CN101602577A - A kind of multicolor visible light left-handed material based on silver dendritic structure - Google Patents
A kind of multicolor visible light left-handed material based on silver dendritic structure Download PDFInfo
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- CN101602577A CN101602577A CNA200810150024XA CN200810150024A CN101602577A CN 101602577 A CN101602577 A CN 101602577A CN A200810150024X A CNA200810150024X A CN A200810150024XA CN 200810150024 A CN200810150024 A CN 200810150024A CN 101602577 A CN101602577 A CN 101602577A
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Abstract
The present invention relates to a kind of multicolor visible light left-handed material based on silver dendritic structure, be specifically related to a kind of chemical electro-deposition method that adopts earlier and in the bigger conductive glass substrate of resistance, prepare the nano silver tree dendritic structures of lack of alignment, and then at the silver dendritic structure surface-coated PVA film of preparation, then that it is superimposed with the less conductive glass of resistance and the composite structure LHM for preparing.This LHM has the multiband transmissison characteristic in visible light 360-800nm, and all has the obvious flat focusing effect under the wavelength of the peak-peak correspondence of transmission passband.
Description
Technical field
The present invention relates to a kind of visible light left-handed material and preparation method thereof, particularly a kind of based on the nano silver tree dendritic structures unit of lack of alignment and laminate structure LHM that has the multiband left-hand transmission passband at visible light wave range of non-conductive medium polyvinyl alcohol (PVA) film and tin indium oxide (ITO) conducting film composition and preparation method thereof.
Background technology
LHM (Left-handed metamaterials, LHMs) be that a kind of specific inductivity (ε) and magnetic permeability (μ) are negative artificial periodic structure material simultaneously, because the electromagnetic phase velocity of propagating is opposite with the group velocity direction therein, thereby show the electromagnetic property of a series of abnormalities, as unusual Doppler effect, unusual Cherenkov radiation, abnormality
Displacement, negative refraction and perfect lens effect etc.The discovery of LHMs and be chosen as one of annual ten big technological breakthroughs 2003 and 2006 by U.S.'s " science " magazine respectively based on " stealthy cape " (Circular cloaking device) of the theoretical preparation of LHM, thus make the research of LHM become forward position and the hot issue in the research fields such as current physics, Materials science and electromagnetism.Present stage, the research of LHM is to multi-direction development, mainly comprise and utilize existing LHM, and more research concentrates on the preparation of visible light frequency band left-hand material and uses the further research of its physical property, the practical application of microwave section LHM, the proposition and the research infrared and the visible light wave range LHM of novel material design concept.
According to existing theory about LHM, the size of LHM structural unit should be less than optical wavelength, so concerning the visible light frequency band left-hand material, there is very big difficulty in its preparation.At present, the investigators in this field all adopt periodically metal Nano structure realization visible light frequency band left-hand effect, and the physical etchings technology of " (top-down) from top to bottom " is adopted in the preparation of this structure mostly.This method needs expensive equipment, the preparation process complexity, the preparation difficulty is big, the area of preparation sample generally can only reach the square micron magnitude, and the LHM of preparation also can only greatly limit the broad research and the application of visible light frequency band left-hand material in single frequency range generation left hand effect.So, seek that simple and direct, inexpensive method is in enormous quantities, large-area preparation low-loss, visible light left-handed material high-effect, multiband become LHM research and key in application.The silver dendritic structure for preparing lack of alignment with the electrochemical deposition method of " (bottom-up) from bottom to top " is realized visible region multiband left hand effect, will promote the research and the application of visible light frequency band left-hand material greatly.
Summary of the invention
The purpose of this invention is to provide sandwich structure multicolor visible light left-handed material of a kind of nano silver tree dendritic structures unit, PVA film non-conductive medium and tin indium oxide (ITO) conducting film and preparation method thereof based on lack of alignment.This LHM has the multiband left-hand transmission passband in visible light frequency band 360nm-800nm scope, the light wave that the left hand passband occurs is had the obvious flat focusing effect.Its preparation method is to be substrate with transparent indium tin oxide-coated glass, adopt the chemical electro-deposition legal system to be equipped with the nano silver tree dendritic structures unit, and then at the silver dendritic structure surface-coated PVA film of preparation, the ITO conductive glass of less with square resistance then (comparing with the conductive glass of depositing silver dendritic structure) is dressed up multilayered structure.(preparation process is shown in accompanying drawing 1A).
Plate electrode chemical electro-deposition method is adopted in the preparation of the nano silver tree dendritic structures among the present invention, and by regulating deposition voltage, can obtain the structural unit diameter in the conductive glass substrate is 100nm-500nm, the silver dendritic structure unit of lack of alignment.
Drop-coating is adopted in the preparation of PVA film, and the concentration by control masking liquid (PVA ultrapure water solution) is 0.5%-1.0% and drips the after drying speed that is coated with, and then the thickness that control is coated in silver dendritic structure surface PVA film is evenly and less than 100nm.
The assembling of multilayered structure LHM is relative closely superimposed with the less conductive glass of the silver dendritic structure sample that applies the PVA film and resistance, then with the two ends compact winding of plastic adhesive tape with superimposed sample.This LHM has the multiband left-hand transmission passband in the wavelength region of visible light wave range 360nm-800nm, and the light wave that the left hand passband occurs is had the obvious flat focusing effect.
Description of drawings
The preparation process synoptic diagram of Fig. 1 multicolor visible light left-handed material
Fig. 2 0.6V is the nano silver tree dendritic structures stereoscan photograph (illustration is a structural unit) of preparation down
Fig. 3 0.8V is the transmission collection of illustrative plates and the flat focus figure of the multicolor visible light left-handed material of preparation down
A. visible transmission collection of illustrative plates
The flat focus figure of B.X direction
The flat focus figure of C.Y direction
Fig. 4 0.6V is the transmission collection of illustrative plates and the flat focus figure of the multicolor visible light left-handed material of preparation down
A. visible transmission collection of illustrative plates
The flat focus figure of B.X direction
The flat focus figure of C.Y direction
Embodiment
1. the unitary preparation of nano silver tree dendritic structures in the conductive glass substrate: adopt dull and stereotyped electricity level chemical electro-deposition method, with square resistance is that tin indium oxide (ITO) transparent conducting glass of 17 Ω is a negative electrode, with surfacing, purity is that 99.9% silver strip is an anode, and the distance between two plate electrodes is 0.2mm.Electrolytic solution is AgNO
3, PEG-20000 and silver colloid mixing ultrapure water solution, energising 30-60 second under DC voltage-stabilizing 0.6V-1.0V, the diameter that can obtain lack of alignment in the conductive glass substrate is the silver dendritic structure unit of 100nm-500nm.
2. the coating of silver dendritic structure surface PVA film: adopt drop-coating, PVA ultrapure water solution with 0.5-1.0% (w/v) is masking liquid, draw the surface of masking liquid dropping with dropper at silver dendritic structure, the surface of masking liquid and silver dendritic structure is fully soaked into and formation layer of even liquid film, then it is inclined in the glass beaker of a 50ml with 70 ° of angles, rim of a cup is added a cover culture dish in case dust falls into and the too fast drying of liquid film.Liquid film can seasoning and form layer of even, the thickness PVA film less than 100nm on the surface of silver dendritic structure after 3 hours.
3. the assembling of multicolor visible light left-handed material: the sample that will apply the PVA film and square resistance are that the conductive glass of 10 Ω is relative closely superimposed, with the two ends compact winding of plastic adhesive tape, promptly obtain the multilayered structure LHM of " silver dendritic structure-PVA film-ito thin film " then with superimposed sample.
4. the optical performance test of LHM: with air as blank, in the vertical incidence mode, LHM sample to preparation in the wavelength region of 360nm-800nm carries out transmittance (T%) test, then sample is carried out flat board and focus on test, when focusing on test, the adjusting detector is 0 μ m-300 μ m apart from the distance of sample, and regulating step-length is 5 μ m.
The performance of implementation procedure of the present invention and material is by embodiment and description of drawings:
Embodiment one: in the preparation process of nano silver tree dendritic structures, adopt dull and stereotyped electricity level chemical electro-deposition method, the conductive glass that is 17 Ω, 50mm * 5mm with square resistance is a negative electrode.With the silver strip (purity is 99.9%) of negative electrode same size specification, surfacing as anode.Two plate electrodes separate by the polyvinyl chloride (PVC) sheets that is 0.2mm by two thickness shown in the accompanying drawing 1B, make two distance between electrodes keep 0.2mm.Accurately taking by weighing 1200mg polyoxyethylene glycol-20000 (analytical pure) adds in the beaker of 50ml, add the ultrapure water that 5ml resistivity is 18.24M Ω-cm again, magnetic agitation to polyoxyethylene glycol-20000 dissolves fully, and adding 5ml concentration then in this solution is the AgNO of 0.2mg/ml
3Ultrapure water solution, the solution in continue stirring and stirring with the distance irradiation of 20cm with the tungsten lamp of 60W, after about 30 minutes, solution can become lilac red, stops stirring and illumination, and with solution transfer under 4 ℃, keep in Dark Place behind the brown drop bottle stand-by.This solution is PEG-20000, silver colloid and AgNO
3Mixing ultrapure water solution, as the electrolytic solution of chemical electro-deposition.After shown in the accompanying drawing 1B two electrodes being installed, electrolytic solution is added (electrolytic solution can suck between two electrodes automatically by capillary force) along the slit between two electrodes with suction pipe, left standstill 5 minutes, electrolytic solution is fully soaked on two electricity level surfaces, energising deposits 1 minute under DC voltage-stabilizing 0.6V then, slowly wash the conductive glass surface of depositing silver dendritic structure with ultrapure water, stay suprabasil electrolytic solution with abundant removal.The pattern of the silver dendritic structure of preparation and size are shown in accompanying drawing 3A, and its element diameter is 200nm-500nm.
Under the constant situation of other mode of deposition, the adjusting deposition voltage is 0.8V, and the branch shape structural unit diameter of preparation is 150nm-300nm; The adjusting deposition voltage is 1.0V, and the branch shape structural unit diameter of preparation is 100nm-200nm.
Embodiment two: in the process of silver dendritic structure surface-coated PVA film, adopt drop-coating.Accurately weighing polyvinyl alcohol 1.25g is in the 250ml beaker, add the 250ml ultrapure water, be heated to boiling under the magnetic agitation, polyvinyl alcohol stops heating after all dissolving, and treats to change the 250ml volumetric flask over to after solution is cooled to room temperature, add ultrapure water to scale (being evaporated the moisture content of loss during the supplementary heating dissolving), then solution is filtered with the middling speed qualitative filter paper, promptly get the used masking liquid of filming (0.5% PVA ultrapure water solution), be kept in the reagent bottle it stand-by.Draw masking liquid with dropper when filming, under dustfree environment, wash away the sample surfaces of depositing silver dendritic structure repeatedly, masking liquid and sample are fully soaked into, and make liquid film at the sample surfaces uniform distribution, be placed on then and add a cover culture dish in the 50ml glass beaker in case because the too fast film forming thickness that causes of liquid film drying is inhomogeneous, after at room temperature placing 4 hours, the liquid film moisture of sample surfaces can be evaporated fully, thereby form layer of even PVA film at sample surfaces, its thickness is about 20nm-30nm.The homogeneity of film thickness can be judged according to the seven colour bar lines that film reflects to form, if the film surface part that applies presents seven colour bar lines, the in uneven thickness of film is described, if there are not local seven colour bar lines, illustrates that film thickness is even.
The concentration that changes PVA is 1% (W/V), keeps other conditions constant, and the thickness of the PVA film that then obtains is about 30nm-50nm.
Embodiment three: in the assembling process of multilayered structure LHM, shown in accompanying drawing 1A, earlier press embodiment one operation steps under the deposition voltage of 0.8V, depositing silver dendritic structure in the conductive glass substrate that square resistance is 17 Ω, show that at the silver dendritic structure of preparation face applies the PVA film with 0.5% PVA masking liquid by the operation steps of embodiment two again, identical with area then side's resistance is that the conductive glass of 17 Ω is superimposed relatively, is assembled into the multilayered structure LHM of " ITO-silver dendritic structure-PVA-ITO " shown in accompanying drawing 1A at its two ends compact winding with plastic adhesive tape.The effective area of this LHM is a lilac red, and its area is 2cm
2This zone light transmission good (seeing accompanying drawing 1C), occur four left hand projection peaks respectively at 400nm, 470nm, 570nm and 700nm place, the intensity at peak is 15.8% to the maximum, and has obvious flat focusing effect (as shown in Figure 3) respectively under corresponding wavelength.
Embodiment four: in the process of preparation nano silver tree dendritic structures, the adjusting deposition voltage is 0.6V, other conditions remain unchanged, LHM by the silver dendritic structure assembling for preparing under this condition five left-hand transmission peaks occur at 370nm, 420nm, 480nm, 550nm and 660nm place respectively, the intensity at peak is 23.1% to the maximum, also has obvious flat focusing effect (as shown in Figure 4) respectively under corresponding wavelength.
Claims (5)
1. multicolor visible light left-handed material based on silver dendritic structure, by the silver dendritic structure unit that is deposited on lack of alignment in the conductive glass substrate and be coated in polyvinyl alcohol (PVA) film on branch shape structural unit surface and not the blank conductive glass of depositing silver dendritic structure form, its principal character is the silver dendritic structure that at first prepares nanoscale in the substrate of tin indium oxide (ITO) film transparent conducting glass, then, then that it is less with side's resistance at the silver dendritic structure surface-coated PVA film of preparation, the blank conductive glass of depositing silver dendritic structure is not superimposed assembles the sandwich structure matrix material.
2. the preparation of multicolor visible light left-handed material as claimed in claim 1, it is characterized in that adopting the chemical electro-deposition method is negative electrode with ITO film transparent conducting glass, and the metal silver strip is an anode, and two interelectrode distances are 0.2mm, and electrolytic solution is AgNO
3, argent colloid and polyoxyethylene glycol-20000 (PEG-20000) mixing ultrapure water solution, galvanic deposit 30-60 second under the DC voltage-stabilizing 0.5-0.9V, sedimentation diameter in the conductive glass substrate be 100nm-1000nm, in the substrate of ITO conductive glass the two-dimentional silver dendritic structure unit of lack of alignment.
3. the preparation of PVA film as claimed in claim 1, to it is characterized in that with 0.5% PVA ultrapure water solution be masking liquid with drop-coating is PVA film below the 100nm at silver dendritic structure surface-coated thickness.
4. the preparation of multicolor visible light left-handed material as claimed in claim 1, it is characterized in that with apply the PVA depositing of thin film the suprabasil silver dendritic structure sample of ITO conductive glass and another sheet not the depositing silver dendritic structure, square resistance is superimposed less than the conductive glass of depositing silver dendritic structure substrate, the sandwich matrix material of formation " silver dendritic structure-PVA film-ITO conducting film ".
5. multicolor visible light left-handed material as claimed in claim 1, it is characterized in that in the wavelength region of visible light 360nm-800nm, the left-hand transmission passband that a plurality of varying strengths can occur, and the light wave that the left hand passband occurs had the obvious flat focusing effect.
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Cited By (7)
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| CN102176544A (en) * | 2011-02-28 | 2011-09-07 | 复旦大学 | Ultrathin microwave wave plate |
| CN102212847A (en) * | 2011-05-04 | 2011-10-12 | 湖南科技大学 | Method for preparing nanometer silver granules |
| CN102312255A (en) * | 2010-07-08 | 2012-01-11 | 西北工业大学 | Chemical preparation method for optical band metamaterial based on fishing net structure |
| CN102480061A (en) * | 2011-05-18 | 2012-05-30 | 深圳光启高等理工研究院 | Antenna based meta-material and method for generating working wavelengths of meta-material panel |
| CN103000999A (en) * | 2011-09-16 | 2013-03-27 | 深圳光启高等理工研究院 | Metamaterial |
| CN103063607A (en) * | 2011-10-20 | 2013-04-24 | 西北工业大学 | Optical refractive index sensor based on metamaterial absorber |
| CN103103608A (en) * | 2011-11-09 | 2013-05-15 | 中国科学院合肥物质科学研究院 | Film formed by silver nanosheets and preparation method and application of film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100368924C (en) * | 2005-05-31 | 2008-02-13 | 西北工业大学 | Negative magnetic permeability material in aperiodic infrared band |
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2008
- 2008-06-11 CN CN200810150024XA patent/CN101602577B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312255A (en) * | 2010-07-08 | 2012-01-11 | 西北工业大学 | Chemical preparation method for optical band metamaterial based on fishing net structure |
| CN102176544A (en) * | 2011-02-28 | 2011-09-07 | 复旦大学 | Ultrathin microwave wave plate |
| CN102176544B (en) * | 2011-02-28 | 2013-10-16 | 复旦大学 | Ultrathin microwave wave plate |
| CN102212847A (en) * | 2011-05-04 | 2011-10-12 | 湖南科技大学 | Method for preparing nanometer silver granules |
| CN102480061A (en) * | 2011-05-18 | 2012-05-30 | 深圳光启高等理工研究院 | Antenna based meta-material and method for generating working wavelengths of meta-material panel |
| CN102480061B (en) * | 2011-05-18 | 2013-03-13 | 深圳光启高等理工研究院 | Antenna based meta-material and method for generating working wavelengths of meta-material panel |
| CN103000999A (en) * | 2011-09-16 | 2013-03-27 | 深圳光启高等理工研究院 | Metamaterial |
| CN103063607A (en) * | 2011-10-20 | 2013-04-24 | 西北工业大学 | Optical refractive index sensor based on metamaterial absorber |
| CN103063607B (en) * | 2011-10-20 | 2015-07-29 | 西北工业大学 | A kind of optical refractive index sensor based on meta-material absorber |
| CN103103608A (en) * | 2011-11-09 | 2013-05-15 | 中国科学院合肥物质科学研究院 | Film formed by silver nanosheets and preparation method and application of film |
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