CN107446380A - Organic/inorganic composite material of two kinds of azo dyes doping and its preparation method and application - Google Patents
Organic/inorganic composite material of two kinds of azo dyes doping and its preparation method and application Download PDFInfo
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- CN107446380A CN107446380A CN201710678362.XA CN201710678362A CN107446380A CN 107446380 A CN107446380 A CN 107446380A CN 201710678362 A CN201710678362 A CN 201710678362A CN 107446380 A CN107446380 A CN 107446380A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo dyes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0079—Azoic dyestuff preparations
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/008—Preparations of disperse dyes or solvent dyes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
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- H01S3/213—Liquids including an organic dye
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04B—TRANSMISSION
- H04B10/00—Transmission systems employing electromagnetic waves other than radio-waves, e.g. infrared, visible or ultraviolet light, or employing corpuscular radiation, e.g. quantum communication
- H04B10/50—Transmitters
- H04B10/501—Structural aspects
- H04B10/506—Multiwavelength transmitters
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04B—TRANSMISSION
- H04B10/00—Transmission systems employing electromagnetic waves other than radio-waves, e.g. infrared, visible or ultraviolet light, or employing corpuscular radiation, e.g. quantum communication
- H04B10/50—Transmitters
- H04B10/572—Wavelength control
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Abstract
The present invention relates to organic/inorganic composite material of two kinds of azo dyes doping and its preparation method and application, and γ (2,3 glycidoxy) propyl trimethoxy silicane, second alcohol and water are mixed, acidic catalyst is added, obtains solution A；Positive four butyl ester of metatitanic acid and acetylacetone,2,4-pentanedione are well mixed and obtain solution B；Solution A and solution B are well mixed, obtain organo-mineral complexing matrix mother liquor；4 hydroxyazobenzenes and Red-1 200 are added into organo-mineral complexing matrix mother liquor, is uniformly mixing to obtain suspension；Suspension is deposited on slide using spin coating technique, forms film, film is thermally treated resulting in the organic/inorganic composite material of two kinds of azo dyes doping.Using sol-gel technique is improved in the present invention, with reference to spin coating technique, two kinds of azo dyes are entrained in together, the material of preparation is provided with the case where the pump light of two beam different wave lengths excites while handles the function of lose-lose optical signal.
Description
Technical field
The invention belongs to optical material field, and in particular to the composite organic-inorganic material of two kinds of azo dyes doping and
Its preparation method and application.
Background technology
Optical computing is placed high hopes by computerdom always, and photon has the bandwidth more much more than electronics, therefore can
Quickly to handle more data, therefore, there is the material of all-optical signal processing ability and device to become the supreme arrogance of a person with great power
Study hotspot.In conventional correlative study, optical memory just for Single wavelength input signal, is seldom related to different wave length mostly
Detection and processing while optical signal, this will reduce efficiency when multi signal is handled and increase loss.Want solve this
Problem, one of which thinking are exactly by adulterating a variety of specifically a variety of light functional dyes, and passing through in material preparation process
The specific preparation parameter of material is adjusted to adjust the wavelength location of multiple characteristic peaks, it is met the needs of multi signal processing.
In recent years, the composite organic-inorganic material based on organic modified silicate is studied proves in integrated optics application
Field has very big value, and this stems primarily from the addition for the organic molecule functional group that can be adulterated so that has full light letter
The integrated optical device of number processing function is possibly realized, and organic molecule can fill up inorganic in inorganic-organic composite
Hole in oxide chain so that material is finer and close.So based on the composite of organic modified silicate in Integrated Light
Application in terms of sub-, scientists are caused in the world and are greatly paid close attention to, using correlation technique, at low temperature (or even it is near
In room temperature) fine and close, low-loss and a few micrometers of thick individual layer high optical quality films are can be obtained by, and cause the photon prepared
Device can be integrated directly with semiconductor light source, detector and various optically functional devices.
But existing technology handles the optical signal of different wave length by different materials, is mainly prepared by device
Multiple material is combined together, is the combination of physical layer, if combination can then produce to be brought into close contact in interface
Optical transmission loss；If discrete combined, then it can increase device size.
The content of the invention
It is an object of the invention to overcome problems of the prior art, there is provided the doping of two kinds of azo dyes it is organic-
Inorganic composite materials and its preparation method and application, by prepare composite organic-inorganic material that two kinds of azo dyes adulterate come
Realize dual signal optical memory.
In order to achieve the above object, the present invention adopts the following technical scheme that：
Comprise the following steps：
(1) γ-(2,3 glycidoxy) propyl trimethoxy silicane, second alcohol and water are mixed, adds acidic catalyst
Agent, obtains solution A, and the mol ratio of wherein γ-(2,3 glycidoxy) propyl trimethoxy silicane and ethanol is 1：4；By mole
Than for 1：4 obtain solution B by positive four butyl ester of metatitanic acid and acetylacetone,2,4-pentanedione are well mixed；
(2) by the mol ratio of γ-(2,3 glycidoxy) propyl trimethoxy silicane and positive four butyl ester of metatitanic acid for (70~
90)：(30~10), solution A and solution B are well mixed, and obtain organic-inorganic composite ground mass mother liquor；
(3) added into organic-inorganic composite ground mass mother liquor account for organic-inorganic composite ground mass mother liquor weight 0.5%~
3% 4- hydroxyazobenzenes and Red-1 200, is uniformly mixing to obtain suspension；
(4) suspension is deposited on slide using spin coating technique, forms film, film is thermally treated resulting in two
The composite organic-inorganic material of kind azo dyes doping.
Further, the mol ratio of second alcohol and water is 1 in step (1)：1.
Further, the acidic catalyst in step (1) is the hydrochloric acid that mass concentration is 37%；Adding hydrochloric acid makes gained molten
Liquid A pH value is 3.1~4.3.
Further, rotating speed is 2500~3500 revs/min in the spin coating technique of step (4).
Further, the heat treatment in step (4) is handled 10~13 minutes at 80~120 DEG C.
Utilize the composite organic-inorganic material of two kinds of azo dyes doping made from preparation method as described above.
The composite organic-inorganic material of two kinds of azo dyes doping as described above is handled in lose-lose optical signal at the same time
Using.
Further, including following processing step：
(1) polarizer, attenuator are sequentially arranged on rear side of the output end for the pump laser fixed respectively in two wavelength, is divided
Light microscopic and speculum, form the first pumping light path and the second pumping light path；In the output of the detecting laser of wavelength continuously adjustabe
End rear side one polarizer of arrangement, forms detection light path；First pumping light path, the second pumping light path and the laser light for detecting light path
Beam is finally converged at a bit, and the composite organic-inorganic material of two kinds of azo dyes doping is positioned over into the point, contaminated in two kinds of azos
Expect the rear side arrangement optical filter of the composite organic-inorganic material of doping；Spectroscope includes reflected light path and is connected with speculum
Transmitted light path, spectroscopical reflected light path and optical filter are all connected with detector, complete light path overlap joint；
(2) laser successively sent to two pump lasers blocks, and for the change of simulation input optical signal, leads to
Cross the signal intensity situation that three detectors separately detect two beam pump lights and a branch of detection light.
Further, the wavelength for the laser that two pump lasers are sent has positioned at what two kinds of azo dyes adulterated respectively
In two characteristic absorption peaks of machine-inorganic composite materials.
Further, the wavelength of two pump lasers is respectively in 532nm and 355nm；The Wavelength tunable of detecting laser
Scope is in 430nm~2300nm.
Compared with prior art, the present invention has technique effect beneficial below：
Using sol-gel technique is improved in the inventive method, prepared with reference to spin coating technique, by two kinds of azo dyes
It has been entrained in together, the effect of dyestuff is no longer just independent of each other, and the influence to material light functional characteristic just becomes one
Individual entirety, it can realize by adulterating two kinds of dyestuffs while handle the purpose of the laser of different wave length, with synthesis temperature is low, work
The advantages that skill requirement is simple and reproducible.
The low temperature organic, inorganic composite film material that material of the present invention is titanium dioxide and organic modified silicate is matrix
Material, by mixing two kinds of different azo dyes small molecule functional groups to possess light functional characteristic, remove its material prepared
There is good pliability and mechanical property, the device of making is easy to process, grinds and polishes outside these advantages, preparation it is thin
Membrane material is provided with the case where the pump light of two beam different wave lengths excites while handles the function of lose-lose optical signal.In addition, this hair
Bright is to be based on having the thick a few micrometers and adjustable single layer optical quality waveguide film of refractive index at low temperature, so being advantageously implemented
Photonic device it is integrated, and photonic device it is integrated be photonic propulsion development important trend.
Low temperature organic-inorganic composite of the present invention is a kind of low temperature Organic-inorganic composite photon of all-optical signal processing
Information material, available for fields such as optical signalling detection, calculating and memories.
Further, for the present invention using wavelength respectively in 532nm and 355nm pump laser, classics are common, are applicable model
Enclose wide so that light path of the present invention can be used for film, liquid, solid material of the test with following two characteristic conditions：1st, it is double
Absworption peak is near 350nm and 500nm；2nd, under above-mentioned two wavelength laser simultaneously radiation situation, deposited in its absorption spectrum
Constant wavelength location is kept in absorption intensity.
Brief description of the drawings
Fig. 1 is the dioxy containing Red-1 200 dyestuff and 4- hydroxyazobenzene small molecule dyes that doping proportion is 1%
Change the abosrption spectrogram of titanium-organic modified silicate thin-film material.
Fig. 2 is the dioxy containing Red-1 200 dyestuff and 4- hydroxyazobenzene small molecule dyes that doping proportion is 1%
Change what titanium-organic modified silicate thin-film material abosrption spectrogram under the mercury lamp light source irradiation of 504nm wavelength changed over time
Situation.
Fig. 3 is the dioxy containing Red-1 200 dyestuff and 4- hydroxyazobenzene small molecule dyes that doping proportion is 1%
Change what titanium-organic modified silicate thin-film material abosrption spectrogram under the mercury lamp light source irradiation of 355nm wavelength changed over time
Situation.
Fig. 4 is the dioxy containing Red-1 200 dyestuff and 4- hydroxyazobenzene small molecule dyes that doping proportion is 1%
Change titanium-organic modified silicate thin-film material abosrption spectrogram under the mercury lamp light source irradiation of 504nm and 355nm wavelength simultaneously
Situation about changing over time.
Fig. 5 is the light path device figure for characterizing thin-film material dual signal optical memory characteristic.Wherein, two beams are as input
The pump wavelength of signal is respectively 532nm and 355nm, and the wavelength for detecting light is 470nm, and laser is continuous laser.Its
Middle P is polarizer；NA is attenuator；BS is spectroscope；M is speculum；D is detector；F is optical filter.
Fig. 6 is to carry out light functional test to the thin-film material of two kinds of dyestuffs of doping using the light path device shown in Fig. 5, its
It is middle change input optical signal mode for successively to two beam laser carry out manual shade, the duration blocked successively be about 3s, 5s,
60s。
Embodiment
The present invention is described in further details below in conjunction with the accompanying drawings.
The preparation method of material of the present invention comprises the following steps：
1) first by 1 mole of γ-(2,3 glycidoxy) propyl trimethoxy silicane, 4 moles of ethanol and 4 moles
Deionized water mixing, then add hydrochloric acid and be used as catalyst, make solution in acid, pH value is 3.1~4.3, wherein hydrochloric acid
Mass concentration 37%；Solution A is used as after being stirred continuously uniformly；Positive four butyl ester of 1 mole of metatitanic acid and 4 moles of acetylacetone,2,4-pentanedione are mixed
Merging is used as solution B after being stirred continuously uniformly.
PH value can influence the position of material absworption peak in the present invention, and pH value is smaller, material absworption peak can overall blue shift, instead
It, pH value is bigger, and material absworption peak can overall red shift.It is whole that this details essentially consists in absworption peak to every characteristic in the present invention
The wavelength of light is detected after body movement to be needed to readjust, and this is also that detection light needs the reason for being wavelength continuously adjustabe laser.
2) by the mol ratio of γ-(2,3 glycidoxy) propyl trimethoxy silicane and positive four butyl ester of metatitanic acid for (70~
90)：(30~10), solution A and solution B are mixed, then constantly stirred the mixed solution at room temperature, you can obtained
The low temperature organic-inorganic composite ground mass mother liquor of even siliceous titanium；
3) give and two kinds of azo dyes are added in organic-inorganic composite ground mass mother liquor, respectively organic-inorganic composite ground mass is female
The 4- hydroxyazobenzenes of liquid weight 0.5%~3% and the Red-1 200 small molecule of matrix weight 0.5%~3%, and at room temperature
Stir so as to obtain suspension；
4) will be obtained above suspended in the case where rotating speed is 2500~3500 turns per minute using spin coating technique
Liquid is deposited on slide, is then handled the film sample deposited 10~13 minutes at a temperature of 80~120 DEG C, you can
To with individual layer and surface is smooth, titanium dioxide-organic modified silicates with the double dyestuffs doping of high optical quality
Base organic-inorganic composite optical wave guide thin-film material.
Embodiment 1
1) first by 1 mole of γ-(2,3 glycidoxy) propyl trimethoxy silicane, 4 moles of ethanol and 4 moles
Deionized water mixing, then add hydrochloric acid and be used as catalyst, make solution in acidity, pH value is 3.5, work after being stirred continuously uniformly
For solution A；As solution B after stirring positive four butyl ester of 1 mole of metatitanic acid and the mixing of 4 moles of acetylacetone,2,4-pentanedione and constantly.
2) it is and then by the mol ratio of γ-(2,3 glycidoxy) propyl trimethoxy silicane and positive four butyl ester of metatitanic acid 80：
20, solution A and solution B are mixed, then constantly stirred the mixed solution at room temperature, you can obtains uniform siliceous titanium
Low temperature organic-inorganic composite ground mass mother liquor；
3) give in organic-inorganic composite ground mass mother liquor and add the 4- hydroxyls of two kinds of azo dyes, respectively matrix weight 1%
The Red-1 200 small molecule of azobenzene and matrix weight 1%, and be stirred at room temperature uniformly so as to obtain suspension；
4) suspension obtained above is deposited in the case where rotating speed is 3000 turns per minute using spin coating technique
On slide, then the film sample deposited is handled 12 minutes at a temperature of 80 DEG C, you can obtain with individual layer and
Surface is smooth, has titanium dioxide-organic modified silicate base organic-inorganic of the double dyestuff doping of high optical quality compound
Optical waveguide film material.
Fig. 1 is the abosrption spectrogram of embodiment 1.It can be seen that the film of two kinds of different azo dyes of doping has two
Individual obvious characteristic absorption peak, respectively near 334nm and 500nm, meanwhile, there is an absorption paddy, near 410nm, be located at
Among two absworption peaks so that two absworption peaks have obvious interval.It can be drawn from Fig. 1 result, two absworption peaks are point
The result that red 1 small molecule is overlapped mutually with cis-isomer in 4- hydroxyazobenzene small molecules with transisomer is dissipated, due to this
The Cis-trans structures isomerization process of two kinds of dye molecules is all rapid and reversible, therefore, is doped with the film of both dyestuffs
Material can be to the light source sensitivity of wavelength near 334nm and 500nm.
Fig. 2 is the situation that abosrption spectrogram changes over time under the light source irradiation of 504nm wavelength of embodiment 1, and light source is
The mercury lamp of optical filter is used.It can be seen that with the increase of light application time, two feature peak intensities of film under
Drop, the intensity for absorbing paddy does not change, and obvious blue shift or red shift do not occur for the position of peak and valley.
Fig. 3 is the situation that abosrption spectrogram changes over time under the light source irradiation of 355nm wavelength of embodiment 1, and light source is
The mercury lamp of optical filter is used.It can be seen that unlike Fig. 2, with the increase, 334nm or so of light application time
Absorption peak strength decline, 500nm or so absworption peak has almost no change, 410nm or so absorption valley strength increase, and
And absorb the position of paddy there occurs obvious blue shift.
Fig. 4 is that abosrption spectrogram changes over time embodiment 1 under the light source irradiation of 504nm and 355nm wavelength simultaneously
Situation, light source is the mercury lamp for having used optical filter.It can be seen that with the increase of light application time, near 334nm
Absorption peak strength substantially reduces, and the absorption peak strength change near 500nm is little, but obvious blue shift occurs for its position, meanwhile,
Absorption valley strength increase near 410nm, blue shift similarly occurs for its position.It is important to note that although in double light sources
Irradiate simultaneously in the case of, the absworption peak of film sample has two wavelength positions from absorbing paddy all there occurs different changes
The absorption intensity put keeps constant, respectively near 400nm and 470nm, therefore selects the continuous of near 470nm Wavelength tunable
Laser is as probe source.
The present invention is contaminated using sol-gel technique and spin coating technique is improved by mixing two kinds of different azo light functions
Material, obtains the light function film with multiple characteristic absorption peaks.The film wavelength be 355nm and 504nm light sources respectively according to
Penetrate down, different degrees of change can occur for two characteristic absorption peak intensities in its uv-visible absorption spectroscopy figure；And this two
Double light sources of kind laser irradiate simultaneously under, two characteristic absorption peak variation tendencies of thin-film material can be sent out when being irradiated with single light source not
Together, it is notable that in this case, 470nm nearby has a fixed wavelength location in the absorption spectrum of film,
Its absorption intensity is constant in the case where double light sources irradiate simultaneously；It is also, original to absorb by force when thering is any one light source to remove
Spending constant wavelength location its absorption intensity can also change.
In order to be characterized to film sample made above based on dual signal optical memory characteristic, using above characteristic, take
The light path device based on pump probe principle is built, the laser of 355nm and 532nm wavelength is arranged to pump light, inputted for two beams
Optical signal；The laser of 470nm wavelength is arranged to detect light, to export optical signal.It is to realize that this material, which is prepared and built with light path,
A kind of method of dual signal optical memory, the optical signal to two kinds of different wave lengths while the work(for being detected and being remembered can be completed
Energy.
Fig. 5 is the light path device figure for characterizing thin-film material dual signal optical memory characteristic.Wherein, two beams are as different
The pump wavelength of input signal is different, respectively 532nm and 355nm, and detection light is used to show that sample enters two beam pump lights
Result after row signal transacting, output wavelength 470nm, sent by laser, laser is continuous laser, wherein visiting
The continuous wavelength scope that light-metering laser can be sent is in 430~2300nm.Two beam pump lights converge in sample after polarization
On, in the presence of illumination, with 4- hydroxyazobenzenes small molecule photic suitable reef knot occurs for the Red-1 200 small molecule in film sample
Structure isomerization, cause change of the film sample in each wavelength location absorption intensity.The effect of detection light is to detect two beams
The radiation situation of pump light, can see with reference to Fig. 2, Fig. 3 and Fig. 4, and when two-beam source is acted on sample simultaneously, sample exists
Absorptivity near 470nm keeps constant；When the light source for removing 355nm, when only retaining 532nm illumination, sample is attached in 470nm
Near absorptivity can decline；Conversely, when the light source for removing 532nm, when only retaining 355nm illumination, sample is near 470nm
Absorptivity can then rise.
Light path of the present invention can be used for testing absworption peak near 350nm and 500nm, and with similar not in by light path
Film, liquid, the solid material of the wavelength location of two kinds of pump light illumination effects of application；The position is set to detect light wave
It is long, it is necessary to explanation, the laser for detecting light is Wavelength tunable, on-fixed value.
The present invention realizes the side of dual signal optical memory based on the composite organic-inorganic material of two kinds of azo dyes doping
The overall output of method light path is the detection intensity variation by sample, and its general principle is to be acted in two beam pump lights
When on sample, the detection luminous intensity of output is constant, and when there is any a branch of pump light to be blocked, that is, the optical signalling inputted becomes
During change, fluctuation occurs in the detection luminous intensity of output.
Fig. 6 is to carry out light functional test to film made from embodiment 1 using the light path device shown in Fig. 5, wherein changing
Become the mode of input optical signal as successively two beam laser are carried out with manual shade, the duration blocked is about 3s, 5s, 60s successively.From
It can be seen from the figure that, when two beam laser are acted on sample simultaneously, the luminous intensity for detecting light output is constant；Work as manual shade
355nm light source, when retaining 532nm illumination, the luminous intensity for detecting light output declines, and the time for blocking light source is longer, defeated
The luminous intensity continuous decrease gone out is more obvious；If conversely, manual shade 532nm light source, and when retaining 355nm illumination, detection
The luminous intensity of light output can then rise, likewise, the time for blocking light source is longer, the luminous intensity continuous decrease of output is more obvious.
After the optical signal blocked recovers, output optical signal can substantially return to the original state of two-source illumination.As above test knot
Fruit coincide with combining the conclusion that the analysis of Fig. 1,2,3 is drawn.The test can be by the spy photometry result of output come to dual input light
Signal is detected and remembered.
Embodiment 2
1) first by 1 mole of γ-(2,3 glycidoxy) propyl trimethoxy silicane, 4 moles of ethanol and 4 moles
Deionized water mixing, then add hydrochloric acid and be used as catalyst, make solution in acidity, pH value is 3.1, work after being stirred continuously uniformly
For solution A；As solution B after stirring positive four butyl ester of 1 mole of metatitanic acid and the mixing of 4 moles of acetylacetone,2,4-pentanedione and constantly.
2) it is and then by the mol ratio of γ-(2,3 glycidoxy) propyl trimethoxy silicane and positive four butyl ester of metatitanic acid 70：
30, solution A and solution B are mixed, then constantly stirred the mixed solution at room temperature, you can obtains uniform siliceous titanium
Low temperature organic-inorganic composite ground mass mother liquor；
3) give in organic-inorganic composite ground mass mother liquor and add the 4- hydroxyls of two kinds of azo dyes, respectively matrix weight 0.5%
The Red-1 200 small molecule of base azobenzene and matrix weight 0.5%, and be stirred at room temperature uniformly so as to obtain suspension；
4) suspension obtained above is deposited in the case where rotating speed is 2500 turns per minute using spin coating technique
On slide, then the film sample deposited is handled 13 minutes at a temperature of 100 DEG C, you can obtain with individual layer and
Surface is smooth, has titanium dioxide-organic modified silicate base organic-inorganic of the double dyestuff doping of high optical quality compound
Optical waveguide film material.
Embodiment 3
1) first by 1 mole of γ-(2,3 glycidoxy) propyl trimethoxy silicane, 4 moles of ethanol and 4 moles
Deionized water mixing, then add hydrochloric acid and be used as catalyst, make solution in acidity, pH value is 4.3, work after being stirred continuously uniformly
For solution A；As solution B after stirring positive four butyl ester of 1 mole of metatitanic acid and the mixing of 4 moles of acetylacetone,2,4-pentanedione and constantly.
2) it is and then by the mol ratio of γ-(2,3 glycidoxy) propyl trimethoxy silicane and positive four butyl ester of metatitanic acid 90：
10, solution A and solution B are mixed, then constantly stirred the mixed solution at room temperature, you can obtains uniform siliceous titanium
Low temperature organic-inorganic composite ground mass mother liquor；
3) give in organic-inorganic composite ground mass mother liquor and add the 4- hydroxyls of two kinds of azo dyes, respectively matrix weight 3%
The Red-1 200 small molecule of azobenzene and matrix weight 3%, and be stirred at room temperature uniformly so as to obtain suspension；
4) suspension obtained above is deposited in the case where rotating speed is 3500 turns per minute using spin coating technique
On slide, then the film sample deposited is handled 10 minutes at a temperature of 120 DEG C, you can obtain with individual layer and
Surface is smooth, has titanium dioxide-organic modified silicate base organic-inorganic of the double dyestuff doping of high optical quality compound
Optical waveguide film material.
In summary, doping Red-1 200 and 4- hydroxyazobenzenes can be prepared using sol-gel process combination spin-coating method
Titanium dioxide-organic modified silicate the film of two kinds of dyestuffs of small molecule, using having added the mercury lamp of optical filter to two feature
Light-sensitive characteristic near absworption peak is tested, and has shown that film sample is each in the case of single light source and two-source illumination
The situation of absorption intensity variation of the individual absworption peak with absorbing paddy, and, it is determined that absorptivity is not in the case of two-source illumination
The wavelength location of change is near 470nm.By using the light path device built by using Fig. 5, by two absworption peaks of film
Neighbouring wavelength 355nm and 532nm is arranged to pump light, i.e. lose-lose optical signal, and absorptivity in the case of two-source illumination is constant
470nm be arranged to detect light, by test by sample detection optical signal i.e. can reach and meanwhile detect two beam pump lights letter
Number purpose.Specifically, when two beam input optical signals are all " 1 ", output optical signal keeps " 0 " constant；When 355nm optical signals
For " 0 ", when 532nm optical signals are " 1 ", output optical signal is " -1 "；When 355nm optical signals are " 1 ", 532nm optical signals are " 0 "
When, output optical signal is " 1 ".The light path device that film sample combination Fig. 5 of double dyestuff doping is proposed can be completed above-mentioned simultaneously
The detection and memory of the different optical signal of two beam wavelength.Possible application scenarios description：The present invention can be applied in full light nerve
In list " cell " research field of network, film sample is one " cell " in neutral net, two beam different wave lengths it is defeated
Optical signal is used for simulating two kinds of different environmental stimulis, such as two objects that analog vision cell is seen, when the two things
When body state does not change, the output signal after " cell " processing keeps constant, when any one object state
When changing, output optical signal can all have detected change corresponding with record.Such dual signal detects simultaneously and processing
Function there is obvious advantage compared with mono signal optical memory, efficiency can be effectively improved and reduce loss, have apply valency
Value.It is pointed out that the application scenarios of the above are only for citing, it is not limited to this, illustrate hereby.
Claims (10)
1. the preparation method of the composite organic-inorganic material of two kinds of azo dyes doping, it is characterised in that：Comprise the following steps：
(1) γ-(2,3 glycidoxy) propyl trimethoxy silicane, second alcohol and water are mixed, adds acidic catalyst, obtain
To solution A, the mol ratio of wherein γ-(2,3 glycidoxy) propyl trimethoxy silicane and ethanol is 1：4；It is in molar ratio
1：4 obtain solution B by positive four butyl ester of metatitanic acid and acetylacetone,2,4-pentanedione are well mixed；
(2) it is (70~90) by the mol ratio of γ-(2,3 glycidoxy) propyl trimethoxy silicane and positive four butyl ester of metatitanic acid：
(30~10), solution A and solution B are well mixed, and obtain organic-inorganic composite ground mass mother liquor；
(3) added into organic-inorganic composite ground mass mother liquor and account for organic-inorganic composite ground mass mother liquor weight 0.5%~3%
4- hydroxyazobenzenes and Red-1 200, are uniformly mixing to obtain suspension；
(4) suspension is deposited on slide using spin coating technique, forms film, film is thermally treated resulting in two kinds of idols
The composite organic-inorganic material of nitrogen dyestuff doping.
2. the preparation method of the composite organic-inorganic material of two kinds of azo dyes doping according to claim 1, its feature
It is：The mol ratio of second alcohol and water is 1 in step (1)：1.
3. the preparation method of the composite organic-inorganic material of two kinds of azo dyes doping according to claim 1, its feature
It is：Acidic catalyst in step (1) is the hydrochloric acid that mass concentration is 37%；Adding hydrochloric acid makes resulting solution A pH value exist
3.1~4.3.
4. the preparation method of the composite organic-inorganic material of two kinds of azo dyes doping according to claim 1, its feature
It is：Rotating speed is 2500~3500 revs/min in the spin coating technique of step (4).
5. the preparation method of the composite organic-inorganic material of two kinds of azo dyes doping according to claim 1, its feature
It is：Heat treatment in step (4) is handled 10~13 minutes at 80~120 DEG C.
6. utilize the composite organic-inorganic material of two kinds of azo dyes doping made from preparation method described in claim 1.
7. the composite organic-inorganic material of two kinds of azo dyes doping as claimed in claim 6 handles dual input light letter at the same time
Application in number.
8. the composite organic-inorganic material of two kinds of azo dyes doping according to claim 7 handles dual input at the same time
Application in optical signal, it is characterised in that：Including following processing step：
(1) polarizer, attenuator, spectroscope are sequentially arranged on rear side of the output end for the pump laser fixed respectively in two wavelength
And speculum, form the first pumping light path and the second pumping light path；After the output end of the detecting laser of wavelength continuously adjustabe
A polarizer is arranged in side, forms detection light path；The laser beam of first pumping light path, the second pumping light path and detection light path is most
Converge at eventually a bit, the composite organic-inorganic material of two kinds of azo dyes doping is positioned over the point, mixed in two kinds of azo dyes
The rear side arrangement optical filter of miscellaneous composite organic-inorganic material；Spectroscope includes reflected light path and is connected with speculum saturating
Light path is penetrated, spectroscopical reflected light path and optical filter are all connected with detector, complete light path overlap joint；
(2) laser successively sent to two pump lasers blocks, and for the change of simulation input optical signal, passes through three
Individual detector separately detects the signal intensity situation of two beam pump lights and a branch of detection light.
9. the composite organic-inorganic material of two kinds of azo dyes doping according to claim 8 handles dual input at the same time
Application in optical signal, it is characterised in that：The wavelength for the laser that two pump lasers are sent is located at two kinds of azo dyes respectively
In two characteristic absorption peaks of the composite organic-inorganic material of doping.
10. the composite organic-inorganic material of two kinds of azo dyes doping according to claim 8 handles dual input at the same time
Application in optical signal, it is characterised in that：The wavelength of two pump lasers is respectively in 532nm and 355nm；Detecting laser
Wavelength tunable scope is in 430nm~2300nm.
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| CN108759119A (en) * | 2018-04-28 | 2018-11-06 | 中国科学院工程热物理研究所 | Solar energy cascade energy storage device |
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