CN102352082B - Preparation method of micron / submicron gold nanoparticle ring and gold ring - Google Patents
Preparation method of micron / submicron gold nanoparticle ring and gold ring Download PDFInfo
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- CN102352082B CN102352082B CN 201110198792 CN201110198792A CN102352082B CN 102352082 B CN102352082 B CN 102352082B CN 201110198792 CN201110198792 CN 201110198792 CN 201110198792 A CN201110198792 A CN 201110198792A CN 102352082 B CN102352082 B CN 102352082B
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Abstract
The invention discloses a preparation method of a micron / submicron gold nanoparticle ring and a gold ring. The method comprises steps of: first preparing an organic gold nanoparticle by a sol-gel method and preparing a membrane manufacturing solution; preparing a gold nanoparticle polymer film; carrying out heat treatment on the gold nanoparticle polymer film to form a micron / submicron gold nanoparticle ring or a micron / submicron gold ring. An inner diameter, an external diameter and an areal density of the gold nanoparticle ring or the gold ring prepared by the method of the invention are easily controllable and adjustable. Besides the method of the invention has simple process, low costs and little time consuming, and is easy for popularization and large scale production and is especially suitable for manufacturing an array template of a micron / submicron gold nanoparticle ring or a micron / submicron gold ring required by a photobiological sensing device.
Description
Technical field
The present invention relates to a kind of micro-nano processing technology, especially relate to the preparation method of a kind of micron/submicron gold nanoparticle ring and Jin Huan.
Background technology
In recent years, because golden nanometer particle has unique chemistry and physicals, and be widely used in biotechnology, chemistry and the numerous areas such as optical sensing technology and environment protection.
Golden nanometer particle, than block gold, has larger specific surface area, shows better chemically reactive, is a kind of good chemical catalysis agent material., with other noble metal nano particles, compare, golden nanometer particle has the stability of better Bc and Geng Gao simultaneously, can be used as a kind of good biological labled material.Particularly golden nanometer particle is under the light field effect, produce local surface plasma resonance (LSPR, Localized Surface Plasmon Resonace), greatly strengthen the interaction of light and material, its unique optical property (as Raman enhancing, enhancement effect of fluorescence) obtains widespread use in fields such as nonlinear optics, nanophotonics, highly sensitive biochemical sensors.For example, the ad hoc structure that golden nanometer particle forms can improve the sensitivity of spectral response to the surrounding environment variations in refractive index effectively, has established the basis for preparing highly sensitive index sensor; On the ad hoc structure formed at golden nanometer particle, the specific bioprobe of link can also be developed the biochemical sensors such as immunoassay, enzymatic determination.Therefore, utilize modern micro-nano processing technology, nanoassemble technology or other physics and chemical process, the ad hoc structure that preparation is comprised of golden nanometer particle, as micron/submicron gold nanoparticle ring and micron/submicron gold ring structure etc., significant.
At present, the preparation method of the micron/submicron gold nanoparticle ring of pertinent literature report and micron/submicron gold ring, mainly to adopt photoetching, electron beam or ion beam etching technology to prepare required Nano/micron/sub-micron pore array mould plate, then with sputter mode deposited gold film on pore array template, process by chemical corrosion again, make required micron/submicron gold ring structure; Perhaps adopt settling process that the golden nanometer particle self-assembly is advanced in nanohole array, then process by chemical corrosion, make the micron/submicron gold nanoparticle ring needed.Above-mentioned preparation method all needs expensive processing units, complex process, and length consuming time and cost are high.
Summary of the invention
It is simple that technical problem to be solved by this invention is to provide a kind of technique, less consuming time and micron/submicron gold nanoparticle ring that cost is low and the preparation method of Jin Huan.
The present invention solves the problems of the technologies described above adopted technical scheme: the preparation method of a kind of micron/submicron gold nanoparticle ring and Jin Huan is characterized in that comprising the following steps:
1. adopt sol-gel method to prepare organic phase golden nanometer particle particle;
2. prepare film making solution, detailed process is: under the condition that is 2.-1,0～30 ℃ in envrionment temperature, the golden nanometer particle particle of organic phase is dissolved in organic solvent fully, obtains the solution of gold nanoparticles that golden content is 0.01g/ml～0.05g/ml; 2.-2, choose polymkeric substance, under the condition that is then 0～30 ℃ in envrionment temperature, polymkeric substance is dissolved in the described organic solvent of same fully to the polymers soln that the content that obtains polymkeric substance is 0.02g/ml～0.2g/ml; 2.-3, solution of gold nanoparticles is sneaked in polymers soln, obtain mixing solutions, wherein, the gold in the golden nanometer particle particle of organic phase and the ratio of quality and the number of copies of polymkeric substance are 1:0.5～1:5; 2.-4, concentrated or dilution mixing solutions obtains film making solution, and in film making solution, the total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.03g/ml～0.3g/ml; 2.-5, utilize ultrasonic wave to film making solution effect 0.3～1 hour, two kinds of solutes of golden nanometer particle particle and polymkeric substance are fully mixed, make two kinds of solutes be dispersed in solvent simultaneously;
3. prepare the golden nanometer particle polymeric film, detailed process is: under the condition that is 0～30 ℃ in envrionment temperature, the film making solution Quick uniform is dripped on a surface that is coated onto substrate base, form the golden nanometer particle polymeric film that thickness is 0.5～50 μ m after solvent evaporates;
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron gold nanoparticle ring or micron/submicron gold ring, detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out to natural air drying; 4.-2, the golden nanometer particle polymeric film after natural air drying is carried out to low-temperature bake, storing temperature is the temperature that approaches solvent boiling point in film making solution, and baking time is 1～3 hour; 4.-3, slowly improve storing temperature to the temperature a little more than protective material boiling point in the golden nanometer particle particle and lower than the decomposition temperature of polymkeric substance, the golden nanometer particle polymeric film is continued to baking 1～3 hour, form micron/submicron gold nanoparticle ring or micron/submicron gold ring; At this, the golden nanometer particle polymeric film that utilizes the film making solution of high density to prepare after heat treatment, can obtain micron/submicron gold nanoparticle ring; The golden nanometer particle polymeric film that utilizes the film making solution of the lower concentration of preparing under low ambient temperature to prepare after heat treatment, can obtain micron/submicron gold ring.
Described step detailed process 1. is: 1.-1, at room temperature, the aqueous solution of chloraurate of 0.01g/ml～0.02g/ml is shifted in organic solvent and forms mixing solutions by consisting of phase-transferring agent, wherein, 4～6 times of the quality that the quality of consisting of phase-transferring agent is hydrochloro-auric acid, 3～4 times of the volume that the volume of organic solvent is aqueous solution of chloraurate; 1.-2, at room temperature, add protective material when stirring described mixing solutions, then continue slowly to add reductive agent under whipped state, stir again more than 3 hours, displace gold ion from solution, form the solution containing the golden nanometer particle particle, wherein, 0.8～3 times of the quality that the protectant quality added is hydrochloro-auric acid, 0.8～2 times of the quality that the quality of the reductive agent added is hydrochloro-auric acid; 1.-3, utilize the concentrated solution containing the golden nanometer particle particle of Rotary Evaporators; 1.-4,1/10～1/8 o'clock of the volume of the organic solvent in the volume of the solution containing the golden nanometer particle particle is evaporated to step 1.-1; use methyl alcohol or dissolve with ethanol containing the impurity in the solution of golden nanometer particle particle; and separate out the golden nanometer particle particle of the organic phase of the agent that is protected after filtration drying parcel by the golden nanometer particle particle is centrifugal with whizzer.
In described step 1.-1, consisting of phase-transferring agent adopts four octyl group brometo de amonios, and organic solvent adopts toluene solution; In described step 1.-2, protective material adopts positive hexylmercaptan or dodecyl mercaptans, and reductive agent adopts sodium borohydride.
The Average Particle Diameters of described organic phase golden nanometer particle particle is 1～10nm.
In described step 2.-1 and described step 2.-2, organic solvent adopts chloroformic solution; In described step 2.-2, polymkeric substance adopts polymethylmethacrylate or polystyrene.
The area density of the micron/submicron gold nanoparticle ring of described step described in 4. and described micron/submicron gold ring is 10
6～10
8cm
-2, the mean inside diameter of described micron/submicron gold nanoparticle ring and described micron/submicron gold ring is 0.2～3.6 μ m, and the mean outside diameter of described micron/submicron gold nanoparticle ring and described micron/submicron gold ring is 0.6～4.2 μ m; Described micron/submicron gold nanoparticle ring is by the golden nanometer particle granulometric composition, and the median size that forms the golden nanometer particle particle of described micron/submicron gold nanoparticle ring is 1～50nm.
compared with prior art, the invention has the advantages that:
The internal-and external diameter of the gold nanoparticle ring that 1) utilizes the inventive method to prepare or gold ring and the area density of ring are easy to control and adjust, and the technique of the inventive method is simple, with low cost, consuming time few, is easy to promote and scale operation.Be particularly suitable for making micron/submicron gold nanoparticle ring or the golden array mould plate encircled of micron/submicron that the Photobiology sensing device needs.
2) in the process of preparation film making solution, by the gold in the golden nanometer particle particle that changes organic phase in film making solution and the ratio of quality and the number of copies of polymkeric substance, can effectively control by endless belt (zone between the internal-and external diameter of the gold nanoparticle ring) width of the gold nanoparticle ring of golden nanometer particle granulometric composition with by endless belt (zone between the internal-and external diameter that the gold encircles) width of the gold ring of the golden nanometer particle granulometric composition of melting.
3), in the process of preparation film making solution, by changing the concentration of film making solution, the ring structure of the micron/submicron gold nanoparticle ring of preparation or micron/submicron gold ring can form different outline shapes; In addition, in the golden nanometer particle polymeric film than being prepared by the low concentration film making solution under low ambient temperature, the golden nanometer particle particle easily is fused together and forms golden ring structure.
4) at the preparation film making solution and prepare the process of golden nanometer particle polymeric film, by changing its envrionment temperature, can effectively control the size of growth bubble, thus the size of the internal diameter of gate ring effectively, and change the width of endless belt.
5) in heat treatment process, under the thermal treatment temp of 180 ℃, can effectively remove and be wrapped in the circumgranular protective material of golden nanometer particle, eliminate the impact of protective material chemical bond.
6) in the process for preparing the golden nanometer particle particle; by changing protectant amount; the size of synthetic golden nanometer particle particle can be effectively controlled, thereby the size of the golden nanometer particle particle in the endless belt of gold nanoparticle ring can be effectively be controlled at.
The accompanying drawing explanation
Fig. 1 is golden optical microscope photograph and the electron scanning micrograph encircled of micron/submicron that embodiment mono-prepares;
Optical microscope photograph and electron scanning micrograph that Fig. 2 is the micron/submicron gold nanoparticle ring for preparing of embodiment bis-;
Optical microscope photograph and electron scanning micrograph that Fig. 3 is the micron/submicron gold nanoparticle ring for preparing of implementation column three;
Optical microscope photograph and electron scanning micrograph that Fig. 4 is the micron/submicron gold nanoparticle ring for preparing of implementation column four.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment mono-:
A kind of preparation method of micron/submicron gold ring, it mainly comprises the following steps:
1. adopt existing sol-gel method to prepare the golden nanometer particle particle of organic phase.The detailed process of the golden nanometer particle particle of preparation organic phase is: 1.-1, at room temperature, and by aqueous solution of chloraurate (hydrochloro-auric acid (HAuCl
4) 0.31g, water 25ml) consisting of phase-transferring agent by 1.5g shifts in the organic solvent of 80ml and forms mixing solutions, 1.-2, at room temperature, the protective material (about stir about 10 minutes) that adds 0.36g when stirring described mixing solutions, then continue the reductive agent (about vigorous stirring 30 minutes) that stirs this solution and slowly add 0.38g, stir again more than 3 hours and displace gold ion from solution, form the solution containing the golden nanometer particle particle, 1.-3, utilize the concentrated solution containing the golden nanometer particle particle of Rotary Evaporators, vaporization temperature is controlled at below 50 ℃, 1.-4, containing the solution evaporation of golden nanometer particle particle during to 1/8 left and right (being the 10ml left and right) of the organic solvent in step 1.-1, when the volume ratio of the volume containing the solution of golden nanometer particle particle and the organic solvent in step 1.-1 is the 1:8 left and right, the methyl alcohol or the ethanol that add 400ml, impurity in solvent soln, reach the purpose of cleaning, and separate out the golden nanometer particle particle is centrifugal by centrifugal method, generate black precipitate, filter, dry black precipitate, obtain required organic phase golden nanometer particle particle (the golden nanometer particle particle of protective material parcel).At this, the add-on of methyl alcohol or ethanol can be fixed according to the practical situation amount, and the purpose that reaches effective cleaning gets final product.
Above-described consisting of phase-transferring agent can adopt four octyl group brometo de amonios; Organic solvent can adopt toluene solution; Protective material can adopt positive hexylmercaptan or dodecyl mercaptans; Reductive agent can adopt sodium borohydride.
In said process; the Average Particle Diameters of the golden nanometer particle particle of organic phase can be controlled by controlling protectant add-on; when the protectant amount added is more; the particle diameter of the golden nanometer particle particle prepared is less; when the protectant amount added is less; the particle diameter of the golden nanometer particle particle prepared is larger, in actual fabrication process, the Average Particle Diameters of the golden nanometer particle particle for preparing can be controlled in 1～10nm scope.
2. prepare film making solution.Detailed process is: under the condition that is 2.-1,5 ℃ in envrionment temperature, the golden nanometer particle particle of organic phase is dissolved in organic solvent fully, obtains the solution of gold nanoparticles that gold content is 0.03g/ml; 2.-2, choose polymkeric substance, under the condition that is then 5 ℃ in envrionment temperature, polymkeric substance is dissolved in above-mentioned same organic solvent fully, obtain polymers soln, in solution, the content of polymkeric substance is 0.2g/ml; 2.-3, solution of gold nanoparticles is sneaked in polymers soln, obtain mixing solutions, wherein, the gold in the golden nanometer particle particle of organic phase and the ratio of quality and the number of copies of polymkeric substance are 1:2; 2.-4, adopt the method solvent flashing of low-temperature heat described mixing solutions to be concentrated or add the described mixing solutions of solvent cut to obtain film making solution, in film making solution, the total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.06g/ml, and by two kinds of solutes, the content in solution determines the concentration of film making solution; 2.-5, utilize ultrasonic wave to film making solution effect 0.7 hour, two kinds of solutes of golden nanometer particle particle and polymkeric substance are fully mixed, make two kinds of solutes be dispersed in solvent simultaneously.
Above-mentioned organic solvent adopts chloroformic solution; Polymkeric substance adopts polymethylmethacrylate or polystyrene, and the molecular weight of polymethylmethacrylate is 35000.
The size and number of the bubble formed in film making solution in addition, is subject to the impact of concentration and the temperature of film making solution.
3. prepare the golden nanometer particle polymeric film.Detailed process is: under the condition that is 5 ℃ in envrionment temperature, the film making solution Quick uniform dripped on a surface that is coated onto substrate base, and along with the volatilization of solvent, the golden nanometer particle polymeric film that formation thickness is 0.5～50 μ m.
Above-mentioned substrate base can adopt the quartz glass substrate of twin polishing or the silicon chip of single-sided polishing, and while adopting the silicon chip of single-sided polishing, film making solution drips on the polished surface that is applied to silicon chip.
At this, the thickness of golden nanometer particle polymeric film depends on concentration and the painting amount of dripping of film making solution and the size of a painting area of dripping the film making solution that is coated in the substrate base surface.The painting amount of dripping and a painting area for certain film making solution, the thickness of golden nanometer particle polymeric film depends primarily on the concentration of film making solution, for example, in the situation that a painting amount is identical with a painting area, approximately thick 5 times of films prepared by the film making solution that film specific concentration prepared by the film making solution that concentration is 0.3g/ml is 0.06g/ml.
In addition; in film-forming process; by changing the film formed envrionment temperature of golden nanometer particle polymer thin; can control the evaporation rate of solvent in film making solution; thereby can effectively control the growth of bubble in the golden nanometer particle polymeric film and at the self assembling process of the golden nanometer particle particle at bubble edge, the micro-ring structure formed to obtain the golden nanometer particle self-assembly by the protective material parcel that different size distributes.
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron gold ring.Detailed process is:
4.-1, at room temperature, the golden nanometer particle polymeric film is carried out to natural air drying; 4.-2, the golden nanometer particle polymeric film after natural air drying is carried out to low-temperature bake, storing temperature is the temperature that approaches solvent boiling point in film making solution, and in actual process desirable 70 ℃, baking time is 1 hour; 4.-3, slowly improve storing temperature to the temperature of the protective material boiling point a little more than in the golden nanometer particle particle and lower than the decomposition temperature of polymkeric substance; can reach 180 ℃ in actual process; the golden nanometer particle polymeric film is continued to baking 2 hours, can form micron/submicron gold ring.Fig. 1 has provided optical microscope photograph and the electron scanning micrograph of the micron/submicron gold ring prepared.As can be seen from Figure 1, the endless belt of the gold ring that the present embodiment prepares is more smooth, and its mean outside diameter is 1 μ m, and mean inside diameter is 0.4 μ m, and the area density of gold ring is about 5 * 10
7cm
-2.
In the actual heat treatment process of the present embodiment, low-temperature bake golden nanometer particle polymeric film, can effectively remove residual solvent; Toast the golden nanometer particle polymeric film with the temperature a little more than protective material boiling point in golden nanometer particle and lower than the decomposition temperature of polymkeric substance again; can effectively remove the protective material of parcel golden nanometer particle particle; simultaneously more golden nanometer particle particle aggregation is around the bubble in the golden nanometer particle polymeric film, and after self-assembly forms micron/submicron gold nanoparticle ring, the golden nanometer particle particle fusion forms micron/submicron gold ring.
Embodiment bis-:
The preparation method of the gold ring of the preparation method of the micron/submicron gold nanoparticle ring of the present embodiment and embodiment mono-is basic identical, difference only is that the concentration of the film making solution of the present embodiment preparation is that the total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.3g/ml, and the gold in two kinds of solutes in the golden nanometer particle particle and the ratio of quality and the number of copies of polymkeric substance are 1:2.Fig. 2 has provided optical microscope photograph and the electron scanning micrograph of the micron/submicron gold nanoparticle ring prepared.As can be seen from Figure 2, the gold nanoparticle ring that the present embodiment prepares is by the golden nanometer particle granulometric composition, and the median size of golden nanometer particle particle is 10nm; Form described gold nanoparticle ring endless belt in the middle of part protuberance and sink in both sides, the mean outside diameter of endless belt is 1.6 μ m, mean inside diameter is 0.9 μ m; The area density of gold nanoparticle ring is 10
7cm
-2.
Embodiment tri-:
The preparation process of the gold nanoparticle ring of the preparation method of the micron/submicron gold nanoparticle ring of the present embodiment and embodiment bis-is basic identical, and difference only is to carry out under condition that the process of the present embodiment preparation film making solution is 15 ℃ in envrionment temperature; Under the environment that is 15 ℃ in temperature, prepare the golden nanometer particle polymeric film.Fig. 3 has provided optical microscope photograph and the electron scanning micrograph of the micron/submicron gold nanoparticle ring prepared.As can be seen from Figure 3, the gold nanoparticle ring that the present embodiment prepares is by the golden nanometer particle granulometric composition, and the median size of golden nanometer particle particle is 25nm; Form described gold nanoparticle ring endless belt in the middle of part protuberance and sink in both sides, the mean outside diameter of endless belt is 2 μ m, mean inside diameter is 1.4 μ m; The area density of gold nanoparticle ring is about 10
7cm
-2.
Embodiment tetra-:
A kind of preparation method of micron/submicron gold nanoparticle ring, the preparation process of the gold ring of its preparation process and embodiment mono-is basic identical, and difference is to carry out under condition that the process of the present embodiment preparation film making solution is 20 ℃ in envrionment temperature; Under the environment that is 20 ℃ in temperature, prepare the golden nanometer particle polymeric film; Under the low temperature that heat treatment process is 70 ℃ at storing temperature, carry out.Fig. 4 has provided optical microscope photograph and the electron scanning micrograph of the micron/submicron gold nanoparticle ring prepared.As can be seen from Figure 4, the gold nanoparticle ring that the present embodiment prepares is by the golden nanometer particle granulometric composition, and the median size of golden nanometer particle particle is 25nm; The zonary structure that forms described gold nanoparticle ring is smooth, and the mean outside diameter of endless belt is 3 μ m, and mean inside diameter is 2 μ m; The area density of gold nanoparticle ring is about 10
7cm
-2.
Embodiment five:
The preparation process of the preparation method of the micron/submicron gold ring of the present embodiment and the gold ring of embodiment mono-is basic identical, difference only is the ratio of quality and the number of copies difference of two kinds of solutes in the film making solution of the present embodiment preparation, and the gold in the golden nanometer particle particle of the present embodiment and the ratio of quality and the number of copies of polymkeric substance are 1:0.7.After on substrate base, a painting prepares the golden nanometer particle polymeric film, form micron/submicron gold cyclopolymer film through Overheating Treatment again, the endless belt of its micron/submicron gold ring is more smooth, and mean outside diameter is 1.8 μ m, mean inside diameter is 0.5 μ m, and the area density of gold ring is about 10
7cm
-2.
Embodiment six:
The preparation method of the micron/submicron gold ring of the preparation method of the micron/submicron gold nanoparticle ring of the present embodiment and embodiment mono-is basic identical, but the preparation parameter difference, and its detailed process is as follows:
1. adopt existing sol-gel method to prepare the golden nanometer particle particle of organic phase.
2. prepare film making solution.Detailed process is: under the condition that is 2.-1,25 ℃ in envrionment temperature, the golden nanometer particle particle of organic phase is dissolved in organic solvent fully, obtains the solution of gold nanoparticles that golden content is 0.03g/ml; 2.-2, choose polymkeric substance, under the condition that is then 25 ℃ in envrionment temperature, polymkeric substance is dissolved in the same organic solvent fully, the polymers soln that the content that obtains polymkeric substance is 0.2g/ml; 2.-3, solution of gold nanoparticles is sneaked in polymers soln, obtain mixing solutions, wherein, the gold in the golden nanometer particle particle and the ratio of quality and the number of copies of polymkeric substance are 1:2; 2.-4, employing low-temperature heating method solvent flashing concentrates described mixing solutions or adds the described mixing solutions of solvent cut to obtain film making solution, in film making solution, the total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.3g/ml, and by two kinds of solutes, the content in solution determines the concentration of film making solution; 2.-5, utilize ultrasonic wave to film making solution effect 0.7 hour, two kinds of solutes of golden nanometer particle particle and polymkeric substance are fully mixed, make two kinds of solutes be dispersed in solvent simultaneously.
3. prepare the golden nanometer particle polymeric film.Detailed process is: under the condition that is 25 ℃ in envrionment temperature, the film making solution Quick uniform dripped on a surface that is coated onto substrate base, and along with the volatilization of solvent, the golden nanometer particle polymeric film that formation thickness is 35 μ m.
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron gold nanoparticle ring.Detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out to natural air drying; 4.-2, the golden nanometer particle polymeric film after natural air drying is carried out to low-temperature bake, storing temperature is the temperature (as solvent is chloroformic solution, storing temperature is desirable 70 ℃) that approaches solvent boiling point in film making solution, and baking time is 3 hours; 4.-3, slowly improve storing temperature to the temperature a little more than protective material boiling point in the golden nanometer particle particle and lower than the decomposition temperature of polymkeric substance, can reach 180 ℃ in actual process, continue baking 1 hour, form micron/submicron gold nanoparticle ring.
The area density of the micron/submicron gold nanoparticle ring that the present embodiment forms is about 5 * 10
6cm
-2, the mean outside diameter of gold nanoparticle ring is 4 μ m, mean inside diameter is 3.5 μ m.Part protuberance in the middle of the endless belt of gold nanoparticle ring and sink in both sides, the median size that forms the golden nanometer particle particle of endless belt is 40nm.
Embodiment seven:
The preparation process of the gold nanoparticle ring of the preparation method of the micron/submicron gold nanoparticle ring of the present embodiment and embodiment bis-is basic identical, but the preparation parameter difference, and detailed process is:
1. adopt existing sol-gel method to prepare the golden nanometer particle particle of organic phase.
2. prepare film making solution.Detailed process is: under the condition that is 2.-1,15 ℃ in envrionment temperature, the golden nanometer particle particle of organic phase is dissolved in organic solvent fully, obtains the solution of gold nanoparticles that golden content is 0.02g/ml; 2.-2, choose polymkeric substance, under the condition that is then 15 ℃ in envrionment temperature, polymkeric substance is dissolved in the same organic solvent fully, obtain the polymers soln that polymer content is 0.06g/ml; 2.-3, solution of gold nanoparticles is sneaked in polymers soln, obtain mixing solutions, wherein, the gold in the golden nanometer particle particle and the ratio of quality and the number of copies of polymkeric substance are 1:4; 2.-4, employing low-temperature heating method solvent flashing concentrates described mixing solutions or adds the described mixing solutions of solvent cut to obtain film making solution, in film making solution, the total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.15g/ml, and by two kinds of solutes, the content in solution determines the concentration of film making solution; 2.-5, utilize ultrasonic wave to film making solution effect 1 hour, two kinds of solutes of golden nanometer particle particle and polymkeric substance are fully mixed, make two kinds of solutes be dispersed in solvent simultaneously.
3. prepare the golden nanometer particle polymeric film.Detailed process is: under the condition that is 15 ℃ in envrionment temperature, the film making solution Quick uniform is dripped on a surface that is coated onto substrate base, after solvent evaporates, forming thickness is the golden nanometer particle polymeric film of 25 μ m left and right.
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron gold nanoparticle ring.Detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out to natural air drying; 4.-2, the golden nanometer particle polymeric film after natural air drying is carried out to low-temperature bake, storing temperature is the temperature (as solvent is chloroform, storing temperature is desirable 70 ℃) that approaches solvent boiling point in film making solution, and baking time is 2 hours; 4.-3, slowly improve storing temperature to the temperature a little more than protective material boiling point in the golden nanometer particle particle and lower than the decomposition temperature of polymkeric substance, can reach 180 ℃ in actual process, continue baking 3 hours, form micron/submicron gold nanoparticle ring.
The area density of the micron/submicron gold nanoparticle ring that the present embodiment forms is about 8 * 10
6cm
-2, the mean outside diameter of gold nanoparticle ring is 1.5 μ m, mean inside diameter is 1.2 μ m.Part protuberance in the middle of the endless belt of gold nanoparticle ring and sink in both sides, the median size that forms the golden nanometer particle particle of endless belt is 25nm.
Below, for passing through relatively each embodiment, feasibility and the validity of the inventive method is described.
In embodiment mono-and embodiment bis-, the envrionment temperature of configuration film making solution and to prepare the envrionment temperature of golden nanometer particle polymeric film identical, gold in golden nanometer particle particle in two kinds of film making solutions is identical with the ratio of quality and the number of copies of polymkeric substance, and the concentration difference of film making solution.In the process for preparing the golden nanometer particle polymeric film, the golden nanometer particle polymeric film prepared by the film making solution of lower concentration is thinner, the bubble generated in film is less, make the easy emersion golden nanometer particle of the golden nanometer particle particle polymeric film surface around bubble and be fused together, form micron/submicron gold ring, as shown in Figure 1; The golden nanometer particle polymeric film prepared for the film making solution of high density is thicker, the bubble generated in film is also larger, make the golden nanometer particle particle be subject to the resistance of peripheral polymer wrapped to be difficult to greatly emersion golden nanometer particle polymeric film surface melting mutually, easily form micron/submicron gold nanoparticle ring, as shown in Figure 2.
Embodiment bis-is identical with the concentration of the film making solution adopted in embodiment tri-, and configures the envrionment temperature of film making solution and prepare golden nanometer particle polymeric film envrionment temperature difference.Comparing embodiment two and embodiment tri-, can find, the lower embodiment bis-for envrionment temperature, the bubble less that the film making solution of configuration produces during for the preparation of the golden nanometer particle polymeric film, the mean inside diameter of the gold nanoparticle ring that the mean inside diameter of the gold nanoparticle ring made makes than embodiment tri-is little; Again due in the film making solution at embodiment bis-and embodiment tri-, gold in the golden nanometer particle particle is identical with the ratio of polymkeric substance, and the ring width band width of the gold nanoparticle ring that the internal diameter that the endless belt width of the gold nanoparticle ring that the internal diameter that embodiment bis-makes is less (internal-and external diameter of gold nanoparticle ring poor) makes than embodiment tri-is larger is large; Simultaneously, under higher envrionment temperature in the self assembling process of golden nanometer particle, in gold nanoparticle ring and near golden nanometer particle easily grow into larger golden nanometer particle particle, and, when envrionment temperature is low, original particle diameter of golden nanometer particle particle remains unchanged substantially.Therefore visible, the median size that forms the golden nanometer particle particle of endless belt in embodiment bis-is 10nm, and the median size that embodiment tri-forms the golden nanometer particle particle of endless belt is 25nm, respectively as shown in Figure 3 and Figure 4.
With regard to embodiment tetra-, each component proportions of its film making solution is identical with embodiment mono-, and the envrionment temperature of configuration film making solution and prepare the envrionment temperature difference of golden nanometer particle polymeric film.Comparing embodiment four and embodiment mono-, the preparation envrionment temperature in embodiment tetra-is higher, and the bubble that the film making solution of configuration produces during for the preparation of the golden nanometer particle polymeric film is relatively large, and the internal diameter of the gold nanoparticle ring made is larger; Due to what adopt in embodiment tetra-and embodiment mono-, be the lower concentration film making solution again, with embodiment bis-, with embodiment tri-, compare, can see the easier emersion of golden nanometer particle particle in the film making solution of embodiment tetra-and embodiment mono-surface to the golden nanometer particle polymeric film, embodiment mono-forms the more smooth gold ring of surface ratio as shown in Figure 1, and embodiment tetra-forms the more smooth gold nanoparticle ring of surface ratio as shown in Figure 4.It may be noted that, the bubble produced during for the preparation of the golden nanometer particle polymeric film due to the film making solution of embodiment tetra-configuration is relatively large, stability is poor than situation in embodiment mono-, easily destroyed while carrying out again the high-temperature heat treatment of 180 ℃, therefore, tetra-of embodiment carry out low-temperature heat treatment under 70 ℃ of storing temperatures.
Embodiment five compares with embodiment mono-, only changed the ratio of quality and the number of copies of gold in the golden nanometer particle particle and polymkeric substance in the film making solution, both have all formed golden ring after heat treatment process, because the mass fraction of the gold in golden nanometer particle particle in embodiment five and polymkeric substance is higher, therefore under identical conditions, golden nanometer particle is easier to assemble the gold ring that the formation ring width is wider than embodiment mono-and internal diameter is larger.
In addition, the Average Particle Diameters of the golden nanometer particle particle prepared in the inventive method is 1～10nm left and right, if prepare at low temperatures the golden nanometer particle polymeric film, the Average Particle Diameters that forms the golden nanometer particle particle encircled is approximate identical with the Average Particle Diameters of the golden nanometer particle particle made, as the Average Particle Diameters that forms the golden nanometer particle particle of ring in embodiment bis-is 10nm; And if prepare the golden nanometer particle polymeric film under comparatively high temps; in the self assembling process of golden nanometer particle; golden nanometer particle particle in endless belt can be fused together; form the larger golden nanometer particle particle of median size, as the Average Particle Diameters of the golden nanometer particle particle of the ring that forms in embodiment tri-and embodiment tetra-is 25nm.
Claims (6)
1. the preparation method of a micron/submicron gold nanoparticle ring is characterized in that comprising the following steps:
1. adopt sol-gel method to prepare the golden nanometer particle particle of organic phase, detailed process is: 1.-1, at room temperature, the aqueous solution of chloraurate of 0.01g/ml～0.02g/ml is shifted in organic solvent and forms mixing solutions by consisting of phase-transferring agent, wherein, 4～6 times of the quality that the quality of consisting of phase-transferring agent is hydrochloro-auric acid, 3～4 times of the volume that the volume of organic solvent is aqueous solution of chloraurate; 1.-2, at room temperature, add protective material when stirring described mixing solutions, then continue slowly to add reductive agent under whipped state, stir again more than 3 hours, displace gold ion from solution, form the solution containing the golden nanometer particle particle, wherein, 0.8～3 times of the quality that the protectant quality added is hydrochloro-auric acid, 0.8～2 times of the quality that the quality of the reductive agent added is hydrochloro-auric acid; 1.-3, utilize the concentrated solution containing the golden nanometer particle particle of Rotary Evaporators; 1.-4,1/10～1/8 o'clock of the volume of the organic solvent in the volume of the solution containing the golden nanometer particle particle is evaporated to step 1.-1, use methyl alcohol or dissolve with ethanol containing the impurity in the solution of golden nanometer particle particle, and separate out the golden nanometer particle particle of the organic phase of the agent that is protected after filtration drying parcel by the golden nanometer particle particle is centrifugal with whizzer;
In described step 1.-1, consisting of phase-transferring agent adopts four octyl group brometo de amonios, and organic solvent adopts toluene solution; In described step 1.-2, protective material adopts positive hexylmercaptan or dodecyl mercaptans, and reductive agent adopts sodium borohydride;
2. prepare film making solution, detailed process is: under the condition that is 2.-1,25 ℃ in envrionment temperature, the golden nanometer particle particle of organic phase is dissolved in organic solvent fully, obtains the solution of gold nanoparticles that golden content is 0.03g/ml; 2.-2, choose polymkeric substance, under the condition that is then 25 ℃ in envrionment temperature, polymkeric substance is dissolved in the described organic solvent of same fully to the polymers soln that the content that obtains polymkeric substance is 0.2g/ml; 2.-3, solution of gold nanoparticles is sneaked in polymers soln, obtain mixing solutions, wherein, the gold in the golden nanometer particle particle of organic phase and the ratio of quality and the number of copies of polymkeric substance are 1:2; 2.-4, concentrated or dilution mixing solutions obtains film making solution, and in film making solution, the total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.3g/ml; 2.-5, utilize ultrasonic wave to film making solution effect 0.7 hour, two kinds of solutes of golden nanometer particle particle and polymkeric substance are fully mixed, make two kinds of solutes be dispersed in solvent simultaneously;
In described step 2.-1 and described step 2.-2, organic solvent adopts chloroformic solution; In described step 2.-2, polymkeric substance adopts polymethylmethacrylate or polystyrene;
3. prepare the golden nanometer particle polymeric film, detailed process is: under the condition that is 25 ℃ in envrionment temperature, the film making solution Quick uniform is dripped on a surface that is coated onto substrate base, form the golden nanometer particle polymeric film that thickness is 35 μ m after solvent evaporates;
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron gold nanoparticle ring, detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out to natural air drying; 4.-2, the golden nanometer particle polymeric film after natural air drying is carried out to low-temperature bake, storing temperature is the temperature that approaches solvent boiling point in film making solution, and baking time is 3 hours; 4.-3, slowly improve storing temperature to the temperature a little more than protective material boiling point in the golden nanometer particle particle and lower than the decomposition temperature of polymkeric substance, the golden nanometer particle polymeric film is proceeded to the baking of 1 hour, form micron/submicron gold nanoparticle ring.
2. the preparation method of a kind of micron/submicron gold nanoparticle ring according to claim 1, is characterized in that the Average Particle Diameters of the golden nanometer particle particle of the organic phase during described step 1. is 1～10nm.
3. the preparation method of a kind of micron/submicron gold nanoparticle ring according to claim 1, is characterized in that the area density of the micron/submicron gold nanoparticle ring described in described step 4. is 5 * 10
6cm
-2, the mean inside diameter of described micron/submicron gold nanoparticle ring is 3.5 μ m, the mean outside diameter of described micron/submicron gold nanoparticle ring is 4 μ m; Described micron/submicron gold nanoparticle ring is by the golden nanometer particle granulometric composition, and the median size that forms the golden nanometer particle particle of described micron/submicron gold nanoparticle ring is 40nm.
4. the preparation method of micron/submicron gold ring is characterized in that comprising the following steps:
1. adopt sol-gel method to prepare the golden nanometer particle particle of organic phase, detailed process is: 1.-1, at room temperature, the aqueous solution of chloraurate of 0.01g/ml～0.02g/ml is shifted in organic solvent and forms mixing solutions by consisting of phase-transferring agent, wherein, 4～6 times of the quality that the quality of consisting of phase-transferring agent is hydrochloro-auric acid, 3～4 times of the volume that the volume of organic solvent is aqueous solution of chloraurate; 1.-2, at room temperature, add protective material when stirring described mixing solutions, then continue slowly to add reductive agent under whipped state, stir again more than 3 hours, displace gold ion from solution, form the solution containing the golden nanometer particle particle, wherein, 0.8～3 times of the quality that the protectant quality added is hydrochloro-auric acid, 0.8～2 times of the quality that the quality of the reductive agent added is hydrochloro-auric acid; 1.-3, utilize the concentrated solution containing the golden nanometer particle particle of Rotary Evaporators; 1.-4,1/10～1/8 o'clock of the volume of the organic solvent in the volume of the solution containing the golden nanometer particle particle is evaporated to step 1.-1, use methyl alcohol or dissolve with ethanol containing the impurity in the solution of golden nanometer particle particle, and separate out the golden nanometer particle particle of the organic phase of the agent that is protected after filtration drying parcel by the golden nanometer particle particle is centrifugal with whizzer;
In described step 1.-1, consisting of phase-transferring agent adopts four octyl group brometo de amonios, and organic solvent adopts toluene solution; In described step 1.-2, protective material adopts positive hexylmercaptan or dodecyl mercaptans, and reductive agent adopts sodium borohydride;
2. prepare film making solution, detailed process is: under the condition that is 2.-1,5 ℃ in envrionment temperature, the golden nanometer particle particle of organic phase is dissolved in organic solvent fully, obtains the solution of gold nanoparticles that golden content is 0.03g/ml; 2.-2, choose polymkeric substance, under the condition that is then 5 ℃ in envrionment temperature, polymkeric substance is dissolved in the described organic solvent of same fully to the polymers soln that the content that obtains polymkeric substance is 0.2g/ml; 2.-3, solution of gold nanoparticles is sneaked in polymers soln, obtain mixing solutions, wherein, the gold in the golden nanometer particle particle of organic phase and the ratio of quality and the number of copies of polymkeric substance are 1:2; 2.-4, concentrated or dilution mixing solutions obtains film making solution, and in film making solution, the total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.06g/ml; 2.-5, utilize ultrasonic wave to film making solution effect 0.7 hour, two kinds of solutes of golden nanometer particle particle and polymkeric substance are fully mixed, make two kinds of solutes be dispersed in solvent simultaneously;
In described step 2.-1 and described step 2.-2, organic solvent adopts chloroformic solution; In described step 2.-2, polymkeric substance adopts polymethylmethacrylate or polystyrene;
3. prepare the golden nanometer particle polymeric film, detailed process is: under the condition that is 5 ℃ in envrionment temperature, the film making solution Quick uniform is dripped on a surface that is coated onto substrate base, form the golden nanometer particle polymeric film that thickness is 0.5～50 μ m after solvent evaporates;
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron gold ring, detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out to natural air drying; 4.-2, the golden nanometer particle polymeric film after natural air drying is carried out to low-temperature bake, storing temperature is the temperature that approaches solvent boiling point in film making solution, and baking time is 1 hour; 4.-3, slowly improve storing temperature to the temperature a little more than protective material boiling point in the golden nanometer particle particle and lower than the decomposition temperature of polymkeric substance, the golden nanometer particle polymeric film is proceeded to the baking of 2 hours, form micron/submicron gold ring.
5. the preparation method of a kind of micron/submicron gold ring according to claim 4, is characterized in that the Average Particle Diameters of the golden nanometer particle particle of the organic phase during described step 1. is 1～10nm.
6. the preparation method of a kind of micron/submicron gold ring according to claim 4, is characterized in that the area density of the micron/submicron gold ring described in described step 4. is 5 * 10
7cm
-2, the mean inside diameter of described micron/submicron gold ring is 0.4 μ m, the mean outside diameter of described micron/submicron gold ring is 1 μ m.
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