CN103769609B - A kind of noble metal-semiconductors coupling structure micro-nano particle, preparation method, application - Google Patents

Abstract

The invention discloses a noble metal-semiconductor composite structure micro-nano particle, a preparation method, and an application. The preparation method includes placing a semiconductor reaction structure in a solution containing a noble metal salt, and focusing a pulsed laser beam on the semiconductor reaction structure after passing through a focusing lens. The surface of the structure is in contact with the solution, thereby generating a plasma plume at the surface of the semiconductor reactive structure. During the reaction process, two (or more) laser beams need to act together (or in linkage) on the same reaction area, one part of the laser beam is in a fully focused state for ablation, and the other part of the laser beam is used for irradiation and induced recombination. While performing pulsed laser ablation, the semiconductor reaction structure is rotated to make the reaction more uniform. The micro-nano particles with a specific and unique noble metal-semiconductor composite structure prepared by the above method can be applied in the fields of microelectronic processing, optics, biology, catalytic chemistry, or medicine.

Description

A kind of noble metal-semiconductor composite structure micro-nano particle, preparation method and application

technical field

The present invention relates to the research field of micro-nano particle preparation technology, in particular to a precious metal-semiconductor composite structure micro-nano particle, preparation method and application. The particle is pulsed laser ablation and induced recombination in a liquid phase environment by using several laser beams Noble metal-semiconductor micro-nano particles with special structure prepared by reaction.

Background technique

Since entering the 21st century, nanomaterials and technology have shown good application prospects in many fields such as electronics, optics, and biomedicine, and have become the frontier research field of nanotechnology, attracting a large number of fields such as physics, chemistry, materials, and biology. Experts and researchers have devoted themselves to the research work in this field. Scientific research over the years has shown that micro-nano particles, especially composite micro-nano particles with special structures, will exhibit many new properties different from those of single-component nanomaterials, resulting in some new phenomena. These new properties and new phenomena are of great significance to people's understanding and utilization of these materials, and will also have a revolutionary impact on future industries and technologies. Noble metals and semiconductors have obvious differences in physical and chemical properties, which enables strong mutual coupling between the components of the composite nanomaterial system composed of the two, which not only enhances the intrinsic characteristics of noble metals and semiconductor materials, Moreover, it is also possible to enable composite structures to exhibit many new properties, thereby breaking through the limitations of the performance of a single component or class of materials. The utilization of these new properties will make noble metal-semiconductor composite nanomaterials create huge potential in important fields such as the research and development of new functional materials, the utilization of new energy materials, environmental protection and harmless degradation, biochemical medicine, and the preparation of micro-nano optoelectronic devices. Chance. In the development of noble metal-semiconductor micro-nano particles, the method of synthesis and assembly will have a huge impact on the characteristics of nanocomposites and the performance of functional devices assembled using them. Among them, the synthesis of noble metal-semiconductor micro-nano particles with specific metastable wrapping composite morphology, including the shape of the particles and the controllable synthesis of their phase structure, is a cutting-edge and extremely challenging research direction , is also an urgent problem to be solved.

At present, the research on the structure and properties of noble metal-semiconductor composite nanomaterials and their micro-nano particles is a hot spot in the field of inorganic functional materials research. It is generally believed that the performance of composite nanomaterials is mainly determined by the coupling characteristics of composite materials, composite morphology, surface effects and particle size effects. A large number of literature reports have pointed out that the performance of composite nanomaterials is determined by the electron transport structure between the two materials and the state of adsorption of surface components: the coupled electronic structure is completely dependent on the composite crystal structure and lattice of the two materials size, while the adsorption state of surface components often leads to changes in photophonon transport or other luminescent properties. Therefore, the synthesis of noble metal-semiconductor nanostructures with special metastable composite morphology will help to greatly expand the exploration and research on the properties and applications of micro-nano particles. For different preparation methods, the factors affecting the synthesis of noble metal-semiconductor composite micro-nano particles are different, but the reaction time, temperature, reaction performance and the use of surfactants will all affect the size of composite nanocrystals. Or the shape, as well as the crystal quality have a significant impact. Therefore, choosing an appropriate reaction method to realize the size and shape preparation of composite micro-nano particles is particularly important for the research and development of materials. So far, a lot of related work at home and abroad has focused on the synthesis and methods of noble metal-semiconductor composite micro-nano particles, such as chemical vapor phase synthesis, molecular beam epitaxy growth technology, hydrothermal method composite technology, etc.; and there are some literatures It is pointed out that people can successfully prepare some interesting composite nanostructures with wrapping morphology. On the other hand, pulsed laser ablation reaction technology, as a developed technology, is very suitable for the preparation of nanomaterials and nanostructures with metastable morphology. The content is very small, and it is used to prepare microstructures such as quantum wells, quantum junctions, and quantum wires. In previous studies, this kind of pulsed laser ablation reaction preparation technology, which is mainly based on physical reactions, was mostly carried out in a vacuum or a thin inert gas environment. Its working principle includes: 1. Focusing the pulsed laser beam on the surface of the reaction target, causing the surface of the reaction target to generate high temperature and melting, thereby forming a plasma plume on the surface of the target; 2. The plasma will be localized in a vacuum or a thin gas environment. The expansion, followed by rapid cooling at the end of the laser pulse, causes the species that were in the plasma to combine and deposit on the substrate due to the quench. By controlling the reaction conditions, the final product can form microstructures such as thin films or nanoparticles. The nanomaterials prepared by this method have uniform structure and high material purity, and can also obtain certain functional structures by controlling the reaction conditions. Therefore, laser ablation deposition is a preparation technique for preparing high-quality micro-nano structured materials. However, ordinary laser ablation reactions are carried out under vacuum or rare gas conditions, so most of the micro-nano structures generated by these reactions are stable structures formed by natural growth, and it is difficult to produce them under vacuum or rare gas conditions. Realize the development of composite materials. Therefore, when people want to obtain some kind of metastable nanoparticles with composite material structure, since their formation is required to be completed under certain metastable conditions, it is difficult to meet the requirements with ordinary pulsed laser ablation deposition technology. .

Contents of the invention

The main purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art, and provide a preparation method of precious metal-semiconductor composite structure micro-nano particles. The method is easy to operate, and the preparation process is fast. Parameters, one-step preparation of micro-nano particles with a unique noble metal-semiconductor composite structure with good application prospects.

Another object of the present invention is to provide noble metal-semiconductor composite micro-nano particles prepared by the above preparation method.

Another object of the present invention is to provide the application of the above-mentioned noble metal-semiconductor composite structure micro-nano particles with special morphology in the fields of microelectronic processing, optics, biology, catalytic chemistry, medicine and the like.

The purpose of the present invention is achieved through the following technical solutions: a preparation method of noble metal-semiconductor composite structure micro-nano particles, the steps are as follows: the semiconductor reaction structure is placed in a solution containing noble metal salt components, and several pulsed laser beams are focused through the After the lens is focused on the surface of the semiconductor reaction structure, the surface material of the semiconductor reaction structure is melted by laser ablation, and then a plasma plume is formed on the upper surface of the semiconductor reaction structure. Several pulsed laser beams pass through the focusing lens and irradiate on the The surface of the semiconductor reaction structure, the noble metal component is precipitated from the solution by laser precipitation around the above-mentioned plasma plume, and is attached to the surface of the semiconductor micro-nano particle under the induction of the laser. It is generated on the semiconductor reaction structure; after a period of time, the pulse laser is stopped to irradiate the semiconductor reaction structure, and the reaction product is taken out by suction filtration, dialysis, separation and drying, and the precious metal-semiconductor composite structure micro-nano particles are obtained. In the present invention, by properly adjusting the laser energy intensity, focusing state, and type of noble metal salt solution, the product of unique noble metal-semiconductor composite structure micro-nano particles can be obtained under appropriate reaction conditions.

Specifically include the following steps:

(1) Fixing the semiconductor reaction structure in a container containing a noble metal salt solution;

(2) Perform pulsed laser ablation reaction: several pulsed laser beams emitted by lasers with different laser wavelengths are respectively focused by a focusing lens and then collectively irradiated on the reaction area on the semiconductor reaction structure, and some of the laser beams are in a fully focused state. It is used for ablation to generate a plasma plume on the surface of the reaction area; another part of the laser beam is focused into a spot with a focal diameter of 3 to 5 times the focal diameter, which is used for irradiation and induced recombination;

(3) After the pulse laser ablation reaction has been carried out for a period of time, stop the pulse laser irradiation on the semiconductor reaction structure, and the reaction product is taken out by suction filtration, dialysis, separation and drying, and then the precious metal-semiconductor composite structure micro-nano particles are obtained.

Preferably, when the pulsed laser ablation reaction is performed in the step (2), the semiconductor reaction structure is rotated in the container. Thus, the reaction can be carried out uniformly.

In order to better realize the present invention, the physical parameters (such as wavelength and pulse width) of the pulsed laser beam emitted by the laser can be adjusted. According to the difference of semiconductor reaction structure and solution, the laser used for ablation and the The type of laser that induces recombination is also adjustable. The laser type mentioned here refers to millisecond laser, nanosecond laser, or femtosecond laser, etc. In actual selection, you can also choose to use "nanosecond laser-nanosecond laser" linkage, or "nanosecond laser-femtosecond laser" "Linkage and so on.

Preferably, the semiconductor reaction structure is a semiconductor target, or a semiconductor single crystal substrate, the surface of which is smoothed. So that the pulsed laser can be smoothly focused on the surface of the semiconductor reaction structure.

Furthermore, the purity of the semiconductor target is greater than 98%, and the materials used in the semiconductor target include germanium, silicon or zinc oxide, gallium nitride and the like.

Preferably, the solution containing noble metal salt components is chloroauric acid solution, or silver nitrate solution, or chloroplatinic acid solution, or palladium chloride solution, or rhodium trichloride solution, or a mixture of at least two of the above solutions .

Preferably, the semiconductor reaction structure has a thickness of 3-5 mm; its shape can be variable, preferably round or square. The container is a quartz container or a tempered glass container, which can be square or circular.

A noble metal-semiconductor compound structure micro-nano particle prepared by the above preparation method, the average size of the micro-nano particle is 100-500nm, and the overall shape is spherical or quasi-spherical; it has the characteristic of noble metal embedding or wrapping on the surface of semiconductor nanoparticles. The noble metal-semiconductor composite structure micro-nano particles have a specific shape, and are micro-nano particles in which noble metals and semiconductors are combined in a certain structure.

The noble metal-semiconductor composite structure micro-nano particles in the present invention can be applied in the fields of microelectronic processing, optics, biology, catalytic chemistry, or medicine. For example, gold-semiconductor nanostructures have strong surface plasmon localized states, which have extremely important research value in the research of some nonlinear optical micro-nano structures, and effectively prepare gold-semiconductor nanostructures with special morphology. Semiconductor composite structure micro-nano particles will better meet the requirements of this material in basic research and application.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

1. For the first time, the present invention uses double-beam (or multi-beam) pulsed lasers to induce matching laser ablation technology to make noble metal-semiconductor composite structure micro-nano particles in liquid phase substances. The harsh operating environment requires that the product can be prepared under normal temperature and pressure conditions.

2. The preparation method of precious metal-semiconductor composite structure micro-nano particles provided by the present invention is a pulsed laser ablation technology that utilizes multi-beam laser auxiliary control in a liquid phase environment. The laser beams are divided into two types according to their functions. In ablation, a method for irradiation and induced recombination, compared with the traditional laser ablation technology in vacuum or rare gas environment and the common single-pulse laser ablation deposition technology in liquid, due to the impact of the irradiated laser on the plasma plume The influence and control of the synthesis and growth process in the liquid phase environment will be very different from that in the general laser ablation method, thus affecting the formation of the final product.

Description of drawings

Fig. 1 is the structural representation of the equipment used in Example 1.

Fig. 2(a) is a field emission scanning electron micrograph of the gold-silicon composite structure micro-nano particles prepared in Example 1.

Fig. 2(b) is a field emission scanning electron micrograph of the silver-silicon composite structure micro-nano particles prepared in Example 2.

Fig. 3(a) is a transmission electron microscope bright-field photo of the gold-silicon composite structure micro-nano particles prepared in Example 1.

Fig. 3(b) is a selected area electron diffraction photo of the gold-silicon composite structure micro-nano particles prepared in Example 1.

Fig. 3(c) is a high-resolution photo of the edge of the gold-silicon composite structure micro-nano particles prepared in Example 1.

Fig. 3(d) is a high-resolution photo of lattice fringes of a specific gold nanoparticle on the gold-silicon composite structure micro-nanoparticle prepared in Example 1.

FIG. 4 is a comparison chart of the ultraviolet-visible-near-infrared absorption spectrum of the gold-silicon composite structure micro-nano particles prepared in Example 1 and the absorption curves of pure silicon nanoparticles and pure gold nanoparticles.

detailed description

The present invention will be further described in detail below in conjunction with the embodiments and the accompanying drawings, but the embodiments of the present invention are not limited thereto.

Example 1

As shown in Figure 1, the device used in this embodiment to prepare noble metal-semiconductor composite structure micro-nano particles includes the first laser 1 (using Nd:YAG pulsed laser, laser wavelength 532nm, pulse width 10ns, energy 50mJ, frequency 10Hz ) and the second laser 2 (using Nd:YAG short pulse laser, laser wavelength 355nm, pulse width 8ns, energy 50mJ, frequency 50Hz), laser total reflection mirror 3, focusing lens 4 (the focal length of which is 500mm), reaction Target 5 (made of monocrystalline silicon), chloroauric acid aqueous solution 6 , rotating base 7 (made of polytetrafluoroethylene), and quartz container 8 . During work, at first the reaction target 5 is fixed on the rotating base 7 and the base is put into the quartz container 8 together with the reaction target, and then an appropriate amount of liquid phase substance chloroauric acid aqueous solution 6 is injected; from the first laser 1 and the second The two beams of pulsed lasers generated in the laser 2 are respectively focused by the laser total reflection mirror group 3 and the focusing lens group 4, and then converged and irradiated on the surface of the reaction target 5 to form a plasma reaction zone formed by the simultaneous action of the two laser beams. These two pulsed laser beams are focused and irradiated on the upper surface of the target in the focused area, and the high energy of one of the focused pulsed lasers is used to melt the surface material of the target through laser ablation and then react on the upper surface of the target. A plasma plume is formed while another beam of irradiating laser light deposits precious metal components out of the liquid environment by laser precipitation around the plasma plume. On the one hand, the plasma plume will be quenched at an extremely fast speed (the time required for the process is on the order of nanoseconds or microseconds) because it is strongly bound by the liquid phase substance; on the other hand, the radiation irradiated on the plasma plume Irradiating the laser will have an effect on the generated plasma plume, that is, further ionize it, and promote the incorporation of the noble metal components precipitated in the liquid phase environment into the quenching process of the plasma plume. When the laser pulse is over, the substance that was in the molten state at the beginning will condense due to cooling, in which the semiconductor components are first combined with each other because they are in the center, and the noble metal components will form at the periphery according to the difference in reaction conditions to form micro- nanoparticles. Utilizing the condition that the laser pulse can be adjusted, adjusting the energy of the laser pulse and even the type of the laser pulse can make the generated micro-nano structure have a specific composite state.

In this example, the preparation of gold-silicon composite structure micro-nano particles is taken as an example, and the preparation method is specifically described as follows:

(1) Fix the reaction target 5 with a purity greater than 99.99%, a diameter of 25 mm, and a thickness of 5 mm on the rotating base 7 , and the rotating base 7 and the reaction target 5 are put into the quartz container 8 together.

(2) Slowly inject high-purity chloroauric acid aqueous solution 6 (concentration: 5 mM) into the quartz container 8 to immerse the reaction target 5 in the chloroauric acid aqueous solution. Adjust the optical path of the laser so that the pulsed laser beams emitted by the first laser 1 and the second laser 2 pass through the laser total reflection mirror 3 and the focusing lens 4 respectively, and then converge and irradiate on the surface of the reaction target 5. The laser frequencies can be selected to be 10Hz and 50Hz respectively , the two laser beams generate a plasma plume on the contacting surface.

(3) While performing pulsed laser ablation, the rotating base 7 is rotated so that the reaction is not limited to a small area on the surface of the target, and the rotation can also make the reaction environment more uniform. During the whole preparation process, the rotating base 7 works at a rotation frequency of 60-85 revolutions per minute, so that the reaction products can be dispersed rapidly after formation, and it is also convenient to make the prepared gold-silicon composite structure micro-nano particles more evenly distributed. The whole process lasts 30 minutes.

(4) After the two pulsed lasers react with the reaction target for 30 minutes, turn off the two lasers respectively. The solution used in the ablation reaction was taken out and filtered by suction to wash away the residual chloroauric acid aqueous solution, and the final sample was subjected to multiple suction filtration, and the prepared sample remaining on the microporous membrane was Take it off, disperse it on the single crystal silicon wafer substrate, and put it into a vacuum oven for drying. Take the single crystal silicon wafer substrate under the field emission electron microscope for magnification and observation, and you can see the prepared gold-silicon composite structure micro-nano particles on the substrate.

Fig. 2(a) is a field emission scanning electron micrograph of the gold-silicon composite structure micro-nano particles prepared in this example. It can be seen from the figure that the diameter of the gold-silicon composite structure micro-nano particles is 300-400nm, and the surface of the particles has a vein structure of gold.

Figure 3(a) and Figure 3(b) are the transmission electron microscope bright field photographs of the gold-silicon composite structure micro-nano particles prepared in this example, and the selected area electron diffraction photographs of the corresponding particles, respectively. According to these two test results, it can be confirmed that the prepared micro-nano particles do have a unique gold-silicon composite structure.

Figure 3(c) and Figure 3(d) are high-resolution photos of the particle edge of the gold-silicon composite structure micro-nano particles prepared in this example, and a specific gold on the gold-silicon composite structure micro-nano particles. High-resolution photo of lattice fringes of nanoparticles. By comparing the lattice fringes, it can be determined that the lattice fringes of the nanoparticles embedded on the surface of the silicon nanospheres are 0.2nm, corresponding to the 111 crystal plane of gold.

Fig. 4 is the comparison figure of the gold-silicon composite structure micro-nano particle ultraviolet-visible-near-infrared absorption spectrum and pure silicon nanoparticle and pure gold nanoparticle absorption curve that the present embodiment prepares, and wherein the absorption curve represented by solid line is gold- Ultraviolet-visible-near-infrared absorption characteristic spectrum of silicon composite structure micro-nano particles. It can be seen from the diagram analysis that the gold-silicon composite structure micro-nano particles prepared by the method of this example have very unique optical absorption characteristics, which are completely different from pure silicon nanoparticles (spectrum shown by the dotted line in the figure) or The optical absorption properties of pure gold nanoparticles (shown by the dotted line in the spectrum) are not simply a superposition of the properties of the two materials. This shows that the gold-silicon composite structure micro-nano particles prepared by the present invention have newer optical properties, and such optical properties will make this gold-silicon composite structure micro-nano particles have the opportunity to become the basis for the preparation of new miniature optoelectronic devices Material.

Through the above characterization means, it can be seen that the gold-silicon composite structure micro-nano particles prepared by the present invention have a unique gold-wrapped silicon structure, in which gold is wrapped in discrete veins or flakes, and a large number of gold nanoparticles are embedded in relatively Surface of large silicon nanospheres. This kind of gold-silicon composite structure micro-nano particles has completely different optical absorption properties from pure silicon nanoparticles or pure gold nanoparticles, and is expected to be used as the basic material for future micro-optoelectronic micro-nano devices.

Example 2

Present embodiment except following feature other structures are with embodiment 1:

Using the equipment used in Example 1, a high-purity (99.99% pure) single crystal silicon reaction target 5 is fixed on a polytetrafluoroethylene base 7, and the base 7 and the reaction target 5 are put into a quartz container 8 middle. Slowly inject a pure silver nitrate solution with a secondary deionization concentration of 5 mM into the quartz container 8, and immerse the target in the solution. The laser optical path is adjusted so that the pulsed laser beams emitted by the first laser 1 and the second laser 2 pass through the laser total reflection mirror 3 and the focusing lens 4 respectively, and then the focused beams are irradiated on the single crystal silicon reaction target 5 together. The operating frequency of the first laser 1 is selected to be 10 Hz, and the operating frequency of the second laser 2 is selected to be 50 Hz. During the pulsed laser ablation process, the rotating base 7 is operated at a rotation frequency of 80 rpm, so that the reaction product can be monodispersed and the reaction conditions can be made uniform. After the pulsed laser interacts with the reaction target for 60 minutes, turn off the two lasers and take out the solution in which the reaction product is dispersed. After vacuum filtration and dialysis, the sample is dropped on a single crystal silicon wafer, and then placed in a vacuum drying oven. Dry it. Finally, the single crystal silicon wafer substrate carrying the sample was observed under an electron microscope, and it can be seen that the silver-silicon composite structure micro-nano particles are all over the single crystal silicon wafer substrate.

Fig. 2(b) is a field emission scanning electron micrograph of the silver-silicon composite structure micro-nano particles prepared in this example. It can be seen from the figure that the diameter of most silver-silicon composite structure micro-nano particles is 300-500nm, showing a spherical shape, and each particle is inlaid with a larger silver nanosphere.

Example 3

Present embodiment except following feature other structures are with embodiment 1:

Using the equipment used in Example 1, a single crystal silicon (purity greater than 99.99%) reaction target 3 with a thickness of 5mm is fixed on the polytetrafluoroethylene rotating base 7, and the rotating base and the target are put into a tempered In the glass container 8, a high-purity palladium chloride solution with a concentration of 1 mM is slowly injected into the container, so that the solution can immerse the target material and the rotating base. The laser optical path is adjusted so that the pulsed laser beams emitted by the two lasers are focused on the upper surface of the single crystal silicon block reaction target after passing through the laser total reflection mirror 3 and the focusing lens 4 . The operating frequency of the laser emitted by the first laser is selected as 5 Hz, and the operating frequency of the laser emitted by the second laser is selected as 30 Hz. During the pulsed laser ablation process, the rotating base was operated at a rotation frequency of 75 rpm, so that the reaction product could be dispersed in the liquid in a monodisperse state without agglomeration. After the pulsed laser irradiates the target for 100 minutes, the reaction product in the tempered glass container is taken out, and after vacuum filtration and repeated washing, the finally obtained sample is dropped on a clean aluminum substrate and placed in the The residual pure water was evaporated in a vacuum oven. Finally, the aluminum sheet substrate loaded with the reaction product is observed under a field emission electron microscope, and it can be seen that palladium-silicon composite structure micro-nano particles are deposited on the substrate.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (9)

1. a preparation method for noble metal-semiconductors coupling structure micro-nano particle, is characterized in that, comprise the steps:

(1) semiconductor reaction structure is fixed in the container that precious metal salt solution material is housed;

(2) pulse laser ablation reaction is carried out: jointly impinge upon on the conversion zone on semiconductor reaction structure after the pulsed laser beam that some bundles are launched by the laser instrument of different optical maser wavelength focuses on respectively by condenser lens, wherein a part of laser beam is focusing effect state, for ablation, conversion zone surface is made to produce plasma plume; The hot spot of another part laser beam focus to be a focal diameter be 3 ~ 5 times of focus diameter, for irradiation and induction compound;

(3) after a period of time is carried out in pulse laser ablation reaction, stop pulse laser irradiates semiconductor reaction structure, product is taken out suction filtration dialysis, is separated and after drying, namely obtains noble metal-semiconductors coupling structure micro-nano particle.

2. the preparation method of noble metal according to claim 1-semiconductors coupling structure micro-nano particle, is characterized in that, when described step (2) carries out pulse laser ablation reaction, semiconductor reaction structure rotates in container.

3. the preparation method of noble metal according to claim 1-semiconductors coupling structure micro-nano particle, it is characterized in that, the physical parameter of the pulsed laser beam that described laser instrument is launched is adjustable, according to the difference of semiconductor reaction structure and solution, for the laser of ablation and also adjustable with the type of the laser of induction compound for irradiation.

4. the preparation method of noble metal according to claim 1-semiconductors coupling structure micro-nano particle, it is characterized in that, described semiconductor reaction structure is semiconductor target, or semiconductor monocrystal substrate, its surface carries out polishing process.

5. the preparation method of noble metal according to claim 4-semiconductors coupling structure micro-nano particle, it is characterized in that, the purity of described semiconductor target is greater than 98%, and the material that semiconductor target adopts comprises germanium, silicon, zinc oxide, gallium nitride;

The described solution containing precious metal salt composition is the mixed liquor of chlorauric acid solution or liquor argenti nitratis ophthalmicus or platinum acid chloride solution or palladium chloride solution or rhodium chloride solution or above-mentioned at least two kinds of solution.

6. the preparation method of noble metal according to claim 1-semiconductors coupling structure micro-nano particle, is characterized in that, the thickness of described semiconductor reaction structure is 3 ~ 5 millimeters; Its shape is circular or square;

Described container is quartz container or safety glass container, and its shape is circular or square.

7. the noble metal prepared by the preparation method described in any one of claim 1 ~ 6 claim-semiconductors coupling structure micro-nano particle.

8. noble metal according to claim 7-semiconductors coupling structure micro-nano particle, it is characterized in that, this micro-nano particle average dimension is 100 ~ 500nm, entirety presents spherical or class is spherical; There is the characteristic that noble metal was fitted together to or was wrapped in semiconductor nanoparticle surface.

9. the noble metal prepared by the preparation method described in any one of the claim 1 ~ 6 claim-application of semiconductors coupling structure micro-nano particle in micro-electronic machining, optics, biology, catalytic chemistry or medical domain.