CN104249151B - A kind of organic/metal nanometer line hetero-junctions, its preparation method and application thereof - Google Patents
A kind of organic/metal nanometer line hetero-junctions, its preparation method and application thereof Download PDFInfo
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- CN104249151B CN104249151B CN201310263266.0A CN201310263266A CN104249151B CN 104249151 B CN104249151 B CN 104249151B CN 201310263266 A CN201310263266 A CN 201310263266A CN 104249151 B CN104249151 B CN 104249151B
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Abstract
The invention discloses the preparation method of a kind of organic/metal nanometer line hetero-junctions, it utilizes organic molecule self assembling process to be in the liquid phase embedded in wherein by the metal nanometer line being scattered in liquid phase, thus obtains the organic/metal nanometer line hetero-junctions of different structure.Preparation method technique provided by the present invention is simple, easy to operate, low cost, and the suitability is wide, can prepare in a large number and environmental friendliness.Utilize organic/metal nanometer line hetero-junctions smooth surface that the method obtains, Medium Wave Guide and metal silver nanowires combining closely, there is the coupling efficiency of the highest photon and surface plasma excimer, the composite material surface that prepared by method before solving is rough, metal and the problem such as medium contact area is little, integral mechanical structure is unstable, can be used for preparing nanophotonics element, such as photonic propulsion multiplexer or nanocomposite optical sensor.
Description
Technical field
The present invention relates to the preparation method and applications of a kind of organic/metal nanometer line hetero-junctions.
Background technology
Photonic device has the advantages such as the incomparable high speed of electronics device, high bandwidth and low energy consumption,
Very important role is play in optical information processing and photonic propulsion calculate.Polymer, inorganic semiconductor
With traditional dielectric materials such as organic materials, it is commonly used to prepare photonic device, but in these devices
The conduction of optical signal is limited by diffraction limit, it is difficult to meet the demand of application in integrated optical circuit.Cause
This, reduce the size of photonic device, realize the manipulation to photon and just have the heaviest under nanoscale
The meaning wanted.Metal nano material, particularly metal nanometer line, the conduction band electron on its surface can be with electricity
Magnetic field intercouples and forms surface plasma excimer (SPPs), and it can break diffraction limit, it is achieved
Optical signal conducts under sub-wavelength dimensions, and this has important application prospect in terms of following integrated optical circuit.
But metal nano material has higher ohmic loss, the conduction distance of optical signal is restricted so that complete
The integrated optical circuit of metal is difficult to.
Then researchers propose, Medium Wave Guide and metal nanometer line are integrated be prepared as nano combined
System, so not only has low-loss advantage of dielectric material but also has metal in terms of the conduction of optical signal
The unique advantage of the sub-wavelength conduction of nano material.Current preparation method mainly has photoetching process and microoperation
Method.It is high that photoetching process prepares this nano composite material cost, and preparation process is complicated, and easily receives at metal
Substantial amounts of photoresist under nanowire surface residual, produces extra conduction loss.Microoperation method preparation process is taken
Time laborious, be highly detrimental to a large amount of preparations of nano composite material, and in this composite construction built,
Medium Wave Guide simply contacts with each other with metal nanometer line, and integrally-built mechanical stability is bad, unfavorable
In the coupling conduction that optical signal is stable between waveguide.It would therefore be highly desirable to find a kind of the most simple and practical
Method comes integrated Medium Wave Guide and metal nanometer line.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of organic/metal nanometer line hetero-junctions.Selection has
Machine molecule prepares Medium Wave Guide, utilizes the self assembly of organic molecule will be scattered in the metal nano in liquid phase
Line is embedded in wherein, is formed with organic media waveguide as trunk, and metal nanometer line is the nano combined knot of branch
Structure.
The present invention is achieved through the following technical solutions:
A kind of method preparing organic/metal nanometer composite material, it is characterised in that described method includes
Following 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) take above-mentioned steps 2) described in the good solution of organic molecule join above-mentioned steps 1) dispersion
System, obtains mixed system；
4), after standing mixed system, the organic/metal nanometer composite material being scattered in solvent is obtained；
5) take above-mentioned steps 4) in solution, drop on substrate, after drying, obtain organic/metal and receive
Nano 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 forming surface with electromagnetic field couples
The metal nanometer line of plasmon.Preferably, described metal nanometer line is selected from silver, gold, aluminum and copper
Deng.
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, methanol, 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%, even more preferably from 0.1%-5%.
According to the present invention, step 2) described in organic molecule organise selected from metal complex or little molecule
Compound.Preferably, described organic molecule closes iridium (Ir (ppy) selected from triphenylpyridinium3), three (1-benzene
Base-isoquinolin) close iridium (III) (Ir (piq)3), ruthenium bipyridyl, 9,10-tolan base anthracene, red glimmering
Alkene, DCM etc..
Described good solvent is organic solvent.Preferably, described good solvent is selected from ethanol, acetone, tetrahydrochysene furan
Mutter, dichloromethane, chloroform and mixture thereof.Preferably, described organic molecule molar concentration is
0.001-40 mM/l, more preferably 0.01-30 mM/l, still more preferably 0.1-20 milli
Mol/L.Described good solution is that above-mentioned organic molecule is dissolved in above-mentioned good solvent the solution obtained.
According to the present invention, in step 3), join step 2) in organic molecule good solution to step
Rapid 1), in the dispersion described in, good solution is 1:500-1:1 with the volume ratio of dispersion, preferably
Ground, for 1:400-1:10；Even more preferably from 1:200-1:100.
According to the present invention, in step 4), time of repose is more than 30 minutes, and temperature is 0-70 DEG C.Molten
Agent is the solvent of dispersed metal nano wire, and the good solvent of organic molecule has volatilized.
According to the present invention, described organic molecule is self-assembly of a diameter of nanometer or micron during standing
The monocrystalline one-dimensional medium waveguide of yardstick, and in this process metal nanometer line is embedded in organic media ripple
In leading.
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 provides for organic/metal nanometer composite material that any of the above-described method prepares.
According to the present invention, metal nanometer line embedding situation in organic trunk includes: metal nanometer line
One end is embedded in organic media waveguide；Or the mid portion of metal nanometer line is embedded in organic Jie
In matter waveguide；Or metal nanometer line entirety is embedded in organic media waveguide；Or varying number
Metal nanometer line is embedded in organic media waveguide；And metal nanometer line branch has different folders from trunk
Angle.
The present invention also provides for organic/metal nanometer line composite that any of the above-described method obtains, preferably
For hetero-junctions.
The present invention also provides for organic/metal nanometer composite material that any of the above-described method prepare in system
Application in standby nanophotonics element.
The present invention also provides for organic/metal nanometer line hetero-junctions that any of the above-described method prepare in system
Application in standby integrated optical circuit.
The present invention also provides for organic/metal nanometer line hetero-junctions that any of the above-described method prepare in system
Application in standby nano-sensor.
The invention have the advantages that:
1) a kind of new method preparing organic/metal nanometer line hetero-junctions, the method low cost are provided
Honest and clean, method is simple, environmentally friendly, can prepare on a large scale.
2), in the organic/metal nanometer line hetero-junctions prepared, organic material is the one-dimensional of mono-crystalline structures
Material, in the conductive process of optical signal, has low-down loss；Metal nanometer line is also tied for crystal
Structure, has the surface of unusual light, greatly reduces the conduction loss of surface plasma excimer.
3) in organic/metal nanometer line hetero-junctions that prepared by the method, organic media waveguide and metal nano
Line integrates by the way of embedding, and frame for movement is highly stable, is conducive to obtaining constitutionally stable
Nanophotonics element or nano-sensor, make light between Medium Wave Guide and metal nanometer line can effectively and
Stable coupling, improves the performance of components and parts.
4) utilize in organic/metal nanometer line hetero-junctions that the method prepares, metal nanometer line and master
Different angles can be had, for the light of the organic/metal nanometer composite material of research different structure between Gan
Son is learned character and is provided very favorable condition, can be used to prepare the composite Nano photonic component of different structure
Or sensor.
5), in organic/metal nanometer line hetero-junctions that prepared by the method, metal nanometer line is embedded in organic
In Medium Wave Guide, metal nanometer line and organic media waveguide have the biggest contact area, can be used to grind
Study carefully the interaction of the exciton in organic material and the surface plasma excimer of metal nanometer line, thus grind
Study carefully new nanophotonics character and nanophotonics element.
Accompanying drawing explanation
Fig. 1 is organic/metal nanometer line hetero-junctions stereoscan photograph that embodiment 1 prepares；
Fig. 2 is organic/metal nanometer line hetero-junctions stereoscan photograph that embodiment 2 prepares；
Fig. 3 is organic/metal nanometer line hetero-junctions stereoscan photograph that embodiment 3 prepares；
Fig. 4 is organic/metal nanometer line hetero-junctions stereoscan photograph that embodiment 4 prepares；
Fig. 5 is organic/metal nanometer line hetero-junctions stereoscan photograph that embodiment 5 prepares；
Fig. 6 is that in embodiment 6, the light field of nanowire heterojunction is micro-and fluorescence micrograph；
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 that in embodiment 7, the light field of nanowire heterojunction is micro-and fluorescence micrograph；
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 is to utilize nanowire heterojunction to realize the signal of nanophotonics multiplexer in embodiment 7
Figure；
Figure 11 is that in embodiment 8, the light field of nanowire heterojunction is micro-and fluorescence micrograph；
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 is to utilize nanowire heterojunction to realize the signal of nanophotonics multiplexer in embodiment 8
Figure；
Figure 14 is that in embodiment 9, the light field of nanowire heterojunction is micro-and fluorescence micrograph；
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 is to utilize nanowire heterojunction to realize the signal of nanophotonics multiplexer in embodiment 9
Figure.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, it will be appreciated by those skilled in the art that this
The bright following example that are not limited to, any improvement made on the basis of the present invention and change are all in the present invention
Protection domain within.
Embodiment 1, prepare organic/metal nanometer line hetero-junctions
The triphenylpyridinium preparing 1 milliliter 1 mM every liter closes iridium (Ir (ppy)3) dichloromethane molten
Liquid；Taking mass percent concentration is 0.1%, a length of 10-20 micron, a diameter of 200 ran
Ethanol solution 10 microlitre of nano silver wire, join in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 100 microlitre joins in the ethanol solution of nano silver wire, obtains
Mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution3The nano wire of/Ag
Hetero-junctions.Taking solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, at quartz base
Dendritic Ir (ppy) is obtained on sheet3The nanowire heterojunction of/Ag.
Fig. 1 is above-mentioned nanowire heterojunction stereoscan photograph on quartz substrate, scanning electron microscope used
INSTRUMENT MODEL is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, in figure
Scale is 400nm.From this figure, it can be seen that nano silver wire is embedded in Ir (ppy)3It is self-assembly of
Organic media waveguide in, connect closely at hetero-junctions, Medium Wave Guide and nano silver wire quilt be described
Well integrate, form 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 every liter closes iridium (Ir (ppy)3) dichloromethane molten
Liquid；Taking mass percent concentration is 0.1%, a length of 10-20 micron, a diameter of 200 ran
Methanol solution 30 microlitre of nano silver wire, join in the methanol of 2 milliliters, under room temperature ultrasonic 10 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 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 solution3The nano wire of/Ag
Hetero-junctions.Taking solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, at quartz base
Dendritic Ir (ppy) is obtained on sheet3The nanowire heterojunction of/Ag.
Fig. 2 is above-mentioned nanowire heterojunction stereoscan photograph on quartz substrate, scanning electron microscope used
INSTRUMENT MODEL is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, in figure
Scale is 500nm.From this figure, it can be seen that many nano silver wires are integrated in one with organic media waveguide
Rise, illustrate to be embedded in Ir (ppy)3In the quantity of nano silver wire can be by changing the silver in addition system
The amount of nano wire controls.
Embodiment 3, prepare organic/metal nanometer line hetero-junctions
The triphenylpyridinium preparing 1 milliliter 1 mM every liter closes iridium (Ir (ppy)3) chloroform molten
Liquid；Taking mass percent concentration is 0.1%, a length of 10-20 micron, a diameter of 200 ran
Ethanol solution 10 microlitre of nano silver wire, join in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 100 microlitre joins in the ethanol solution of nano silver wire, obtains
Mixed system.At a temperature of 50 DEG C, stand 2 hours, obtain dendroid Ir (ppy) in the solution3/ Ag's
Nanowire heterojunction.Take solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes,
Dendritic Ir (ppy) is obtained on quartz substrate3The nanowire heterojunction of/Ag.
Fig. 3 is above-mentioned nanowire heterojunction stereoscan photograph on quartz substrate, scanning electron microscope used
INSTRUMENT MODEL is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, in figure
Scale is 3um.From this figure, it can be seen that the diameter of organic media waveguide is about 3 microns, more than room
The diameter 1-1.5 micron of the organic media waveguide of the lower preparation of temperature, illustrates that the size of organic media waveguide is permissible
Regulate by changing dwell temperature, connect closely at composite hetero-junctions, medium ripple is described
Lead and well integrated with nano silver wire, 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 every liter closes iridium (Ir (ppy)3) dichloromethane molten
Liquid；Taking mass percent concentration is 0.1%, a length of 10-20 micron, a diameter of 100 ran
Ethanol solution 10 microlitre of nano silver wire, join in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 100 microlitre joins in the ethanol solution of nano silver wire, obtains
Mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution3The nano wire of/Ag
Hetero-junctions.Taking solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, at quartz base
Dendritic Ir (ppy) is obtained on sheet3The nanowire heterojunction of/Ag.
Fig. 4 is above-mentioned nanowire heterojunction stereoscan photograph on quartz substrate, scanning electron microscope used
INSTRUMENT MODEL is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, in figure
Scale is 400nm.From this figure, it can be seen that a diameter of 80 nanometers of the nano silver wire in hetero-junctions,
Illustrate that the size of nano silver wire can be regulated and controled by the size of the nano silver wire that change adds.Composite construction
In, connect closely at hetero-junctions, Medium Wave Guide is well integrated with nano silver wire,
Form 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 every liter closes iridium (Ir (ppy)3) dichloromethane molten
Liquid；Taking mass percent concentration is 0.1%, a length of 5-10 micron, a diameter of 200 ran
Ethanol solution 10 microlitre of nano silver wire, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 100 microlitre joins in the ethanol solution of nano silver wire, obtains
Mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution3The nano wire of/Ag
Hetero-junctions.Taking solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, at quartz base
Dendritic Ir (ppy) is obtained on sheet3The nanowire heterojunction of/Ag.
Fig. 5 is above-mentioned nanowire heterojunction stereoscan photograph on quartz substrate, scanning electron microscope used
INSTRUMENT MODEL is HitachiS-4800, and voltage is 15 kilovolts, and sample carries out metal spraying pretreatment, in figure
Scale is 400nm.From this figure, it can be seen that when its a length of 5-10 micron, nano silver wire is with one
The mode that end is embedded is integrated with organic media waveguide, because when nano silver wire is shorter, one end is embedded
Probability increase；When its a length of 10-20 micron, nano silver wire is mainly embedded with mid portion
Mode is integrated with organic media waveguide, such as the result obtained in above-described embodiment 1-4.Explanation is embedded in
Ir(ppy)3In the length of nano silver wire that can be added by change of the embedded mode of nano silver wire come
Regulation and control, 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 every liter closes iridium (Ir (ppy)3) dichloromethane molten
Liquid；Taking mass percent concentration is 0.1%, a length of 5-10 micron, a diameter of 200 ran
Ethanol solution 10 microlitre of nano silver wire, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 10 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 100 microlitre joins in the ethanol solution of nano silver wire, obtains
Mixed system.Left at room temperature 2 hours, obtains dendroid Ir (ppy) in the solution3The nano wire of/Ag
Hetero-junctions.Taking solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, at quartz base
Dendritic Ir (ppy) is obtained on sheet3The nanowire heterojunction of/Ag.
Prepare dendritic organic/metal nanometer line hetero-junctions.Such as the microscope light field of Fig. 6 and glimmering
Shown in light microphotograph (Nikon Ti-U, scale is 10um), structure has a nano silver wire,
Its one end is embedded in organic media waveguide, and the angle of the two is 45 degree, nano silver wire a length of
7 microns, a diameter of 150 nanometers, a diameter of 1.5 microns of organic media waveguide, a length of 100 micro-
Rice.
Produce with the argon ion continuous wave laser (Spectra-Physics, Beamlok2065) of 351 nanometers
Raw laser beam focusing organic media waveguide one end (focusing objective len is Nikon CFLU Plan,
50 ×, N.A.=0.8).Fiber waveguide wave vector angle in the wave vector and organic media of SPPs is 45
When spending, SPPs can effectively be excited, and as shown in Figure 6, the end points of nano silver wire scatters the strongest
Green glow, it can be seen that an obvious green bright spot, this explanation optical signal can be effectively from organic media
Waveguide is coupled in nano silver wire, it is achieved optical signal conduction under sub-wavelength dimensions；When SPPs's
When wave vector is 135 degree with the fiber waveguide wave vector angle in organic media, SPPs can not be excited, such as Fig. 6
Shown in, the most invisible green light scatters out from nano silver wire end points.
Both the above mode of excitation illustrates, the optical signal at Medium Wave Guide two ends conduction to hetero-junctions, warp
Cross the screening of this structure, can optionally conduct out from the end points of nano silver wire, it is achieved nanometer light
Son learns multiplexer, handles optical signal under sub-wavelength dimensions.Fig. 7 is the Yin Na in the case of two kinds
The fluorescence spectrum of rice noodle end points scattered light (spectra collection CCD type number is Princeton Instruments,
ProEm:512B), from spectrum we it can further be seen that this structure has outstanding optical signal selects
Performance.Additionally, knowable to the wave-length coverage of spectrum, the selectivity applicable wavelengths scope of this structure is the widest,
Therefore, the optical signal of other wavelength, as passive fiber waveguide, is selected by available organic media waveguide
Property coupling output.
Embodiment 7, organic/metal nanometer line hetero-junctions is utilized to realize nanophotonics element
The triphenylpyridinium preparing 1 milliliter 1 mM every liter closes iridium (Ir (ppy)3) dichloromethane molten
Liquid；Taking mass percent concentration is 0.1%, a length of 5-10 micron, a diameter of 200 ran
Ethanol solution 30 microlitre of nano silver wire, joins in the ethanol of 2 milliliters, under room temperature ultrasonic 15 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 150 microlitre joins in the ethanol solution of nano silver wire, obtains
Mixed system.Left at room temperature 2.5 hours, obtains dendroid Ir (ppy) in the solution3The nanometer of/Ag
Line hetero-junctions.Taking solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, at quartz
Dendritic Ir (ppy) is obtained on substrate3The nanowire heterojunction of/Ag.
Prepare the organic/metal nanometer line hetero-junctions of racemosus.Microscope light field and fluorescence such as Fig. 8
Shown in microphotograph (Nikon Ti-U, scale is 10um), composite construction comprises two silver nanoparticles
Line, respectively tendency side end points, angle is each about 45 degree；The length of nano silver wire is respectively 6 and 11
Micron, diameter is about 200 nanometers, a diameter of 1.3 microns of organic media waveguide, a length of 100 micro-
Rice.
Produce with the argon ion continuous wave laser (Spectra-Physics, Beamlok2065) of 351 nanometers
Raw laser beam focusing 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 three positions of right-hand member are excited respectively.
It will be seen that when exciting left end, optical signal couples output from the nano silver wire of right-hand member；When exciting centre
Time, the while of optical signal, the nano silver wire coupling from two ends exports；When exciting right-hand member, optical signal then only from
The nano silver wire coupling output of left end.
During from Fig. 8 it will be seen that optical signal exports, nano silver wire scatters obvious green spot,
When being difficult to coupling output, it is impossible to observe green scattered light.Fig. 9 is the fluorescence spectrum of three kinds of mode of excitation
(spectra collection CCD type number is Princeton Instruments, ProEm:512B), furtherly
Clear optical signal selectivity conduction in such an embodiment, it is achieved that nanophotonics multiplexer (schematic diagram
10), under sub-wavelength dimensions, multiple photonic propulsion signals are handled.Additionally, from the wavelength model of spectrum
Enclosing and understand, the selectivity applicable wavelengths scope of this structure is the widest, therefore, and available organic media waveguide
As passive fiber waveguide, the optical signal of other wavelength is carried out selectively coupled output.
Embodiment 8, organic/metal nanometer line hetero-junctions is utilized to realize nanophotonics element
The triphenylpyridinium preparing 1 milliliter 1 mM every liter closes iridium (Ir (ppy)3) dichloromethane molten
Liquid；Taking mass percent concentration is 0.1%, a length of 5-10 micron, a diameter of 200 ran
Ethanol solution 60 microlitre of nano silver wire, joins in the ethanol of 5 milliliters, under room temperature ultrasonic 15 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 500 microlitre joins in the ethanol solution of nano silver wire, obtains
Mixed system.Left at room temperature 3 hours, obtains dendroid Ir (ppy) in the solution3The nano wire of/Ag
Hetero-junctions.Taking solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, at quartz base
Dendritic Ir (ppy) is obtained on sheet3The nanowire heterojunction of/Ag.
Prepare the organic/metal nanometer line hetero-junctions of racemosus.Microscope light field and fluorescence such as Figure 11
Shown in microphotograph (Nikon Ti-U, scale is 10um), composite construction comprises two silver nanoparticles
Line, respectively tendency offside end points, angle is each about 50 degree；A length of the 5.5 of nano silver wire and 10 is micro-
Rice, diameter is about 200 nanometers, a diameter of 1.4 microns of organic media waveguide, a length of 80 microns.
Produce with the argon ion continuous wave laser (Spectra-Physics, Beamlok2065) of 351 nanometers
Raw laser beam focusing 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 three positions of right-hand member are excited respectively.
It will be seen that when exciting left end, optical signal couples output from the nano silver wire of left end；When exciting centre
Time, optical signal can not be from nano silver wire coupling output；When exciting right-hand member, optical signal is then only from right-hand member
Nano silver wire coupling output.
During from Figure 11 it will be seen that optical signal exports, nano silver wire scatters obvious green light
Speckle, it is difficult to during coupling output, it is impossible to observe green scattered light.Figure 12 is the glimmering of three kinds of mode of excitation
Light spectrum (spectra collection CCD type number is Princeton Instruments, ProEm:512B), enters
One step illustrates optical signal selectivity conduction in such an embodiment, it is achieved that nanophotonics multiplexer
(Figure 13), under sub-wavelength dimensions, multiple photonic propulsion signals are handled.Additionally, from the ripple of spectrum
Long scope understands, and the selectivity applicable wavelengths scope of this structure is the widest, therefore, and available organic media
Waveguide, as passive fiber waveguide, carries 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 every liter closes iridium (Ir (ppy)3) dichloromethane molten
Liquid；Taking mass percent concentration is 0.1%, a length of 5-10 micron, a diameter of 200 ran
Ethanol solution 40 microlitre of nano silver wire, joins in the ethanol of 5 milliliters, under room temperature ultrasonic 20 seconds；
Take the above-mentioned Ir (ppy) prepared3Solution 600 microlitre joins in the ethanol solution of nano silver wire, obtains
Mixed system.Left at room temperature 3.5 hours, obtains dendroid Ir (ppy) in the solution3The nanometer of/Ag
Line hetero-junctions.Taking solution 30 microlitre, be added drop-wise on quartz substrate, drying at room temperature 30 minutes, at quartz
Dendritic Ir (ppy) is obtained on substrate3The nanowire heterojunction of/Ag.
Prepare the organic/metal nanometer line hetero-junctions of racemosus.Microscope light field and fluorescence such as Figure 14
Shown in microphotograph (Nikon Ti-U, scale is 10um), composite construction comprises two silver nanoparticles
Line, is all inclined to side, and angle is each about 45 degree；A length of 8 and 9 microns of nano silver wire, diameter
About 200 nanometers, a diameter of 1.2 microns of organic media waveguide, a length of 90 microns.
Produce with the argon ion continuous wave laser (Spectra-Physics, Beamlok2065) of 351 nanometers
Raw laser beam focusing 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 three positions of right-hand member are excited respectively.
It will be seen that when exciting left end, optical signal is simultaneously from two nano silver wire coupling outputs；In exciting
Between time, 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.
During from Figure 14 it will be seen that optical signal exports, nano silver wire scatters obvious green light
Speckle, it is impossible to during coupling output, it is impossible to observe green scattered light.Figure 15 is the glimmering of three kinds of mode of excitation
Light spectrum (spectra collection CCD type number is Princeton Instruments, ProEm:512B), enters
One step illustrates optical signal selectivity conduction in such an embodiment, it is achieved that nanophotonics multiplexer
Multiple photonic propulsion signals are handled under sub-wavelength dimensions by (signal Figure 16).Additionally, from spectrum
Wave-length coverage understand, the selectivity applicable wavelengths scope of this structure is the widest, therefore, available organic
Medium Wave Guide, as passive fiber waveguide, carries out selectively coupled output to the optical signal of other wavelength.
Claims (24)
1. the method preparing organic/metal nanometer line composite, it is characterised in that described method includes
Following 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) take above-mentioned steps 2) described in the good solution of organic molecule join above-mentioned steps 1) in dispersion
System, obtains mixed system；
4), after standing, the organic/metal nanometer line composite being scattered in solvent is obtained；
5) take above-mentioned steps 4) in solution, drop on substrate, after drying, obtain organic/metal nanometer line
Composite；
Wherein said organic molecule closes iridium (Ir (ppy) selected from triphenylpyridinium3), three (1-phenyl-isoquinolin)
Close iridium (III) (Ir (piq)3), ruthenium bipyridyl, 9,10-tolan base anthracene, rubrene, DCM, described
Organic/metal nanometer composite material is organic/metal nanometer line hetero-junctions.
Method the most according to claim 1, it is characterised in that described organic/metal nanometer line composite wood
Material is the one-dimensional material of mono-crystalline structures.
Method the most according to claim 1, it is characterised in that described metal nanometer line is crystal structure.
Method the most according to claim 1, it is characterised in that described step 1) in metal nano line selection
Self energy forms the metal nanometer line of surface plasma excimer with electromagnetic field couples.
Method the most according to claim 2, it is characterised in that described step 1) in metal nanometer line
Being selected from can be with the metal nanometer line of electromagnetic field couples formation surface plasma excimer.
Method the most according to claim 3, it is characterised in that described step 1) in metal nanometer line
Being selected from can be with the metal nanometer line of electromagnetic field couples formation surface plasma excimer.
7. according to the method according to any one of claim 1-6, it is characterised in that described metal nanometer line
Selected from silver, gold, aluminum and copper.
8. according to the method according to any one of claim 1-6, it is characterised in that described solvent is selected from can
The small molecule solvent of dispersed metal nano wire.
Method the most according to claim 8, it is characterised in that described solvent is selected from water, methanol, second
Alcohol, acetone.
10. according to the method according to any one of claim 1-6, it is characterised in that described metal nanometer line
The mass percent concentration of dispersion be 0.0001-20%.
11. according to the method according to any one of claim 1-6, it is characterised in that described good solvent is for having
Machine solvent.
12. methods according to claim 11, it is characterised in that described good solvent selected from ethanol, third
Ketone, oxolane, dichloromethane, chloroform.
13. according to the method according to any one of claim 1-6, it is characterised in that described organic molecule rubs
You are 0.001-40 mM every liter at concentration.
14. according to the method according to any one of claim 1-6, it is characterised in that in step 3) in,
Join step 2) in the good solution of organic molecule to step 1) described in dispersion in, good solution with
The volume ratio of dispersion is 1:500-1:1.
15. according to the method according to any one of claim 1-6, it is characterised in that in step 4) in,
Time of repose is more than 30 minutes, and temperature is 0-70 DEG C.
16. according to the method according to any one of claim 1-6, it is characterised in that in step 4) in,
Described solvent is the solvent of dispersed metal nano wire, and the good solvent of organic molecule has volatilized.
17. according to the method according to any one of claim 1-6, it is characterised in that organic molecule is standing
During be self-assembly of the monocrystalline one-dimensional medium waveguide of a diameter of nanometer or micro-meter scale, and in this process
Middle described metal nanometer line is embedded in organic media waveguide.
18. according to the method according to any one of claim 1-6, it is characterised in that in step 5) in,
Substrate for use is glass substrate, quartz substrate, silicon chip.
19. methods according to claim 18, wherein substrate for use is electro-conductive glass substrate.
20. organic/the metal nanometer composite materials obtained by the method according to any one of claim 1-19.
21. organic/metal nanometer composite materials according to claim 20 are preparing organic/metal nano
Application in optical waveguide material.
22. organic/metal nanometer composite materials according to claim 20 are preparing organic/metal nano
Application in logic processing elements.
23. organic/metal nanometer composite materials according to claim 20 are preparing organic/metal nano
Application in optical signal multiplexer.
24. organic/metal nanometer composite materials according to claim 20 are preparing organic/metal nano
Application in compound sensor.
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