CN102352082A - 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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- CN102352082A CN102352082A CN2011101987924A CN201110198792A CN102352082A CN 102352082 A CN102352082 A CN 102352082A CN 2011101987924 A CN2011101987924 A CN 2011101987924A CN 201110198792 A CN201110198792 A CN 201110198792A CN 102352082 A CN102352082 A CN 102352082A
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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 golden nanometer particle ring and gold ring.
Background technology
In recent years, because golden nanometer particle has unique chemical and physicals, and be widely used in biotechnology, chemistry and numerous areas such as optical sensing technology and environment protection.
Golden nanometer particle has bigger specific surface area than block gold, shows better chemically reactive, is a kind of excellent in chemical catalystic material.Simultaneously, compare with other noble metal nano particles, golden nanometer particle has the stability of better Bc and Geng Gao, 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 (like 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 is formed 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; The specific bioprobe of link can also be developed biochemical sensors such as immunoassay, enzymatic determination on the ad hoc structure that golden nanometer particle is formed.Therefore, utilize modern micro-nano processing technology, nanometer self-assembling technique or other physics and chemical process, the ad hoc structure that preparation is made up of golden nanometer particle, like micron/submicron golden nanometer particle ring and micron/submicron gold ring structure etc., significant.
At present; The preparation method of the micron/submicron golden nanometer particle ring of pertinent literature report and micron/submicron gold ring; Mainly be 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; Handle through chemical corrosion again, make required micron/submicron gold ring structure; Perhaps adopt settling process that the golden nanometer particle self-assembly is advanced in the nanohole array, handle through chemical corrosion again, make the micron/submicron golden nanometer particle ring that needs.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 provides a kind of technology, the preparation method of less consuming time and micron/submicron golden nanometer particle ring that cost is low and gold ring.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the preparation method of a kind of micron/submicron golden nanometer particle ring and gold ring is characterized in that may further comprise the steps:
1. adopt sol-gel method to prepare organic phase golden nanometer particle particle;
2.-1, be under 0～30 ℃ the condition in envrionment temperature 2. prepare film making solution, detailed process is:, the golden nanometer particle particle of organic phase is dissolved in the organic solvent fully, the content that obtains gold is the solution of gold nanoparticles of 0.01g/ml～0.05g/ml; 2.-2, choose polymkeric substance, under envrionment temperature is 0～30 ℃ condition, polymkeric substance is dissolved in in a kind of described organic solvent fully then, the content that obtains polymkeric substance is the polymers soln of 0.02g/ml～0.2g/ml; 2.-3, solution of gold nanoparticles is sneaked in the 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, concentrate or diluted mixture solution obtains 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 in the film making solution; 2.-5, utilize ultrasonic wave to film making solution effect 0.3～1 hour, make two kinds of solute thorough mixing of golden nanometer particle particle and polymkeric substance, two kinds of solutes are dispersed in the solvent;
3. prepare the golden nanometer particle polymeric film; Detailed process is: be under 0～30 ℃ the condition in envrionment temperature; The film making solution rapid and uniform is dripped on the surface that is coated onto substrate base, and forming thickness after the solvent evaporates is the golden nanometer particle polymeric film of 0.5～50 μ m;
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron golden nanometer particle ring or micron/submicron gold ring, detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out natural air drying; 4.-2, the golden nanometer particle polymeric film behind the natural air drying is carried out low-temperature bake, storing temperature is the temperature near solvent boiling point in the film making solution, and storing time is 1～3 hour; 4.-3, slowly improve storing temperature to a little more than the temperature of protective material boiling point in the golden nanometer particle particle and be lower than the decomposition temperature of polymkeric substance; The golden nanometer particle polymeric film is continued baking 1～3 hour, form micron/submicron golden nanometer particle ring or micron/submicron gold ring; At this, utilize golden nanometer particle polymeric film that the film making solution of high density prepares after heat treatment, can obtain micron/submicron golden nanometer particle ring; Utilize under the low ambient temperature golden nanometer particle polymeric film that the film making solution of the lower concentration of preparation prepares after heat treatment, can obtain micron/submicron gold and encircle.
Described step detailed process 1. is: 1.-1, at room temperature; The aqueous solution of chloraurate of 0.01g/ml～0.02g/ml shifted into through consisting of phase-transferring agent form mixing solutions in the organic solvent; Wherein, The quality of consisting of phase-transferring agent is 4～6 times of quality of hydrochloro-auric acid, and volume of organic solvent is 3～4 times of volume of aqueous solution of chloraurate; 1.-2, at room temperature; When stirring described mixing solutions, add protective material; Under whipped state, continue slowly to add reductive agent then; Restir is more than 3 hours; From the mid-gold ion that swaps out of solution, formation contains golden nanometer particle particulate solution, wherein; The protectant quality that adds is 0.8～3 times of quality of hydrochloro-auric acid, and the quality of the reductive agent of adding is 0.8～2 times of quality of hydrochloro-auric acid; 1.-3, utilize Rotary Evaporators to concentrate and contain golden nanometer particle particulate solution; 1.-4, be evaporated to 1/10～1/8 o'clock of the volume of organic solvent of step in 1.-1 at the volume that contains golden nanometer particle particulate solution; Use methyl alcohol or dissolve with ethanol to contain the impurity in the golden nanometer particle particulate solution; And separate out the golden nanometer particle particle of the organic phase of the agent that is protected behind filtration drying parcel with the golden nanometer particle particle is centrifugal with whizzer.
Described step 1.-1 in consisting of phase-transferring agent adopt four octyl group brometo de amonios, organic solvent adopts toluene solution; Described step 1.-2 in protective material adopt positive hexylmercaptan or dodecyl mercaptans, reductive agent adopts sodium borohydride.
Described organic phase golden nanometer particle particulate median size size is 1～10nm.
Described step 2.-1 with described step 2.-2 in organic solvent adopt chloroformic solution; Described step 2.-2 in polymkeric substance adopt polymethylmethacrylate or polystyrene.
The area density of the micron/submicron golden nanometer particle 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 golden nanometer particle ring and described micron/submicron gold ring is 0.2～3.6 μ m, and the mean outside diameter of described micron/submicron golden nanometer particle ring and described micron/submicron gold ring is 0.6～4.2 μ m; Described micron/submicron golden nanometer particle ring is by the golden nanometer particle granulometric composition, and the golden nanometer particle particulate median size of forming described micron/submicron golden nanometer particle ring is 1～50nm.
Compared with prior art, the invention has the advantages that:
1) utilize the golden nanometer particle ring that the inventive method prepares or the interior external diameter of gold ring and the area density of ring to be easy to control and adjustment, and the technology 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 golden nanometer particle ring or the golden array mould plate that encircles of micron/submicron that the Photobiology sensing device needs.
2) in the process of preparation film making solution; Through the gold in the golden nanometer particle particle that changes organic phase in the film making solution and the ratio of quality and the number of copies of polymkeric substance, can control effectively by endless belt (zone between the interior external diameter of the golden nanometer particle ring) width of the golden nanometer particle ring of golden nanometer particle granulometric composition with by endless belt (zone between the interior external diameter that the gold encircles) width of the gold ring of fused golden nanometer particle granulometric composition.
3) in the process of preparation film making solution, through changing the concentration of film making solution, the ring structure of the micron of preparation/submicron golden nanometer particle ring or micron/submicron gold ring can form different contoured shapes; In addition, in than the golden nanometer particle polymeric film by the preparation of low concentration film making solution under the low ambient temperature, the golden nanometer particle particle is fused together easily and forms golden ring structure.
4) in the process of preparation film making solution and preparation golden nanometer particle polymeric film, through changing its envrionment temperature, the size of control growing bubble effectively, thereby the size of the internal diameter of gate ring effectively, and change the width of endless belt.
5) in heat treatment process, under 180 ℃ thermal treatment temp, can remove effectively and be wrapped in the circumgranular protective material of golden nanometer particle, eliminate the protective material effect of chemical bond.
6) in preparation golden nanometer particle particulate process; Through changing protectant amount; Synthetic golden nanometer particle particle grain size size can be controlled effectively, thereby the golden nanometer particle particle grain size size in the endless belt of golden nanometer particle ring can be controlled at effectively.
Description of drawings
The optical microscope photograph and the electron scanning micrograph of the micron that Fig. 1 prepares for embodiment one/submicron gold ring;
The optical microscope photograph and the electron scanning micrograph of the micron that Fig. 2 prepares for embodiment two/submicron golden nanometer particle ring;
Fig. 3 is the optical microscope photograph and the electron scanning micrograph of micron/submicron golden nanometer particle ring of implementing row three and preparing;
Fig. 4 is the optical microscope photograph and the electron scanning micrograph of micron/submicron golden nanometer particle ring of implementing row four and preparing.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment one:
A kind of preparation method of micron/submicron gold ring, it mainly may further comprise the steps:
1. adopt existing sol-gel method to prepare the golden nanometer particle particle of organic phase.The golden nanometer particle particulate detailed process of preparation organic phase is: 1.-1, at room temperature, and with aqueous solution of chloraurate (hydrochloro-auric acid (HAuCl
4) 0.31g, water 25ml) consisting of phase-transferring agent through 1.5g shifts in the organic solvent of 80ml into 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; The reductive agent (about vigorous stirring 30 minutes) that continues to stir this solution then and slowly add 0.38g; From the mid-gold ion that swaps out of solution, formation contains golden nanometer particle particulate solution to restir more than 3 hours; 1.-3, utilize Rotary Evaporators to concentrate to contain golden nanometer particle particulate solution, vaporization temperature is controlled at below 50 ℃; 1.-4; When containing about 1/8 (being about 10ml) of the organic solvent of golden nanometer particle particulate solution evaporation to step in 1.-1; Promptly when the volume that contains golden nanometer particle particulate solution and the step volume of organic solvent in 1.-1 than for the 1:8 left and right sides time; The methyl alcohol or the ethanol that add 400ml; Impurity in the solvent soln; Reach the purpose of cleaning; And separate out the golden nanometer particle particle is centrifugal through centrifugation method; Generate black precipitate; Filter; Dry black precipitate promptly gets required organic phase golden nanometer particle particle (the golden nanometer particle particle of protective material parcel).At this, methyl alcohol or alcoholic acid add-on 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 big I of golden nanometer particle particulate median size of organic phase is controlled through controlling protectant add-on; When the protectant amount that adds more for a long time; The golden nanometer particle particle grain size for preparing is less; When the protectant amount that adds more after a little while; The golden nanometer particle particle grain size for preparing is bigger, in actual fabrication process, the golden nanometer particle particulate median size size for preparing can be controlled in 1～10nm scope.
2. prepare film making solution.2.-1, be under 5 ℃ the condition in envrionment temperature detailed process is:, the golden nanometer particle particle of organic phase is dissolved in the organic solvent fully, obtains the solution of gold nanoparticles that gold content is 0.03g/ml; 2.-2, choose polymkeric substance, under envrionment temperature is 5 ℃ condition, polymkeric substance is dissolved in above-mentioned same a kind of organic solvent fully then, obtain polymers soln, the content of polymkeric substance is 0.2g/ml in the solution; 2.-3, solution of gold nanoparticles is sneaked in the 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, the method solvent flashing of employing low-temperature heat concentrates described mixing solutions or adds the described mixing solutions of solvent cut and obtains film making solution; The total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.06g/ml in the film making solution, and the concentration of film making solution is by the content decision of two kinds of solutes in solution; 2.-5, utilize ultrasonic wave to film making solution effect 0.7 hour, make two kinds of solute thorough mixing of golden nanometer particle particle and polymkeric substance, two kinds of solutes are dispersed in the solvent.
Above-mentioned organic solvent adopts chloroformic solution; Polymkeric substance adopts polymethylmethacrylate or polystyrene, and the molecular weight of polymethylmethacrylate is 35000.
In addition, the size of the bubble that forms in the film making solution and quantity are subjected to the concentration and the Influence of Temperature of film making solution.
3. prepare the golden nanometer particle polymeric film.Detailed process is: be under 5 ℃ the condition, the film making solution rapid and uniform to be dripped on the surface that is coated onto substrate base in envrionment temperature, along with the volatilization of solvent, forming thickness is the golden nanometer particle polymeric film of 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 film making solution drips on the polished surface that is applied to silicon chip when adopting the silicon chip of single-sided polishing.
At this, the thickness of golden nanometer particle polymeric film depends on dripping the amount of being coated with and dripping the size that is coated with area of a concentration of the film making solution that is coated in the substrate base surface and film making solution.The amount of being coated with of dripping for certain film making solution is coated with area with dripping; The thickness of golden nanometer particle polymeric film depends primarily on the concentration of film making solution; For example; Be coated with under the identical situation of area with dripping dripping the amount of being coated with, concentration is that the film specific concentration of the film making solution preparation of 0.3g/ml is about thick 5 times of the film of the film making solution preparation of 0.06g/ml.
In addition; In film-forming process; Through changing the film formed envrionment temperature of golden nanometer particle polymer thin; Can control the evaporation rate of solvent in the film making solution; Thereby can control the growth of bubble in the golden nanometer particle polymeric film effectively and at the golden nanometer particle particulate self assembling process at bubble edge, to obtain little ring structure that the golden nanometer particle self-assembly by the protective material parcel that different size distributes forms.
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 natural air drying; 4.-2, the golden nanometer particle polymeric film behind the natural air drying is carried out low-temperature bake, storing temperature is the temperature near solvent boiling point in the film making solution, and in the actual process desirable 70 ℃, storing time is 1 hour; 4.-3, slowly improve storing temperature to a little more than the temperature of the protective material boiling point in the golden nanometer particle particle and be lower than the decomposition temperature of polymkeric substance; Can reach 180 ℃ in the actual process; The golden nanometer particle polymeric film is continued baking 2 hours, can form micron/submicron gold ring.Fig. 1 has provided the optical microscope photograph and the electron scanning micrograph of the micron/submicron gold ring for preparing.As can be seen from Figure 1, the endless belt of the gold ring that 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 present embodiment, low-temperature bake golden nanometer particle polymeric film can effectively be removed residual solvent; Again with a little more than the temperature of protective material boiling point in the golden nanometer particle and be lower than the decomposition temperature baking golden nanometer particle polymeric film of polymkeric substance; Can effectively remove parcel golden nanometer particle particulate protective material; Around the bubble of simultaneously more golden nanometer particle particle aggregation in the golden nanometer particle polymeric film, self-assembly forms behind the micron/submicron golden nanometer particle ring golden nanometer particle particle fusion and forms that micron/submicron is golden to be encircled.
Embodiment two:
The preparation method of the micron of present embodiment/preparation method of submicron golden nanometer particle ring and the gold ring of embodiment one is basic identical; Difference only is that the concentration of the film making solution of 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 the optical microscope photograph and the electron scanning micrograph of the micron/submicron golden nanometer particle ring for preparing.As can be seen from Figure 2, the golden nanometer particle ring that present embodiment prepares is by the golden nanometer particle granulometric composition, and golden nanometer particle particulate median size is 10nm; Form described golden nanometer particle ring endless belt in the middle of protuberance and sink in both sides partly, the mean outside diameter of endless belt is 1.6 μ m, mean inside diameter is 0.9 μ m; The area density of golden nanometer particle ring is 10
7Cm
-2
Embodiment three:
The preparation process of the micron of present embodiment/preparation method of submicron golden nanometer particle ring and the golden nanometer particle ring of embodiment two is basic identical, and difference only is that the process of present embodiment preparation film making solution is to carry out under 15 ℃ the condition in envrionment temperature; Be under 15 ℃ the environment in temperature, preparation golden nanometer particle polymeric film.Fig. 3 has provided the optical microscope photograph and the electron scanning micrograph of the micron/submicron golden nanometer particle ring for preparing.As can be seen from Figure 3, the golden nanometer particle ring that present embodiment prepares is by the golden nanometer particle granulometric composition, and golden nanometer particle particulate median size is 25nm; Form described golden nanometer particle ring endless belt in the middle of protuberance and sink in both sides partly, the mean outside diameter of endless belt is 2 μ m, mean inside diameter is 1.4 μ m; The area density of golden nanometer particle ring is about 10
7Cm
-2
Embodiment four:
A kind of preparation method of micron/submicron golden nanometer particle ring, the preparation process of the gold ring of its preparation process and embodiment one is basic identical, and difference is that the process of present embodiment preparation film making solution is to carry out under 20 ℃ the condition in envrionment temperature; Be under 20 ℃ the environment in temperature, preparation golden nanometer particle polymeric film; Heat treatment process is to carry out under 70 ℃ the low temperature at storing temperature.Fig. 4 has provided the optical microscope photograph and the electron scanning micrograph of the micron/submicron golden nanometer particle ring for preparing.As can be seen from Figure 4, the golden nanometer particle ring that present embodiment prepares is by the golden nanometer particle granulometric composition, and golden nanometer particle particulate median size is 25nm; The zonary structure of forming described golden nanometer particle 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 golden nanometer particle ring is about 10
7Cm
-2
Embodiment five:
The preparation process of the micron of present embodiment/preparation method of submicron gold ring and the gold ring of embodiment one is basic identical; Difference only is that the ratio of quality and the number of copies of two kinds of solutes in the film making solution of present embodiment preparation is different, and the gold in the golden nanometer particle particle of present embodiment and the ratio of quality and the number of copies of polymkeric substance are 1:0.7.When dripping on the substrate base be coated with preparation golden nanometer particle polymeric film after; 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 of present embodiment/preparation method of submicron golden nanometer particle ring and the micron of embodiment one/submicron gold ring is basic identical, but preparation parameter is different, and its detailed process is following:
1. adopt existing sol-gel method to prepare the golden nanometer particle particle of organic phase.
2. prepare film making solution.2.-1, be under 25 ℃ the condition in envrionment temperature detailed process is:, the golden nanometer particle particle of organic phase is dissolved in the organic solvent fully, the content that obtains gold is the solution of gold nanoparticles of 0.03g/ml; 2.-2, choose polymkeric substance, under envrionment temperature is 25 ℃ condition, polymkeric substance is dissolved in in a kind of organic solvent fully then, the content that obtains polymkeric substance is the polymers soln of 0.2g/ml; 2.-3, solution of gold nanoparticles is sneaked in the 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 and obtains film making solution; The total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.3g/ml in the film making solution, and the concentration of film making solution is by the content decision of two kinds of solutes in solution; 2.-5, utilize ultrasonic wave to film making solution effect 0.7 hour, make two kinds of solute thorough mixing of golden nanometer particle particle and polymkeric substance, two kinds of solutes are dispersed in the solvent.
3. prepare the golden nanometer particle polymeric film.Detailed process is: be under 25 ℃ the condition, the film making solution rapid and uniform to be dripped on the surface that is coated onto substrate base in envrionment temperature, along with the volatilization of solvent, forming thickness is the golden nanometer particle polymeric film of 35 μ m.
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron golden nanometer particle ring.Detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out natural air drying; 4.-2, the golden nanometer particle polymeric film behind the natural air drying is carried out low-temperature bake, storing temperature is the temperature (like solvent is chloroformic solution, and storing temperature is desirable 70 ℃) near solvent boiling point in the film making solution, and storing time is 3 hours; 4.-3, slowly improve storing temperature to a little more than the temperature of protective material boiling point in the golden nanometer particle particle and be lower than the decomposition temperature of polymkeric substance, can reach 180 ℃ in the actual process, continue baking 1 hour, promptly form micron/submicron golden nanometer particle ring.
The area density of micron/submicron golden nanometer particle ring that present embodiment forms is about 5 * 10
6Cm
-2, the mean outside diameter of golden nanometer particle ring is 4 μ m, mean inside diameter is 3.5 μ m.Protuberance and sink in both sides partly in the middle of the endless belt of golden nanometer particle ring, the golden nanometer particle particulate median size of forming endless belt is 40nm.
Embodiment seven:
The preparation process of the micron of present embodiment/preparation method of submicron golden nanometer particle ring and the golden nanometer particle ring of embodiment two is basic identical, but preparation parameter is different, 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.2.-1, be under 15 ℃ the condition in envrionment temperature detailed process is:, the golden nanometer particle particle of organic phase is dissolved in the organic solvent fully, the content that obtains gold is the solution of gold nanoparticles of 0.02g/ml; 2.-2, choose polymkeric substance, under envrionment temperature is 15 ℃ condition, polymkeric substance is dissolved in in a kind of organic solvent fully then, obtain the polymers soln that polymer content is 0.06g/ml; 2.-3, solution of gold nanoparticles is sneaked in the 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 and obtains film making solution; The total content of golden nanometer particle particle and two kinds of solutes of polymkeric substance is 0.15g/ml in the film making solution, and the concentration of film making solution is by the content decision of two kinds of solutes in solution; 2.-5, utilize ultrasonic wave to film making solution effect 1 hour, make two kinds of solute thorough mixing of golden nanometer particle particle and polymkeric substance, two kinds of solutes are dispersed in the solvent.
3. prepare the golden nanometer particle polymeric film.Detailed process is: be under 15 ℃ the condition, the film making solution rapid and uniform to be dripped on the surface that is coated onto substrate base in envrionment temperature, after the solvent evaporates, forming thickness is the golden nanometer particle polymeric film about 25 μ m.
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron golden nanometer particle ring.Detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out natural air drying; 4.-2, the golden nanometer particle polymeric film behind the natural air drying is carried out low-temperature bake, storing temperature is the temperature (like solvent is chloroform, and storing temperature is desirable 70 ℃) near solvent boiling point in the film making solution, and storing time is 2 hours; 4.-3, slowly improve storing temperature to a little more than the temperature of protective material boiling point in the golden nanometer particle particle and be lower than the decomposition temperature of polymkeric substance, can reach 180 ℃ in the actual process, continue baking 3 hours, promptly form micron/submicron golden nanometer particle ring.
The area density of micron/submicron golden nanometer particle ring that present embodiment forms is about 8 * 10
6Cm
-2, the mean outside diameter of golden nanometer particle ring is 1.5 μ m, mean inside diameter is 1.2 μ m.Protuberance and sink in both sides partly in the middle of the endless belt of golden nanometer particle ring, the golden nanometer particle particulate median size of forming endless belt is 25nm.
Below, the feasibility and the validity of the inventive method is described for through comparing each embodiment.
In embodiment one and embodiment two; The envrionment temperature of the envrionment temperature of configuration film making solution and preparation golden nanometer particle polymeric film is identical; Gold in the 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 of film making solution is different.In the process of preparation golden nanometer particle polymeric film; Golden nanometer particle polymeric film by the preparation of the film making solution of lower concentration is thinner; The bubble that generates in the film is less; Make around the bubble the easy emersion golden nanometer particle of golden nanometer particle particle polymeric film surface 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 that generates in the film is also bigger; Make the golden nanometer particle particle be subjected to the resistance of the polymkeric substance parcel of periphery to be difficult to emersion golden nanometer particle polymeric film surface and fusion each other greatly; Form micron/submicron golden nanometer particle ring easily, as shown in Figure 2.
The concentration of the film making solution that adopts among embodiment two and the embodiment three is identical, and the envrionment temperature of configuration film making solution and preparation golden nanometer particle polymeric film envrionment temperature are different.Comparing embodiment two and embodiment three; Can find; For the lower embodiment two of envrionment temperature; The bubble that the film making solution of configuration produces when being used to prepare the golden nanometer particle polymeric film is less relatively, and the mean inside diameter of the golden nanometer particle ring that makes is little than the mean inside diameter of the golden nanometer particle ring that embodiment three makes; Again because in the film making solution of embodiment two and embodiment three; Gold in the golden nanometer particle particle is identical with the ratio of polymkeric substance, and then the ring width band width of the golden nanometer particle ring that the internal diameter that makes than embodiment three of the endless belt width of the less golden nanometer particle ring of the internal diameter that makes of embodiment two (the interior external diameter of golden nanometer particle ring poor) is bigger is big; Simultaneously; Under higher envrionment temperature in the self assembling process of golden nanometer particle; In the golden nanometer particle ring and near golden nanometer particle grow into bigger golden nanometer particle particle easily, and when envrionment temperature was low, the original particle diameter of golden nanometer particle particulate remained unchanged basically.Therefore visible, the golden nanometer particle particulate median size of forming endless belt among the embodiment two is 10nm, and the golden nanometer particle particulate median size that embodiment three forms endless belt is 25nm, respectively like Fig. 3 and shown in Figure 4.
With regard to embodiment four, each component proportions of its film making solution is identical with embodiment one, and the envrionment temperature of the envrionment temperature of configuration film making solution and preparation golden nanometer particle polymeric film is different.Comparing embodiment four and embodiment one, the preparation envrionment temperature among the embodiment four is higher, and the bubble that the film making solution of configuration produces when being used to prepare the golden nanometer particle polymeric film is relatively large, and the internal diameter of the golden nanometer particle ring that then makes is bigger; Be the lower concentration film making solution owing to what adopt among embodiment four and the embodiment one again; Compare with embodiment three with embodiment two; Can see in the film making solution of embodiment four and embodiment one the golden nanometer particle particle more easily emersion to the surface of golden nanometer particle polymeric film; Embodiment one forms the more smooth gold ring of surface ratio as shown in Figure 1, and embodiment four forms the more smooth golden nanometer particle ring of surface ratio as shown in Figure 4.It may be noted that; Because the bubble that the film making solution of embodiment four configurations produces when being used to prepare the golden nanometer particle polymeric film is relatively large; Stability is poor than situation among the embodiment one; Be destroyed easily when carrying out 180 ℃ high-temperature heat treatment again; Therefore, four of embodiment carry out low-temperature heat treatment under 70 ℃ of storing temperatures.
Embodiment five compares with embodiment one; 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 gold among the embodiment five in the golden nanometer particle particle is higher with the ratio of quality and the number of copies of polymkeric substance, therefore golden nanometer particle is easier to assemble the gold ring that the formation ring width is wideer than embodiment one and internal diameter is bigger under identical conditions.
In addition; The golden nanometer particle particulate median size size for preparing in the inventive method is about 1～10nm; If prepare the golden nanometer particle polymeric film at low temperatures; The golden nanometer particle particulate median size size that then forms ring is approximate identical with the golden nanometer particle particulate median size size that makes, and is 10nm like the golden nanometer particle particulate median size size that forms ring among the embodiment two; And if under comparatively high temps preparation golden nanometer particle polymeric film; Then in the self assembling process of golden nanometer particle; Golden nanometer particle particle in the endless belt can be fused together; Forming the bigger golden nanometer particle particle of median size, is 25nm like the golden nanometer particle particulate median size size of the ring that forms among embodiment three and the embodiment four.
Claims (6)
1. the preparation method of micron/submicron golden nanometer particle ring and gold ring is characterized in that may further comprise the steps:
1. adopt sol-gel method to prepare the golden nanometer particle particle of organic phase;
2.-1, be under 0～30 ℃ the condition in envrionment temperature 2. prepare film making solution, detailed process is:, the golden nanometer particle particle of organic phase is dissolved in the organic solvent fully, the content that obtains gold is the solution of gold nanoparticles of 0.01g/ml～0.05g/ml; 2.-2, choose polymkeric substance, under envrionment temperature is 0～30 ℃ condition, polymkeric substance is dissolved in in a kind of described organic solvent fully then, the content that obtains polymkeric substance is the polymers soln of 0.02g/ml～0.2g/ml; 2.-3, solution of gold nanoparticles is sneaked in the 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, concentrate or diluted mixture solution obtains 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 in the film making solution; 2.-5, utilize ultrasonic wave to film making solution effect 0.3～1 hour, make two kinds of solute thorough mixing of golden nanometer particle particle and polymkeric substance, two kinds of solutes are dispersed in the solvent;
3. prepare the golden nanometer particle polymeric film; Detailed process is: be under 0～30 ℃ the condition in envrionment temperature; The film making solution rapid and uniform is dripped on the surface that is coated onto substrate base, and forming thickness after the solvent evaporates is the golden nanometer particle polymeric film of 0.5～50 μ m;
4. the golden nanometer particle polymeric film is heat-treated, form micron/submicron golden nanometer particle ring or micron/submicron gold ring, detailed process is: 4.-1, at room temperature, the golden nanometer particle polymeric film is carried out natural air drying; 4.-2, the golden nanometer particle polymeric film behind the natural air drying is carried out low-temperature bake, storing temperature is the temperature near solvent boiling point in the film making solution, and storing time is 1～3 hour; 4.-3, slowly improve storing temperature to a little more than the temperature of protective material boiling point in the golden nanometer particle particle and be lower than the decomposition temperature of polymkeric substance; The golden nanometer particle polymeric film is proceeded 1～3 hour baking, form micron/submicron golden nanometer particle ring or micron/submicron gold ring.
2. the preparation method of a kind of micron/submicron golden nanometer particle ring according to claim 1 and gold ring; It is characterized in that described step detailed process 1. is: 1.-1, at room temperature; The aqueous solution of chloraurate of 0.01g/ml～0.02g/ml shifted into through consisting of phase-transferring agent form mixing solutions in the organic solvent; Wherein, The quality of consisting of phase-transferring agent is 4～6 times of quality of hydrochloro-auric acid, and volume of organic solvent is 3～4 times of volume of aqueous solution of chloraurate; 1.-2, at room temperature; When stirring described mixing solutions, add protective material; Under whipped state, continue slowly to add reductive agent then; Restir is more than 3 hours; From the mid-gold ion that swaps out of solution, formation contains golden nanometer particle particulate solution, wherein; The protectant quality that adds is 0.8～3 times of quality of hydrochloro-auric acid, and the quality of the reductive agent of adding is 0.8～2 times of quality of hydrochloro-auric acid; 1.-3, utilize Rotary Evaporators to concentrate and contain golden nanometer particle particulate solution; 1.-4, be evaporated to 1/10～1/8 o'clock of the volume of organic solvent of step in 1.-1 at the volume that contains golden nanometer particle particulate solution; Use methyl alcohol or dissolve with ethanol to contain the impurity in the golden nanometer particle particulate solution; And separate out the golden nanometer particle particle of the organic phase of the agent that is protected behind filtration drying parcel with the golden nanometer particle particle is centrifugal with whizzer.
3. the preparation method of a kind of micron/submicron golden nanometer particle ring according to claim 2 and gold ring is characterized in that consisting of phase-transferring agent adopts four octyl group brometo de amonios during described step 1.-1, and organic solvent adopts toluene solution; Described step 1.-2 in protective material adopt positive hexylmercaptan or dodecyl mercaptans, reductive agent adopts sodium borohydride.
4. according to the preparation method of each described a kind of micron/submicron golden nanometer particle ring in the claim 1 to 3, it is characterized in that the golden nanometer particle particulate median size size of described organic phase is 1～10nm with the gold ring.
5. the preparation method of a kind of micron/submicron golden nanometer particle ring according to claim 4 and gold ring, it is characterized in that described step 2.-1 with described step 2.-2 in organic solvent adopt chloroformic solution; Described step 2.-2 in polymkeric substance adopt polymethylmethacrylate or polystyrene.
6. the preparation method of a kind of micron/submicron golden nanometer particle ring according to claim 5 and gold ring is characterized in that the area density of micron/submicron golden nanometer particle ring described in described step 4. and described micron/submicron gold ring is 10
6～10
8Cm
-2, the mean inside diameter of described micron/submicron golden nanometer particle ring and described micron/submicron gold ring is 0.2～3.6 μ m, the mean outside diameter of described micron/submicron golden nanometer particle ring and described micron/submicron gold ring is 0.6～4.2 μ m; Described micron/submicron golden nanometer particle ring is by the golden nanometer particle granulometric composition, and the golden nanometer particle particulate median size of forming described micron/submicron golden nanometer particle ring is 1～50nm.
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| CN105606587A (en) * | 2015-12-31 | 2016-05-25 | 宁波大学 | Enrofloxacin detection method based on silver nanoparticles and carborundum paper SERS substrate |
| CN106159110A (en) * | 2016-09-14 | 2016-11-23 | Tcl集团股份有限公司 | A kind of AgNWs thin film, light emitting diode with quantum dots and preparation method thereof |
| CN112305786A (en) * | 2020-10-26 | 2021-02-02 | 江西师范大学 | Vector near-field light regulation and control device and method based on circular-ring-shaped particle array |
| CN114002163A (en) * | 2021-10-13 | 2022-02-01 | 华中科技大学 | Gold nanowire film with ultraviolet multimode coupling function, and preparation method and application thereof |
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| JP2006104255A (en) * | 2004-10-01 | 2006-04-20 | Ube Ind Ltd | Metal nanorod-polymer composite and method for producing the same |
| CN101015862A (en) * | 2007-03-02 | 2007-08-15 | 江南大学 | Process for preparing gold nano particle by using aqueous phase soft mould plate method |
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| JP2006104255A (en) * | 2004-10-01 | 2006-04-20 | Ube Ind Ltd | Metal nanorod-polymer composite and method for producing the same |
| CN101015862A (en) * | 2007-03-02 | 2007-08-15 | 江南大学 | Process for preparing gold nano particle by using aqueous phase soft mould plate method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105606587A (en) * | 2015-12-31 | 2016-05-25 | 宁波大学 | Enrofloxacin detection method based on silver nanoparticles and carborundum paper SERS substrate |
| CN105606587B (en) * | 2015-12-31 | 2018-09-28 | 宁波大学 | Enrofloxacin detection method based on nano-Ag particles Yu carborundum paper SERS substrates |
| CN106159110A (en) * | 2016-09-14 | 2016-11-23 | Tcl集团股份有限公司 | A kind of AgNWs thin film, light emitting diode with quantum dots and preparation method thereof |
| CN112305786A (en) * | 2020-10-26 | 2021-02-02 | 江西师范大学 | Vector near-field light regulation and control device and method based on circular-ring-shaped particle array |
| CN112305786B (en) * | 2020-10-26 | 2023-10-20 | 江西师范大学 | Vector near-field light regulation and control device and method based on annular particle array |
| CN114002163A (en) * | 2021-10-13 | 2022-02-01 | 华中科技大学 | Gold nanowire film with ultraviolet multimode coupling function, and preparation method and application thereof |
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