CN110106488A - A kind of preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array - Google Patents
A kind of preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array, compact arranged polystyrene colloid crystal is prepared in a manner of self assembly first, using polystyrene colloid crystal as template, pass through deposition thereof, removing template is removed in annealing, the layer gold of deposition melts in situ, and mechanism is cured by your moral of Oswald and forms spherical gold nano grain, obtain the gold nano grain oldered array of not close arrangement, then gold nano grain oldered array is placed in the silver nitrate solution of 0.01~1.5mol/L and the mixed liquor of hydroquinone buffer solution and keeps preset time, obtain flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array.Preparation method of the invention is simple, quick, environmentally friendly, economical, can grow flower-shaped hierarchical structure Nano silver piece in gold nano grain array surface without excessive complicated organic solvent and expensive equipment, laminated structure homoepitaxial is on gold nano grain surface.
Description
Technical field
The invention belongs to technical field of nano material more particularly to a kind of orderly battle arrays of flower-shaped hierarchical structure Au@Ag nanometer sheet
The preparation method of column.
Background technique
In recent years, about there are many preparation methods of array, including electron beam lithography, ion beam etching technology, light
Lithography, self-assembling technique, template etc..Electronics is etched, for ion beam etching technology and photoetching technique, what is used is set
Standby all more expensive, preparation method is more complicated, is restricted it in terms of practical application, so in the preparation of numerous arrays
In method, self assembly is relatively mature methods and techniques, and the field that research is more.Self assembly refers to nano unit
By the interaction of non-covalent bond, the process of spontaneous organization or aggregation one metastable ordered structure of formation, certain
The common method of array is constructed in range.It is wherein to be designed, be aided with by the structure of different levels based on nano unit
Necessary chemical modification or process for treating surface are utilized and are regulated and controled to the mode of the interaction between nano unit, from
And construct various dimensions, multi-level complicated nanostructure.But current preparation method complex steps, need it is more organic molten
Liquid and expensive equipment.
Summary of the invention
The present invention provides a kind of preparation methods of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array, first with from group
Dress mode prepares compact arranged polystyrene colloid crystal, heavy by magnetron sputtering using polystyrene colloid crystal as template
Removing template is removed in product layer gold, annealing, and the layer gold of deposition melts in situ, and cures mechanism by your moral of Oswald and form spherical gold nano
Particle obtains the gold nano grain of the uniform not close arrangement of large area (square centimeter grade), unit size of the non-solid matter of six sides
Then gold nano grain oldered array is placed into the growth solution of Nano silver piece by oldered array, can be in gold nano grain
The flower-shaped hierarchical structure Nano silver piece of surface homoepitaxial.
To solve the above problems, the technical solution of the present invention is as follows:
A kind of preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array, comprising the following steps:
A1: polystyrene colloid crystal is prepared in the method for air liquid interface self assembly；
A2: using the polystyrene colloid crystal as template, through magnetron sputtering deposition thereof-annealing, remove polystyrene
Colloidal crystal template obtains gold nano grain oldered array；
A3: the gold nano grain oldered array is placed in the growth solution of Nano silver piece, keeps 5~30min, is obtained
The Au@Ag nanometer sheet oldered array of flower-shaped hierarchical structure；
Wherein, the growth solution of the Nano silver piece is the mixed liquor of hydroquinone buffer solution and silver nitrate solution, institute
The concentration for stating silver nitrate solution is 0.01~1.5mol/L, the PH=3.6 of the hydroquinone buffer solution.Only hydroquinone
When the PH=3.6 of buffer solution, Nano silver piece could be grown on the surface of gold nano grain, obtain the Au@of flower-shaped hierarchical structure
Ag nanometer sheet oldered array；
Preferably, the hydroquinone buffer solution be 0.1/L mol hydroquinone, 0.10mol/L sodium citrate,
The mixed liquor of 0.10mol/L citric acid adjusts PH=3.6 through acetic acid.
Specifically, the step A1 specifically:
A001: being cleaned by ultrasonic 60min for sheet glass, be then placed in baking oven and be dried, finally clear in UV ozone
Hydrophilic treated is carried out in washing machine；
A002: polystyrene microsphere suspension is mixed with isometric ethyl alcohol, ultrasonic vibration obtains polystyrene microsphere
Alcohol mixeding liquid；
A003: deionized water is injected on the step A001 treated sheet glass, one layer of liquid film is formed, then passes through
The method of air liquid interface self assembly, by polystyrene microsphere, close-packed arrays form polyphenyl after moisture evaporation on the glass sheet
Ethylene colloidal crystal.
Preferably, the annealing is specially that the sample of magnetron sputtering deposition thereof is placed in the pipe with reducing atmosphere
In formula furnace, holding temperature is 1000 DEG C, soaking time 2h, is heated up with the heating rate of 5 DEG C/min.
Preferably, the reducing atmosphere is the mixed atmosphere of nitrogen and hydrogen, wherein the volume content of the hydrogen is
2%.
The present invention due to using the technology described above, makes it have the following advantages that and actively imitate compared with prior art
Fruit:
(1) present invention can prepare clean surface (no surface-active using single layer polystyrene colloid crystal as template
Agent, reducing agent) non-solid matter gold nano grain oldered array, characterized by field emission scanning electron microscope, it can be seen that gained
The gold nano grain array sizes arrived it is single dispersion and pattern it is uniform；
(2) preparation method of the invention is simple, quick, economical, without excessive complicated organic solvent and expensive equipment
Flower-shaped hierarchical structure Nano silver piece can be grown in gold nano grain array surface, laminated structure homoepitaxial is in gold nano
Grain surface；The flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array of 2D can be orderly, non-close in large area (square centimeter) range
Row is controllable, quickly prepares；The process of the preparation method is environmentally protective, any poisonous and hazardous substance is not used, in addition the system
Preparation Method solves the problems, such as that the flower-shaped hierarchical structure of conventional method preparation needs expensive electrodeposition apparatus, preparation process
Simply, the advantages such as low in cost, non-environmental-pollution.
(3) the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that preparation method through the invention obtains has big
Oldered array in areal extent, and there is coarse flower-shaped hierarchical structure, material is provided for high constructing for SERS substrate of sensitivity
Basis.
Detailed description of the invention
Fig. 1 is preparation method flow chart of the invention；
Fig. 2 is that template prepares 2D gold nano grain oldered array schematic diagram；
Fig. 3 is the scanning electron microscope (SEM) photograph of polystyrene colloid crystal；
Fig. 4 is the scanning electron microscope (SEM) photograph of gold nano grain oldered array；
Fig. 5 is to keep the flower-shaped hierarchical structure Au@Ag nanometer sheet of 5min to have in Nano silver piece growth solution in embodiment 1
The scanning electron microscope (SEM) photograph one of sequence array；
Fig. 6 is to keep the flower-shaped hierarchical structure Au@Ag nanometer sheet of 5min to have in Nano silver piece growth solution in embodiment 1
The scanning electron microscope (SEM) photograph two of sequence array；
Fig. 7 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 10min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph one of oldered array；
Fig. 8 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 10min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph two of oldered array；
Fig. 9 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 15min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph one of oldered array；
Figure 10 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 15min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph two of oldered array；
Figure 11 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 20min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph one of oldered array；
Figure 12 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 20min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph two of oldered array；
Figure 13 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 25min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph one of oldered array；
Figure 14 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 25min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph two of oldered array；
Figure 15 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 30min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph one of oldered array；
Figure 16 is the flower-shaped hierarchical structure Au@Ag nanometer sheet for keeping 30min in embodiment 1 in Nano silver piece growth solution
The scanning electron microscope (SEM) photograph two of oldered array；
Figure 17 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 0.01mol/L
The scanning electron microscope (SEM) photograph one of column；
Figure 18 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 0.01mol/L
The scanning electron microscope (SEM) photograph two of column；
Figure 19 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 0.05mol/L
The scanning electron microscope (SEM) photograph one of column；
Figure 20 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 0.05mol/L
The scanning electron microscope (SEM) photograph two of column；
Figure 21 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 0.10mol/L
The scanning electron microscope (SEM) photograph one of column；
Figure 22 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 0.10mol/L
The scanning electron microscope (SEM) photograph two of column；
Figure 23 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 0.15mol/L
The scanning electron microscope (SEM) photograph one of column；
Figure 24 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 0.15mol/L
The scanning electron microscope (SEM) photograph two of column；
Figure 25 is the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that the concentration of silver nitrate in embodiment 2 is 1mol/L
Scanning electron microscope (SEM) photograph one；
Figure 26 is the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that the concentration of silver nitrate in embodiment 2 is 1mol/L
Scanning electron microscope (SEM) photograph two；
Figure 27 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 1.5mol/L
The scanning electron microscope (SEM) photograph one of column；
Figure 28 is the orderly battle array of flower-shaped hierarchical structure Au@Ag nanometer sheet that the concentration of silver nitrate in embodiment 2 is 1.5mol/L
The scanning electron microscope (SEM) photograph two of column.
Specific embodiment
It is orderly to a kind of flower-shaped hierarchical structure Au@Ag nanometer sheet proposed by the present invention below in conjunction with the drawings and specific embodiments
The preparation method of array is described in further detail.According to following explanation and claims, advantages and features of the invention will
It becomes apparent from.
Referring to Fig. 1, Fig. 2, a kind of preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array, including following step
It is rapid:
A1: polystyrene colloid crystal is prepared in the method for air liquid interface self assembly；
Specifically, the step A1 specifically:
A001: being cleaned by ultrasonic 60min for sheet glass, be then placed in baking oven and be dried, finally clear in UV ozone
Hydrophilic treated is carried out in washing machine；
A002: polystyrene microsphere suspension is mixed with isometric ethyl alcohol, ultrasonic vibration obtains polystyrene microsphere
Alcohol mixeding liquid；
A003: deionized water is injected on the step A001 treated sheet glass, one layer of liquid film is formed, then passes through
The method of air liquid interface self assembly, by polystyrene microsphere, close-packed arrays form polyphenyl after moisture evaporation on the glass sheet
Ethylene colloidal crystal；
A2: using the polystyrene colloid crystal as template, through magnetron sputtering deposition thereof-annealing, remove polystyrene
Colloidal crystal template obtains gold nano grain oldered array；
Preferably, the annealing is specially that the sample of magnetron sputtering deposition thereof is placed in the pipe with reducing atmosphere
In formula furnace, holding temperature is 1000 DEG C, soaking time 2h, is heated up with the heating rate of 5 DEG C/min, the golden film in annealing process
It shrinks, fusing, solidification in situ, finally obtains orderly gold nano grain oldered array；
Further, the reducing atmosphere is the mixed atmosphere of nitrogen and hydrogen, wherein the volume content of the hydrogen
It is 2%；
A3: the gold nano grain oldered array is placed in the growth solution of Nano silver piece, in the growth of Nano silver piece
The different time is kept in solution, can get the Au@Ag nanometer sheet oldered array of different flower-shaped hierarchical structures；The Nano silver piece
Growth solution be hydroquinone buffer solution and silver nitrate solution mixed liquor, wherein the concentration of the silver nitrate solution is
The silver nitrate solution of various concentration is arranged in 0.01~1.5mol/L, the PH=3.6 of hydroquinone buffer solution, can get difference
The Au@Ag nanometer sheet oldered array of flower-shaped hierarchical structure；Hydroquinone restores silver nitrate as reducing agent, while hydroquinone is made
For surfactant, the direction of growth of silver nano-grain is induced, gold nanosphere provides position for the deposition of silver nano-grain, simultaneously
It is catalyzed entire reduction reaction, the Nano silver piece of flower-shaped classification is finally grown on gold nano grain surface, obtains the flower-shaped of large area
Hierarchical structure Au@Ag nanometer sheet oldered array；
Preferably, the hydroquinone buffer solution be 0.1mol/L hydroquinone, 0.10mol/L sodium citrate,
The mixed liquor of 0.10mol/L citric acid adjusts PH=3.6 through acetic acid.
The present invention is using single layer polystyrene colloid crystal as template, and can preparing clean surface, (surfactant-free is gone back
Former agent) non-solid matter gold nano grain oldered array, characterized by field emission scanning electron microscope, it can be seen that obtained gold
Nano-grain array having a size of it is single dispersion and pattern it is uniform；
Preparation method of the invention is simple, quick, economical, without excessive complicated organic solvent and expensive equipment
Flower-shaped hierarchical structure Nano silver piece is grown in gold nano grain array surface, laminated structure homoepitaxial is in gold nano grain table
Face；The flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array of 2D can orderly, non-solid matter can in large area (square centimeter) range
Control, quickly preparation；The process of the preparation method is environmentally protective, any poisonous and hazardous substance is not used, in addition the preparation side
Method solves the problems, such as that the flower-shaped hierarchical structure of conventional method preparation needs expensive electrodeposition apparatus, preparation process letter
The advantages such as single, low in cost, non-environmental-pollution.
The flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that preparation method through the invention obtains has in big face
Oldered array in product range, and there is coarse hierarchical structure, material foundation is provided for high constructing for SERS substrate of sensitivity.
Embodiment 1
(1) 2D polystyrene colloid crystal template is prepared by air liquid interface self-assembling method, the specific steps are as follows: first
First, sheet glass is sequentially placed into acetone, ethyl alcohol and deionized water and is cleaned by ultrasonic 60 minutes, then the sheet glass after cleaning is put into
It is dried in baking oven, after sheet glass is dried completely, is transferred in UV ozone cleaning machine and carries out hydrophilic treated (irradiation
30 minutes)；Take 1 milliliter of polystyrene microsphere suspension (partial size of polystyrene microsphere is 500nm) and isometric ethyl alcohol
Mixing, sonic oscillation 15 minutes, obtains uniform polystyrene microsphere alcohol mixeding liquid；Then deionization is injected on the glass sheet
Water forms one layer of liquid film, and polystyrene microsphere alcohol mixeding liquid is then added dropwise dropwise, is added 100 microlitres to sheet glass, to water
After dividing evaporation, polystyrene microsphere colloidal crystal is formed.
(2) polystyrene microsphere colloidal crystal is transferred to silica on piece by the water surface, to its moisture evaporating completely
It is complete, recycle magnetron sputtering to deposit gold nano layer, specific deposition method is as follows, and adjusting electric current is 20mA, and vacuum degree is
100Pa, sedimentation time are 8 minutes；The sample that gold will finally be deposited, is placed in tube furnace, leads to upper protective atmosphere (nitrogen/hydrogen
Gas, hydrogen volume content: 2%) it is, with 5 DEG C/min heating, be raised to 1000 DEG C, heat preservation 2 hour after, cooling, in this process,
Golden film shrinks, melts, original position solidifies, and finally obtains the gold nano grain oldered array for the not close arrangement that partial size is 200nm.
(3) the hydroquinone buffer solution of PH=3.6 is prepared first, contains 0.10mol/L sodium citrate in buffer solution,
0.10mol/L citric acid and 0.10mol/L hydroquinone, pass through the pH of vinegar acid-conditioning solution；The growth-promoting media of Ag nanometer sheet is:
What the buffer solution and 0.30 milliliter of 1.0mol/L silver nitrate solution of 1.70 milliliters of hydroquinones mixed；In dark room conditions
Under, the gold nano grain oldered array of not close arrangement is placed into the nanometer sheet growth-promoting media of silver and is kept for different time (5,
10,15,20,25,30 minutes)；It is dried after the sample finally obtained is washed with deionized, under condition of nitrogen gas to get difference is arrived
The flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array of the 2D of shape.
Using the pattern of field emission microscope observation polystyrene colloid crystal and gold nano grain oldered array, ginseng
See that Fig. 3 is the scanning electron microscope (SEM) photograph of prepared polystyrene colloid crystal, partial size is the polyphenyl second of 500nm as we can see from the figure
Alkene bead close-packed arrays, and be single layer structure, Fig. 4 is the electron microscope of gold nano grain oldered array, it is seen from figure 4 that gold nano
The particle oldered array oldered array uniform for the non-solid matter of six sides of large area (square centimeter grade), unit size, gold nano
The partial size of grain is 200nm.
The flower-shaped hierarchical structure Au Ag nanometer sheet of 2D for observing the different retention times using field emission microscope is orderly
The pattern of array, Fig. 5, Fig. 6 be kept in Nano silver piece growth solution 5 minutes Au@Ag nanometer sheet oldered array scanning
Electron microscope, Fig. 5 are low power figure, and Fig. 6 is high power figure, and Cong Tuzhong sees that Nano silver piece is grown in the surface of gold nano grain；
Fig. 7, Fig. 8 be kept in Nano silver piece growth solution 10 minutes Au@Ag nanometer sheet oldered array scanning electricity
Mirror figure, Fig. 7 are low power figure, and Fig. 8 is high power figure, and Cong Tuzhong sees, the size compared to Fig. 5, Fig. 6 Nano silver piece increases, and Au Ag receives
Rice piece size is about 250nm；
Fig. 9, Figure 10 be kept in Nano silver piece growth solution 15 minutes Au@Ag nanometer sheet oldered array scanning electricity
Mirror figure, Fig. 9 are low power figure, and Figure 10 is high power figure, and with the increase of retention time, the size of Nano silver piece also increases, and Au@Ag receives
Rice piece size is about 350nm, and the thickness of Ag nanometer sheet is about 10nm；
Figure 11, Figure 12 be kept in Nano silver piece growth solution 20 minutes Au@Ag nanometer sheet oldered array scanning
Electron microscope, Figure 11 are low power figure, and Figure 12 is high power figure, and Au@Ag nanometer sheet size is about 500nm as we can see from the figure, growth
Density is higher than Fig. 8, Fig. 9, and the thickness of Ag nanometer sheet is about 20nm；
Figure 13, Figure 14 be kept in Nano silver piece growth solution 25 minutes Au@Ag nanometer sheet oldered array scanning
Electron microscope, Figure 13 are low power figure, and Figure 14 is high power figure, and Au@Ag nanometer sheet size is about 500nm, and the thickness of Ag nanometer sheet is about
30nm；
Figure 15, Figure 16 be kept in Nano silver piece growth solution 30 minutes Au@Ag nanometer sheet oldered array scanning
Electron microscope, Figure 15 are low power figure, and Figure 16 is high power figure, and Au@Ag nanometer sheet size is about 450nm, and the thickness of Ag nanometer sheet is about
50nm。
Comparison keeps different time in Nano silver piece growth solution, and obtained flower-shaped hierarchical structure Au@Ag nanometer sheet has
The structure of sequence array, when discovery time is shorter, Nano silver piece be not it is particularly evident, density is relatively low, as time increases, arrives
In the reaction time range of 20~30min, Au@Ag nanometer sheet can be obviously observed in Hexagonal array, the order of array obtains
Completely to retain, and the Ag nanometer sheet of these sharp edges is grown in the form of inserted sheet on Au nano particle.Using high magnification numbe into
The observation of one step finds (Figure 12, Figure 14, Figure 16), carries some small Ag nano particles in Ag nanometer sheet, these small Ag nano particles
Growth is launched outward along Ag nanometer sheet.The coarse hierarchical structure of this surface abnormalities mentions for high constructing for SERS substrate of sensitivity
Material foundation is supplied.Flower-shaped hierarchical structure Au@Ag nanometer sheet two-dimensional ordered array has big specific surface area, good coarse
Degree, improves the sensitivity of its SERS substrate.
Embodiment 2
In addition to adjusting silver nitrate concentration (0.01,0.05,0.1,0.15,1,1.5mol/ in Nano silver piece growth solution
L), gold nano grain oldered array is placed in Nano silver piece growth solution and is kept for 20 minutes, in step all with embodiment 1 one
Sample.
Using the pattern of the different flower-shaped hierarchical structure Au@Ag nanometer sheet oldered arrays of field emission microscope observation, figure
17, Figure 18 is the scanning electron microscope for the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that the concentration of silver nitrate is 0.01mol/L
Figure, Figure 17 are low power figure, and Figure 18 is high power figure, and Au Ag nanometers of leaf length are about 210nm as seen from the figure；
Figure 19, Figure 20 are the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that the concentration of silver nitrate is 0.05mol/L
Scanning electron microscope (SEM) photograph, Figure 19 are low power figure, and Figure 20 is high power figure, and Au Ag nanometers of leaf length are about 230nm as seen from the figure；
Figure 21, Figure 22 are the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that the concentration of silver nitrate is 0.1mol/L
Scanning electron microscope (SEM) photograph, Figure 21 are low power figure, and Figure 22 is high power figure, and Au Ag nanometers of leaf length are about 250nm as seen from the figure；
Figure 23, Figure 24 are the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that the concentration of silver nitrate is 0.15mol/L
Scanning electron microscope (SEM) photograph, Figure 23 are low power figure, and Figure 24 is high power figure, and Au Ag nanometers of leaf length are about 300nm as seen from the figure；
Figure 25, Figure 26 are sweeping for the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that the concentration of silver nitrate is 1mol/L
Electron microscope is retouched, Figure 25 is low power figure, and Figure 26 is high power figure, and Au Ag nanometers of leaf length are about 500nm as seen from the figure；
Figure 27, Figure 28 are the flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array that the concentration of silver nitrate is 1.5mol/L
Scanning electron microscope (SEM) photograph, Figure 27 are low power figure, and Figure 28 is high power figure, and Au Ag nanometers of leaf length are about 450nm as seen from the figure.
Compare the silver nitrate solution of various concentration, the flower-shaped hierarchical structure Au Ag nanometer sheet of Ag nanometers of chip architectures of obtained Au
The structure of oldered array, when discovery concentration is lower, Nano silver piece be not it is particularly evident, density is relatively low, with the increase of concentration,
Into the concentration range of 1~1.5mol/L, Au@Ag nanometer sheet can be obviously observed in Hexagonal array, the order of array obtains
Completely to retain, and the Ag nanometer sheet of these sharp edges is grown in the form of inserted sheet on Au nano particle.Using high magnification numbe into
The observation of one step finds (Figure 26, Figure 28), carries some small Ag nano particles in Ag nanometer sheet, these small Ag nano particles are along Ag
Nanometer sheet launches outward growth.The coarse hierarchical structure of this surface abnormalities provides material for high constructing for SERS substrate of sensitivity
Material basis.Flower-shaped hierarchical structure Au@Ag nanometer sheet two-dimensional ordered array has big specific surface area, good roughness, improves
The sensitivity of its SERS substrate.
Embodiments of the present invention are explained in detail above in conjunction with attached drawing, but the present invention is not limited to above-mentioned implementations
Mode.Even if to the present invention, various changes can be made, if these variations belong to the model of the claims in the present invention and its equivalent technologies
Within enclosing, then still fall within the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array, which comprises the following steps:
A1: polystyrene colloid crystal is prepared in the method for air liquid interface self assembly；
A2: using the polystyrene colloid crystal as template, through magnetron sputtering deposition thereof-annealing, remove polystyrene colloid
Crystal template obtains gold nano grain oldered array；
A3: the gold nano grain oldered array is placed in the growth solution of Nano silver piece, keeps 5~30min, is obtained flower-shaped
The Au@Ag nanometer sheet oldered array of hierarchical structure；
Wherein, the growth solution of the Nano silver piece is the mixed liquor of hydroquinone buffer solution and silver nitrate solution, the nitre
The concentration of sour silver solution is 0.01~1.5mol/L, the PH=3.6 of the hydroquinone buffer solution.
2. the preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array according to claim 1, feature exist
In, the hydroquinone buffer solution be 0.1mol/L hydroquinone, 0.1mol/L sodium citrate, 0.1mol/L citric acid it is mixed
Liquid is closed, adjusts PH=3.6 through acetic acid.
3. the preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array according to claim 1, feature exist
In the step A1 specifically:
A001: being cleaned by ultrasonic 60min for sheet glass, be then placed in baking oven and be dried, finally in UV ozone cleaning machine
Middle carry out hydrophilic treated；
A002: polystyrene microsphere suspension is mixed with isometric ethyl alcohol, ultrasonic vibration obtains polystyrene microsphere ethyl alcohol
Mixed liquor；
A003: injecting deionized water on the step A001 treated sheet glass, form one layer of liquid film, then by gas/
The method of liquid interface self assembly, by polystyrene microsphere, close-packed arrays form polystyrene after moisture evaporation on the glass sheet
Colloidal crystal.
4. the preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array according to claim 1, feature exist
In the annealing is specially that the sample of magnetron sputtering deposition thereof is placed in the tube furnace with reducing atmosphere, is kept the temperature
Temperature is 1000 DEG C, soaking time 2h, is heated up with the heating rate of 5 DEG C/min.
5. the preparation method of flower-shaped hierarchical structure Au@Ag nanometer sheet oldered array according to claim 4, feature exist
In the reducing atmosphere is the mixed atmosphere of nitrogen and hydrogen, wherein the volume content of the hydrogen is 2%.
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| CN113385680A (en) * | 2021-05-19 | 2021-09-14 | 杭州电子科技大学 | Preparation method of metal nanosheet |
| CN113433110A (en) * | 2021-06-22 | 2021-09-24 | 西安邮电大学 | Preparation method for generating substrate with honeysuckle dendritic crystal flower-like nano structure by in-situ substitution method |
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| CN113433110A (en) * | 2021-06-22 | 2021-09-24 | 西安邮电大学 | Preparation method for generating substrate with honeysuckle dendritic crystal flower-like nano structure by in-situ substitution method |
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