nearest
Research shows that " hot spot " has very big enhancing to SERS signal, treating detection substance has very high sensitivity, it might even be possible to realize
Single Molecule Detection.
Since noble metal nano structure is in photoelectricity, the fields such as sensor and catalytic applications have unique property, therefore quilt
Research extensively.In particular, being ordered in orderly cyclic array, their some performances will be increased substantially.For example, by under
Method on and, noble metal nano particles self assembly can form hot spot.The random distribution of hot spot normally results in SERS signal
Unevenly.Orderly periodical noble metal array (such as gold, silver, platinum) imparts substrate with good SERS uniformity.
It is highly dense in order to obtain with good reproducibility and highly sensitive SERS substrate, preparation small size (< 100nm)
It is crucial for spending orderly hot spot array.
Summary of the invention
The object of the present invention is to provide a kind of superhigh-density ordered silver nanoparticle ball arrays.
Another object of the present invention is to provide above-mentioned superhigh-density ordered silver nanoparticle balls as surface Raman enhancement activity
Base material, the application in detection phenolic comp ' ds pollution.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of superhigh-density ordered silver nanoparticle ball arrays, are prepared with the following method:
S1. superhigh-density ordered aluminium nanometer hole AAO array mould plate sample is prepared；
S2. in the silverskin of the surface hot evaporation 10nm thickness of the AAO array mould plate sample；
S3. the sample after hot dip silverskin is annealed 3h in 150 DEG C of nitrogen atmospheres, obtains superhigh-density ordered silver
Nanometer ball array.
Preferably, superhigh-density ordered aluminium nanometer hole AAO array mould plate sample is prepared using the method for secondary oxidation in S1；
It includes once oxidation that the method using secondary oxidation, which prepares superhigh-density ordered aluminium oxide nano hole AAO array mould plate sample,
And secondary oxidation,
The once oxidation is by aluminium flake sample in 0.3wt.%H2SO4, temperature is 0.6 DEG C, under the electrochemical conditions of 24V,
After oxidation for 24 hours, aluminium flake sample is then transferred to 1.8wt.% chromic acid and 6wt.%H3PO4, temperature be in 43 DEG C of mixed solution
Except oxide layer obtained；
The secondary oxidation is in 0.3wt.%H2SO4, temperature is 0.6 DEG C, under the electrochemical conditions of 24V, continues to aoxidize
180s to get arrive the AAO array mould plate sample.
Preferably, aluminium flake sample is before carrying out once oxidation, and anneal 4h under 400 DEG C of nitrogen atmospheres, then in electrification
It is polished under the conditions of；The aluminium flake sample purity is 99.999%.
Preferably, the hot evaporation chamber that thermal evaporation coating system is utilized in S2, in the surface heat of the AAO array mould plate sample
The Ag films of one layer of pre-set thickness are deposited；The intracavitary pressure of hot evaporation is evacuated to 6 × 10-4Pa to obtain vacuum degree, hot evaporation
Rate is 0.1/S, and the sample tray velocity of rotation where the AAO array mould plate sample is 20r/min.
Preferably, specifically comprise the following steps: for the AAO array mould plate sample to be transferred in quick anneal oven in S3,
Then first lead to nitrogen 5mins, guarantee that sample is annealed in nitrogen atmosphere, avoid sample from being oxidized, then start to warm up to 150
DEG C, 3h is kept the temperature, superhigh-density ordered silver nanoparticle ball array is obtained.
The present invention protects the superhigh-density ordered silver nanoparticle ball array as surface Raman enhancement active substrate simultaneously
Application of the material in detection phenolic comp ' ds pollution.
Present invention simultaneously provides a kind of methods for detecting phenolic comp ' ds pollution, using the superhigh-density ordered silver nanoparticle ball
Array as surface Raman enhancement active base material, then by above-mentioned surface Raman enhancement active base material be immersed in containing
It is detected in the solution of phenolic comp ' ds pollution；
Wherein, the concentration containing phenolic comp ' ds pollution is 10-2 ~10-8Mol/L, soaking time are 1 hour, will be inhaled after immersion
The base material of attached phenolic comp ' ds pollution, which is placed under Raman spectrometer laser, to be irradiated, and optical maser wavelength is 633 nm, and power selection is
0.1 mW。
The applicant provides in the patent application No. is 201610658664.6 a kind of prepares orderly silver nanoparticle ball battle array
The method of column uses orderly aluminium nano bowl OAB array to prepare template sample, and carries out under 500 DEG C of elevated temperature in vacuo
Anneal 1h, and compared with the present invention, the array of templates of applicant is AAO array, and anneals for the nitrogen at 150 DEG C, prepares
In condition, the present invention is more simple, and energy consumption is lower.
Meanwhile the present invention has carried out the comparison (as shown in Figure 9) of above two material property, finds provided by the invention super
The orderly silver nanoparticle ball array of high density is for detecting phenolic comp ' ds pollution, and sensitivity is higher, and application prospect is more preferable.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
Superhigh-density ordered silver nanoparticle ball array provided by the invention is not necessarily to AAO template being transferred to other substrates, also without
Need to remove extra metallic aluminium, thus can large area prepare orderly Ag nanometer ball array, prepared superhigh-density ordered silver
Nanometer ball array can be used as active (SERS) substrate of surface Raman enhancement for detecting phenolic comp ' ds pollution, detection phenolic comp ' ds pollution spirit
Sensitivity is high.Preparation process temperature is low simultaneously, and energy consumption is small, and application prospect is good.
Detailed description of the invention
Fig. 1 is the method based on superhigh-density ordered silver nanoparticle ball array detection phenolic comp ' ds pollution in the embodiment of the present invention 1
Flow diagram；
Fig. 2 is the SEM(Scanning Electron Microscope of application example AAO template of the present invention, scanning electron
Microscope) exterior view, amplification factor is 100,000 times；
Fig. 3 is that application example of the present invention passes through the superhigh-density ordered silver nanoparticle ball array obtained after 150 DEG C of vacuum annealings
The SEM exterior view of array structure, amplification factor are 100,000 times；
Fig. 4 is the low power TEM(Transmission of the superhigh-density ordered silver nanoparticle ball array substrate of application example of the present invention
Electron microscope, transmission electron microscope)；
Fig. 5 is the size statistic figure of the superhigh-density ordered silver nanoparticle ball array of present invention application, has counted 225 in total
Ball.
Fig. 6 is the pictorial diagram of the superhigh-density ordered silver nanoparticle ball array of Centimeter Level of the present invention.
Fig. 7 is that detectable concentration of the present invention is 10-8 The Raman curve graph of M parathion-methyl concentration, methyl is to sulphur as seen from the figure
The Characteristic Raman peak position of phosphorus is in 856 cm−1(P-O stretching vibration) 1110 cm-1(C-N), 1345 cm−1(C-H bending vibration),
With 1591 cm−1At (phenyl stretching vibration).
Fig. 8 is parathion-methyl in 1345 cm−1Place, the corresponding relationship of raman scattering intensity and concentration show pesticide methyl pair
Sulphur phosphorus has the linear response between concentration and signal in superhigh-density ordered silver nanoparticle ball array substrate.
Fig. 9 is to disclose in superhigh-density ordered silver nanoparticle ball array prepared by the present invention and 201610658664 .6 of patent
Silver nanoparticle ball array performance comparison figure.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1:
The orderly metal nanoparticle of large area, high density can be formed directly in AAO template using wetness technique is moved back.
Size, the density of nanoparticle are determined in the nanostructure of the thickness template of metallic film, and this simple method is inexpensive, big
Area prepares superhigh-density ordered metal nano ball array and provides possibility.Currently, using PS bead as template, in conjunction with
Dewetting(moves back wetting) technology, be successfully realized the preparation of orderly metal (gold, silver, copper, cobalt, nickel) nanometer ball array.
But preparing orderly noble metal nano array of structures of the gap within 100 nanometers is still a challenge.In order to
Realize the preparation of gap orderly noble metal nano array of structures within 100nm.Y. Lei et al. is real using ultra-thin AAO template
The preparation of orderly silver nano-grain array is showed, spacing is adjustable, and minimum spacing can control in 10nm or less.However, Y.
AAO template must be transferred to other substrates, therefore large area preparation difficult to realize by Lei.
It is based on moving back wetness technique to solve the above problems, the embodiment of the present invention provides one kind, the hot evaporation directly on AAO
Then Ag anneals without shifting AAO template, prepares a kind of superhigh-density ordered silver nanoparticle ball array, this method prepares superelevation
The orderly silver nanoparticle ball array of density has ultra high density, and the degree of order is high, and size distribution is small, and stepping back temperature only needs 150 degree, reduces
Energy consumption and cost, while can realize the advantages that prepared by large area.
As shown in Figure 1, the above embodiment of the present invention is described in detail below in conjunction with application example:
The preparation of AAO template: the method by aluminium flake sample secondary oxidation prepares AAO template sample, the aluminium
Piece sample purity is 99.999%, the method for the secondary oxidation further include: once oxidation is by aluminium flake sample in 0.3wt.%
H2SO4, temperature is 0.6 DEG C, after aoxidizing for 24 hours under the electrochemical conditions of 24V, then by aluminium flake sample be transferred to 1.8wt.% chromic acid and
6wt.%H3PO4, temperature be to remove above-mentioned oxide layer obtained in 43 DEG C of mixed solution；Secondary oxidation be with once oxidation
Identical condition, i.e. 0.3wt.%H2SO4, temperature is 0.6 DEG C, under 24V, continues to aoxidize 180s to get arriving as shown in Fig. 2, for this
The SEM exterior view of invention application example AAO template, amplification factor are 100,000 times.
Post-processing: according to the AAO template that ultrasonic cleaning prepares the step of acetone, ethyl alcohol, deionized water, ultrasonic power is
180W, the ultrasonic cleaning time is respectively 10min, it is ensured that AAO template surface is without other impurity.
Hot evaporation metallic film: the sample cleaned up is put into hot evaporation equipment, and AAO template is softer, is transferred to heat
Must be careful when vapo(u)rization system, once deformation occurs causes sample uneven for sample, it will have a direct impact on the uniformity of film.When heat is steamed
Plating chamber vacuum is evacuated to 6 × 10-4After Pa, slow high current silver into boat is melted into liquid.Electric current is adjusted at this time to speed is deposited
Rate is stablized in 0.1/S, opens sample baffle after then adjusting sample tray revolving speed 20r/min.Hot evaporation silver film thickness is
10nm, in general, slower rate, the uniformity of film is preferable, and the quality of the uniformity of film will have a direct impact on the size of nanosphere
Uniformity.
Superhigh-density ordered silver nanoparticle ball array substrate preparation: since the Ag of Nano grade is easy to oxidize, so having plated Ag
Sample should be transferred in RTP immediately after film, then lead to nitrogen protection, sample is prevented to be oxidized, after 5mins, by cavity plus
Then heat keeps the temperature 3h to 150 DEG C.During this, according to Oswald, your moral cures mechanism, and the Ag film deposited before is actually
It is made of the inhomogenous nanoscale little particle of size, at high temperature, nanoscale bulky grain starts to swallow little particle, due to AAO
The limitation of template, bulky grain swallow short grained quantity and are limited, and the little particle that bulky grain has swallowed periphery later can not be again
Continue to grow up, has a very big ball in final each hole to get superhigh-density ordered silver nanoparticle ball array structure is arrived.Such as
Shown in Fig. 3, pass through the SEM exterior view of the array structure obtained after annealing under 150 DEG C of nitrogen atmospheres for application example of the present invention,
Amplification factor is 100,000 times.Fig. 4 is the low power TEM of the superhigh-density ordered silver nanoparticle ball array substrate of application example of the present invention.Such as
Shown in Fig. 5, for the size statistic figure of the superhigh-density ordered silver nanoparticle ball of present invention application, 225 balls have been counted in total.Fig. 6 is
The pictorial diagram of the superhigh-density ordered silver nanoparticle ball array of Centimeter Level of the present invention.
SERS substrate performance characterization: by sample bubble 1h in by the solution to parathion-methyl, naturally dry is then taken out.
Fig. 7 and Fig. 8 is detection various concentration toluene-ω-thiol (10 in application example SERS substrate of the present invention-2M ~10-8M Raman)
Curve graph, Cong Tuzhong is it can be found that our detectable limit is 10-7M has very high sensitivity.In addition we compared
The orderly silver nanoparticle ball array that sequence Ag nanosphere is prepared in the OAB template disclosed in AAO template and 201610658664 .6
Raman performance, as shown in figure 9, Raman sensitivity of the discovery Ag nanosphere on AAO is higher.
Above-mentioned technical proposal makes the orderly silver nanoparticle ball array of preparation have high density, without being transferred to other bases
Bottom can large area preparation, preparation process is simple, and reproducible, preparation cost is low, and preparation process temperature is low, and energy consumption is small.It is made
Standby superhigh-density ordered silver nanoparticle ball array can be used as active (SERS) substrate of surface Raman enhancement for detecting phenols pollution
Object detects phenolic comp ' ds pollution high sensitivity.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of superhigh-density ordered silver nanoparticle ball array, which is characterized in that be prepared with the following method:
S1. superhigh-density ordered aluminium nanometer hole AAO array mould plate sample is prepared；
S2. in the silverskin of the surface hot evaporation 10nm thickness of the AAO array mould plate sample；
S3. the sample after hot dip silverskin is annealed 3h in 150 DEG C of nitrogen atmospheres, obtains superhigh-density ordered silver nanoparticle
Ball array.
2. superhigh-density ordered silver nanoparticle ball array according to claim 1, which is characterized in that utilize secondary oxidation in S1
Method prepare superhigh-density ordered aluminium nanometer hole AAO array mould plate sample；The method using secondary oxidation prepares superelevation
Density ordered aluminum oxide nanometer hole AAO array mould plate sample includes once oxidation and secondary oxidation,
The once oxidation is by aluminium flake sample in 0.3wt.%H2SO4, temperature is 0.6 DEG C, under the electrochemical conditions of 24V, oxidation
After for 24 hours, aluminium flake sample is then transferred to 1.8wt.% chromic acid and 6wt.%H3PO4, temperature be to be removed in 43 DEG C of mixed solution
Oxide layer obtained；
The secondary oxidation is in 0.3wt.%H2SO4, temperature is 0.6 DEG C, under the electrochemical conditions of 24V, continues to aoxidize 180s,
Obtain the AAO array mould plate sample.
3. superhigh-density ordered silver nanoparticle ball array according to claim 1, which is characterized in that aluminium flake sample is carrying out once
Before oxidation, anneal 4h under 400 DEG C of nitrogen atmospheres, then polishes under electrochemical conditions；The aluminium flake sample purity is
99.999%.
4. superhigh-density ordered silver nanoparticle ball array according to claim 1, which is characterized in that utilize thermal evaporation plated film in S2
The hot evaporation chamber of system, in the Ag films of one layer of pre-set thickness of surface hot evaporation of the AAO array mould plate sample；The heat is steamed
It plates intracavitary pressure and is evacuated to 6 × 10-4To obtain vacuum degree, the rate of hot evaporation is PaAAO array mould plate sample institute
Sample tray velocity of rotation be 20r/min.
5. superhigh-density ordered silver nanoparticle ball array according to claim 1, which is characterized in that specifically include following step in S3
It is rapid: the AAO array mould plate sample being transferred in quick anneal oven, nitrogen 5mins is then first led to, guarantees sample in nitrogen atmosphere
Middle annealing is enclosed, sample is avoided to be oxidized, is then started to warm up to 150 DEG C, 3h is kept the temperature, obtains superhigh-density ordered silver nanoparticle spherical array
Column.
6. a kind of any superhigh-density ordered silver nanoparticle ball array of claim 1 to 5 is as surface Raman enhancement activity
Application of the base material in detection phenolic comp ' ds pollution.
7. a kind of method for detecting phenolic comp ' ds pollution, which is characterized in that using any ultra high density of claim 1 to 5
Orderly silver nanoparticle ball array is as surface Raman enhancement active base material, then by above-mentioned surface Raman enhancement active group ground
Material, which is immersed in the solution containing phenolic comp ' ds pollution, to be detected；
Wherein, the concentration containing phenolic comp ' ds pollution is 10-2~10-8Mol/L, soaking time are 1 hour, will adsorb phenol after immersion
The base material of pollutant, which is placed under Raman spectrometer laser, to be irradiated, optical maser wavelength 633nm, power selection 0.1mW.
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| CN108802006A (en) * | 2018-05-28 | 2018-11-13 | 宁德师范学院 | A kind of computational methods of preparation and its surface enhanced factor with SERS substrates |
| CN110205587A (en) * | 2019-07-09 | 2019-09-06 | 河南师范大学 | A kind of method of template annealing preparation large area regular array gold nano grain array |
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| CN112981443B (en) * | 2021-02-22 | 2022-04-19 | 吉林大学 | Foam nickel with nano silver film deposited on surface, preparation method and application thereof |
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