CN101284313B - Composition containing metal fine particles, and production method for producing metal fine particles - Google Patents
Composition containing metal fine particles, and production method for producing metal fine particles Download PDFInfo
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- CN101284313B CN101284313B CN2008100929050A CN200810092905A CN101284313B CN 101284313 B CN101284313 B CN 101284313B CN 2008100929050 A CN2008100929050 A CN 2008100929050A CN 200810092905 A CN200810092905 A CN 200810092905A CN 101284313 B CN101284313 B CN 101284313B
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Abstract
The object of the present is to provide a method for manufacturing metal microparticles by reducing metal ion in water liquid containing surfactant, which is characterized in that aspect ratio of the matel microparticle is controlled by means of manufacturing the same in an environment with acid or alkali. The present invention also relates to compounds containing the microparticle.
Description
The application is application number the dividing an application for the PCT application in country's stage that enters of " metal particle, contain the manufacture method of the composition and the metal particle of this particulate " that be CN200480025144.7 (international filing date is on September 2nd, 2004), denomination of invention.
Technical field
The present invention relates to that any wavelength in the wavelength region may from the visible light to the near infrared light is had optionally light absorption function, and the width of its absorbance height and absorption spectrum is narrow, metal particle with sharp-pointed extinction characteristic, preferably relates to the bar-shaped golden particulate (hereinafter referred to as gold nanorods) of golden particulate, particularly nanometer size.
In addition, the present invention relates to the manufacture method of metal particle, this method can easily be controlled the aspect ratio of metal particle.
And then, the present invention relates to contain above-mentioned metal particle or adopt composition of the metal particle that above-mentioned manufacture method obtains etc.
The application's mother application to the spy of application on September 5th, 2003 be willing to the spy of application on April 9th, 2003-314208 number 1 be willing to 2004-116253 number, and the spy of application on April 9th, 2004 be willing to advocate priority 2004-116254 number, here cite its content.
Background technology
To the metal particle irradiates light, just be called as the RESONANCE ABSORPTION phenomenon that plasmon absorbs.In this RESONANCE ABSORPTION phenomenon, different according to the kind of metal with shape, the absorbing wavelength difference.For example, disperseed the collaurum of spherical golden particulate near 530nm, to have the uptake zone in the water.Know by contrast, when golden particulate being made bar-shaped about minor axis 10nm, except having near the absorption that results from the 530nm of minor axis of rod, also have and result from absorption (people such as S-S.Chang, Langmuir, 1999 of long wavelength side of major axis of rod, 15, the 701-709 pages or leaves).
Proposed to contain the scheme (spy opens flat 11-80647 communique) that this fine particle of noble metal uses as the optical material of filter etc. as the resin combination of the coloured material of coating or resin combination.In addition, as the filter material, know: contain the colour filter (spy opens the 2001-108815 communique) of dyestuff and have and contain the dyestuff with specific chemical structure and the filter of filming (spy opens the 2002-22935 communique) of metal complex simultaneously with specific chemical structure.About the former colour filter, the colour filter of the flagpole pattern that has red, green, blue three looks on transparent substrates is provided, about the latter's filter, exemplify out at 750nm-1, light transmission is the filter of 0.01-30% under the wavelength region may of 100nm.
On the other hand, know that also the plasmon excitation of utilizing metal particle forms the method for metal fine figure (spy opens the 2001-64794 communique).This is to utilize at level and smooth semiconductor surface or solid metal surface carrying metal particulate, and metal particle is corresponding to plasmon excitation and the method for linear extension.
As previously discussed, know the fact of fine particle of noble metal, but this fine particle of noble metal is spherical as the coloured material use of coating or resin combination.For example, can access the plasmon colour developing of spherical golden particulate, be defined to luminous raies such as indigo plant, royal purple, purple.Therefore, utilized composition or coating that the plasmon of spherical golden particulate absorbs or the base material of the said composition of having kneaded to be limited to tones such as indigo plant, royal purple, purple.
The above-mentioned colour filter that contains dyestuff etc. with specific chemical structure, dyestuff that is contained and pigment and metal particle relatively, hear resistance, light resistance, and resistance to chemical reagents poor, therefore, fade or the reduction of absorption function through long-time just the generation mostly, the low problem of reliability is arranged.On the other hand, in the method for surface of solids growing metal particulate, owing to, therefore can not make it to be dispersed in all kinds of solvents, the adhesive coating difficulty supporting this metal particle of growth under the state of the surface of solids.In addition, in above-mentioned communique, the plasmon of metal particle absorbs the growth only be used to the metal particle in the building-up process, does not utilize to result from the optionally light absorption function of specific wavelength of major axis of metal particle.
The present invention be solve in the past colour filter or the invention of the problems referred to above of having such as the wire narrowing method of metal particle, by metal particle being made aspect ratio, just can bring into play the tone that spherical metal particle can not get in the past greater than 1.1 bar-shaped particulate, metal nano-rod just.In addition, be provided at the metal particle that the coloured material of excellences such as wavelength absorption characteristic and hear resistance or suit uses in the optical filter material.
Metal nano-rod waits in expectation at the filter material, near-infrared-absorbing material, colouring agent, the cosmetics that have utilized its optical absorption characteristics and has utilized the conductive material of electric conductivity or wiring material, electromagnetic shielding material etc. to be utilized in the purposes widely.
As the method for making this metal nano-rod, know electrochemical reducing, chemical reduction method, photoreduction met hod, ultrasonic irradiation method etc. in the past.
Electrochemical reducing, for example be in the electrolyte that has added surfactant, to use golden plate anode and platinum plate negative electrode and the constant current that circulates to make the method for golden particulate, the gold ion that produces from anode is reduced at negative electrode, form golden particulate, this gold particulate is grown into bar-shaped under the effect of surfactant, becomes the gold nanorods of nanometer size.Have report to point out: in electrolysis, silver plate is immersed in the electrolyte, its dipping surface is to excellent length influential (Langmuir,, No. 15,701-709 page or leaf in 1999)., the solution-off amount of silver or solution-off speed are different and different according to the surface state of silver plate, therefore adjust the impregnation area of silver plate, and the aspect ratio of fully controlling metal nano-rod is difficult.
Chemical reduction method, for example be in aqueous solution of chloraurate, to add reducing agent, the reduction gold chloride generates golden nanometer particle, obtains " planting grain ", this kind grain is transferred in the aqueous solution of chloraurate, in liquid, make it to grow up method (J.Phys.Chem.B, the calendar year 2001 of making gold nanorods thus, No. 105,4065 pages-4067 pages).In the method, transfer to the amount of the kind grain in the growth response groove by change, just can control rod length, but need the reactive tank that generates kind of the reactive tank of grain and kind of grain is grown up, the troublesome poeration of manufacturing process.
Photoreduction met hod is to the aqueous solution of chloraurate irradiation ultraviolet radiation, and the gold chloride in the reduction liquid is with the method (J.Am.Chem.Soc.2002, No. 124,14316 pages-14318 pages) of making golden particulate.This photoreduction met hod does not need to resemble and uses 2 grooves the chemical reduction method, in addition, can penetrate time control rod length according to illumination, but slow problem of the time that responds.
The present invention is the invention of the above-mentioned problem in the metal particle manufacture method that solves in the past, is provided at when making metal nano-rod, can easily control the manufacture method and the composition that contains the metal particle that adopts this method manufacturing of the aspect ratio of metal particle.
Also have, the invention provides the preferred occupation mode of metal particle composition.
Summary of the invention
More specifically say, the invention provides following metal particle, its manufacture method, reach metal particle composition etc.
(1) a kind of metal particle is characterized in that, aspect ratio is 1.1-8.0, and the maximum absorption wavelength that plasmon absorbs is 400nm-1,200nm, and the absorptivity on the peak position of maximum absorption wavelength is 6,000-20,000L/molcm (measures concentration 1.6 * 10
-4Mol/L, solvent: water).
(2) a kind of metal particle is characterized in that, aspect ratio is 1.1-8.0, and the maximum absorption wavelength that plasmon absorbs is 550nm-1,200nm, and the half value of the absorption spectrum of maximum absorption wavelength is wide to be 200nm or following.
(3) according to above-mentioned (1) or (2) described metal particle, wherein, metal particle is a gold nanorods, and the maximum absorption wavelength that plasmon absorbs is 550nm-1,200nm.
(4) according to above-mentioned (3) described gold nanorods, wherein, to make by carrying out photo-reduction after the gold chloride in the chemical reducing solution, the absorptivity on the peak position of maximum absorption wavelength is 6,000-20,000L/molcm (measures concentration 1.6 * 10
-4Mol/L, solvent: water), the half value of the absorption spectrum of maximum absorption wavelength is wide to be 200nm or following.
(5) a kind of composition that contains above-mentioned (1) or (2) described metal particle.
(6) according to above-mentioned (5) described composition, wherein, also further contain dispersant and adhesive, described dispersant contains at least one side of nitrogen-atoms and sulphur atom.
(7) a kind of manufacture method of metal particle, it is the method that the reducing metal ion is made metal particle in containing the aqueous solution of surfactant, it is characterized in that,, control the aspect ratio of metal particle by under the environment that has added acid or alkali, making metal particle.
(8) according to the manufacture method of above-mentioned (7) described metal particle, wherein, as acid use be selected from nitric acid, sulfuric acid, hydrochloric acid, hydrobromic any, use any that is selected from NaOH, potassium hydroxide, ammoniacal liquor as alkali.
(9) a kind of manufacture method of metal particle, it is the method that the reducing metal ion is made metal particle in containing the aqueous solution of surfactant, it is characterized in that, carries out reduction reaction by adjusting the liquid temperature, controls the aspect ratio of metal particle.
(10) according to the manufacture method of above-mentioned (7) described metal particle, wherein, the method of reducing metal ion in containing the aqueous solution of surfactant, be electronation, electrochemical reduction, photo-reduction or any method that has made up electronation and photo-reduction, the metal particle of manufacturing is a metal nano-rod.
(11) according to the manufacture method of above-mentioned (7) described metal particle, wherein, the method of reducing metal ion in containing the aqueous solution of surfactant, be to have added with following chemical formula A, B, and the electrochemical reducing that uses as electrolyte of a kind of the surfactant represented of C or 2 kinds or the above aqueous solution, reduce the aspect ratio of metal particle by adding acid, perhaps, increase the aspect ratio of metal particle by interpolation alkali.
CH
3(CH
2)
nN
+(CH
3)
3Br
-(n is the integer of 1-15) ... A
(CH
3(CH
2)
n)
4N
+Br
-(n is the integer of 1-15) ... B
(CH
3(CH
2)
n)
2N
+(CH
3)
2Br
-(n is the integer of 7-17) ... C
(12) according to the manufacture method of above-mentioned (7) described metal particle, wherein, the method for reducing metal ion is to have made up the electronation of using reducing agent and the method for photo-reduction, increases the aspect ratio of metal particle by adding acid, perhaps, reduce the aspect ratio of metal particle by interpolation alkali.
(13) according to the manufacture method of above-mentioned (12) described metal particle, wherein, use and added ascorbic acid, citric acid or its salt; Hydrochloric acid hydroxylamine, hydrazine compound, butanedioic acid or its salt; Perhaps amine is as the metal ion aqueous solution of above-mentioned reducing agent, as above-mentioned acid, use be selected from nitric acid, sulfuric acid, hydrochloric acid, hydrobromic any, use any that is selected from NaOH, potassium hydroxide, ammoniacal liquor as above-mentioned alkali.
(14) according to the manufacture method of above-mentioned (9) described metal particle, wherein, contain the liquid temperature of the aqueous solution of metal ion by raising, reduce the aspect ratio of metal particle, perhaps, by reducing the aspect ratio that the liquid temperature increases metal particle.
(15) a kind of composition that contains the metal particle of the manufacture method manufacturing of adopting above-mentioned (7) or (9) described metal particle.
(16) a kind ofly adopt coating composition that above-mentioned (5) or (15) described composition forms, film, transparent coating or film.
(17) a kind of filter material, wiring material, electrode material, catalyst, colouring agent, cosmetics, near-infrared-absorbing material, anti-forgery ink, electromagnetic shielding material, surface of containing above-mentioned (1) or (2) described metal particle strengthens fluorescent optical sensor, biomarker, nanometer waveguide, recording materials, recording element, polarized material, delivery system (DDS) pharmaceutical carrier, biology sensor, DNA chip, investigational agent.
(18) a kind of filter material, wiring material, electrode material, catalyst, colouring agent, cosmetics, near-infrared-absorbing material, anti-forgery ink, electromagnetic shielding material, surface of containing the metal particle that adopts above-mentioned (7) or (9) described manufacture method manufacturing strengthens fluorescent optical sensor, biomarker, nanometer waveguide, recording materials, recording element, polarized material, delivery system (DDS) pharmaceutical carrier, biology sensor, DNA chip, investigational agent.
Description of drawings
Fig. 1 is the abosrption spectrogram of the gold nanorods aqueous dispersions of embodiment 1.
Fig. 2 is the abosrption spectrogram of the gold nanorods concentrate of embodiment 2.
Fig. 3 is the transmitted light spectrogram of filming that the coating that contains gold nanorods by embodiment 3 obtains.
Fig. 4 is the result's of expression embodiment 4 a abosrption spectrogram.
Fig. 5 is the result's of expression embodiment 5 a abosrption spectrogram.
Fig. 6 is the result's of expression embodiment 6 a abosrption spectrogram.
The specific embodiment
Below illustrate in greater detail the present invention.
Metal particle of the present invention at first is described.
The 1st metal particle of the present invention, aspect ratio is 1.1-8.0, the maximum absorption wavelength that plasmon absorbs is 400nm-1,200nm, and also the absorptivity on the peak position of maximum absorption wavelength is 6,000-20, and 000L/molcm (measures concentration 1.6 * 10
-4Mol/L, solvent: water).
The 2nd metal particle of the present invention, aspect ratio is 1.1-8.0, the maximum absorption wavelength that plasmon absorbs is 550nm-1,200nm, and also the half value of the absorption spectrum of maximum absorption wavelength is wide to be 200nm or following.
Above-mentioned metal particle of the present invention, preferably gold nanorods.Gold nanorods has the optionally wavelength absorption function based on long axis length.Specifically, result from the absorbance of long axis length greater than near the absorbance that results from the 530nm of minor axis, at 550nm-1, the wavelength region may of 200nm demonstrates maximum wavelength and absorbs.
When aspect ratio less than 1.1 the time, approach spherical particle, therefore be difficult to obtain the wavelength absorption function under 550nm or the above long wavelength zone.On the other hand, when aspect ratio greater than 8.0 the time, the half value of the absorption spectrum of maximum absorption wavelength is wide easily greater than 200nm, is difficult to obtain sharp-pointed extinction characteristic.
Usually, absorbance A based on the absorptivity ε of the material of light institute transmission, the optical path length L that the quartz system cell of this material is housed, and material concentration C, provides by Lambert Beer formula [1] shown below.This absorptivity ε is the distinctive value of material that light passes through, and absorptivity ε is big more, and absorbance A is big more, obtains the high absorption spectrum of peak value.
A＝εLC …〔1〕
Gold nanorods of the present invention, the golden particle concentration in measuring sample solution is 1.6 * 10
-4Mol/L (solvent: water), the optical path length of cell is the occasion of 1cm, for 550nm-1, the wavelength of 200nm, absorptivity is 6,000-20,000L/molcm.Therefore, the absorbance of the peak position of maximum absorption wavelength roughly is 0.96-3.2.
In gold nanorods of the present invention, the half value of the absorption spectrum of maximum absorption wavelength is wide to be below the 200nm.Fig. 1 is the abosrption spectrogram that gold nanorods of the present invention is scattered in the occasion in the water.As shown in Figure 1, the peak position of the maximum absorption wavelength of gold nanorods of the present invention is 822nm, and the absorbance of peak position is about 1.53.Further, the half value position of absorbance is respectively the about 910nm that reaches at long wavelength side at about 760nm of short wavelength side, and the half value of absorption spectrum is wide to be about 150nm.
Metal particles such as gold nanorods of the present invention can add dispersant and decentralized medium, adhesive (resin) and make composition.Metal particle composition of the present invention for example can be by being scattered in metal particle in the decentralized medium in the presence of dispersant, and this dispersion liquid mixed with adhesive (resin) and obtain.
As above-mentioned dispersant, for example enumerate: number-average molecular weight be several thousand or above, in main chain, have a adsorption site for the high nitrogen-atoms of the adsorptivity of gold nanorods and sulphur atom etc., and, have the alkaline high-molecular type dispersing agent that has a plurality of side chains of affinity for non-water system organic solvents such as water and alcohol.As preferred commercially available dispersant, enumerate Solsperse13940, Solsperse24000SC, Solsperse28000, Solsperse32000 (above is Avecia company goods), Flowlen DOPA-15B, Flowlen DOPA-17 (above is chemical company of common prosperity society goods), Ajisper PB815 and Ajisper PB711 (above is aginomoto Fine-Techno company goods) etc.
When use contains the synthetic solvent of gold chloride and softex kw (CTAB) etc., sometimes at resulting metal particle surface attachment CTAB etc., but in this occasion, by adding above-mentioned dispersant, be adsorbed on the displacement of the CTAB on metal particle surface and above-mentioned dispersant, therefore can improve dispersiveness for resin etc.
As above-mentioned adhesive (resin), if usually in coating purposes or moulding purposes, use have radioparent various resin for luminous ray to the light near infrared light zone, then can especially restrictedly not use.For example, enumerate various organic resins and free-radical polymerised oligomer and monomers (according to circumstances also using) such as acrylic resin, mylar, alkyd resins, ammonia ester resin, silicone resin, fluororesin, epoxy resin, polycarbonate resin, Corvic, polyvinyl alcohol with curing agent or radical polymerization initiator as representational.
Metal particle composition of the present invention can contain solvent as required.Spendable solvent can suit to select above-mentioned adhesive to dissolve or the solvent of stable dispersion.Specifically, as representational, except water, also enumerate alcohols such as methyl alcohol, ethanol, propyl alcohol, hexanol, ethylene glycol; Ester ring type hydrocarbon such as aromatic hydrocarbon such as dimethylbenzene and toluene, cyclohexane; Ketone such as acetone and MEK; Ester such as ethyl acetate and butyl acetate class; The ether of ethylene glycol monobutyl ether etc. etc.; Perhaps their mixture, but be not limited to these materials.That is to say that metal particle composition of the present invention can be that metal particle is scattered in the water and the aqueous dispersions that obtains.The using method of this metal particle composition is not defined.
In metal particle composition of the present invention,, can add dyestuff or pigment for purposes such as colour corrections.In addition, can also use wavelength absorption scope roughly the same or different two kinds or above gold nanorods.
Resulting metal particle composition except can using as coating composition, coating composition etc., can also be used with various forms such as filming of containing that said composition forms, film or sheet materials.
And metal particle composition of the present invention can also and be used with base material such as transparent glass or plastics.With the such base material and the occasion of usefulness, metal particle composition can adopt various coating processes such as brushing, spraying, roller coat, spin coating, dip-coating to be coated on the base material.
In addition, not only coating can also be adopted and metal particle composition be injected mold and the method for the method of moulding, injection mo(u)lding, knead into adhesive (resin) and the method for moulding wait and use.And operational version is not limited to these.
To in adhesive (resin), cooperate the occasion of the composition of this metal particle as the material use of filter, the content of metal particle, with respect to adhesive (resin) 100 weight portions, preferred 0.01 weight portion-90 weight portion.When the addition of metal particle is less than 0.01 weight portion, be difficult to fully obtain desirable effect.On the other hand, addition is during more than 90 weight portions, and is unfavorable aspect cost.
For example, the transparent polymer film of the golden particulate into kneaded in resin or have the transparent base of golden microparticulate in the coating on surface can be used as absorbing wavelength 800nm-1, and the filter material of the specific wavelength of the near infrared range of 200nm uses.
Above-mentioned filter for example can adopt following method to obtain.
(a) on transparent base, directly be coated with or the printed book inventive compositions, form cured coating film as luminous ray near infrared light absorption filter.(b) composition of the present invention is formed membranaceous or tabular etc., obtain luminous ray near infrared light absorption filter, with resulting filter lamination or surround on the transparent base.(c) article shaped that will possess above-mentioned cured coating film that composition of the present invention forms or film etc. is stacked on transparent the glass system base material or plastics system base material, this laminated body is as luminous ray near infrared light absorption filter, stacked again or surround on other base material.
Above-mentioned filming or the preferably about 0.01 μ m-1mm of thickness of filter considered cost and transmitance etc., more preferably 0.05 μ m-300 μ m.
Resulting metal particle or metal particle composition; except can be used as previously described filter material, can also strengthen the material use of fluorescent optical sensor, biomarker, nanometer waveguide, recording materials, recording element, polarized material, delivery system (DDS) pharmaceutical carrier, biology sensor, DNA chip or investigational agent as wiring material, electrode material, catalyst, colouring agent, cosmetics, near-infrared-absorbing material, anti-forgery ink, electromagnetic shielding material, surface.
The material that has disperseed metal particle of the present invention and obtain in solution, the material that can be used as anti-forgery ink uses.This anti-forgery ink is used for detection method with specific wavelength absorbability, scattered light or the fluorescence of metal nano-rod.For example,, absorb the character of specific wavelength under the wavelength region may of 500nm, therefore, set the detection wavelength in this scope because gold nanorods has at 600-1.By with the specific absorption wavelength set at 760-1, the near infrared range of 500nm obtains invisible printing ink transparent under the visible region, because this invisible printing ink can discern under near infrared range, so can use as anti-forgery ink.The film that obtains owing to this anti-forgery ink of coating contains metal particle of the present invention, metal nano-rod just, so weatherability, hear resistance, reaches the resistance to chemical reagents excellence.
The surface-treated dispersant that is used for metal nano-rod, compatible with the solvent that uses just can, so the solvent of anti-forgery ink selection that can suit.
In addition, metal particle of the present invention can also use as colouring agent.Metal particle of the present invention, be metal nano-rod, in the time of in being scattered in oily material, naked eyes are difficult to be identified as particulate forms, when coating, obtain high the filming of the transparency.Therefore, in the occasion of using as the colouring agent of cosmetics, even a small amount of the use, but the cosmetics that obtain strong coloring force and have high color saturation.
Metal particle of the present invention can also use as conductive materials.The conductive paste that contains metal particle of the present invention can be used as wiring material or electrode material.Wait wiring and electrode, electric conductivity and the resistance to migration excellence that this conductive paste of coating also dry (roasting) forms on insulating substrate by printing.Using metal particle of the present invention to obtain the occasion of conductive paste,, preferably add the adhesive of 1-20 weight portion with respect to metal nano-rod 100 weight portions.
As everyone knows, by glass substrate surface to high-density the fixing metal particulate, be metal nanoparticle, the phenomenon of infrared ray absorbing or fluorescence radiation is increased spoke.Utilize the spectroscopic methodology of this phenomenon, be called as " surface-reinforced infrared spectrum method (SEIRS) ", " surface strengthens fluorescent spectrometry (SEFS) " respectively.Therein, SEFS is considered to the simplicity excellence.Metal particle of the present invention is suitable as the sensor material based on this surface-reinforced infrared spectrum method or surface enhancing fluorescent spectrometry.For example, because there is the little wavelength region may of absorbance in gold nanorods in the wavelength region may of 550nm-800nm, therefore on glass substrate, fixed the substrate of the gold nanorods of handling with silane finish (3-sulfydryl oxypropyl trimethyl silane etc.) to high-density, be suitable for adopting in this wavelength region may and send the SEFS spectroscopic methodology sensor that the fluorescent material (for example rhodamine is a fluorchrome etc.) of fluorescence serves as a mark with mercaptan end.
Metal particle of the present invention can also utilize near infrared in response biomarker.For example, 750nm-1, the near infrared ray of 100nm is absorbed by organic matter hardly, but gold nanorods can be according to its aspect ratio at 750nm-1, and the wavelength region may of 100nm has distinctive extinction characteristic.Therefore, when the privileged site of biology dyes with gold nanorods, by near infrared irradiation, at this position near infrared absorption taking place, therefore can hold its position.Therefore, for because the suspension of sample or painted and adopt the immeasurable biomaterial with thickness of existing method institute also can be observed the arbitrary portion that dyes with gold nanorods.
Specifically, use the gold nanorods of the present invention of linings such as the high compound of employing biological affinity, for example polyethylene glycol, phospholipid, sugar chain, antibody, with biological stain.With the gold nanorods of polyethylene glycol or phospholipid lining, not local existence in specific internal organs or tissue and the purpose that is suitable for dyeing equably.Polyethylene glycol particularly, owing to be difficult to be subjected to biological decomposition, and permeability cell is also high, therefore is suitable as the biological stain lining material.On the other hand, sugar chain and antibody because accumulate in specific internal organs or the tissue, therefore are suitable for the purpose with specific internal organs or tissue staining.By using the gold nanorods that adopts these material linings, also can observe for the biomaterial that can not observe in the past.
When with metal particle of the present invention with the mode high density of one dimension and when arranging regularly because the interaction of the near field of light that nearby generates at nano particle, making interparticle light propagate becomes possibility, in view of the above, can make the nanometer waveguide that is suitable for one-dimensional wave guide.For example, can adopt following method to make the nanometer waveguide.At first, use AFM (AFM) or PSTM (STM) to arrange metal nano-rod one-dimensionally as manipulation device.Then, at the fixing photism nano particle (zinc oxide, CdTe etc.) of the end of the formation of the metal nano-rod of arranging one-dimensionally, make the Fibre Optical Sensor of near-field microscope be positioned at the end of the formation of opposition side.Can adopt such structure to make the nanometer waveguide.Metal nano-rod of the present invention is suitable as the material of such nanometer waveguide.
The following describes the manufacture method of metal particle.
The 1st manufacture method of the present invention, the manufacture method that relates to metal particle, it is a reducing metal ion in containing the aqueous solution of surfactant, make the method for metal particle, it is characterized in that, by under the environment that has added acid or alkali, promoting the manufacturing of metal particle, control the aspect ratio of metal particle.
In addition, the 2nd manufacture method of the present invention, the manufacture method that relates to metal particle, it is characterized in that, it is a reducing metal ion in containing the aqueous solution of surfactant, and makes the method for metal particle, in the method, carry out reduction reaction by adjusting the liquid temperature, control the aspect ratio of metal particle.
In manufacture method of the present invention,, can use nitric acid, sulfuric acid, hydrochloric acid, hydrobromic acid etc. as acid.In addition, as alkali, can use NaOH, potassium hydroxide, ammoniacal liquor etc.
As the method for reducing metal ion in containing the aqueous solution of surfactant in the manufacture method of the present invention, electronation, electrochemical reduction, photo-reduction or any method that has made up the method for electronation and photo-reduction can both be suitable for.
Chemical reduction method, such as previously explained, be the method for utilizing reducing agent reducing metal ion.Electrochemical reducing is a circulating current in electrolyte, in the method for cathodic reduction from the metal ion of anode solution-off.Photoreduction met hod is to shine for example method of ultraviolet reduced metal particle.Having made up the method for electronation and photo-reduction, is the method that has made up above-mentioned chemical reduction method and photoreduction met hod.
More specifically say, in adding acid or alkali the 1st manufacture method,,, can control the aspect ratio of metal nano-rod by in electrolyte, adding acid or alkali and the constant current that circulates in the occasion that adopts electrochemical reducing with the aspect ratio of control metal particle.
Such as previously described, electrochemical reducing is from the metal ion of anode solution-off and make the method for metal particle in cathodic reduction.For example, by use added with following chemical formula A, B, and a kind of the surfactant represented of C or 2 kinds or the above aqueous solution as electrolyte, can make metal nano-rod expeditiously.
CH
3(CH
2)
nN
+(CH
3)
3Br
-(n is the integer of 1-15) ... A
(CH
3(CH
2)
n)
4N
+Br
-(n is the integer of 1-15) ... B
(CH
3(CH
2)
n)
2N
+(CH
3)
2Br
-(n is the integer of 7-17) ... C
With the representational surfactant that above-mentioned chemical formula A represents, be softex kw [CTAB:CH
3(CH
2)
15N
+(CH
3)
3Br
-].With the representational surfactant that above-mentioned chemical formula B represents, be TBAB [TC4AB] etc.In addition, with the representational surfactant that above-mentioned chemical formula C represents, be two (dodecyl) dimethyl ammonium bromide [DDAB:[CH
3(CH
2)
11]
2N
+(CH
3)
2Br
-].
In addition, by also using ketone, can make the generation of metal nano-rod stable.
In the 1st manufacture method of the present invention, preferably added above-mentioned A, B, and at least a kind the aqueous solution of C in add above-mentioned acid or alkali and carry out electrolysis.
As the method that has made up electronation and photo-reduction, know: use the solution that in containing the aqueous metal salt of surfactant, has added reducing agent as reaction solution, to this solution irradiation ultraviolet radiation, thus the method for manufacturing metal nano-rod.By in this reaction solution, adding acid or alkali irradiation ultraviolet radiation afterwards, can control the aspect ratio of metal nano-rod.
As the reducing agent that in the said method that has made up electronation and photo-reduction, uses, the preferred more weak reducing agent of reducing power.More specifically say, can enumerate ascorbic acid, citric acid or its salt; Hydrochloric acid hydroxylamine, hydrazine compound, butanedioic acid or its salt; Perhaps amine etc.
As the preferred acid of adding in having added the metal ion aqueous solution of reducing agent, can enumerate nitric acid, sulfuric acid, hydrochloric acid, hydrobromic acid etc.In addition, as the alkali of preferred interpolation, can enumerate NaOH, potassium hydroxide, ammoniacal liquor etc.
In the method that has made up electronation and photo-reduction, more specifically say, make in the method for metal nano-rod utilizing electronation and ultraviolet ray irradiation, use contain with above-mentioned chemical formula A, B, and a kind of the surfactant represented of C or 2 kinds or the above aqueous solution in added slaine solution as reaction solution, in this reaction solution, add reducing agent such as ascorbic acid and carry out electronation.When adding ascorbic acid, reaction solution becomes transparent because of reduction reaction.
By ketones such as interpolation acetone in above-mentioned reaction solution, can be with the reaction of formation stabilisation of metal nano-rod.When silver salt such as interpolation silver nitrate, silver chlorate, silver bromide, can promote the axial growth of metal nano-rod.
Then, add nitric acid, sulfuric acid, hydrochloric acid, hydrobromic acid etc. in the above-mentioned reaction solution that becomes transparent adding reducing agent, perhaps, add NaOH, potassium hydroxide, ammoniacal liquor etc. as alkali.By to this solution irradiation ultraviolet radiation, control the aspect ratio of metal nano-rod.The ultraviolet irradiation time is preferably about a few minutes.In addition, after the ultraviolet ray irradiation, can be statically placed in the dark place as required.
If reduction of metal ion method difference, then the function of acid of being added or alkali is also different.For example, electrochemical reducing is compared with the method that has made up electronation and photo-reduction, and the function of acid or alkali is different fully.
In the occasion that has adopted electrochemical reducing,, can reduce the aspect ratio of metal particle by adding the acid of defined amount.On the contrary, by adding the alkali of defined amount, can increase the aspect ratio of metal particle.
On the other hand, in the method that has made up electronation and photo-reduction,, the aspect ratio of metal particle can be increased,, the aspect ratio of metal particle can be reduced by adding the alkali of defined amount by adding the acid of defined amount.The defined amount of acid or alkali is according to the difference of the amount of the kind of acid of using or alkali or other additives and difference.
Preferred gold nanorods can adopt the method that has made up electronation and photo-reduction to obtain among the metal particle of the invention described above.More specifically say, after the gold chloride in the reducing solution chemically, carry out in the synthetic method of photo-reduction, can by adjust the electronation condition, and the photo-reduction condition be that the illumination condition of penetrating obtains.For example, in the chlorauric acid solution that uses as synthetic solvent, add softex kw (CTAB), its concentration is adjusted to 0.24-0.8mol/L, to wherein adding acetone, cyclohexane, again to wherein adding reducing agent such as ascorbic acid, thus the reduction gold chloride.After this electronation, carry out illumination and penetrate, gold nanorods is grown up.This occasion by add the 0.01-1.0wt% cyclohexane with CTAB, can make the peak position of maximum absorption wavelength move to long wavelength side.In addition, by adjusting light-struck time or intensity, or, the aspect ratio of golden particulate can be controlled, golden particulate can be accessed in view of the above with desirable aspect ratio under the environment of blocking light, leaving standstill or the like after the irradiation.
Carry out in the 2nd manufacture method of the present invention of reduction reaction in adjustment liquid temperature, for example in the occasion that adopts electrochemical reducing, the scope that maintains defined by the liquid temperature with electrolyte just can be controlled the aspect ratio of metal nano-rod to carry out cell reaction.In addition, adopting chemical reduction method, photoreduction met hod or making up the occasion of the method for electronation and photo-reduction, the scope that maintains defined by the liquid temperature with reaction solution just can be controlled the aspect ratio of metal nano-rod to react.
More specifically say, the occasion of the method for electronation and photo-reduction has been made up in employing, maintain the scope of defined by the liquid temperature of will in containing the aqueous metal salt of surfactant, add the reaction solution of reducing agent, and irradiation ultraviolet radiation, control the aspect ratio of metal nano-rod.
In the present invention's the 2nd manufacture method of adjusting the liquid temperature, can perhaps, increase the aspect ratio of metal particle by reduction liquid temperature by improving the aspect ratio that the liquid temperature reduces metal particle.Specifically, the liquid temperature specific surface activating agent temperature height of separating out, aspect ratio is more little, and the growing amount of spheroidal particle is many more.Separating out near the temperature, it is big that aspect ratio becomes.When liquid temperature specific surface activating agent separate out temperature when low, the growing amount of metal nano-rod tails off.For example, the temperature of separating out of CTAB is about 25 ℃.Therefore, consider the occasion of output, the upper limit of liquid temperature is suitable with 40 ℃-60 ℃, preferred 26 ℃-30 ℃ of lower limit.And, consider that the liquid temperature is than separating out the temperature height, aspect ratio is more little, and aspect ratio becomes big this fact near separating out temperature, in order to obtain desirable aspect ratio, preferably further adjusts the liquid temperature in the said temperature scope.
Specifically represent the present invention by the following examples.Following embodiment relates generally to gold nanorods, demonstrates the light absorption function under the 800nm-900nm wavelength region may, but by changing the aspect ratio of gold nanorods, for 550nm-1, the wavelength region may of 200nm also can have same light absorption function.Spectral characteristic adopts the Japanese beam split goods V-570 of Co., Ltd. to measure.In addition, under the situation of other metals, also can access same result.
The manufacture method of gold particulate
In the CTAB of 0.50mol/L aqueous solution 50ml, add aqueous solution of chloraurate 5ml, acetone 1ml, cyclohexane 1ml, cyclohexanone 1ml, and the silver nitrate aqueous solution 5ml of 10mmol/L of 24mmol/L, make reaction solution.In this reaction solution, add ascorbic acid (AS) aqueous solution 5ml of 40mmol/L, carry out electronation.Be varied to transparent solution from orange immediately just adding AS aqueous solution afterreaction solution.With pack into the beaker of capacity 100ml of the solution that becomes transparent, from beaker top to the ultraviolet ray of synthetic solvent direct irradiation UV irradiator (high-pressure mercury-vapor lamp) 5 minutes.After illumination is penetrated, leave standstill to former state, after 1 hour, transfer to and preserve in the container, this solution with water is diluted to 10 times of (volume ratio, golden particle concentrations 1.6 * 10
-4Mol/L), make the absorption spectromtry sample solution.Fig. 1 expresses the absorption spectrum of this solution.
As shown in the figure, this gold particulate (gold nanorods), the peak position of maximum absorption wavelength is changed to 822nm, and the half value position of absorbance is respectively about 760nm of short wavelength side and about 910nm of long wavelength side, and therefore, the half value of absorption spectrum is wide to be about 150nm.In addition, at golden particle concentration 1.6 * 10
-4Therefore under the length 1cm of mol/L, cell, the absorbance of the peak position of maximum absorption wavelength is 1.53, and the absorptivity of being calculated by Lambert Beer formula [1] is about 9,563L/molcm.
With the surface-treated golden particulate of dispersant
(the Avecia corporate system: Solsperse24000SC) 0.1g dissolves with toluene 10g with dispersant, in this dispersant toluene solution, be added in gold nanorods (the average length 10nm of minor axis, the average length 42nm of major axis, aspect ratio 4.2) aqueous dispersions 50g synthetic among the embodiment 1, stirred 10 minutes with mixer (rotating speed 300rpm).In this solution, add ethanol 30g, left standstill 24 hours.By adding ethanol, the solubility of CTAB uprises, and is adsorbed on the lip-deep CTAB of gold nanorods and breaks away from, and the nitrogen position of dispersant is adsorbed on the gold nanorods, with the CTAB displacement, carries out surface treatment in view of the above.
The toluene that the mixed liquor that leaves standstill is separated into water white water and bright-coloured redness mutually.Then, only extract organic solvent layer, re-use evaporimeter and remove remaining toluene, obtain the gold nanorods concentrate (golden particulate containing ratio 10wt%, solid shape are divided 40wt%) of toluene.This concentrate with dilution with toluene to 10000 times (volume ratio) time, is not caused cohesion, and gold nanorods stably is scattered here and there.Fig. 2 expresses the absorption spectrum of this dispersion liquid.
As shown in Figure 2, by the surface treatment of above-mentioned dispersant, absorption spectrum changes, and the peak position of maximum absorption wavelength moves to 864nm from 822nm.This is due to the variations in refractive index of surface mass of gold nanorods.
Embodiment 3
Gold microparticle compositions and film
The gold nanorods concentrate 5g of embodiment 2 is mixed among the mixture 20g that free-radical polymerised ammonia ester is oligomer and radical polymerization initiator, makes coating.This coating at room temperature placed 3 months under the state of shield light or more than, also not variable color or generate precipitation is stable.
This coating is coated on (golden particulate containing ratio 1wt%, dry film thickness 10 μ m) on the glass plate, has measured transmitted spectrum.Fig. 3 expresses this result.As shown in the figure, the transmissivity of (870nm) is minimum near the wavelength suitable with the peak position of the maximum absorption wavelength of Fig. 2, has confirmed that specific wavelength is absorbed by gold nanorods.
Embodiment 4
(A liquid)
In the CTAB of concentration 480mmol/L aqueous solution 405ml, add aqueous solution of chloraurate 34ml, acetone 6ml, cyclohexanone 0.7ml, and the silver nitrate aqueous solution 25ml of 10mmol/L of concentration 24mmol/L, make reaction solution.In this reaction solution, add the aqueous ascorbic acid 33ml of concentration 40mmol/L, carry out electronation.Reaction solution is varied to transparent solution from orange immediately after just adding ascorbic acid.From the top direct irradiation 10mW/cm that becomes transparent solution
2Or the ultraviolet ray of following high-pressure mercury-vapor lamp 5 minutes.
(B liquid)
To with the A liquid phase with condition under preparation and carried out adding in the reaction solution of electronation the nitric acid 150 μ l of commercially available concentration (about 60%), from the top direct irradiation 10mW/cm of solution
2Or the ultraviolet ray of following high-pressure mercury-vapor lamp 5 minutes.
(C liquid)
To with the A liquid phase with condition under preparation and carried out adding in the reaction solution of electronation the sodium hydrate aqueous solution 2.5ml of 1mol/L, from the top direct irradiation 10mW/cm of solution
2Or the ultraviolet ray of following high-pressure mercury-vapor lamp 5 minutes.
Fig. 4 expresses the absorption spectrum of A liquid, B liquid, C liquid.As shown in the figure, demonstrate: with the A liquor ratio, the extinction peak that has added the B liquid of nitric acid is transferred to long wavelength side, and the aspect ratio of gold nanorods becomes big 5.0 (major axis 45.0nm) to B liquid from 4.7 (major axis 42.3nm) of A liquid.Demonstrate in addition: the extinction peak that has added the C liquid of sodium hydrate aqueous solution is transferred to short wavelength side, and the aspect ratio of gold nanorods diminishes, and is 3.0 (major axis 27.0nm).
Embodiment 5
(A liquid)
In the CTAB of concentration 480mmol/L aqueous solution 405ml, add aqueous solution of chloraurate 34ml, acetone 6ml, cyclohexanone 0.7ml, and the silver nitrate aqueous solution 25ml of 10mmol/L of concentration 24mmol/L, make reaction solution.In this reaction solution, add the aqueous ascorbic acid 33ml of concentration 40mmol/L, carry out electronation.Reaction solution is varied to transparent solution from orange immediately after just adding aqueous ascorbic acid.The solution that becomes transparent is remained on 40 ℃, from the top direct irradiation 10mW/cm of solution
2Or the ultraviolet ray of following high-pressure mercury-vapor lamp 5 minutes.
(B liquid)
Will with the A liquid phase with condition under preparation and the reaction solution that carried out electronation remain on 26 ℃, from the top direct irradiation 10mW/cm of solution
2Or the ultraviolet ray of following high-pressure mercury-vapor lamp 5 minutes.
Fig. 5 expresses the absorption spectrum of A liquid, B liquid.As shown in the figure, demonstrate: the A liquor ratio high with solution temperature, the extinction peak of the B liquid that solution temperature is low is transferred to long wavelength side, and the aspect ratio of gold nanorods becomes big 5.3 (major axis 47.7nm) to B liquid from 4.6 (major axis 41.4nm) of A liquid.
Embodiment 6
In 1 premium on currency, add surfactant and acetone, cyclohexane, cyclohexanone, the nitric acid of commercially available concentration (about 60%) or the sodium hydrate aqueous solution of 1mol/L, prepared electrolyte A, B, the C of the composition shown in the following table 1.
Table 1
| A liquid | B liquid | C liquid | |
| CTAB | 240mmol/l | 240mmol/l | 240mmol/l |
| [CH 3(CH 2) 3] 4N +Br - | 7.3mmol/l | 7.3mmol/l | 7.3mmol/l |
| [CH 3(CH 2) 5] 4N +Br - | 17.0mmol/l | 17.0mmol/l | 17.0mmol/l |
| Acetone | 13ml | 13ml | 13ml |
| Cyclohexane | 13.5ml | 13.5ml | 13.5ml |
| Cyclohexanone | 2.6ml | 2.6ml | 2.6ml |
| Acid or alkali | Do not add (pH4.1) | Add nitric acid till pH3 | Add NaOH till pH7.1 |
On one side with the ratio of 80 μ/min to the silver nitrate aqueous solution that wherein adds 3.0mol/L, be corrosion resistant plate (SUS304 plate) Yi Bian to make anode be golden plate, make negative electrode, carry out constant-current electrolysis in 4 hours with 5.0mA.Fig. 6 expresses the absorption spectrum of A liquid after the electrolysis, B liquid, C liquid.As shown in the figure, demonstrate: with the A liquor ratio, the extinction peak that has added the B liquid of nitric acid is transferred to short wavelength side, and the aspect ratio of gold nanorods diminishes to 4.8 (major axis 43.2nm) of B liquid from 5.5 (major axis 49.5nm) of A liquid.Demonstrate in addition: the extinction peak that has added the C liquid of sodium hydrate aqueous solution is transferred to long wavelength side, and it is big that the aspect ratio of gold nanorods becomes, and is 5.8 (major axis 52.2nm).
Industrial applicability
Metal particle of the present invention (metal nano-rod), aspect ratio is 1.1-8.0, result from the rod major axis, at 400nm-1, the visible light of 200nm has optionally wavelength absorption function to the near-infrared wavelength zone. Therefore, can make it to bring into play various tones.
In addition, metal particle of the present invention, the absorptivity on the peak position of maximum absorption wavelength is 6,000-20,000L/molcm (measures concentration 1.6 * 10-4Mol/L, solvent: water), have excellent absorbance, and the half value of the absorption spectrum of maximum absorption wavelength is wide to be 200nm or following, the width of absorption spectrum is narrow. Therefore, owing to have sharp-pointed extinction characteristic, therefore little to the impact of wavelength on every side, can access saturate tone.
In addition, metal particle of the present invention is the metal quality, so heat resistance, light resistance, and resistance to chemical reagents excellence, and therefore, the composition that contains this metal particle also can not fade or take place the reduction of absorption function, reliability height in long-term use.
Manufacturing method according to the invention can easily be controlled the aspect ratio of metal nano-rod, can make expeditiously the metal nano-rod with target aspect ratio.
Can access the coating composition that adopts metal particle composition of the present invention to form, film, transparent coating or film.
In addition, the metal particle that adopts manufacture method of the present invention to make can be used as the filter material, wiring material, electrode material, catalyst, colouring agent, cosmetics, near-infrared-absorbing material, anti-forgery ink, electromagnetic shielding material, the surface that comprise this metal particle and strengthen fluorescent optical sensor, biomarker, nanometer waveguide, recording materials, recording element, polarized material, delivery system (DDS) pharmaceutical carrier, biology sensor, DNA chip, investigational agent.
Claims (2)
1. the manufacture method of a metal particle, it is the method that the reducing metal ion is made metal particle in containing the aqueous solution of surfactant, it is characterized in that, by make metal particle under the environment that has added acid or alkali, control the aspect ratio of metal particle
Wherein, the method of reducing metal ion in containing the aqueous solution of surfactant, be to have added with following chemical formula A, B, and the electrochemical reducing that uses as electrolyte of the aqueous solution more than a kind or 2 kinds of the surfactant represented of C, reduce the aspect ratio of metal particle by adding acid, perhaps, increase the aspect ratio of metal particle by interpolation alkali
CH
3(CH
2)
nN
+(CH
3)
3Br
-, n is the integer of 1-15 ... A
(CH
3(CH
2)
n)
4N
+Br
-, n is the integer of 1-15 ... B
(CH
3(CH
2)
n)
2N
+(CH
3)
2Br
-, n is the integer of 7-17 ... C.
2. the manufacture method of metal particle according to claim 1, wherein, as acid use be selected from nitric acid, sulfuric acid, hydrochloric acid, hydrobromic any, use any that is selected from NaOH, potassium hydroxide, ammoniacal liquor as alkali.
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| JP2004116254A JP2005298891A (en) | 2004-04-09 | 2004-04-09 | Process for producing metal microparticle and composition containing the same |
| JP2004116253 | 2004-04-09 | ||
| JP2004-116254 | 2004-04-09 | ||
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| CN101343778B (en) * | 2008-08-29 | 2011-04-06 | 北京航空航天大学 | Process for producing golden nano stick with short length-diameter ratio |
| JP5942297B2 (en) * | 2011-03-08 | 2016-06-29 | 国立研究開発法人科学技術振興機構 | Method for producing electrode structure having nanogap length, plating solution and nanodevice |
| WO2013080473A1 (en) * | 2011-11-30 | 2013-06-06 | ソニー株式会社 | Chemical sensor, chemical sensor module, chemical substance detector and method for detecting chemical substance |
| CN102998321A (en) * | 2012-05-11 | 2013-03-27 | 深圳市树德堂文化发展有限公司 | Anti-counterfeiting subject matter, preparation method and detection method thereof |
| EP2999536B1 (en) * | 2013-05-21 | 2020-09-02 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Chemical conversion process |
| KR20170032315A (en) | 2014-07-15 | 2017-03-22 | 이섬 리서치 디벨러프먼트 컴파니 오브 더 히브루 유니버시티 오브 예루살렘 엘티디. | Patterns of fluorescent seeded nanorods |
| TWI680103B (en) * | 2015-01-27 | 2019-12-21 | 日商住友金屬礦山股份有限公司 | Near-infrared absorbing fine particle dispersion and manufacturing method thereof |
| US20160327853A1 (en) * | 2015-05-08 | 2016-11-10 | Honeywell International Inc. | Transparent active window display |
| CN111065473B (en) * | 2017-09-15 | 2022-04-19 | 旭化成株式会社 | Metal particle ring structure, metal particle ring structure coated with insulating material, and composition |
| CN111665674B (en) * | 2020-06-17 | 2021-10-01 | 中国科学技术大学 | Selective light absorption-electrochromic film, preparation method thereof and selective light absorption-electrochromic device |
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| Gil-Jae Lee etal.Preparation of silver nanorods through the control of temperature and pH of reaction medium，Materials Chemistry and Physics.Materials Chemistry and Physics.2004,84(2),197-204. * |
| JP昭62-61630A 1987.03.18 |
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