CN103769609B - A kind of noble metal-semiconductors coupling structure micro-nano particle, preparation method, application - Google Patents
A kind of noble metal-semiconductors coupling structure micro-nano particle, preparation method, application Download PDFInfo
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Abstract
The invention discloses a kind of noble metal-semiconductors coupling structure micro-nano particle, preparation method, application, this preparation method comprises the solution be placed in by semiconductor reaction structure containing precious metal salt composition, make the surface that pulsed laser beam contacts with solution by focusing on semiconductor reaction structure after condenser lens, thus produce plasma plume on the surface of semiconductor reaction structure.Need two bundles (or multi beam) laser common (or interlock) in course of reaction and act on same conversion zone, a part of laser beam is focusing effect state, and for ablation, another part laser beam is used for irradiation and induction compound.While carrying out pulse laser ablation, semiconductor reaction structure is rotated, become more even to make reaction.The specific unique noble metal-semiconductors coupling structure micro-nano particle that has prepared by said method can be applicable to the fields such as micro-electronic machining, optics, biology, catalytic chemistry or medical science.
Description
Technical field
The present invention relates to micro--Na particle Study on Preparation Technology field, in particular to a kind of noble metal-semiconductors coupling structure micro-nano particle, preparation method, application, this particle utilizes some Shu Jiguang in liquid phase environment, carry out pulse laser ablation and the noble metal with the special construction-semiconductor micro-nano particle of inducing recombination reaction to prepare.
Background technology
Since entering 21 century, nanometer material and technology has all shown good application prospect in various fields such as electronics, optics, biomedicines, and become the research frontier of nanosecond science and technology, attract the expert in the fields such as a large amount of physics, chemistry, material, biology and researcher to put in the research work in this field.Scientific research for many years shows, micro--Na particle, particularly has the composite micro-nano particle of special construction, can show a lot of new features different from one-component nano material, produce the phenomenon that some are new.These new features and new phenomenon are familiar with these materials to people and are utilized these materials to have great importance, and this also can produce revolutionary impact to the industry in future and technology simultaneously.Noble metal and semiconductor have obvious difference in physicochemical properties, the effect of intercoupling by force can be produced between this each component of composite nano materials system that both utilizations are formed, not only can strengthen noble metal and semi-conducting material intrinsic speciality separately, but also composite construction may be allowed to show many new features, thus break through the limitation of one-component or classification material property.The utilization of these new features can make noble metal-semiconductor composite nano material create huge chance at key areas such as the preparations of the utilization of the research and development of New function material, new energy materials, environmental protection and innoxious degraded, biochemical medicine, micro-nano photoelectric device.In the development of noble metal-semiconductor micro-nano particle, which kind of mode is adopted to carry out synthesizing and assembling and will produce tremendous influence to the performance of the characteristic of nano composite material and the function element utilizing it to assemble.Wherein, there is the synthesis of the noble metal-semiconductor micro-nano particle of specific metastable state parcel complex morphological, including the shape of particle and synthesize the controllability of its phase structure, is the high research direction of a frontier nature and challenge, is also a problem urgently to be resolved hurrily simultaneously.
At present, the stuctures and properties research of noble metal-semiconductor composite nano material and micro--Na particle thereof is a focus of inorganic functional material research field.It is generally acknowledged that the coupled characteristic of performance primarily of composite of composite nano materials, compound pattern, skin effect and Particle size effect determined.A large amount of bibliographical information introductions has been had to point out, the performance of composite nano materials is that the state of being adsorbed by electronic transmission structures between bi-material and surface component decides: couple electronic structure places one's entire reliance upon the composite crystalline structure of bi-material and lattice dimensions, and the adsorbed state of surface component then often causes optical phonon to transport or the variation phenomenon of other luminescent properties aspects.Therefore, the synthesis with the noble metal-nanometer semiconductor structure of special metastable complex morphological is greatly expanded contributing to micro-performance of-Na particle and the Exploration & stu dy of application aspect.For different preparation methods, the factor affecting noble metal-semiconductors coupling micro-nano particle synthesis respectively has its difference, but reaction time wherein, temperature, reactivity worth and surfactant use etc., all can produce significant impact to the size of composite nm-grain Ge or shape and crystal mass.Therefore select suitable reactive mode to realize the size and dimension preparation of the micro--Na particle of compound, the manufacture and exploit of material is just seemed and is even more important.In the synthesis having had many relevant work to concentrate on research noble metal-semiconductors coupling micro-nano particle up to now at home and abroad and method, such as chemical gaseous phase synthesis, molecular beam epitaxial growth technology, hydro-thermal method complex technique etc.; And people successfully can prepare some interesting parcel form composite nanostructures to have some documents to point out.On the other hand, pulse laser ablation reaction technology as a kind of by grow up, be very suitable for preparing the technology with metastable pattern phase nano material and nanostructured, with its feature such as controlled, reaction atmosphere impurity content is few within the specific limits, and be used to prepare as micro-structurals such as SQW, Quantum Junction, quantum wires.In passing research, this main pulse laser ablation reaction technology of preparing based on physical reactions, majority carries out in vacuum or thin inert gas environment.Its action principle comprises: 1, make pulsed laser beam focus on reaction target surface, make reaction target surface produce high temperature and melting, thus form plasma plume at target material surface; 2, plasma can expand by local under vacuum or rarefied gas environment, can cool rapidly subsequently because laser pulse terminates, and makes place's material in the plasma originally combine due to quenching and deposit on substrate.End product can be made to form the micro-structural such as film or nano particle by controlling reaction condition.The nanometer material structure prepared in this way is even, and material purity is high, but also can obtain certain functional structure by controlling reaction condition.Therefore laser ablation deposition is a kind of technology of preparing preparing high-quality micro-nano structure material.But, common laser ablation reaction is all carry out under vacuum or low density gas condition, therefore these react the micro-nano structure generated is mostly the Stable structure that self-sow is formed, and is also difficult to the development realizing composite under vacuum or low density gas condition.Therefore when people go for certain there is the metastable state nano particle of composite structure time, due to they formation require complete under certain metastable condition, then be just difficult to meet the demands by common pulsed laser ablation deposition technology.
Summary of the invention
Main purpose of the present invention is that the shortcoming overcoming prior art is with not enough, the preparation method of a kind of noble metal-semiconductors coupling structure micro-nano particle is provided, the method is easy and simple to handle, preparation process is quick, can by regulating laser and solution parameter in liquid phase environment, a step prepares the micro-nano particle having unique noble metal-semiconductors coupling structure with better application prospect.
Another object of the present invention is to provide the noble metal-semiconductors coupling structure micro-nano particle utilizing above-mentioned preparation method to be prepared into.
Another object of the present invention is to provide the above-mentioned noble metal-application of semiconductors coupling structure micro-nano particle in the fields such as micro-electronic machining, optics, biology, catalytic chemistry, medical science with special appearance.
Object of the present invention is realized by following technical scheme: the preparation method of a kind of noble metal-semiconductors coupling structure micro-nano particle, step is as follows: semiconductor reaction structure is placed in the solution containing precious metal salt composition, some bundle of pulsed laser light beams are through the surface focusing on this semiconductor reaction structure after condenser lens, the surface mass melting of semiconductor reaction structure is made also and then at the upper surface of this semiconductor reaction structure to form plasma plume by laser ablation, some bundle of pulsed laser light beams are through the surface of irradiation after condenser lens at semiconductor reaction structure, by laser precipitation effect, noble metal component is separated out from solution around above-mentioned plasma plume, and under the inducing action of laser, be attached to the surface of semiconductor micro-nano particle, described semiconductor micro-nano particle is generated on semiconductor reaction structure by laser action, after a period of time, 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.The present invention is by suitably regulating laser energy intensity, focus state, and the type of precious metal salt solution, can obtain the product of unique noble metal-semiconductors coupling structure micro-nano particle under suitable reaction condition.
Specifically 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.
Preferably, when described step (2) carries out pulse laser ablation reaction, semiconductor reaction structure rotates in container.Thus reaction can be made to carry out evenly.
In order to realize the present invention better, the physical parameter (such as wavelength, pulse width) 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.Type of laser described here refers to a millisecond laser, nanosecond laser, or femtosecond laser etc., when actual selecting, also can select to adopt " nanosecond laser-nanosecond laser " interlock, or " nanosecond laser-femtosecond laser " interlock etc.
Preferably, described semiconductor reaction structure is semiconductor target, or semiconductor monocrystal substrate, and its surface carries out polishing process.So that pulse laser can focus on semiconductor reaction structure surface smoothly.
Further, the purity of described semiconductor target is greater than 98%, and the material that semiconductor target adopts comprises germanium, silicon or zinc oxide, gallium nitride etc.
As preferably, 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.
Preferably, the thickness of described semiconductor reaction structure is 3 ~ 5 millimeters; Its shape can be indefinite, circular or square.Described container is quartz container or safety glass container, can be square or circle.
The noble metal utilizing above-mentioned preparation method to be prepared into-semiconductors coupling structure micro-nano particle, this micro-nano particle average dimension is 100 ~ 500nm, and 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.Described noble metal-semiconductors coupling structure micro-nano particle has specific morphology, is the micro-nano particle that noble metal is combined with a fixed structure and semiconductor junction.
Noble metal in described the present invention-semiconductors coupling structure micro-nano particle can obtain application in the fields such as micro-electronic machining, optics, biology, catalytic chemistry or medical science.Such as, gold-nanometer semiconductor structure has very strong surface phasmon localized modes, in the research of some nonlinear optics micro-nano structures, there is epochmaking researching value, and effectively prepare the gold-semiconductors coupling structure micro-nano particle with special appearance and can meet the requirement of this material in basic research and application aspect better.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
1, the present invention utilizes two-beam (or multi beam) pulse laser to carry out Induced matching laser ablation technology first and has made noble metal-semiconductors coupling structure micro-nano particle in liquid phase substance, the method is simple and efficient to handle, with low cost, and there is no harsh operating environment requirement, the preparation of product can be realized under normal temperature and pressure conditions.
2, noble metal provided by the invention-semiconductors coupling structure micro-nano preparation method of granules, in liquid phase environment, utilize multiple laser to assist control the pulse laser ablation technology of carrying out, laser beam is divided into two kinds by its effect, a kind of for ablation, a kind of for irradiation and induction compound, compared with ablation deposition technology in the laser ablation technology in traditional vacuum or rarefied gas environment and common single-pulse laser liquid, due to impact and the control of irradiation laser article on plasma plumage, the synthesis occurred in liquid phase environment and growth course can with being very different in general laser ablation methods, thus have influence on the formation of end product.
Accompanying drawing explanation
Fig. 1 is the structural representation that embodiment 1 uses equipment.
The field emission scanning electron microscope photo of the gold that Fig. 2 (a) is prepared for embodiment 1-silicon composite structure micro-nano particle.
The field emission scanning electron microscope photo of the silver that Fig. 2 (b) is prepared for embodiment 2-silicon composite structure micro-nano particle.
The transmission electron microscope photograph via bright field of the gold that Fig. 3 (a) is prepared for embodiment 1-silicon composite structure micro-nano particle.
The SEAD photo of the gold that Fig. 3 (b) is prepared for embodiment 1-silicon composite structure micro-nano particle.
The high-resolution photo at the gold that Fig. 3 (c) is prepared for embodiment 1-silicon composite structure micro-nano particle edge.
The high-resolution lattice fringe photo of a gold nano grain of mask body on the gold that Fig. 3 (d) is prepared for embodiment 1-silicon composite structure micro-nano particle.
Fig. 4 is the gold-silicon composite structure micro-nano particle UV-visible-near infrared absorption of the present embodiment 1 preparation and the comparison diagram of pure silicon nano particle and proof gold nanoparticle absorbance curve.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
As shown in Figure 1, the present embodiment carries out the device that noble metal-preparation of semiconductors coupling structure micro-nano particle adopts and comprises the first laser instrument 1(employing Nd:YAG pulse laser, optical maser wavelength 532nm, pulsewidth 10ns, energy is 50mJ, frequency is 10Hz) and second laser 2(employing Nd:YAG short-pulse laser, optical maser wavelength 355nm, pulsewidth 8ns, energy is 50mJ, frequency is 50Hz), laser total reflection mirror 3, its focal length of condenser lens 4(is 500mm), reaction target 5(material is monocrystalline silicon), aqueous solution of chloraurate 6, rotating basis 7(material is polytetrafluoroethylene (PTFE)), quartz container 8.During work, first reaction target 5 to be fixed on rotating basis 7 and pedestal is put into quartz container 8 together with reaction target, then injecting appropriate liquid phase substance aqueous solution of chloraurate 6; After the two bundle of pulsed laser produced from the first laser instrument 1 and second laser 2 focuses on respectively by laser total reflection mirror group 3 and focus lens group 4, converge the surface being radiated at reaction target 5, form one and acted on by double beams laser and the plasma reaction district that formed simultaneously.This two bundle of pulsed laser light beam focus on and irradiation at the target upper surface of focal zone, utilize the high-energy of wherein a branch of focusing pulse laser, make the surface mass melting of target also and then at reaction target target upper surface form plasma plume by laser ablation, noble metal component can be separated out by laser precipitation effect by another bundle irradiation laser around plasma plume from liquid phase environment simultaneously.On the one hand, plasma plume, because be subject to the strong constraint of liquid phase substance, understands (process required time is at nanosecond or musec order) cancellation at a terrific speed; On the other hand, the irradiation laser of irradiation in plasma plume to the plasma plume generation effect produced, namely can make its ionization, and impels the noble metal component separated out in liquid phase environment to be incorporated in the cancellation process of plasma plume further.After laser pulse terminates, the material being in molten state during beginning can condense because of cooling, wherein first semiconductor component be combined with each other because being in center, and noble metal component then can be formed in its peripheral difference according to reaction condition and generate micro--Na particle.Utilize laser pulse energy to be conditioned this condition, the size of pulsed laser energy or even the type of laser pulse are adjusted, the micro-nano structure of generation just can be made to have specific combined state.
The present embodiment, to prepare gold-silicon composite structure micro-nano particle, illustrates preparation method as follows:
(1) purity is greater than 99.99%, diameter is 25mm, the reaction target 5 of thick 5mm is fixed on rotating basis 7, rotating basis 7 puts into quartz container 8 together with reaction target 5.
(2) in quartz container 8, slowly injecting high-purity aqueous solution of chloraurate 6(concentration is 5mM), make aqueous solution of chloraurate submergence react target 5.Regulate laser optical path, make the pulsed laser beam of the first laser instrument 1 and second laser 2 transmitting respectively by after laser total reflection mirror 3 and condenser lens 4, converge the surface being radiated at reaction target 5, laser frequency can be selected to be respectively 10Hz and 50Hz, and two bundle laser produce plasma plume at contact surface.
(3) while carrying out pulse laser ablation, rotating basis 7 is rotated, carry out to make a reacting zonule that only can not be confined to target material surface, rotate simultaneously and reaction environment also can be made more even.In whole preparation process, rotating basis 7 is with the speed work of 60 ~ 85 revs/min, and product can be scattered rapidly after its formation, is also convenient to make the distribution of the gold of preparation-silicon composite structure micro-nano particle more even.Whole process lasts 30 minutes.
(4) after two bundle of pulsed laser and reaction target response carry out 30 minutes, two laser instruments are closed respectively.The solution carrying out using in ablation reaction is taken out and is carried out filtered off with suction, to wash away residual aqueous solution of chloraurate, and repeatedly suction filtration process is carried out to final sample, the sample of preparing stayed on miillpore filter is taken off, be dispersed on monocrystalline silicon piece substrate, put into vacuum drying chamber and carry out drying.Monocrystalline silicon piece substrate is taken amplifying observation under field emission microscope, namely see gold-silicon composite structure micro-nano particle substrate having preparation.
The field emission scanning electron microscope photo of the gold that Fig. 2 (a) is prepared for the present embodiment-silicon composite structure micro-nano particle.As seen from the figure, the diameter of gold-silicon composite structure micro-nano particle is at 300 ~ 400nm, and the surface of particle has the vein structure of gold.
Fig. 3 (a), Fig. 3 (b) are respectively the transmission electron microscope photograph via bright field of gold-silicon composite structure micro-nano particle prepared by the present embodiment, and the SEAD photo of corresponding particle.According to these two kinds of test results, can confirm that the micro-nano particle obtained has a kind of gold-silicon composite structure of uniqueness really.
Fig. 3 (c), Fig. 3 (d) are respectively the high-resolution photo at the particle edge of gold-silicon composite structure micro-nano particle prepared by the present embodiment, and on gold-silicon composite structure micro-nano particle the high-resolution lattice fringe photo of a gold nano grain of mask body.By the comparison to lattice fringe, can determine that the lattice fringe of the nano particle being embedded in silicon nanosphere surface is 0.2nm, correspond to 111 crystal faces of gold.
Fig. 4 is the comparison diagram of gold-silicon composite structure micro-nano particle UV-visible-near infrared absorption of preparing of the present embodiment and pure silicon nano particle and proof gold nanoparticle absorbance curve, and the absorption curve that wherein solid line represents is the ultraviolet-visible-near infrared absorption characteristic spectrum of gold-silicon composite structure micro-nano particle.Can be found out by map analysis, the gold be prepared from by the present embodiment method-silicon composite structure micro-nano particle has very unique optical absorption characteristic, be different from the optical absorption characteristic of pure silicon nano particle (as shown in figure dotted line spectrum) or proof gold nano particle (as shown in phantom in FIG. spectrum) completely, neither the simple superposition of characteristic of this bi-material.This illustrates that the gold-silicon composite structure micro-nano particle prepared by the present invention is provided with the optical property of modern, and such optical characteristics will make this gold-silicon composite structure micro-nano particle have an opportunity to become the basic material preparing new micro photo electric device.
By above-mentioned characterization method, the gold that known the present invention prepares-silicon composite structure micro-nano particle has unique gold parcel silicon structure, wherein gold is with discrete train of thought shape or sheet parcel, and is embedded in the surface of larger silicon nanosphere with a large amount of gold nano grain.This gold-silicon composite structure micro-nano particle has and pure silicon nano particle or the diverse optical absorption characteristic of proof gold nano particle, is hopeful the basic material that can be used as following micro photo electric micro-nano device.
Embodiment 2
The present embodiment except following characteristics other structures with embodiment 1:
Adopt the equipment that embodiment 1 is used, the monocrystalline silicon of one piece high-purity (purity is 99.99%) reaction target 5 is fixed on polytetrafluoroethylene (PTFE) pedestal 7, pedestal 7 is put into quartz container 8 together with reaction target 5.In quartz container 8, slowly inject pure secondary go to be the liquor argenti nitratis ophthalmicus of 5mM, and target to be immersed in solution from concentration.Regulate laser optical path, make the pulsed laser beam of the first laser instrument 1 and second laser 2 transmitting respectively by after laser total reflection mirror 3 and condenser lens 4, focused beam common irradiation is on monocrystalline silicon reaction target 5.The operating frequency of the first laser instrument 1 selects 10Hz, and the operating frequency of second laser 2 selects 50Hz.In the process of carrying out pulse laser ablation, make rotating basis 7 with the speed work of 80 revs/min, single dispersing shape can be presented to make product and make reaction condition even.When pulse laser and the effect of reaction target are after 60 minutes, close two laser instruments and the solution scattering product is taken out, after vacuum filtration and dialysis, sample drop being placed on monocrystalline silicon piece, then putting into vacuum drying chamber and carry out drying process.Finally the monocrystalline silicon piece substrate that carry sample is put into observed under electron microscope, can see and monocrystalline silicon piece substrate spreads all over silver-silicon composite structure micro-nano particle.
The field emission scanning electron microscope photo of the silver that Fig. 2 (b) prepares for the present embodiment-silicon composite structure micro-nano particle.As seen from the figure, the diameter of most silver-silicon composite structure micro-nano particle presents class spherical at 300 ~ 500nm, and each particle has a larger silver nanoparticle ball inlay.
Embodiment 3
The present embodiment except following characteristics other structures with embodiment 1:
Adopt the equipment that embodiment 1 is used, monocrystalline silicon (purity is greater than 99.99%) the reaction target 3 being 5mm one piece of thickness is fixed on polytetrafluoroethylene (PTFE) rotating basis 7, rotating basis is put into a safety glass container 8 together with target, and in container, slow implantation concentration is high-purity palladium chloride solution of 1mM, enables solution submergence target and rotating basis.Regulating laser optical path, making the pulsed laser beam of two laser instruments transmittings by focusing on the upper surface of monocrystalline silicon deblocking reaction target after laser total reflection mirror 3 and condenser lens 4.The operating frequency of the first laser instrument institute Emission Lasers is chosen as 5Hz, and the operating frequency of second laser institute Emission Lasers is chosen as 30Hz.In the process of carrying out pulse laser ablation, make rotating basis with the speed work of 75 revs/min, thus make product can intersperse among in liquid and can not form reunion with single dispersing shape.When pulsed laser irradiation target is after 100 minutes, product in safety glass container is taken out, through vacuum filtration with after repeatedly rinsing, by the sample drop that finally obtains on the clean aluminium flake substrate of a slice, and put it in vacuum drying chamber remaining evaporating pure water to fall.Observe under finally the aluminium flake substrate being loaded with product being put into field emission microscope, can see that deposited on substrates has palladium-silicon composite structure micro-nano particle.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within 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.
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| CN105834434B (en) * | 2016-04-27 | 2017-12-05 | 广东工业大学 | A kind of chemical laser composite preparation process of the controllable copper micro-nano particle of particle diameter distribution |
| CN106041060B (en) * | 2016-05-31 | 2018-02-16 | 华中科技大学 | A kind of method for preparing nano composite material using laser welding in the liquid phase |
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| EP3839628A1 (en) * | 2019-12-20 | 2021-06-23 | The Chinese University Of Hong Kong | Method for a photon induced material deposition and a device therefor |
| CN112376020B (en) * | 2020-10-28 | 2021-07-20 | 武汉大学 | Method for forming orientation, chirality and complex structure by laser-induced growth of nano unit |
| CN114210992B (en) * | 2021-12-17 | 2024-04-09 | 武汉工程大学 | Gold micro-nano pine needle composite structure and preparation method thereof |
| CN114515901A (en) * | 2022-01-21 | 2022-05-20 | 广州大学 | Preparation method of silicon nanospheres |
| CN115709990A (en) * | 2022-10-07 | 2023-02-24 | 新乡医学院 | Method for preparing non-metal doped porous graphene material by laser-induced solid phase |
| CN117505887A (en) * | 2023-10-31 | 2024-02-06 | 中国科学技术大学苏州高等研究院 | Zinc oxide semiconductor laser additive manufacturing system and process method |
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