CN108303765A - The tree-like phasmon waveguide composite nanostructure synthesis of racemosus and optical control method - Google Patents

The tree-like phasmon waveguide composite nanostructure synthesis of racemosus and optical control method Download PDF

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CN108303765A
CN108303765A CN201810086867.1A CN201810086867A CN108303765A CN 108303765 A CN108303765 A CN 108303765A CN 201810086867 A CN201810086867 A CN 201810086867A CN 108303765 A CN108303765 A CN 108303765A
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张晓阳
张彤
秦妍妍
薛小枚
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Southeast University
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Abstract

The present invention includes a kind of synthesis of the tree-like phasmon waveguide composite nanostructure of racemosus and its optical control method, the synthetic method include multiple steps, and each step accurately controls.The thickness of the trunk of tree-like nanostructure and the dendritic nano-structure grown on it accurately controls, it is superimposed with shell in tree-like nanostructured surface or quantum dot without shell forms the compound tree-like nanostructure of quantum dot, no shell quantum dot can be used for the applications such as chemical catalysis, environmental monitoring, bio-sensing.Light is from the incidence of nano wire one end, and through nano wire and dendritic morphology, excitation has shell quantum dot light emitting, can be used for the applications such as remote sensing Raman, new laser.The intensity and polarization state that incident light can be changed by optical control, control the quantum dot light emitting of specific region, can eliminate the crosstalk effect of interference diffraction effect generation between scattering center, so as to be detected for the high-resolution of sub-wavelength.

Description

The tree-like phasmon waveguide composite nanostructure synthesis of racemosus and optical control method
Technical field
The present invention relates to field of nanometer material technology and chemical-biological field, more particularly to a kind of tree-like phasmon waveguide of racemosus The synthesis of composite nanostructure and optical control method.
Background technology
Phasmon waveguide is the waveguide of sub-wavelength dimensions, and photon can be confined to waveguide surface and nearby transmitted, to Diffraction limit can be broken through, photon is manipulated on sub-wavelength or even nanoscale, thus is deposited in biochemistry detection, data All various aspects such as storage, chip interconnection, solar cell have broad application prospects, and have obtained extensive research concern.Silver nanoparticle Line is a kind of phasmon waveguide, because its can by chemical method high-volume synthesis, it is nontoxic the features such as cause to study extensively. But since under identical frequency, the wave vector of surface phasmon is bigger than light wave vector, this makes nano silver wire can not be in sky It is directly excited by plane wave in gas or vacuum, the pattern that can only use one end that one end is encouraged to scatter.Due to nano silver wire surface light Sliding, during light is propagated from the excitation end of nano wire to the other end, most light are exponentially decayed in nano silver wire side, The line external space can not be effectively scattered to, cannot be fully used, this greatly limits the application range of nano silver wire, new It can transmit and the complicated nanostructure of significantly scattering phasmon signal has active demand.
Distal end remote sensing excitation is to enhance an effective means of Effect on Detecting, in environmental monitoring, biological detection, chemical-biological The fields such as sensing have important application foreground.In order to enhance dispersion effect, have tried to quantum dot being bundled on nano silver wire, But the quantum dot of existing quantum dot composite nanostructure is to be sprinkling upon nanowire surface at random, this makes quantum dot only be distributed in The side of nano wire, light can only be traveled in the local space closer apart from nano wire by quantum point scattering, be greatly limited The transmission path and transmission range of light make it be difficult to realize practical application of the nanostructure in terms of the remote sensing excitation of distal end.Therefore Need to propose a kind of new there is a large amount of scattering centers, and the structure that can transmit light at a distance by multiple paths.
Optical control technology based on surface phasmon is drawn in recent years since its required laser energy is low, device is simple Extensive concern is played.Lower laser energy density can prevent the destruction to active somatic cell, therefore, can be in the medical field Active somatic cell and DNA manipulations etc. are applied.Existing micronano optical structure is in intensive, the adjacent scattering of scattering center arrangement When distance is closer between center, it is also easy to produce interference and diffraction between scattered wave, causes crosstalk.In cancer treatment procedure, if by this In kind micronano optical element injection human body, scattering light can not only destroy cancer cell, but also be likely to the health of injury surrounding Tissue.Urgently develop can precision destruction specific position cancer cell without to health tissue generate damage nanocomposite optical Structure.
Invention content
Technical problem：The purpose of the invention is to overcome the shortcoming of prior art, it is proposed that a kind of racemosus is tree-like The synthetic method and optical control method of phasmon waveguide composite nanostructure, this method synthetic method is simple, reproducible, It is easy to industrial mass production；The trunk and branch's nanostructure thickness of prepared tree-like nanostructure are controllable, dendritic Nanostructure increases the quantity of scattering center, extends the propagable space of light；It is superimposed with shell in tree-like nanostructured surface Or the quantum dot without shell forms the compound tree-like nanostructure of quantum dot, no shell quantum dot can be used for chemical catalysis, environmental monitoring, life The applications such as object sensing, light have reached shell quantum dot from the incidence of nano wire one end, through nano wire and dendritic morphology, and excitation has shell quantum Point shines, and can be used for the applications such as remote sensing Raman, new laser.The intensity and polarization of incident light can be changed by optical control State controls the quantum dot light emitting of specific region, can eliminate the crosstalk effect of interference diffraction effect generation between scattering center.
Technical solution：A kind of synthesis of the tree-like phasmon waveguide composite nanostructure of racemosus of the present invention and optical control Method includes the following steps：
Step 1：The synthesis of tree-like nanostructure：
A. chemical reduction method synthesizes the controllable nano silver wire of thickness using the trunk as tree-like nanostructure：Prepare nitric acid The ethylene glycol mixed solution of silver, polyvinylpyrrolidone PVP and sodium chloride, a concentration of 0.001- of silver nitrate in the reaction system 5mmol/L, and fully reaction 1-8h at high temperature, obtain nano silver wire solution I；
B. cleaning treatment nano silver wire makes its surface form defect：The nano silver wire solution I is fully washed 2-3 times Surface conditioning agent A is added afterwards, is sufficiently mixed and stirs, the nano silver wire surface of otherwise smooth forms one after being cleaned by inorganic agent Or multiple defects, obtain nano silver wire solution II, the trunk of as tree-like nanostructure；
C. the controllable dendritic nano-structure of thickness is grown at nano silver wire surface defect to form tree-like nanostructure：Match The mixed aqueous solution of silver nitrate processed, PVP, weak reductant B and photochemical catalyst C, is sufficiently mixed and stirs, then into mixed solution It is disposable to rapidly join strong reductant D, and Single wavelength narrow linewidth blue light source illumination is used immediately, Induced by Blue Light generates high yield Silver-colored decahedron continues to stir under the conditions of being protected from light, and obtains the precursor solution III of branch；
D. the precursor solution III of the branch, nano silver wire solution II are sufficiently mixed, are placed under white light source and continue Illumination, under illumination condition, silver-colored seed surface activity improves, and is connected with each other and is formed in nanowire surface fault location continued propagation Silver nanometer tree branches structure obtains tree-like nano-structured solution；
Step 2：The synthesis of the compound tree-like nanostructure of quantum dot：
B. it is synthesized without shell quantum dot：The mixed solution of chromium oxide, stearic acid and octadecylene ODE is heated to 170-230 DEG C, It waits for that solution is cooled to room temperature, octadecylamine ODA and trioctylphosphine TOPO is added, is under protection of argon gas heated to mixed solution 250-330 DEG C, at this temperature, sulphur, selenium or tellurium are dissolved in tributyl phosphate TBP, sulphur, selenium or tellurium simple substance are in the reaction system A concentration of 0.001-10mmol/L；Then it is diluted to obtain mixed solution IV with ODE, mixed solution IV is injected into rapidly reactant In system, reaction mixture is cooled to room temperature, and obtains no shell quantum dot solution；
B. nucleocapsid package quantum dot synthesis：The ethane solution of nanocrystalline E is sufficiently mixed with ODA and ODE, and to reactant System vacuumizes, and the hexane in removal system and remaining air are then passed through argon gas, injects cadmium solution at high temperature, reacts 5- The ODE solution of sulphur is injected after 10min, is fully reacted postcooling to room temperature, is obtained the quantum dot solution of cadmium sulfide package；
C. removing tree-like nanostructured surface capping agent makes its surface be easy to be superimposed quantum dot：By tree-like nano-structured solution High speed centrifugation 1-2 times, the capping agent on removal branch surface, and it is configured to the solution V of a concentration of 0.001-10mmol/L；By nothing Quantum dot solution high speed centrifugation 2-3 times of shell and nucleocapsid package, and it is configured to the aqueous solution VI of a concentration of 0.001-10mmol/L；
D. quantum dot modification and phase inversion are to make it easier to be superimposed upon tree-like nanostructured surface：By dithiol key molecular melting In water, it is configured to the solution of a concentration of 0.001-10mmol/L, it is mixed and be sufficiently stirred with solution VI, it is ensured that dithiol The thiol bond of key molecule one end is adsorbed on quantum dot surface completely, and other end thiol bond is exposed in deionized water, after centrifugation Quantum dot be dissolved in organic solvent F, obtain the mixed solution VII of a concentration of 0.001-10mmol/L；By amphipathic molecule Ethanol solution instill solution VII in, until formed floccule, flocculent deposit is extracted by high speed centrifugation, be dissolved in from In sub- water, solution VIII is obtained；
E. the compound tree-like nano-heterogeneous structure of quantum dot is formed：Solution V and solution VIII are mixed, stir 1-2h, it is ensured that molten Exposed thiol bond is fully adsorbed with the tree-like nanostructure in solution V in liquid, final to synthesize the dendritic tree-like of random incorporation The novel nano composite heterogenous junction structure that nanostructure and the quantum dot bound on its surface are collectively formed, and then realize luminescence enhancement Or be quenched and electricity Schottky contacts or Ohmic contact, generate thermoelectronic effect.
Wherein：
The trunk of tree-like nanostructure is the nano silver wire straight wave guide of controlled diameter, two dimension, quasi- two dimension or three-dimensional various Metal waveguide structure, the material for synthesizing nano wire also change alloy or polymer material into.
The surface conditioning agent A is acetone, toluene, cyclopentanone, dimethylformamide DMF, hydrogen peroxide, hydrochloric acid or nitre Acid, wherein a concentration of 0.001-10mmol/L of surface conditioning agent in the reaction system.
The weak reductant B is sodium citrate, glucose or vitamin C, and photochemical catalyst C is L-arginine, strong to restore Agent D is sodium borohydride, potassium borohydride or lithium aluminium hydride reduction, wherein sodium citrate, PVP, L-arginine, silver nitrate, sodium borohydride Volume ratio is 60-100:1-5:6-15:2-6:20-50, branch diameter are controllable from 10nm to 400nm.
The nucleocapsid package quantum dot synthesis nanocrystalline E used is cadmium sulfide, cadmium telluride or cadmium selenide.
The organic solvent F is n-hexane, chloroform or toluene.
The amphipathic molecule is mercaptopropionic acid MPA, cetyl trimethylammonium bromide CTAB, PVP or tetrafluoro boric acid Nitre NOBF4。
The quantum dot being bundled in tree-like nanostructure is also changed to dopamine or imuran.
The optical control method of the tree-like phasmon waveguide composite nanostructure of racemosus of the synthetic method synthesis of the present invention, For this method in one end thang-kng of tree-like nanostructure trunk, light is transmitted to dendritic nano-structure, dendritic nano junction by nano wire Structure is divided, and has light to have shell quantum dot is energized to shine by what region was superimposed；Light intensity realization by controlling incident light has shell amount The regulation and control of son point light emission luminance, the polarization state by controlling incident light realize that selectively control different zones have a shell quantum Point shines.
Nano silver wire has surface phasmon effect, can encourage the electromagnetic wave along metal and Air Interface transmission.But Since under identical frequency, the wave vector of surface phasmon is bigger than light wave vector, this nano silver wire for making surface smooth It can not directly be excited by plane wave in air or vacuum, the pattern that can only use one end that one end be encouraged to scatter, and in light from receiving During the excitation end of rice noodles is propagated to the other end, most light are exponentially decayed in nano silver wire side, cannot be obtained It makes full use of.
Surface enhanced Raman scattering (SERS) spectrum is that a kind of sensitivity is high, it is possible to provide the chemical constitution of sample to be tested is believed The technology of breath is with a wide range of applications in terms of biochemistry imaging and remote sensing.SERS enhancing effects are received with substrate is formed The metal species of rice structure, size and shape are closely related, the excitation formed by surface phasmon resonance and scattering field Enhancing can greatly enhance SERS effects.The edge and protruding point of anisotropy nano particle are the stronger areas of electromagnetic field Domain, wherein scattering, which enhances strongest position, is known as scattering center, namely " hot spot ", the nano gap being between nano particle In.Better SERS " hot spot " spatial distribution can be formed by the way that different types of nano particle to be coupled in system, in turn The preferably detection of homogeneity and repeatability can be provided.
Dendroid is silver nanostructured due to its unique pattern and structure, makes it have special optical characteristics.Sharp Corner angle and multilevel branch make dendroid is silver nanostructured to have excellent SERS effects, and can be used for preparing highly sensitive and height multiple The SERS active-substrate of existing property.Dispersed light can be played the role of by growing dendritic structure on nano silver wire surface, be greatly increased The transmission path quantity of light, extends the propagable space of light, so that light is propagated farther, improve to trunk excitation light Utilization rate；The big surface area of dendritic structure can greatly increase analyzed substance and detect the contact between substrate simultaneously, increase The strong effect of Raman detection.
Advantageous effect：The present invention has the following advantages that compared with prior art：
1. nobody proposed the tree-like phasmon waveguide composite nanostructure of racemosus prepared by the present invention before this, tool There is originality.The thickness of nano wire trunk and dendritic nano-structure accurately controls, and dendritic nano-structure substantially increases The quantity of nanostructure scattering center, makes Raman scattering be greatly enhanced, it is made to can be used for distal end remote sensing excitation.Trunk and branch When shape nanostructure is thicker, the loss that phasmon waveguide generates during transmitting light is relatively low；Trunk and dendritic nano junction When structure is thinner, phasmon waveguide is preferable to the local effect of light, ratio that can be by control reaction reagent and light application time control The size of diameter of the nano wire trunk and dendritic nano-structure that generate, the area of the length of branch and dendritic network are made, is obtained The tree-like phasmon waveguiding structure of the correspondence pattern of required function can be achieved.When dendritic network area is larger, it is possible to provide more The scattering center of dispersion improves the utilization rate of incident light to the space of extensible light propagation.
2. the tree-like phasmon waveguide composite nanostructure of racemosus that the present invention prepares realizes material of different nature, And it is compound between zero-dimensional quantum dots, one-dimensional nano line and two-dimensional dendritic nanostructure these different dimensions nanostructures. Branch surface is superimposed quantum dot, can greatly increase the quantity of scattering center, and can realize distal end remote sensing excitation, substantially increases The utilization rate of light.Exposed quantum dot is bound, it can be achieved that catalysis oxidation and catalytic degradation in tree-like nanostructured surface, and can be made For SERS probes, there is important application foreground in fields such as environmental monitoring, biological detection, chemical-biological sensings.When for shining, Nucleocapsid package can solve the problems, such as the exposed fluorescent quenching brought of quantum dot, in the amount of tree-like nanostructured surface binding nucleocapsid package Son point forms the compound tree-like nanostructure of quantum dot, and light is encouraged from tree-like trunk one end, and branch is traveled to through trunk, then by branch Quantum dot is traveled to, quantum dot light emitting is encouraged, forms novel nano light source, it can also be used to which nanometer illuminates, and light intensity can be swashed by trunk The optical signal encouraged provides, and opens completely new application direction.
3. the present invention has developed the tree-like phasmon waveguide composite nanostructure of racemosus of multidimensional for the first time, and can be used newly Optical control method Effective Regulation.Tree-like nanostructure difference position can be encouraged by the polarization state and intensity of tuning incident light The quantum dot light emitting set can eliminate the crosstalk effect of interference diffraction effect generation between scattering center, so as to be used for sub-wavelength High-resolution detection.By this nanostructure be used for treatment of cancer, can precision destruction specific position cancer cell without to people Body health tissues generate damage, and active somatic cell and DNA manipulation that can be in the medical field etc. is applied.This is active simultaneously Composite nanostructure can also form novel optical transmitting set.This tree-like phasmon waveguide composite nanostructure of racemosus is expected to receiving It is used widely in the fields such as rice photoelectric material, chemical-biological sensing, environmental monitoring, biological detection and medical treatment.
4. chemical reagent used in the method for the present invention is nontoxic, heating temperature is relatively low, and experimental period is short；This hair Apparatus and process is simple used in bright, and operating process is convenient.Therefore be it is a kind of it is simple, flexibly, the synthetic method of low energy consumption, from green From the point of view of colour chemistry, extensive use can get.
Description of the drawings
Fig. 1 is the tree-like nano composite structure of racemosus shape and the schematic diagram of light path.1 is nano wire trunk in figure, and 2 be growth Dendritic morphology on trunk, 31 quantum dots wrapped up for nucleocapsid, 32 be exposed quantum dot, and 33 be that luminous nucleocapsid wraps up Quantum dot.Light is encouraged from " nanotrees " trunk one end, travels to dendritic morphology through trunk, then travel to quantum by dendritic morphology Point, the quantum dot light emitting of excitation nucleocapsid package, it is unglazed by the quantum dot in region do not shine.
Fig. 2 is optical control schematic diagram.When the polarization state difference of incident light, the quantum dot light emitting of corresponding different zones is empty It is light-emitting zone in wire frame.
Fig. 3 is the optical microscope image of tree-like nano composite structure prepared by experiment.
Fig. 4 is that tree-like nano-heterogeneous structure compound to quantum dot carries out the partial schematic diagram of optical manipulation and corresponding resonance Spectrogram.Wherein, A indicates the quantum dot of the nucleocapsid package grown on the Waveguide branching of left side, is grown on the Waveguide branching of B expressions right side The quantum dot of nucleocapsid package, D indicates the space length between quantum dot A and B, when X expressions do not carry out optics regulation and control, quantum dot A The photoresponse situation generated with B, Y indicate that incident light polarization angle is θ1When the photoresponse situation that generates of quantum dot A and B, Z indicate into It is θ to penetrate light polarization angle2When the photoresponse situation that generates of quantum dot A and B.
Specific implementation mode
It is further illustrated the present invention below by specific embodiment and comparative example：
Embodiment：
1. preparing the ethylene glycol solution of 0.1M silver nitrates, 0.2M sodium chloride, 0.6M PVP, mixed solution fills at 160 DEG C Divide reaction 2h.
2. taking 10ml mixed solutions, 0.5ml acetone is added, is sufficiently stirred.
5ml sodium citrates (0.5M), 0.5ml L-arginines (0.05M), 0.15ml PVP are added in 3.7ml deionized waters (0.5M), 0.2ml silver nitrates (0.5M).After solution stirs evenly, 2ml sodium borohydrides (0.4M) are slowly dropped into, solution is being protected from light Under the conditions of continue stir 20min.
4. solution prepared by 7ml steps 3 is taken to be mixed into the solution of step 1 preparation, mixed solution, which is placed under white light LEDs, to be irradiated 2h obtains tree-like nano-structured solution.
5. the mixed solution of 0.2mmol chromium oxide, 0.8mmol stearic acid and 2g ODE is heated to 200 DEG C, wait for that solution is cold But to room temperature, 1.5g ODA and 0.5g TOPO is added, reaction system is heated to 280 DEG C.At this temperature, 2mmol sulphur is molten In TBP, then mixed solution is injected in reaction system rapidly with after 1.37g ODE dilute solutions.Reaction mixture is cold But to room temperature, no shell quantum dot solution is obtained.
6. the hexane solution of 2.44g cadmium sulfides and 1.5g ODA and 5g ODE are sufficiently mixed, reaction system is first at 100 DEG C At a temperature of vacuumize 30min.Then it is passed through argon gas into reaction system, reaction solution is heated to 240 DEG C.Inject 0.49ml cadmiums Solution, reacts the ODE solution (0.04M) of injection sulphur after 8min, fully reacts postcooling to room temperature, obtains the amount of cadmium sulfide package Son point solution.
7. by silver nanometer tree branches solution high speed centrifugation 1-2 times, the capping agent on removal branch surface, and be configured to a concentration of The solution of 5mmol/L.The quantum dot solution high speed centrifugation that no shell or nucleocapsid are wrapped up 2 times, removes the capping agent on its surface, and match It is set to the solution of a concentration of 4mmol/L.
8. in deionized water by dithiol key molecular melting, the solution of a concentration of 5mmol/L is configured to, by itself and quantum Point solution mixing, is sufficiently stirred 2h, after high speed centrifugation 3 times, is configured to the toluene solution of a concentration of 4mmol/L.By the ethyl alcohol of MPA Solution instills in solution, and until forming floccule, centrifugation extracts flocculent deposit, is dissolved in deionized water.
9. processed branch solution and quantum dot solution are mixed, 1h is stirred, the compound tree-like nanostructure of quantum dot is obtained.
10. Fig. 4 is the partial schematic diagram of the compound tree-like nano-heterogeneous structure of quantum dot and corresponding resonance spectrogram, quantum dot Space D between A and B is 10nm.As shown in label X, when not carrying out optics regulation and control, quantum dot A and B shine simultaneously, due to A, B Between spacing it is minimum, while shine when can interfere, to generate crosstalk effect.Label Y and Z are shown to be grasped by optics When control changes the polarization state of incident light, the photoresponse situation that A and B are generated, the incident intensity of Y and Z is identical, angle of polarization θ1And θ2 Between have minute differences, by adjusting the polarization state of incident light, controllable quantum dot A and B individually shine, dry to eliminate Crosstalk benefit caused by relating to.
In addition, those skilled in the art can also make other variations in spirit of that invention, these are smart according to the present invention certainly Change made by god, should all be included in scope of the present invention.

Claims (9)

1. a kind of synthetic method of the tree-like phasmon waveguide composite nanostructure of racemosus, it is characterised in that this method includes following Step：
Step 1：The synthesis of tree-like nanostructure：
A. chemical reduction method synthesizes the controllable nano silver wire of thickness using the trunk as tree-like nanostructure：It prepares silver nitrate, gather The ethylene glycol mixed solution of vinylpyrrolidone PVP and sodium chloride, a concentration of 0.001- of silver nitrate in the reaction system 5mmol/L, and fully reaction 1-8h at high temperature, obtain nano silver wire solution I；
B. cleaning treatment nano silver wire makes its surface form defect：Add after the nano silver wire solution I is fully washed 2-3 times Enter surface conditioning agent A, be sufficiently mixed and stir, the nano silver wire surface of otherwise smooth forms one or more after being cleaned by inorganic agent A defect obtains nano silver wire solution II, the trunk of as tree-like nanostructure；
C. the controllable dendritic nano-structure of thickness is grown at nano silver wire surface defect to form tree-like nanostructure：Prepare nitre The mixed aqueous solution of sour silver, PVP, weak reductant B and photochemical catalyst C, is sufficiently mixed and stirs, then primary into mixed solution Property rapidly join strong reductant D, and use Single wavelength narrow linewidth blue light source illumination immediately, Induced by Blue Light generates the silver ten of high yield Face body continues to stir under the conditions of being protected from light, and obtains the precursor solution III of branch；
D. the precursor solution III of the branch, nano silver wire solution II are sufficiently mixed, are placed in continuous light under white light source, Under illumination condition, silver-colored seed surface activity improves, and is connected with each other and forms silver in nanowire surface fault location continued propagation and receives Rice dendritic structure, obtains tree-like nano-structured solution；
Step 2：The synthesis of the compound tree-like nanostructure of quantum dot：
A. it is synthesized without shell quantum dot：The mixed solution of chromium oxide, stearic acid and octadecylene ODE is heated to 170-230 DEG C, is waited for molten Liquid is cooled to room temperature, and octadecylamine ODA and trioctylphosphine TOPO is added, mixed solution is heated to 250- under protection of argon gas 330 DEG C, at this temperature, sulphur, selenium or tellurium are dissolved in tributyl phosphate TBP, sulphur, selenium or tellurium simple substance in the reaction system dense Degree is 0.001-10mmol/L；Then it is diluted to obtain mixed solution IV with ODE, mixed solution IV is injected into rapidly reaction system In, reaction mixture is cooled to room temperature, and obtains no shell quantum dot solution；
B. nucleocapsid package quantum dot synthesis：The ethane solution of nanocrystalline E is sufficiently mixed with ODA and ODE, and reaction system is taken out Vacuum, the hexane in removal system and remaining air, are then passed through argon gas, inject cadmium solution at high temperature, react 5-10min The ODE solution of sulphur is injected afterwards, is fully reacted postcooling to room temperature, is obtained the quantum dot solution of cadmium sulfide package；
C. removing tree-like nanostructured surface capping agent makes its surface be easy to be superimposed quantum dot：By tree-like nano-structured solution high speed Centrifugation 1-2 times, the capping agent on removal branch surface, and it is configured to the solution V of a concentration of 0.001-10mmol/L；Will without shell and The quantum dot solution high speed centrifugation of nucleocapsid package 2-3 times, and it is configured to the aqueous solution VI of a concentration of 0.001-10mmol/L；
D. quantum dot modification and phase inversion are to make it easier to be superimposed upon tree-like nanostructured surface：By dithiol key molecular melting in water In, it is configured to the solution of a concentration of 0.001-10mmol/L, it is mixed and be sufficiently stirred with solution VI, it is ensured that dithiol key point The thiol bond of sub- one end is adsorbed on quantum dot surface completely, and other end thiol bond is exposed in deionized water, by the amount after centrifugation Son point is dissolved in organic solvent F, obtains the mixed solution VII of a concentration of 0.001-10mmol/L；By the ethyl alcohol of amphipathic molecule Solution instills in solution VII, until forming floccule, extracts flocculent deposit by high speed centrifugation, is dissolved in deionized water In, obtain solution VIII；
E. the compound tree-like nano-heterogeneous structure of quantum dot is formed：Solution V and solution VIII are mixed, stir 1-2h, it is ensured that in solution Exposed thiol bond is fully adsorbed with the tree-like nanostructure in solution V, the final dendritic tree-like nanometer for synthesizing random incorporation The novel nano composite heterogenous junction structure that structure and the quantum dot bound on its surface are collectively formed, and then realize luminescence enhancement or quench It goes out and electricity Schottky contacts or Ohmic contact, generates thermoelectronic effect.
2. a kind of synthetic method of the tree-like phasmon waveguide composite nanostructure of racemosus as described in claim 1, feature It is：The trunk of tree-like nanostructure is nano silver wire straight wave guide, two dimension, quasi- two dimension or the three-dimensional various metals of controlled diameter Waveguiding structure, the material for synthesizing nano wire also change alloy or polymer material into.
3. a kind of synthetic method of the tree-like phasmon waveguide composite nanostructure of racemosus as described in claim 1, feature It is：The surface conditioning agent A be acetone, toluene, cyclopentanone, dimethylformamide DMF, hydrogen peroxide, hydrochloric acid or nitric acid, In, a concentration of 0.001-10mmol/L of surface conditioning agent in the reaction system.
4. a kind of synthetic method of the tree-like phasmon waveguide composite nanostructure of racemosus as described in claim 1, feature It is：The weak reductant B is sodium citrate, glucose or vitamin C, and photochemical catalyst C is L-arginine, strong reductant D For sodium borohydride, potassium borohydride or lithium aluminium hydride reduction, the wherein volume of sodium citrate, PVP, L-arginine, silver nitrate, sodium borohydride Than for 60-100:1-5:6-15:2-6:20-50, branch diameter are controllable from 10nm to 400nm.
5. a kind of synthetic method of the tree-like phasmon waveguide composite nanostructure of racemosus as described in claim 1, feature It is：The nucleocapsid package quantum dot synthesis nanocrystalline E used is cadmium sulfide, cadmium telluride or cadmium selenide.
6. a kind of synthetic method of the tree-like phasmon waveguide composite nanostructure of racemosus as described in claim 1, feature It is：The organic solvent F is n-hexane, chloroform or toluene.
7. a kind of synthetic method of the tree-like phasmon waveguide composite nanostructure of racemosus as described in claim 1, feature It is：The amphipathic molecule is mercaptopropionic acid MPA, cetyl trimethylammonium bromide CTAB, PVP or nitronium tetrafluoroborate NOBF4。
8. a kind of synthetic method of the tree-like phasmon waveguide composite nanostructure of racemosus as described in claim 1, feature It is：The quantum dot being bundled in tree-like nanostructure is also changed to dopamine or imuran.
9. a kind of light of the tree-like phasmon waveguide composite nanostructure of racemosus of synthetic method synthesis as described in claim 1 Learn control method, it is characterised in that：For this method in one end thang-kng of tree-like nanostructure trunk, light is transmitted to branch by nano wire Shape nanostructure, dendritic nano-structure light splitting have light to have shell quantum dot is energized to shine by what region was superimposed；By control into The light intensity for penetrating light realizes the regulation and control for having shell quantum dot light emitting brightness, and the polarization state by controlling incident light realizes selectively control Different zones processed have shell quantum dot light emitting.
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