CN101561614B - Solid naphthalocyanine device with optical limiting properties - Google Patents
Solid naphthalocyanine device with optical limiting properties Download PDFInfo
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- CN101561614B CN101561614B CN2008101043808A CN200810104380A CN101561614B CN 101561614 B CN101561614 B CN 101561614B CN 2008101043808 A CN2008101043808 A CN 2008101043808A CN 200810104380 A CN200810104380 A CN 200810104380A CN 101561614 B CN101561614 B CN 101561614B
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- naphthalocyanine
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- 239000007787 solid Substances 0.000 title claims abstract description 48
- 230000000670 limiting effect Effects 0.000 title claims abstract description 29
- 230000003287 optical effect Effects 0.000 title claims abstract description 29
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 61
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229910052733 gallium Inorganic materials 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000004458 analytical method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YWJFSYILTJLPBZ-UHFFFAOYSA-N [O].C(C)(C)(C)C1=CC=CC=C1 Chemical compound [O].C(C)(C)(C)C1=CC=CC=C1 YWJFSYILTJLPBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000002156 mixing Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- PLOAKLCWXJMXSX-UHFFFAOYSA-N C1=CC=CC2=CC=CC=C12.[In] Chemical compound C1=CC=CC2=CC=CC=C12.[In] PLOAKLCWXJMXSX-UHFFFAOYSA-N 0.000 description 3
- DZZCFXGQVJDAHK-UHFFFAOYSA-N [Sn].C1=CC=CC2=CC=CC=C12 Chemical compound [Sn].C1=CC=CC2=CC=CC=C12 DZZCFXGQVJDAHK-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- -1 naphthalene phthalocyanine compound Chemical class 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
The invention relates to a solid naphthalocyanine device with excellent optical limiting properties. The device is made by the following steps: adding tetraethoxysilane, diglycidyl ether propyltrimethoxy siloxane, analytically pure ethanol and acidic aqueous solution to a reactor; stirring in an enclosed reactor for 2-3h, then opening the reactor and continuing stirring for 1-2h; adding a naphthalocyanine solution and stirring to cause the mixture to become viscous; transferring the viscous mixture to a mould, and taking out after drying to obtain the novel solid naphthalocyanine device with optical limiting properties. The device is made by an organosilicon modification method combined with doped inorganic salt, and by doping naphthalocyanine with a larger pi electron conjugated system toform a continuous random network system with bonded chemical bonds of organic components and inorganic components instead of physical hybrid. The device has good laser resistance and excellent optical limiting properties.
Description
Technical field
The invention belongs to the technical field of Prepared by Sol Gel Method solid state device, be specifically related to adopt organic-silicon-modified method and doping inorganic salts to combine, mix naphthalene phthalocyanine simultaneously and the solid naphthalocyanine device that is prepared into optical limiting properties with bigger pi-electron conjugated system.
Technical background
As the laser technology of modern high technology war important means, be widely used in military field.In all kinds of laser weapons, laser disturbs with the blinding weapon and is begun one's study in worldwide and use in the eighties in 20th century.The target of attack of this class weapon is human eye and some important electron communication apparatus and devices.Along with the development of this class weapon, the research of corresponding laser protective material and device has caused people's great attention.Wherein, light amplitude limit material is as one of important materials of lasing safety, and its research has extremely important meaning.
Light amplitude limit (Optical limiting) is meant the increase along with incident laser energy, the repressed a kind of nonlinear optical response of the transmitance of medium.A kind of good light amplitude limit material has high linear transmittance T
Lin, low luminous energy threshold value (Optical threshold), low limit transmitance T
LimAnd fast laser response.Phthalocyanine is because its special big ring electron conjugated structure system, make it fast to the response of laser, has good optical limiting property, the naphthalene phthalocyanine of especially bigger conjugated system, better optical limiting properties is arranged, can be used as a kind of novel light amplitude limit material (Science, 1996,273,1533).At the initial stage, many researchs concentrate on the research of the light amplitude limit of phthalocyanine solution, but with regard to actual, realize the application of the light amplitude limit of phthalocyanine, phthalocyanine preparation must be become solid state device.Current, people utilize original sol-gel technique or other method to prepare some phthalocyanine solid films and solid state device (Macromol.Symp.2006,235,9 and Chem.Phys.Lett.2004,389,119), still, we repeat these preparation-obtained these solidification phthalocyanine materials of experiment and there is easy embrittlement in the device majority, thermal diffusivity is bad, problems such as anti-laser ability are unfavorable for processing, thereby its practical application are restricted.Along with the not section of research deeply, people are on the basis of original sol-gel technique, the compound of some long-chains that mixed is with the flexibility of improving solid state device and the shortcoming of embrittlement easily.Wherein, organic-silicon-modified method has caused that people pay attention to (Solid State Ionics 1994,110,125) widely.Yet these class methods have and exist new problem, are exactly bad, the anti-laser ability of thermal diffusivity, and material is aging easily etc.
Summary of the invention
The object of the present invention is to provide a kind of novel solid naphthalocyanine device with good optical limiting properties.
The present invention has overcome the defective of easy to be cracked and anti-laser ability of the solid phthalocyanine device of prior art for preparing, adopt organic-silicon-modified method and doping inorganic salts to combine, mix naphthalene phthalocyanine simultaneously with bigger pi-electron conjugated system, form the network system of the continuous random chemical bond combination of organic and inorganic component, and be not mixing of physics, good anti-laser ability is not only arranged, and good optical limiting properties is arranged.
A kind of solid naphthalocyanine device with optical limiting properties of the present invention is prepared by following method:
Ethyl orthosilicate (TEOS), glycidol ether propyl trimethoxy silicane (KH560), analysis straight alcohol and acidic aqueous solution are joined in the reactor, after stirring 2～3 hours under the condition of closed reactor, opening reactor again continues to stir 1～2 hour, add naphthalene phthalocyanine solution then, stirring makes mixed liquor become (general mixing time is 2～4 hours) behind the thickness, the mixed liquor of the thickness that becomes is transferred in the mould, the back taking-up of at least 2 week of drying can make the solid naphthalocyanine device with optical limiting properties.
Described ethyl orthosilicate: glycidol ether propyl trimethoxy silicane: analyze straight alcohol: acidic aqueous solution: the volume ratio of naphthalene phthalocyanine solution is 1: 1～10: 0～2: 0.5～2: 0.2～1; Preferred volume ratio is: 1: 5: 2: 2: 0.2～1; The pH value of described acidic aqueous solution is 0～3, and preferred pH value is 0～1; Described acidic aqueous solution can be inorganic acid solution or organic acid soln, and described acid is not had special restriction, and general mineral acid can be hydrochloric acid, sulfuric acid or perchloric acid etc., and general organic acid can be acid or glacial acetic acid etc.
Described glycidol ether propyl trimethoxy silicane (KH560) molecular formula is as follows, can use the commercial goods:
The structural formula of described naphthalene phthalocyanine is as follows:
Wherein, M is Ga, In or SnCl; The periphery substituent group R is to 2-methyl-2-phenylpropane oxygen base (t-BuPhO-); But the synthetic list of references J.Phys.Chem.B2006 of naphthalene phthalocyanine, 110,12230, with 5, dibasic naphthalene dintrile of 6-and MCl
3The cyclization preparation.Naphthalene phthalocyanine after synthetic is through UV-vis, H
1Means such as-NMR, MALDI-TOF and ultimate analysis characterize, and can confirm as said structure.UV-vis shows that the Q band of naphthalene phthalocyanine is absorbed in about 800nm, and comparing with phthalocyanine has wideer nonlinear optics window.
Described analysis straight alcohol can add also and can not add, and does not add when analyzing straight alcohol, can shorten drying time; Add when analyzing straight alcohol, can increase the hydrolysis degree of ethyl orthosilicate and glycidol ether propyl trimethoxy silicane.
The concentration of described naphthalene phthalocyanine solution is 5 * 10
-6Mol/L～4 * 10
-3Mol/L; The organic solvent of dissolving naphthalene phthalocyanine does not have special restriction, all effumability organic solvents that can dissolve the naphthalene phthalocyanine all can, preferred solvent is CH
2Cl
2
Described mould can be silica dish.
Described drying is preferably vacuum drying, and baking temperature is preferably 60 ℃～120 ℃.
The invention has the advantages that:
1. solid state device provided by the invention has very good optical limiting properties.The light limiting threshold can be less than 0.10Jcm
-2
2. solid state device provided by the invention has extraordinary anti-laser ability.Maximum anti-laser energy density can reach 30Jcm
-2
3. the solid state device transparency provided by the invention is good and plastic in silica dish, makes the smooth surface with premium properties, transparent hard solid naphthalocyanine device, can directly realize the practical application of its optical limiting properties as device.
Description of drawings
The comparison diagram of Fig. 1 embodiment of the invention 4 gained solid state devices and solution.
The optical limiting properties figure of Fig. 2 embodiment of the invention 4 gained solid state devices.
Embodiment
1. the preparation of naphthalene phthalocyanine and sign
With 6,7-two 2-methyl-2-phenylpropane oxygen bases-2,3-naphthalene dintrile 4.74g (10mmol) analyzes pure amylalcohol 10ml and joins in the there-necked flask of 50ml, after oil bath is heated to 60 ℃, add 1 of 1ml, 8-diazacyclo [5,4,0] hendecene-7 (DBU) is as catalyzer, slowly be warming up to 110 ℃ of heating after 2 hours, add the anhydrous GaCl of 0.45g
3And temperature is raised to 140 ℃, reflux stirred after 36 hours, stop heating, when the solution cool to room temperature, adding volume ratio is 1: 1 the methyl alcohol and the mixed solution 50ml of water, after filtration, washing obtains yellowish green crude product, is that the mixed solvent of 20: 1 methylene chloride and tetrahydrofuran (THF) is crossed the naphthalene phthalocyanine compound that obtains gallium behind the silica gel pillar, productive rate 62% as developping agent with volume ratio.UV, visible light (THF) λ max:799,340nm; Mass spectrum (MALDI-TOF): 2001.1 (M
+), 1966.2 (M
+-Cl), 1817.1 (M
+-Cl-OR), 1669.0 (M
+-Cl-2OR);
1H-NMR (DMSO-d6,400Hz): 9.05 (s, 8H), 8.29 (s, 8H), 7.51-7.53 (d, 16H), 7.36-7.39 (d, 16H), 1.38 (s, 72H); Ultimate analysis (%): calculated value C 76.75, H 5.99, and N 5.60; Measured value C 76.73, H 5.76, and N 5.96.
With 6,7-two 2-methyl-2-phenylpropane oxygen bases-2,3-naphthalene dintrile 4.74g (10mmol), analyze pure amylalcohol 10ml and join in the there-necked flask of 50ml, after oil bath was heated to 60 ℃, the DBU that adds 1ml was as catalyzer, slowly be warming up to 110 ℃ of heating after 2 hours, add the anhydrous InCl of 0.55g
3And temperature is raised to 140 ℃, reflux stirred after 36 hours, stop heating, when the solution cool to room temperature, adding volume ratio is 1: 1 the methyl alcohol and the mixed solution 50ml of water, after filtration, washing obtains yellowish green group of product, is that the mixed solvent of 20: 1 methylene chloride and tetrahydrofuran is crossed the naphthalene phthalocyanine compound that obtains indium behind the silica gel pillar, productive rate 58% as developping agent with volume ratio.UV, visible light (THF) λ max:802,339nm; Mass spectrum (MALDI-TOF): 2046.2 (M
+), 2010.6 (M
+-Cl), 1861.5 (M
+-Cl-OR);
1H-NMR (DMSO-d6,400Hz): 9.17 (s, 8H), 8.41 (s, 8H), 7.56-7.67 (d, 16H), 7.37-7.45 (d, 16H), 1.39 (s, 72H); Ultimate analysis (%): calculated value C 75.06, H 5.86, and N 5.47; Measured value C 75.72, H 5.74, and N 5.76.
With 6,7-two 2-methyl-2-phenylpropane oxygen bases-2,3-naphthalene dintrile 4.74g (10mmol), the anhydrous SnCl of 0.46g
21-naphthalene chloride 10ml joins in the there-necked flask of 50ml, after oil bath is heated to 190 ℃, react and stop reaction after 4 hours, when the solution cool to room temperature, add the 50ml normal hexane, after filtration, washing obtains yellowish green group of product, the mixed solvent that with volume ratio is 20: 1 methylene chloride and tetrahydrofuran is crossed the naphthalene phthalocyanine compound that obtains tin behind the silica gel pillar, productive rate 55% as developping agent.UV, visible light (THF) λ max:821,346nm; Mass spectrum (MALDI-TOF): 2085.6 (M
+), 2014.5 (M
+-2Cl), 1485.8 (M
+-4OR);
1H-NMR (CDCl
3, 400Hz): 9.54 (s, 8H), 8.55 (s, 8H), 7.50-7.55 (d, 16H), 7.27-7.33 (d, 16H), 1.44 (s, 72H); Ultimate analysis (%): measured value C 73.64, H 5.75, and N 5.37; Measured value C 73.44, H 5.04, and N 5.83.
2. the preparation of solid state device
After the aqueous hydrochloric acid solution 1ml mixing with ethyl orthosilicate 1ml, glycidol ether propyl trimethoxy silicane 5ml, analysis straight alcohol 2ml, pH=2, under the condition of closed reactor, stirred 2 hours, open reactor then and continue to stir 2 hours, add 4 * 10 again
-3The CH of M gallium naphthalene phthalocyanine (product of embodiment 1)
2Cl
2Solution 0.2ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 35mm, in the silica dish of high 3mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good dry 3 weeks below 120 ℃ in baking oven.Initial transmission 66%, nonlinear attenuation factor NAF is 20, threshold value is 0.096Jcm
-2, maximum anti-laser ability can reach 30Jcm
-2
The research of the light amplitude limit of solid state device is to utilize the Nd:YAG ps pulsed laser and ns pulsed laser systematic survey of 532nm to obtain.The light amplitude limit parameter that obtains has light limiting threshold, nonlinear attenuation factor NAF (NonlinearAttenuation Factor) etc.Fig. 1 is the comparison diagram of embodiment 4 gained solid state devices and solution, the initial transmission of gallium naphthalene phthalocyanine is 66%, gallium naphthalene phthalocyanine solid state device has better good optical limiting property as can be seen, Fig. 2 is the optical limiting properties figure of embodiment 4 gained solid state devices, as can be seen from the figure the light limiting threshold of solid state device is 0.096 Jiao/square centimeter, the value of NAF is 20, is significantly improved with comparing of solution.These results show that solid naphthalocyanine device provided by the invention has good optical limiting properties.
After the aqueous sulfuric acid 0.2ml mixing with ethyl orthosilicate 2ml, glycidol ether propyl trimethoxy silicane 2ml, analysis straight alcohol 2ml, pH=2, under the condition of closed reactor, stirred 2 hours, and then open reactor and continue to stir 2 hours, add 4 * 10 again
-3The CH of M gallium naphthalene phthalocyanine (product of embodiment 1)
2Cl
2Solution 1ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 40mm, in the silica dish of high 3mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good dry 3 weeks below 120 ℃ in baking oven.Initial transmission 63%, nonlinear attenuation factor NAF is 19.5, threshold value is 0.10Jcm
-2, maximum anti-laser ability can reach 25Jcm
-2
After ethyl orthosilicate 1ml, glycidol ether propyl trimethoxy silicane 5ml, concentrated hydrochloric acid aqueous solution (36.5%) 2ml mixing, under the condition of closed reactor, stirred 2 hours, and then open reactor and continue to stir 2 hours, add 4 * 10 again
-3The CH of M gallium naphthalene phthalocyanine (product of embodiment 1)
2Cl
2Solution 0.2ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 50mm, in the silica dish of high 5mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good dry 2 weeks below 120 ℃ in baking oven.Initial transmission 65%, nonlinear attenuation factor NAF is 20, threshold value is 0.095Jcm
-2, maximum anti-laser ability can reach 30Jcm
-2
After the aqueous hydrochloric acid solution 1ml mixing with ethyl orthosilicate 1ml, glycidol ether propyl trimethoxy silicane 5ml, analysis straight alcohol 2ml, pH=2, under the condition of closed reactor, stirred 2 hours, and then open reactor and continue to stir 2 hours, add 4 * 10 again
-3The CH of M indium naphthalene phthalocyanine (product of embodiment 2)
2Cl
2Solution 0.5ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 35mm, in the silica dish of high 3mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good dry 3 weeks below 120 ℃ in baking oven.Initial transmission 56%, nonlinear attenuation factor NAF is 22, threshold value is 0.11Jcm
-2, maximum anti-laser ability can reach 30Jcm
-2
After the aqueous hydrochloric acid solution 0.5ml mixing with ethyl orthosilicate 2ml, glycidol ether propyl trimethoxy silicane 2ml, analysis straight alcohol 2ml, pH=2, under the condition of closed reactor, stirred 2 hours, and then open reactor and continue to stir 2 hours, add 4 * 10 again
-3The CH of M indium naphthalene phthalocyanine (product of embodiment 2)
2Cl
2Solution 0.5ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 40mm, in the silica dish of high 2mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good below 120 ℃ following dry 3 weeks in baking oven.Initial transmission 55%, nonlinear attenuation factor NAF is 20.3, threshold value is 0.12Jcm
-2, maximum anti-laser ability can reach 25Jcm
-2
After ethyl orthosilicate 1ml, glycidol ether propyl trimethoxy silicane 5ml, concentrated hydrochloric acid aqueous solution (36.5%) 2ml mixing, under the condition of closed reactor, stirred 2 hours, and then open reactor and continue to stir 2 hours, add 4 * 10 again
-3The CH of M indium naphthalene phthalocyanine (product of embodiment 2)
2Cl
2Solution 1ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 35mm, in the silica dish of high 3mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good below 120 ℃ following dry 2 weeks in baking oven.Initial transmission 53%, nonlinear attenuation factor NAF is 22, threshold value is 0.11Jcm
-2, maximum anti-laser ability can reach 30Jcm
-2
After the aqueous hydrochloric acid solution 1ml mixing with ethyl orthosilicate 1ml, glycidol ether propyl trimethoxy silicane 5ml, analysis straight alcohol 2ml, pH=2, under the condition of closed reactor, stirred 2 hours, and then open reactor and continue to stir 2 hours, add 1 * 10 again
-3The CH of M tin naphthalene phthalocyanine (product of embodiment 3)
2Cl
2Solution 1ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 40mm, in the silica dish of high 3mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good dry 3 weeks below 120 ℃ in baking oven.Initial transmission 70%, nonlinear attenuation factor NAF is 18, threshold value is 0.16Jcm
-2, maximum anti-laser ability can reach 30Jcm
-2
After the aqueous acetic acid 1ml mixing with ethyl orthosilicate 2ml, glycidol ether propyl trimethoxy silicane 2ml, analysis straight alcohol 2ml, pH=2, under the condition of closed reactor, stirred 2 hours, and then open reactor and continue to stir 2 hours, add 1 * 10 again
-3The CH of M tin naphthalene phthalocyanine (product of embodiment 3)
2Cl
2Solution 1ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 50mm, in the silica dish of high 10mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good dry 3 weeks below 120 ℃ in baking oven.Initial transmission 68%, nonlinear attenuation factor NAF is 17, threshold value is 0.18Jcm
-2, maximum anti-laser ability can reach 25Jcm
-2
After ethyl orthosilicate 1ml, glycidol ether propyl trimethoxy silicane 5ml, analysis straight alcohol 2ml, concentrated hydrochloric acid aqueous solution (36.5%) 2ml mixing, under the condition of closed reactor, stirred 2 hours, and then open reactor and continue to stir 2 hours, add 1 * 10 again
-3The CH of M tin naphthalene phthalocyanine (product of embodiment 3)
2Cl
2Solution 1ml continue to stir 3 hours after solution becomes gets thickness, transfers to diameter 35mm, in the silica dish of high 3mm, can obtain the device of transparent and homogeneous, hardness height, gallium solid naphthalocyanine that compactness is good dry 2 weeks below 120 ℃ in baking oven.Initial transmission 71%, nonlinear attenuation factor NAF is 18, threshold value is 0.15Jcm
-2, maximum anti-laser ability can reach 30Jcm
-2
The optical physics performance test of the naphthalene phthalocyanine solid state device that embodiment 4,7 and 12 obtains is as follows:
The mensuration of solid state device absorption spectrum records on Hatichi 3010 spectrometers, incident light is shone directly on the sample, and compare as a reference with the special quartz cell of a same size.The Q band of comparing under the absorption spectrum that obtains and the solution is absorbed with certain red shift, shows that the solid state device of naphthalene phthalocyanine has lower S
1The attitude energy level helps the generation of ISC more.Fluorescence spectrum records on the HatichiF-4500 fluorescence spectrophotometer, and the measurement of fluorescence lifetime records on Edinburgh FL900 spectrometer with the single photon counting technology.The transient absorption spectra of nanosecond is by Nd:YAG ps pulsed laser and ns pulsed laser systematic survey, the triplet state quantum yield of the naphthalene phthalocyanine solid state device that obtains and the triplet lifetime triplet lifetime under the solution.For the naphthalocyanine device of gallium, indium, tin, their triplet state quantum yields are respectively 0.83,0.95,0.95, be dispersed in THF solution in 0.70,0.88,0.90 compare, be significantly improved.Their triplet lifetime are respectively 116.4 microseconds, 17.3 microseconds, 28.2 microseconds, compare with 89.9 microseconds, 6.7 microseconds, 11.2 microseconds of solution, also are significantly improved.These parameters have shown that all naphthalene phthalocyanine solid state device has the condition that produces good optical limiting properties.
Claims (5)
1. solid naphthalocyanine device with optical limiting properties is prepared by following method:
Ethyl orthosilicate, glycidol ether propyl trimethoxy silicane, analysis straight alcohol and acidic aqueous solution are joined in the reactor, after stirring 2～3 hours under the condition of closed reactor, opening reactor again continues to stir 1～2 hour, add naphthalene phthalocyanine solution then, stirring becomes behind the thickness mixed liquor, the mixed liquor of the thickness that becomes is transferred in the mould, and take out dry back, makes the solid naphthalocyanine device with optical limiting properties;
Described ethyl orthosilicate: glycidol ether propyl trimethoxy silicane: analyze straight alcohol: acidic aqueous solution: the volume ratio of naphthalene phthalocyanine solution is 1: 1～10: 0～2: 0.5～2: 0.2～1;
The pH value of described acidic aqueous solution is 0～3;
The concentration of described naphthalene phthalocyanine solution is 5 * 10
-6Mol/L～4 * 10
-3Mol/L;
The structure of described naphthalene phthalocyanine is:
Wherein, M is Ga, In or SnCl; R is to 2-methyl-2-phenylpropane oxygen base.
2. the solid naphthalocyanine device with optical limiting properties according to claim 1 is characterized in that: described ethyl orthosilicate: the glycidol ether propyl trimethoxy silicane: analyze straight alcohol: acidic aqueous solution: the volume ratio of naphthalene phthalocyanine solution is 1: 5: 2: 2: 0.2～1.
3. the solid naphthalocyanine device with optical limiting properties according to claim 1 is characterized in that: the solvent that dissolves described naphthalene phthalocyanine is CH
2Cl
2
4. the solid naphthalocyanine device with optical limiting properties according to claim 1 is characterized in that: described acid is hydrochloric acid, sulfuric acid or acetic acid.
5. the solid naphthalocyanine device with optical limiting properties according to claim 1 is characterized in that: described drying is vacuum drying, and baking temperature is 60 ℃～120 ℃.
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| CN103275089B (en) * | 2013-06-12 | 2015-08-05 | 长春理工大学 | Single hydroxy ethoxy asymmetric chloro indium metal phthalocyanine and preparation method thereof and application |
| CN107219704A (en) * | 2016-03-21 | 2017-09-29 | 中国科学院理化技术研究所 | With D- π-A- π-D structures cyano group substitution talan analog derivative as two-photon optical limiting materials application |
| CN108822260B (en) * | 2018-04-27 | 2019-12-31 | 江西理工大学 | Aggregation-free phthalocyanine grafted MA-VA polymer optical amplitude limiting material and preparation method thereof |
| CN112159519B (en) * | 2020-09-24 | 2021-07-06 | 中国科学院长春光学精密机械与物理研究所 | Porous poly-phthalocyanine laser protection material with carbon bridging and preparation method thereof |
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| US6620863B1 (en) * | 1998-04-10 | 2003-09-16 | The United States Of America As Represented By The Secretary Of The Air Force | Optical element of light limiting dopant distributed in viscoelastic host material |
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Non-Patent Citations (2)
| Title |
|---|
| Shuangqing Wang ET AL.Optical-Limiting and Photophysical Properties of Two Soluble Chloroindium Phthalocyanines with α-and β-Alkoxyl Substituents.ChemPhysChem.2006,7935-941. * |
| 王双青.甘泉.沈淑引.许慧君.杨国强.一种可溶性氯铟酞菁化合物的光限幅性能研究.化学学报.2004,62(22),2209-2212. * |
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