CN104249151A - Organic/metal nanowire heterojunction, as well as preparation method and application thereof - Google Patents
Organic/metal nanowire heterojunction, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic/metal nanowire heterojunction, as well as a preparation method and application thereof. Due to the self assembly process of organic molecules in liquid phase, metal nanowires dispersed in the liquid phase are embedded therein, so the organic/metal nanowire heterojunctions of different structures are obtained. The preparation method provided by the invention is simple in process, convenient to operate, low in cost and wide in application, can be used for massive preparation and is environment-friendly. The organic/metal nanowire heterojunction obtained by the method has a smooth surface, a medium waveguide and a metal silver nanowire can be very tightly combined together, very high coupling efficiency of photons and surface plasmon polaritons is achieved, the problems that the surface of the composite material, prepared by the previous method, is unsmooth, the contact area between metal and a medium is small, the integral mechanical structure is unstable and the like are solved, and the method can be used for preparing nanophotonics elements such as a photonics multiplexer or a nano optical sensor.
Description
Technical field
The present invention relates to a kind of organic/preparation method of metal nanometer line hetero-junctions and application thereof.
Background technology
Photonic device has the advantages such as the incomparable high speed of electronics device, high bandwidth and low energy consumption, in optical information processing and photonic propulsion calculate, play very important role.The dielectric material that polymer, inorganic semiconductor and organic material etc. are traditional, be commonly used to prepare photonic device, but the conduction of optical signal is subject to the restriction of diffraction limit in these devices, is difficult to meet the demand applied in integrated optical circuit.Therefore, reduce the size of photonic device, realize just having very important significance to the manipulation of photon under nanoscale.Metal nano material, particularly metal nanometer line, the conduction band electron on its surface can intercouple with electromagnetic field and form surface plasma excimer (SPPs), it can break diffraction limit, realize optical signal to conduct under sub-wavelength dimensions, this has important application prospect in the integrated optical circuit in future.But metal nano material has higher ohmic loss, the conduction distance of optical signal is restricted, and makes all-metal integrated optical circuit be difficult to realize.
So researchers propose, Medium Wave Guide and metal nanometer line are integrated and is prepared into nano composite system, the unique advantage of low-loss advantage not only in the conduction of optical signal like this with dielectric material but also the conduction of the sub-wavelength with metal nano material.Current preparation method mainly contains photoetching process and microoperation method.It is high that photoetching process prepares this nano composite material cost, and preparation process is complicated, and easily a large amount of under metal nanometer line remained on surface photoresists, produce extra conduction loss.Microoperation method preparation process wastes time and energy, be unfavorable for very much a large amount of preparations of nano composite material, and in this composite construction built, Medium Wave Guide and metal nanometer line simply contact with each other, integrally-built mechanical stability is bad, is unfavorable for the coupling conduction that optical signal is stable between waveguide.Therefore, urgently find a kind of more simple and practical method and come integrated Medium Wave Guide and metal nanometer line.
Summary of the invention
The object of this invention is to provide a kind of organic/preparation method of metal nanometer line hetero-junctions.Select organic molecule to prepare Medium Wave Guide, utilize the self assembly of organic molecule to be embedded in wherein by the metal nanometer line be scattered in liquid phase, formed with organic media waveguide for trunk, metal nanometer line is the nano composite structure of branch.
The present invention is achieved through the following technical solutions:
Prepare a method for organic/metal nanometer composite material, it is characterized in that, described method comprises the steps:
1) metal nanometer line is scattered in solvent, obtains the dispersion of metal nanometer line;
2) organic molecule is dissolved in good solvent, obtains the good solution of organic molecule;
3) get above-mentioned steps 2) described in the good solution of organic molecule join above-mentioned steps 1) dispersion, obtain mixed system;
4) leave standstill after mixed system, obtain being scattered in solvent organic/metal nanometer composite material;
5) get above-mentioned steps 4) in solution, drop on substrate, after drying, obtain organic/metal nanometer composite material.
According to the present invention, described organic/metal nanometer composite material is organic/metal nanometer line hetero-junctions.
According to the present invention, described organic material is the one-dimensional material of mono-crystalline structures.
According to the present invention, described metal nanometer line is crystal structure.
According to the present invention, in described step 1), metal nanometer line is selected from and can forms the metal nanometer line of surface plasma excimer with electromagnetic field couples.Preferably, described metal nanometer line is selected from silver, gold, aluminium and copper etc.
According to the present invention, described solvent is selected from the small molecule solvent of dispersible metal nano wire.Preferably, described solvent is selected from water, methyl alcohol, ethanol, acetone etc.
According to the present invention, the mass percent concentration of described metal nanometer line dispersion is 0.0001-20%.Preferably, concentration is 0.001-18%, more preferably 0.01%-10%, also more preferably 0.1%-5%.
According to the present invention, step 2) described in organic molecule be selected from metal complex or small molecular organic compounds.Preferably, described organic molecule is selected from triphenylpyridinium and closes iridium (Ir (ppy)
3), three (1-phenyl-isoquinolin) close iridium (III) (Ir (piq)
3), ruthenium bipyridyl, 9,10-tolans base anthracenes, rubrene, DCM etc.
Described good solvent is organic solvent.Preferably, described good solvent is selected from ethanol, acetone, oxolane, carrene, chloroform and composition thereof.Preferably, described organic molecule molar concentration is 0.001-40 mM/l, is more preferably 0.01-30 mM/l, is also more preferably 0.1-20 mM/l.Described good solution is that above-mentioned organic molecule is dissolved in the solution obtained in above-mentioned good solvent.
According to the present invention, in step 3), join step 2) in the good solution of organic molecule in the dispersion described in step 1), the volume ratio of good solution and dispersion is 1:500-1:1, preferably, is 1:400-1:10; Also more preferably 1:200-1:100.
According to the present invention, in step 4), time of repose is greater than 30 minutes, and temperature is 0-70 DEG C.Solvent is the solvent of dispersed metal nano wire, and the good solvent of organic molecule volatilizees.
According to the present invention, the self assembly in standing process of described organic molecule forms the monocrystalline one-dimensional medium waveguide that diameter is nanometer or micro-meter scale, and is embedded in organic media waveguide by metal nanometer line in this process.
According to the present invention, in step 5), substrate for use is various conventional substrates, as glass substrate, quartz substrate, silicon chip or electro-conductive glass substrate are all applicable to this method.
The present invention also provide above-mentioned any one method to prepare organic/metal nanometer composite material.
According to the present invention, the embedding situation of metal nanometer line in organic trunk comprises: one end of metal nanometer line is embedded in organic media waveguide; Or the mid portion of metal nanometer line is embedded in organic media waveguide; Or metal nanometer line entirety is embedded in organic media waveguide; Or the metal nanometer line of varying number is embedded in organic media waveguide; And metal nanometer line branch and trunk have different angles.
The present invention also provide above-mentioned any one method to obtain organic/metal nanometer line composite, be preferably hetero-junctions.
The present invention also provide above-mentioned any one method to prepare organic/metal nanometer composite material preparing the application in nanophotonics element.
The present invention also provide above-mentioned any one method to prepare organic/metal nanometer line hetero-junctions preparation integrated optical circuit in application.
The present invention also provide above-mentioned any one method to prepare organic/metal nanometer line hetero-junctions preparing the application in nano-sensor.
The present invention has actively useful effect:
1) provide a kind of preparation newly organic/method of metal nanometer line hetero-junctions, the method is with low cost, and method is simple, environmentally friendly, can prepare on a large scale.
2) prepare organic/metal nanometer line hetero-junctions in, organic material is the one-dimensional material of mono-crystalline structures, in the conductive process of optical signal, has low-down loss; Metal nanometer line is also crystal structure, has the surface of unusual light, greatly reduces the conduction loss of surface plasma excimer.
3) in prepared by the method organic/metal nanometer line hetero-junctions, organic media waveguide and metal nanometer line are integrated by the mode embedded, frame for movement is highly stable, be conducive to obtaining constitutionally stable nanophotonics element or nano-sensor, what make that light can be effective and stable between Medium Wave Guide with metal nanometer line is coupled, and improves the performance of components and parts.
4) utilize the method to prepare organic/metal nanometer line hetero-junctions in, different angles can be had between metal nanometer line from trunk, for research different structure organic/the photonic propulsion character of metal nanometer composite material provides very favorable condition, can be used to composite Nano photonic component or the sensor of preparing different structure.
5) in prepared by the method organic/metal nanometer line hetero-junctions, metal nanometer line is embedded in organic media waveguide, metal nanometer line and organic media waveguide have very large contact area, can be used to study the interaction of the surface plasma excimer of exciton in organic material and metal nanometer line, thus study new nanophotonics character and nanophotonics element.
Accompanying drawing explanation
Fig. 1 be embodiment 1 prepare organic/metal nanometer line hetero-junctions stereoscan photograph;
Fig. 2 be embodiment 2 prepare organic/metal nanometer line hetero-junctions stereoscan photograph;
Fig. 3 be embodiment 3 prepare organic/metal nanometer line hetero-junctions stereoscan photograph;
Fig. 4 be embodiment 4 prepare organic/metal nanometer line hetero-junctions stereoscan photograph;
Fig. 5 be embodiment 5 prepare organic/metal nanometer line hetero-junctions stereoscan photograph;
Fig. 6 is the micro-and fluorescence micrograph of the light field of nanowire heterojunction in embodiment 6;
Fig. 7 is the fluorescence spectrum of the scattered light of the nano silver wire end points of nanowire heterojunction in embodiment 6;
Fig. 8 is the micro-and fluorescence micrograph of the light field of nanowire heterojunction in embodiment 7;
Fig. 9 is the fluorescence spectrum of the scattered light of the nano silver wire end points of nanowire heterojunction in embodiment 7;
Figure 10 utilizes nanowire heterojunction to realize the schematic diagram of nanophotonics multiplexer in embodiment 7;
Figure 11 is the micro-and fluorescence micrograph of the light field of nanowire heterojunction in embodiment 8;
Figure 12 is the fluorescence spectrum of the scattered light of the nano silver wire end points of nanowire heterojunction in embodiment 8;
Figure 13 utilizes nanowire heterojunction to realize the schematic diagram of nanophotonics multiplexer in embodiment 8;
Figure 14 is the micro-and fluorescence micrograph of the light field of nanowire heterojunction in embodiment 9;
Figure 15 is the fluorescence spectrum of the scattered light of the nano silver wire end points of nanowire heterojunction in embodiment 9;
Figure 16 utilizes nanowire heterojunction to realize the schematic diagram of nanophotonics multiplexer in embodiment 9.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but it will be appreciated by those skilled in the art that the present invention is not limited to following examples, and any improvement of making on basis of the present invention and change are all within protection scope of the present invention.
Embodiment 1, prepare organic/metal nanometer line hetero-junctions
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) dichloromethane solution; Getting mass percent concentration is 0.1%, and length is 10-20 micron, and diameter is ethanolic solution 10 microlitre of the nano silver wire of 200 ran, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 100 microlitre joins in the ethanolic solution of nano silver wire, obtains mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Fig. 1 is the stereoscan photograph of above-mentioned nanowire heterojunction on quartz substrate, and ESEM INSTRUMENT MODEL used is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, and in figure, scale is 400nm.Can be seen by this figure, nano silver wire is embedded in Ir (ppy)
3in the organic media waveguide that self assembly is formed, hetero-junctions place connects closely, illustrates that Medium Wave Guide and nano silver wire are well integrated, and forms the entirety that a frame for movement is highly stable.
Embodiment 2, prepare organic/metal nanometer line hetero-junctions
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) dichloromethane solution; Getting mass percent concentration is 0.1%, and length is 10-20 micron, and diameter is methanol solution 30 microlitre of the nano silver wire of 200 ran, joins in the methyl alcohol of 2 milliliters, under room temperature ultrasonic 10 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 100 microlitre joins in the methanol solution of nano silver wire, obtains mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Fig. 2 is the stereoscan photograph of above-mentioned nanowire heterojunction on quartz substrate, and ESEM INSTRUMENT MODEL used is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, and in figure, scale is 500nm.Can be seen by this figure, many nano silver wires and organic media waveguide integrate, and illustrate and are embedded in Ir (ppy)
3in the quantity of nano silver wire can control by changing the amount that add nano silver wire in system.
Embodiment 3, prepare organic/metal nanometer line hetero-junctions
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) chloroform soln; Getting mass percent concentration is 0.1%, and length is 10-20 micron, and diameter is ethanolic solution 10 microlitre of the nano silver wire of 200 ran, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 100 microlitre joins in the ethanolic solution of nano silver wire, obtains mixed system.At 50 DEG C of temperature, leave standstill 2 hours, obtain dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Fig. 3 is the stereoscan photograph of above-mentioned nanowire heterojunction on quartz substrate, and ESEM INSTRUMENT MODEL used is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, and in figure, scale is 3um.Can be seen by this figure, the diameter of organic media waveguide is about 3 microns, the diameter 1-1.5 micron of the organic media waveguide prepared under being greater than room temperature, illustrate that the size of organic media waveguide can regulate by changing dwell temperature, composite hetero-junctions place connects closely, illustrate that Medium Wave Guide and nano silver wire are well integrated, form the entirety that a frame for movement is highly stable.
Embodiment 4, prepare organic/metal nanometer line hetero-junctions
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) dichloromethane solution; Getting mass percent concentration is 0.1%, and length is 10-20 micron, and diameter is ethanolic solution 10 microlitre of the nano silver wire of 100 ran, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 100 microlitre joins in the ethanolic solution of nano silver wire, obtains mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Fig. 4 is the stereoscan photograph of above-mentioned nanowire heterojunction on quartz substrate, and ESEM INSTRUMENT MODEL used is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, and in figure, scale is 400nm.Can be seen by this figure, the diameter of the nano silver wire in hetero-junctions is 80 nanometers, illustrates that the size of nano silver wire can be regulated and controled by the size changing the nano silver wire added.In composite construction, hetero-junctions place connects closely, and Medium Wave Guide and nano silver wire are well integrated, and forms the entirety that a frame for movement is highly stable.
Embodiment 5, prepare organic/metal nanometer line hetero-junctions
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) dichloromethane solution; Getting mass percent concentration is 0.1%, and length is 5-10 micron, and diameter is ethanolic solution 10 microlitre of the nano silver wire of 200 ran, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 100 microlitre joins in the ethanolic solution of nano silver wire, obtains mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Fig. 5 is the stereoscan photograph of above-mentioned nanowire heterojunction on quartz substrate, and ESEM INSTRUMENT MODEL used is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, and in figure, scale is 400nm.Can be seen by this figure, when its length is 5-10 micron, the mode that nano silver wire is embedded with one end and organic media waveguide integrated because when nano silver wire is shorter, the probability that one end is embedded increases; When its length is 10-20 micron, the mode that nano silver wire is mainly embedded with mid portion and organic media waveguide integrated, as the result obtained in above-described embodiment 1-4.Explanation is embedded in Ir (ppy)
3in the embedded mode of nano silver wire can regulate and control by changing the length of nano silver wire that add, thus realize the nanophotonics element of different structure.
Embodiment 6, organic/metal nanometer line hetero-junctions is utilized to realize nanophotonics element
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) dichloromethane solution; Getting mass percent concentration is 0.1%, and length is 5-10 micron, and diameter is ethanolic solution 10 microlitre of the nano silver wire of 200 ran, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 100 microlitre joins in the ethanolic solution of nano silver wire, obtains mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Prepare dendritic organic/metal nanometer line hetero-junctions.(Nikon Ti-U as shown in the microscope light field of Fig. 6 and fluorescence micrograph, scale is 10um), a nano silver wire is had in structure, its one end is embedded in organic media waveguide, the angle of the two is 45 degree, and the length of nano silver wire is 7 microns, and diameter is 150 nanometers, the diameter of organic media waveguide is 1.5 microns, and length is 100 microns.
The laser beam focusing produced with the argon ion continuous wave laser (Spectra-Physics, Beamlok2065) of 351 nanometers organic media waveguide one end (focusing objective len is Nikon CFLU Plan, 50 ×, N.A.=0.8).When the fiber waveguide wave vector angle in the wave vector and organic media of SPPs is 45 degree, SPPs can effectively be excited, as shown in Figure 6, the end points of nano silver wire scatters very strong green glow, an obvious green bright spot can be seen, this illustrates that optical signal can effectively be coupled in nano silver wire from organic media waveguide, realizes the conduction of optical signal under sub-wavelength dimensions; When the fiber waveguide wave vector angle in the wave vector and organic media of SPPs is 135 degree, SPPs can not be excited, and as shown in Figure 6, almost cannot see green light and scatters out from nano silver wire end points.
Above two kinds of mode of excitation explanations, conduct to the optical signal of hetero-junctions from Medium Wave Guide two ends, through the screening of this structure, can optionally conduct out from the end points of nano silver wire, realize nanophotonics multiplexer, under sub-wavelength dimensions, optical signal is handled.Fig. 7 is the fluorescence spectrum (spectra collection CCD model is Princeton Instruments, ProEm:512B) of the nano silver wire end points scattered light in two kinds of situations, and from spectrum, we can see that this structure has outstanding optical signal selectivity further.In addition, from the wave-length coverage of spectrum, the selective applicable wavelengths scope of this structure is very wide, therefore, organic media waveguide can be utilized as passive fiber waveguide, carry out selectively coupled output to the optical signal of other wavelength.
Embodiment 7, organic/metal nanometer line hetero-junctions is utilized to realize nanophotonics element
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) dichloromethane solution; Getting mass percent concentration is 0.1%, and length is 5-10 micron, and diameter is ethanolic solution 30 microlitre of the nano silver wire of 200 ran, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 15 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 150 microlitre joins in the ethanolic solution of nano silver wire, obtains mixed system.Left at room temperature 2.5 hours, obtains dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Prepare racemosus organic/metal nanometer line hetero-junctions.As shown in the microscope light field of Fig. 8 and fluorescence micrograph (Nikon Ti-U, scale is 10um), comprise two nano silver wires in composite construction, be inclined to side end points respectively, angle is all about 45 degree; The length of nano silver wire is respectively 6 and 11 microns, and diameter is about 200 nanometers, and the diameter of organic media waveguide is 1.3 microns, and length is 100 microns.
The laser beam focusing produced with the argon ion continuous wave laser (Spectra-Physics, Beamlok2065) of 351 nanometers organic media waveguide one end (focusing objective len is Nikon CFLU Plan, 50 ×, N.A.=0.8).As shown in Figure 8, left end, centre and right-hand member three positions are excited respectively.Can see, when exciting left end, optical signal is from the nano silver wire coupling output of right-hand member; When exciting centre, optical signal is simultaneously from the nano silver wire coupling output at two ends; When exciting right-hand member, optical signal is then only from the nano silver wire coupling output of left end.
From Fig. 8, we can see, when optical signal exports, nano silver wire scatters obvious green spot, when being difficult to coupling output, can not observe green scattered light.Fig. 9 is that (spectra collection CCD model is Princeton Instruments for the fluorescence spectrum of three kinds of mode of excitation, ProEm:512B), further illustrate optical signal selective conduction in such an embodiment, achieve nanophotonics multiplexer (signal Figure 10), under sub-wavelength dimensions, multiple photonic propulsion signal is handled.In addition, from the wave-length coverage of spectrum, the selective applicable wavelengths scope of this structure is very wide, therefore, organic media waveguide can be utilized as passive fiber waveguide, carry out selectively coupled output to the optical signal of other wavelength.
Embodiment 8, organic/metal nanometer line hetero-junctions is utilized to realize nanophotonics element
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) dichloromethane solution; Getting mass percent concentration is 0.1%, and length is 5-10 micron, and diameter is ethanolic solution 60 microlitre of the nano silver wire of 200 ran, joins in the ethanol of 5 milliliters, under room temperature ultrasonic 15 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 500 microlitre joins in the ethanolic solution of nano silver wire, obtains mixed system.Left at room temperature 3 hours, obtains dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Prepare racemosus organic/metal nanometer line hetero-junctions.As shown in the microscope light field of Figure 11 and fluorescence micrograph (Nikon Ti-U, scale is 10um), comprise two nano silver wires in composite construction, be inclined to offside end points respectively, angle is all about 50 degree; The length of nano silver wire is 5.5 and 10 microns, and diameter is about 200 nanometers, and the diameter of organic media waveguide is 1.4 microns, and length is 80 microns.
The laser beam focusing produced with the argon ion continuous wave laser (Spectra-Physics, Beamlok2065) of 351 nanometers organic media waveguide one end (focusing objective len is Nikon CFLU Plan, 50 ×, N.A.=0.8).As shown in figure 11, left end, centre and right-hand member three positions are excited respectively.Can see, when exciting left end, optical signal is from the nano silver wire coupling output of left end; When exciting centre, optical signal can not from nano silver wire coupling output; When exciting right-hand member, optical signal is then only from the nano silver wire coupling output of right-hand member.
From Figure 11, we can see, when optical signal exports, nano silver wire scatters obvious green spot, when being difficult to coupling output, can not observe green scattered light.Figure 12 is that (spectra collection CCD model is Princeton Instruments for the fluorescence spectrum of three kinds of mode of excitation, ProEm:512B), further illustrate optical signal selective conduction in such an embodiment, achieve nanophotonics multiplexer (Figure 13), under sub-wavelength dimensions, multiple photonic propulsion signal is handled.In addition, from the wave-length coverage of spectrum, the selective applicable wavelengths scope of this structure is very wide, therefore, organic media waveguide can be utilized as passive fiber waveguide, carry out selectively coupled output to the optical signal of other wavelength.
Embodiment 9, organic/metal nanometer line hetero-junctions is utilized to realize nanophotonics element
The triphenylpyridinium preparing 1 milliliter 1 mM often liter closes iridium (Ir (ppy)
3) dichloromethane solution; Getting mass percent concentration is 0.1%, and length is 5-10 micron, and diameter is ethanolic solution 40 microlitre of the nano silver wire of 200 ran, joins in the ethanol of 5 milliliters, under room temperature ultrasonic 20 seconds; Get the above-mentioned Ir (ppy) prepared
3solution 600 microlitre joins in the ethanolic solution of nano silver wire, obtains mixed system.Left at room temperature 3.5 hours, obtains dendroid Ir (ppy) in the solution
3the nanowire heterojunction of/Ag.Get solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, quartz substrate obtains dendritic Ir (ppy)
3the nanowire heterojunction of/Ag.
Prepare racemosus organic/metal nanometer line hetero-junctions.As shown in the microscope light field of Figure 14 and fluorescence micrograph (Nikon Ti-U, scale is 10um), comprise two nano silver wires in composite construction, be all inclined to side, angle is all about 45 degree; The length of nano silver wire is 8 and 9 microns, and diameter is about 200 nanometers, and the diameter of organic media waveguide is 1.2 microns, and length is 90 microns.
The laser beam focusing produced with the argon ion continuous wave laser (Spectra-Physics, Beamlok2065) of 351 nanometers organic media waveguide one end (focusing objective len is Nikon CFLU Plan, 50 ×, N.A.=0.8).As shown in figure 14, left end, centre and right-hand member three positions are excited respectively.Can see, when exciting left end, optical signal is simultaneously from two nano silver wire coupling output; When exciting centre, optical signal can only from right-hand member nano silver wire coupling output; When exciting right-hand member, optical signal then can not from nano silver wire coupling output.
From Figure 14, we can see, optical signal export time, nano silver wire scatters obvious green spot, can not coupling output time, green scattered light can not be observed.Figure 15 is that (spectra collection CCD model is Princeton Instruments for the fluorescence spectrum of three kinds of mode of excitation, ProEm:512B), further illustrate optical signal selective conduction in such an embodiment, achieve nanophotonics multiplexer (signal Figure 16), under sub-wavelength dimensions, multiple photonic propulsion signal is handled.In addition, from the wave-length coverage of spectrum, the selective applicable wavelengths scope of this structure is very wide, therefore, organic media waveguide can be utilized as passive fiber waveguide, carry out selectively coupled output to the optical signal of other wavelength.
Claims (9)
1. prepare a method for organic/metal nanometer line composite, it is characterized in that, described method comprises the steps:
1) metal nanometer line is scattered in solvent, obtains the dispersion of metal nanometer line;
2) organic molecule is dissolved in good solvent, obtains the good solution of organic molecule;
3) get above-mentioned steps 2) described in the good solution of organic molecule join above-mentioned steps 1) in dispersion, obtain mixed system;
4) after leaving standstill, obtain being scattered in solvent organic/metal nanometer line composite;
5) get above-mentioned steps 4) in solution, drop on substrate, after drying, obtain organic/metal nanometer line composite.
2. method according to claim 1, is characterized in that, described organic/metal nanometer composite material is organic/metal nanometer line hetero-junctions.
Preferably, described organic material is the one-dimensional material of mono-crystalline structures.
More preferably, described metal nanometer line is crystal structure.
3. according to the method for claim 1 or 2, it is characterized in that, in described step 1), metal nanometer line is selected from and can forms the metal nanometer line of surface plasma excimer with electromagnetic field couples.Preferably, described metal nanometer line is selected from silver, gold, aluminium and copper etc.
4. according to the method for any one of claim 1-3, it is characterized in that, described solvent is selected from the small molecule solvent of dispersible metal nano wire.Preferably, described solvent is selected from water, methyl alcohol, ethanol, acetone etc.
Preferably, the mass percent concentration of described metal nanometer line dispersion is 0.0001-20%.
Preferably, step 2) described in organic molecule be selected from metal complex or small molecular organic compounds.Preferably, described organic molecule is selected from triphenylpyridinium and closes iridium (Ir (ppy)
3), three (1-phenyl-isoquinolin) close iridium (III) (Ir (piq)
3), ruthenium bipyridyl, 9,10-tolans base anthracenes, rubrene, DCM etc.
Described good solvent is organic solvent.Preferably, described good solvent is selected from ethanol, acetone, oxolane, carrene, chloroform etc.Preferably, described organic molecule molar concentration is 0.001-40 mM often liter.Preferably, in step 3), join step 2) in the good solution of organic molecule in the dispersion described in step 1), the volume ratio of good solution and dispersion is 1:500-1:1.
Preferably, in step 4), time of repose is greater than 30 minutes, and temperature is 0-70 DEG C.Solvent is the solvent of dispersed metal nano wire, and the good solvent of organic molecule volatilizees.Organic molecule self assembly in standing process forms the monocrystalline one-dimensional medium waveguide that diameter is nanometer or micro-meter scale, and is embedded in organic media waveguide by metal nanometer line in this process.
Preferably, in step 5), substrate for use is various conventional substrates, as glass substrate, quartz substrate, silicon chip or electro-conductive glass substrate.
5. the method for any one of claim 1-4 prepares organic/metal nanometer composite material.
6. the application of organic/metal nanometer composite material in the organic/metal nano optical waveguide material of preparation.
7. the application of organic/metal nanometer composite material in the organic/metal nano logic processing elements of preparation.
8. the application of organic/metal nanometer composite material in the organic/metal nano optical signal multiplexer of preparation.
9. the application of organic/metal nanometer composite material in the organic/metal nano compound sensor of preparation.
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| CN108732662A (en) * | 2017-04-20 | 2018-11-02 | 中国科学院化学研究所 | A kind of micro- disk of organic flexible/metal nanometer line hetero-junctions and preparation method thereof |
| CN109212639A (en) * | 2017-07-04 | 2019-01-15 | 中国科学院化学研究所 | A kind of multinode perovskite metal hetero-junction and its preparation method and application |
| CN109212640A (en) * | 2017-07-04 | 2019-01-15 | 中国科学院化学研究所 | Organic/metal nanometer line hetero-junctions of one kind and its preparation method and application |
| CN113410386A (en) * | 2021-06-17 | 2021-09-17 | 哈尔滨工业大学 | Method for preparing nanowire with M/M-TCNQ Schottky junction |
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| CN109212640B (en) * | 2017-07-04 | 2020-08-21 | 中国科学院化学研究所 | Organic/metal nanowire heterojunction and preparation method and application thereof |
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| CN113410386B (en) * | 2021-06-17 | 2023-03-14 | 哈尔滨工业大学 | Method for preparing nanowire with M/M-TCNQ Schottky junction |
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