CN101368294B - Surface finished zinc oxide nanometer stick array and preparation method thereof - Google Patents
Surface finished zinc oxide nanometer stick array and preparation method thereof Download PDFInfo
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- CN101368294B CN101368294B CN2007101203215A CN200710120321A CN101368294B CN 101368294 B CN101368294 B CN 101368294B CN 2007101203215 A CN2007101203215 A CN 2007101203215A CN 200710120321 A CN200710120321 A CN 200710120321A CN 101368294 B CN101368294 B CN 101368294B
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Abstract
The invention discloses a ZnO nano-rod array with the surface modified by organic functional molecules and a preparation method thereof. The preparation method is characterized in that the ZnO nano-rod array is dipped in organic solution of organic molecules and the ZnO nano-rod array is obtained after leaching and drying. The preparation method is simple and convenient and post-treatment is simple; the materials are easy to preserve; the ZnO nano-rod array can be directly prepared on various substrates and can be produced in large scale. The ZnO nano-rod array is widely applicable in piezoelectricity, field emission, field effect transistors, solar cells, electric switches, sensors and the like.
Description
Technical field
The present invention relates to a kind of nanometic zinc oxide rod array and preparation method thereof, particularly relate to nanometic zinc oxide rod array of a kind of finishing functional organic molecule and preparation method thereof.
Background technology
The present invention relates to the inorganic-organic hybridization material, cause extensive concern (Ahmad, Z. owing to its special morphological structure makes it have excellent mechanics, calorifics, electricity and optical property; Sarwar, M.I.; Mark, J.E.Mater Chem, 1997,7,259; Lan, T.; Pinnavaia, T.J.Chem.Mater.1994,6,2216; Sanchez, C.; Alonso, B.; Chapusot, F.Sol-gel Sci﹠amp; Tech, 1994,2,161.).The inorganic-organic hybridization material has the advantage of organic materials, as: molecule and energy state structure can manually design, photoelectric efficiency height, the fast and molecular flexibility of response, the advantage that also has inorganic materials, features such as mutability as electronic structure diversity, hot photochemical stable, composition and performance, realized having complementary functions and cooperate optimization of inorganic-organic materials, can the more excellent functional materials of obtained performance, be the focus and the forward position of present material research.The inorganic-organic hybridization material at first by sol-gel method preparation (US Pat[P] .4102 696, DOS273490, DOS2734692, Bayer AG.), continuous development through recent two decades has obtained the achievement that attracts people's attention, and its synthetic method has obtained continuous improvement and perfect.Up to now, the inorganic-organic hybridization preparation methods mainly contains following several: sol-gel method, original position dispersion copolymerization method, graft process, (Eusworkth, U.W. such as blending method; Novak, B.M.J.Am.Chem.Soc.1991,113,7542; Okamoto, M.; Morita, S.Ploymer, 2000,41,3887; Wu, J.; Lerner, M.Chem.Mater.1993,5,835; Giannelis, E.P.Adv.Mater.1996,8,29.).
Zinc oxide is a kind of novel direct II-VI family semiconductor material with wide forbidden band, and stable phase at normal temperatures is hexagonal wurtzite structure, and its energy gap is 3.37eV under the room temperature, and exciton bind energy is 60meV (OzgurU, A.; Liu, C.J Appl.Phys.2005,98,041301; Klingshim C.Phys.Stat.Sol.B, 1975,71,547.).These excellent specific properties that zinc oxide had, it is had very widely at numerous areas uses: for example, can be used as display device of piezoelectric, transparent conductive film, thin film type gas-sensitive sensor, luminescent material, surface acoustic wave element, hetero junction laser diode, ultraviolet laser and short wavelength or the like (Wenas, W.W.; Yamada, A.; Takahashi, K.Appl.Phys.1991,70,7119; Ohta, H.; Kawamura, K.; Orita, M.Appl.Phys.Lett., 2000,77,475.).The potential using value of zinc oxide at aspects such as photodiode, field effect transistor, piezoelectric device, transmitters also is subjected to people and pays close attention to (Goldberger, J. widely; Sirbuly, D.J.; Law, M.; Yang, P.D.J.Phys.Chem.B 2005,109, and 9; Law, M.; Sirbuly, D.J.; Johnson, J.C.; Goldberger, J.; Saykally, R.J.; Yang, P.D.Science 2004,305, and 1269; Kong, X.Y.; Ding, Y.; Yang, R.; Wang, Z.L.Science 2004,303, and 1348; Zou, B.S.; Volkov, V.V.; Wang, Z.L.Chem.Mater.1999,11,3037.Ng, H.T.; Han, J.; Yamada, T.; Nguyen, P.; Chen, Y.P.; Meyyappan, M.Nano.Lett.2004,4,1247; .Bonanni, M.; Spanhel, L.; Lerch, M.; Fuglein, E.; Muller, G.; Jermann, F.Chem.Mater.1998,10,304; Banerijee, D.; Ren, Z.F.; Jo, S.H.Adv.Mater.2002,16,2028; Sharma, P.; Sreenivas, K.Appl.Phys.Lett.2002,83,3615.).
At room temperature, the fluorescence spectrum of zinc oxide comprises two emission bands (Fonoberov, V.A.; Balandin, A.A.Appl.Phys.Lett.2004,85,5971; Lim, J.M.; Shin, K.C.; Kim, H.W.; Lee, C.M.J.Lumin.2004,109,181.).An emission band is positioned at ultraviolet region, and this is the intrinsic emission band (UE) of zinc oxide; Another emission band is positioned at visible region, is because the VISIBLE LIGHT EMISSION band (VE) that different types of defective causes.Studies show that dissimilar defective correspondences luminous (Wu, the J.-J. at the visible region different positions; Liu, S.-C.J.Phys.Chem.B 2002; 106,9546; Kroger, F.A.; Vink, H.J.J.Chem.Phys.1954,22,250; Prosanov, I.Y.; Politov, A.A.Inorg.Mater.1995,31,663; Hahn, D.; Nink, R.Physik.Cond.Mater.1965,3,311; Liu, M.A.; Kitai, H.; Mascher, P.J.Lumin.1992,54,35; Zhao, Q.X.; Klason, P.; Willander, M.H.; Zhong, M.; Lu, W.; Yang, J.H.Appl.Phys.Lett.2005,87,211912.).
All the time, people are devoted to explain defective and its relation luminous in visible-range in the zincite crystal always.Meanwhile, people also wish by the defective in the controlled oxidation zinc, regulate its luminous intensity and position in visible-range.In nearest report, the condition that the researchist quenches by control has been regulated zinc oxide in ultraviolet, emission (Wang, Z. in gold-tinted and the green range; Lin, C.; Liu, X.; Li, G.; Luo, Y.; Quan, Z.; Xiang, H.; Lin, J.J.Phys.Chem.B 2006,110, and 9469.).Zinc oxide material can also excite light intensity or control polarizability to be regulated (Hsu, N.E. by change in the intensity of ultraviolet region and visible region emission; Hung, W.K.; Chen, Y.F.J.Appl.Phys.2004.96,4671; Shi, W.S.; Cheng, B.; Zhang, L.; Samulski, E.T.J.Appl.Phys.2005,98,083502.).
Summary of the invention
The purpose of this invention is to provide nanometic zinc oxide rod array of a kind of finishing organic molecule and preparation method thereof.
The method of the nanometic zinc oxide rod array of preparation finishing organic molecule provided by the invention is that nanometic zinc oxide rod array is soaked in the organic solution of functional organic molecule, through drip washing, drying, promptly obtains described nanometic zinc oxide rod array.
Wherein, functional organic molecule is the derivatives of porphyrin of formula IA structure, the oligomerization phenylene ethylene derivative of formula IB structure,
(formula IA) (formula IB)
Among the formula IA, R
1Be carboxyl or hydrogen atom, R
2Be carboxyl, hydroxyl or sulfydryl; R is the C3-C18 alkyl among the formula IB, R
3Be carboxyl, ester group or hydrogen atom, R
4Be carboxyl.Preferably, derivatives of porphyrin is 5,10,15,20-four (4-carboxyl phenyl)-porphyrin, 5,10,15,20-four (3-carboxyl-4-hydroxy phenyl)-porphyrin; Described oligomerization phenylene ethylene derivative is 1-(4-carbamoyl methyl base styryl)-4-(4-carboxyl styrene thiazolinyl)-2,5-two octane-iso oxygen base benzene, 1,4-two (4-carboxyl styrene thiazolinyl)-2,5-two hot alkoxy benzenes.
In preparation process of the present invention, the concentration of the organic solution of used functional organic molecule is 1 * 10
-6-1 * 10
-4Mol/L; Be preferably 1 * 10
-4Mol/L.The solvent of organic solution is methyl alcohol, ethanol, tetrahydrofuran (THF); Be preferably methyl alcohol.Soaking the used time is 12-96h; Be preferably 48h.The used leacheate of drip washing is methyl alcohol, ethanol, tetrahydrofuran (THF); Be preferably methyl alcohol.
Compare with nanometic zinc oxide rod array; the nanometic zinc oxide rod array of the finishing organic molecule that obtains according to above-mentioned preparation method; its ultraviolet-visible spectrum and fluorescence intensity all change, and have the characteristic that can regulate, also belong to protection scope of the present invention.
Preparation method of the present invention is simple and easy to do, can directly prepare on various substrates, and last handling process is simple; The zinc oxide nano array of prepared finishing organic molecule is easy to preserve, and can carry out big area production, can be widely used in aspects such as piezoelectricity, an emission, field-effect transistor, solar cell, electric switch, transmitter.
Description of drawings
Fig. 1 is the uv-visible absorption spectra of the nanometic zinc oxide rod array of finishing organic molecule of the present invention.Wherein, Fig. 1 a is the nanometic zinc oxide rod array that TCPP modifies; Fig. 1 b is the nanometic zinc oxide rod array that TCHPP modifies; Fig. 1 c is the nanometic zinc oxide rod array that OPV1 modifies; Fig. 1 d is the nanometic zinc oxide rod array that OPV2 modifies.
Fig. 2 is the stereoscan photograph (SEM) of nanometic zinc oxide rod array of the present invention.Wherein, Fig. 2 a, Fig. 2 b are at the epontic nanometic zinc oxide rod array of quartz plate; Fig. 2 c is the nanometic zinc oxide rod array that TCPP modifies; Fig. 2 d is the nanometic zinc oxide rod array that TCHPP modifies; Fig. 2 e is the nanometic zinc oxide rod array that OPV1 modifies; Fig. 2 f is the nanometic zinc oxide rod array that OPV2 modifies.
Fig. 3 is the stereoscan photograph (SEM) of nanometic zinc oxide rod array of the present invention.Wherein, Fig. 3 a is the nanometic zinc oxide rod array that TCPP modifies; Fig. 3 b is the nanometic zinc oxide rod array that TCHPP modifies.
Fig. 4 is the uv-visible absorption spectra of the nanometic zinc oxide rod array of finishing organic molecule of the present invention.Wherein, Fig. 4 a is the nanometic zinc oxide rod array that TCPP modifies; Fig. 4 b is the nanometic zinc oxide rod array that TCHPP modifies.
Fig. 5 is the variation relation figure of the fluorescence of the nanometic zinc oxide rod array modified of derivatives of porphyrin of the present invention with the hydridization time.Fig. 5 a is TCPP; Fig. 5 b is TCHPP.Solid black lines is the fluorescence intensity of the nanometic zinc oxide rod array for preparing among the figure on quartz substrate, and direction shown in the arrow be the variation tendency of prolongation (measurement in the per 24 hours once) fluorescence spectrum with soak time.
Embodiment
The present invention prepares the method for the nanometic zinc oxide rod array of finishing organic molecule, is nanometic zinc oxide rod array is soaked in the organic solution of functional organic molecule, through drip washing, drying, promptly obtains described nanometic zinc oxide rod array;
Among the above-mentioned preparation method, functional organic molecule is the organic molecule that contains functional groups such as carboxyl, hydroxyl, sulfydryl, and is more common, and derivatives of porphyrin (formula IA) and oligomerization phenylene ethylene derivative (formula IB) are arranged:
(formula IA) (formula IB)
Among the formula IA, R
1Be carboxyl or hydrogen atom, R
2Be carboxyl, hydroxyl or sulfydryl; Among the formula IB, R is C3-C18 alkyl (straight chain or side chain), can be used for increasing the solvability of organic molecule, R
3Be carboxyl, ester group or hydrogen atom, R
4Be carboxyl.
Preferably, derivatives of porphyrin is 5,10,15,20-four (4-carboxyl phenyl)-porphyrin (TCPP), 5,10,15,20-four (3-carboxyl-4-hydroxy phenyl)-porphyrin (TCHPP); Oligomerization phenylene ethylene derivative is 1-(4-carbamoyl methyl base styryl)-4-(4-carboxyl styrene thiazolinyl)-2,5-two octane-iso oxygen base benzene (OPV1), 1, and 4-two (4-carboxyl styrene thiazolinyl)-2,5-two hot alkoxy benzenes (OPV2), its structure is as follows:
The solvent that is used to dissolve these functional organic molecules has methyl alcohol, ethanol, tetrahydrofuran (THF) etc., is preferably methyl alcohol.The concentration of functional organic molecule is 1 * 10
-6-1 * 10
-4Mol/L, preferred 1 * 10
-4Mol/L.The soak time of the used array of the present invention in organic solution is 12-96h, preferred 48h.The used leacheate of drip washing step has methyl alcohol, ethanol, tetrahydrofuran (THF) etc., is preferably methyl alcohol.
The present invention regulates the intensity of fluorescence of nanometic zinc oxide rod array at visible region and ultraviolet region by the method for chemically modified, its principle is: by tetracarboxylic porphyrin and four salicyl porphyrins the absorption of zinc oxide surface and with the synergy of the complexing of zinc, produce the zinc defective on the nanometic zinc oxide rod array surface.Change the method for soak time, be controlled at the amount that zinc oxide surface produces defective, thereby reach the effect that the fluorescence of nanometic zinc oxide rod array is regulated.Wherein the difference of the functional group of modified porphyrin molecule has very big influence to the regulating effect of this fluorescence, for example, the porphyrin molecule and the zinc oxide nano rod that contain the Whitfield's ointment group have strong complexing action, so regulate the best results of the fluorescence of nanometic zinc oxide rod array with it.
Utilize the ultraviolet-visible fluorescence spectrum to judge the situation that combines of zinc oxide nano array and functional organic molecule; The configuration of surface of utilizing scanning electron microscope (SEM) to observe the growing state of zinc oxide nano array, configuration of surface and modify organic functional molecular nano-array afterwards; Utilize fluorescence spectrum to analyze the fluorescence of zinc oxide nano array.When measuring, zinc oxide nano array can be directly used in the test of ultraviolet-visible spectrum; Behind the substrate metal spraying with zinc oxide nano array, be bonded on the sample table, can carry out the test of SEM with conductive resin.
Wherein, used nanometic zinc oxide rod array can be according to document (Feng, X.; Feng, L.; Jin, M.; Zhai, J.; Jiang, L.; Zhu, D.J.Am.Chem.Soc.2004,126,62.) reported method is prepared, and main synthesis step is:
Zn (OAc) with 1.10 grams (5mmol)
22H
2O is dissolved in the 50ml boiling ethanol, then solution is cooled to room temperature, separates out white little crystal anhydrous Zn (OAc)
2Again this solution is cooled to 0 ℃.Other gets 0.29 gram (7mmol) LiOHH
2Be dissolved under the O room temperature in the 50ml ethanol, its dissolving of ultrasonic quickening is cooled to 0 ℃, and this alkaline solution is dropwise added above-mentioned Zn (OAc) under 0 ℃ of strong mixing
2In the solution.Bleach when solution is about 0.1 gram in the LiOH residual content.Solution stirred 6 hours down at 0 ℃.Take out part solution, precipitate with the normal hexane of 2 times of amounts, the centrifugal white zinc oxide that promptly obtains is scattered in the ethanol after washing once with normal hexane again.Even with the Zinc oxide nanoparticle particle diameter that this method makes, about 3～4nm.Aforementioned zinc oxide colloid evenly is spun on the quartz plate of cleaning, and quartz plate was annealed 2 hours in 400 ℃ of following air, get final product the quartz plate that evenly covers of zinc oxide.Vertically put into the aqueous solution that contains 0.01mol/L zinc nitrate and 0.01mol/L hexamethylenetetramine after the cooling, 90 ℃ were heated 3 hours down.Be attached with the translucent thing of one deck white on the quartz plate, wash repeatedly to remove the unnecessary ion and the ammonium salt of absorption, promptly obtain nanometic zinc oxide rod array with deionized water.
TCPP, TCHPP, these four kinds of organism of OPV1, OPV2 can be according to document (Gauuan, P.J.F.; Trova, M.P.; Boros, L.G.; Bocckino, S.B.; Crapo, J.D.; Day, B.J.Bioorg.﹠amp; Med.Chem.2002,10,3013; Campbell, W.T.; McDosald, N.R.J.Org.Chem.1959,24,1246.) reported method is prepared.
Wherein, the synthesis step of porphyrin molecule (TCPP) is: with 4-methoxycarbonyl benzaldehyde (7.6g, 46.2mmol) and the pyrroles (3.2mL 46.2mmol) is dissolved in the dry CHCl of 1200mL
3In, nitrogen protection continues to stir the diethyl ether solution that adds the 0.1mL boron trifluoride after 30 minutes down.Continue under the room temperature to stir after 2 hours to add the 2.3g tetrachlorobenzoquinone again, reaction is overnight under the lucifuge condition.Concentration of reaction solution is eluent with the chloroform through silica gel column chromatography repeatedly, and obtaining purple crystals 3.4g final the separation.This purple crystals is dissolved in the 30ml ethanol, at the aqueous solution 5ml (mass concentration is 50%) that adds KOH.With reaction solution 60 ℃ down stir 5 hours after, with dilute hydrochloric acid (2N) with the reaction solution neutrality that neutralizes.Again its filtration can be obtained product.
The characterization result of porphyrin molecule (TCPP) is as follows:
1H NMR (400MHz, CD
3OD) δ=8.7 (s, 8H), 8.3 (d, J=8.1Hz, 8H), 7.5 (d, J=8.1Hz, 8H) .-2.6 (s, 2H) .MALDI-TOF MS:m/z:790.7
The synthesis step of porphyrin molecule (TCHPP) is: with 5-formyl radical wintergreen oil (8.3g, 46.2mmol) and the pyrroles (3.2mL 46.2mmol) is dissolved in the dry trichloromethane (CHCl of 1200mL
3) in, nitrogen protection continues to stir the diethyl ether solution that adds the 0.1mL boron trifluoride after 30 minutes down.Continue under the room temperature to stir after 2 hours to add the 2.3g tetrachlorobenzoquinone again, reaction is overnight under the lucifuge condition.Concentration of reaction solution is eluent with the chloroform through silica gel column chromatography repeatedly, and obtaining purple crystals 2.6g final the separation.This purple crystals is dissolved in the 30ml ethanol, at the aqueous solution 5ml (mass concentration is 50%) that adds KOH.With reaction solution 60 ℃ down stir 5 hours after, with dilute hydrochloric acid (2M) with the reaction solution neutrality that neutralizes.Again its filtration can be obtained product.
The characterization result of porphyrin molecule (TCHPP) is as follows:
1H NMR (400MHz, CD
3OD (deuterium-for methyl alcohol)) δ=8.9 (s, 8H), 8.6 (s, 4H), 8.1 (d, J=8.1Hz, 4H), 7.2 (d, J=8.1Hz, 4H) .-2.7 (s, 2H) .MALDI-TOF (mass spectrum) MS:m/z:854.7
Oligomerization phenylene ethylene derivative (OPV1; OPV2) synthesis step is: two phosphatide (0.8g are being housed; 1.07mmol) and 4-methoxycarbonyl benzaldehyde (0.35g; 2.18mmol) tetrahydrofuran (THF) (selecting fresh distillatory for use) (25mL) in the 50mL round-bottomed flask of solution; the adding sodium hydride (52mg, 2.17mmol).Be warmed up to 50 ℃ of reaction solutions and be stirred 30min, some plate monitoring reaction.Subsequently with less water cancellation reaction.Reaction soln is filtered, and direct upper prop separated after decompression was spin-dried for solvent, and eluent is selected sherwood oil: ethyl acetate=2: 1 (v/v).Product is green solid 0.35g.This green solid is dissolved in the 30ml ethanol, at the aqueous solution 5ml (mass concentration is 50%) that adds KOH.With reaction solution 60 ℃ down stir 1 hour after, with dilute hydrochloric acid (2N) with the reaction solution neutrality that neutralizes.Direct upper prop separated after decompression was spin-dried for solvent, and eluent is selected trichloromethane: methyl alcohol=2: 1 (v/v) can obtain OPV1 and OPV2 respectively.
The characterization result of OPV1 is as follows:
1H NMR (400MHz, CD
3Cl) δ=11.7 (s, 8H), 7.8 (d, J=8.3Hz, 4H), 7.6 (d, J=8.3Hz, 4H), 6.82 (s 2H), 7.2 (s 1H), 7.1 (s, 1H), 6.7 (s, 2H), 0.9-1.7 (m, 34H) .MALDI-TOF MS:m/z:640.4.
The characterization result of OPV2 is as follows:
1H NMR (400MHz, CD
3Cl) δ=11.7 (s, 8H), 7.8 (d, J=8.3Hz, 4H), 7.6 (d, J=8.3Hz, 4H), 6.82 (s 2H), 7.2 (s 1H), 7.1 (s, 1H), 6.7 (s, 2H), 0.9-1.7 (m, 34H) .MALDI-TOF MS:m/z:626.6.
Embodiment 1,5,10,15, the preparation of the nanometic zinc oxide rod array that 20-four (4-carboxyl phenyl)-porphyrin (TCPP) is modified
According to above-mentioned document (Feng, X.; Feng, L.; Jin, M.; Zhai, J.; Jiang, L.; Zhu, D.J.Am.Chem.Soc.2004,126,62.) reported method is at quartz substrate (the surface preparation nanometic zinc oxide rod array of 2cm * 2cm).Prepare 50 milliliters of the methanol solutions of organic molecule (TCPP, TCHPP, OPV1 and OPV2) in volumetric flask respectively, concentration is 1 * 10
-4Mol/L.Get 10 milliliters of above-mentioned solution respectively in weighing bottle (25 millimeters * 40 millimeters), the nanometic zinc oxide rod array of preparation is soaked in this solution, after at room temperature leaving standstill 48 hours, take out the quartz plate that soaks, use the surface of a large amount of methanol solution drip washing quartz plates at once repeatedly, in air, make its seasoning then, can obtain the nanometic zinc oxide rod array of finishing organic molecule.
Fig. 1 is the uv-visible absorption spectra figure of gained nanometic zinc oxide rod array.Wherein, Fig. 1 a is the nanometic zinc oxide rod array that TCPP modifies; Fig. 1 b is the nanometic zinc oxide rod array that TCHPP modifies; Fig. 1 c is the nanometic zinc oxide rod array that OPV1 modifies; Fig. 1 d is the nanometic zinc oxide rod array that OPV2 modifies.The uv-visible absorption spectra of the itself when solid line among four figure is all represented nanometic zinc oxide rod array unmodified organic molecule.As known in the figure, with the nanometic zinc oxide rod array after the organic molecule modification, its uv-visible absorption spectra is the stack of the absorption spectrum of the absorption spectrum of zinc oxide and organic molecule, shows that the used organic molecule of the present invention successfully is modified at the zinc oxide nano rod surface.
Fig. 2 is scanning electron microscope (SEM) photo of gained nanometic zinc oxide rod array.Wherein, Fig. 2 a, Fig. 2 b are the photo at the SEM of the epontic nanometic zinc oxide rod array of quartz substrate.This test result shows, the preparation method who provides according to described document, can be on quartz substrate big area growing zinc oxide nanorod arrays regularly, the diameter of zinc oxide nano rod is the 50-100 nanometer, shown in Fig. 2 b.Fig. 2 c to Fig. 2 f is the SEM photo of the nanometic zinc oxide rod array after organic molecule is modified.As seen, modified after the organic functional molecular, the zinc oxide nano rod surface becomes coarse, and diameter is the 50-120 nanometer.
Embodiment 2,5,10,15, the preparation of the nanometic zinc oxide rod array that 20-four (4-carboxyl phenyl)-porphyrin (TCPP) is modified
50 milliliters of the methanol solutions of preparation TCPP in volumetric flask, volumetric molar concentration is 1 * 10
-6Mol/L.Get 10 milliliters of above-mentioned solution in weighing bottle (25 millimeters * 40 millimeters), the nanometic zinc oxide rod array of the quartz substrate that prepared is soaked in this solution, after at room temperature leaving standstill 48 hours, take out the quartz plate that soaks, use the surface of a large amount of methanol solution drip washing quartz plates at once repeatedly, in air, make its seasoning then, promptly can obtain the nanometic zinc oxide rod array of finishing TCPP.
Fig. 3 a is scanning electron microscope (SEM) photo of gained nanometic zinc oxide rod array.Nanometic zinc oxide rod array soaks 48h in the organic solution of this concentration, the no considerable change in surface.UV spectrum shows as the characteristic absorbance of zinc oxide, does not demonstrate the absorption peak of porphyrin.This is because because the volumetric molar concentration of employed TCPP organic molecule is very low, behind 48h with the amount of zinc oxide surface effect seldom, fail to observe spectrographic and change, shown in Fig. 4 a.
Embodiment 3,5,10,15, the preparation of the nanometic zinc oxide rod array that 20-four (3-carboxyl-4-hydroxy phenyl)-porphyrin (TCHPP) is modified
50 milliliters of the methanol solutions of preparation TCHPP in volumetric flask, volumetric molar concentration is 1 * 10
-6Mol/L.Get 10 milliliters of above-mentioned solution in weighing bottle (25 millimeters * 40 millimeters), the nanometic zinc oxide rod array of the quartz substrate that prepared is soaked in this solution, after at room temperature leaving standstill 48 hours, take out the quartz plate that soaks, use the surface of a large amount of methanol solution drip washing quartz plates at once repeatedly, in air, make its seasoning then, promptly can obtain the nanometic zinc oxide rod array of finishing TCHPP.
Fig. 3 b is scanning electron microscope (SEM) photo of gained nanometic zinc oxide rod array.Nanometic zinc oxide rod array soaks 48h in the organic solution of this concentration, the no considerable change in surface.UV spectrum does not demonstrate the absorption peak of porphyrin yet, only shows as the characteristic absorbance of zinc oxide, shown in Fig. 4 b.
Comparing embodiment 1-3 can find, (minimum is 1 * 10 when the concentration of selected organic functional molecular solution is hanged down
-6Mol/L), nanometic zinc oxide rod array soaks 48h in solution, the no considerable change in surface; And improve the concentration of organic functional molecular solution, as 1 * 10
-6-1 * 10
-4Soak nanometic zinc oxide rod array in the solution in the mol/L concentration range, can obtain the nanometic zinc oxide rod array of finishing organic molecule; And concentration increases, and can also reduce the time of immersion.But the maximum concentration of available organic functional molecular is subjected to the restriction of its solubleness, in general, if concentration is higher than 1 * 10
-4Mol/L then in immersion process, has nanometic zinc oxide rod array was separated out and be deposited on to more organic molecule in solution surface, thereby has influence on the surperficial regularity of the nanometic zinc oxide rod array of hydridization.Therefore, the concentration of organic functional molecular solution is with 1 * 10
-6-1 * 10
-4Mol/L is advisable.
Embodiment 4,5,10,15, the nanometic zinc oxide rod array that 20-four (4-carboxyl phenyl)-porphyrin (TCPP) modifies fluorescence regulate
According to the step of embodiment 1, the nanometic zinc oxide rod array of quartz substrate is soaked in respectively in the methanol solution of TCPP, TCHPP.After soaking 24 hours, take out quartz plate, use the surface of a large amount of methanol solution drip washing quartz plates at once repeatedly, in air, directly carry out the test of fluorescence spectrum after the seasoning.After this every immersion repeats one time above-mentioned steps after 24 hours, measure first order fluorescence spectrum, and excitation wavelength is 325nm.
The fluorescence intensity of the nanometic zinc oxide rod array that Fig. 5 modifies for the gained derivatives of porphyrin is with the variation relation figure of hydridization time.Among the figure, a is TCPP; B is TCHPP.Solid black lines is illustrated in the fluorescence intensity of the nanometic zinc oxide rod array for preparing on the quartz substrate among the figure, and direction shown in the arrow is the variation tendency of prolongation (measuring once in the per 24 hours) fluorescence spectrum with soak time.Fluorescence spectrum shows that along with the change of soak time in TCPP, TCHPP solution, the ZnO nanometer stick array is in the ratio considerable change of visible region and ultraviolet region fluorescence intensity.As shown in table 1, with the prolongation of soak time, it is big that the fluorescence intensity ratio of visible region and ultraviolet region becomes, until reaching balance.
Table 1: the fluorescence intensity ratio of different hybrid systems visible regions and ultraviolet region
The variation of nanometic zinc oxide rod array on spectrum of the modification organic molecule of the present invention's preparation shows, can carry out the adjusting of series to the character of this hybrid systems by changing the hydridization time, thereby optimize the application of material at aspects such as piezoelectric, an emission, solar cells.
Claims (11)
1. the preparation method of the nanometic zinc oxide rod array of a finishing functional organic molecule is that nanometic zinc oxide rod array is soaked in the organic solution of functional organic molecule, through drip washing, drying, obtains described nanometic zinc oxide rod array; Described functional organic molecule is the derivatives of porphyrin of formula IA structure or the oligomerization phenylene ethylene derivative of formula IB structure,
(formula IA) (formula IB)
Among the formula IA, R
1Be carboxyl or hydrogen atom, R
2Be carboxyl, hydroxyl or sulfydryl; Among the formula IB, R is the C3-C18 alkyl, R
3Be carboxyl, ester group or hydrogen atom, R
4Be carboxyl.
2. preparation method according to claim 1 is characterized in that: the derivatives of porphyrin of described formula IA structure is 5,10,15,20-four (4-carboxyl phenyl)-porphyrin, 5,10,15,20-four (3-carboxyl-4-hydroxy phenyl)-porphyrin; The oligomerization phenylene ethylene derivative of described formula IB structure is 1-(4-carbamoyl methyl base styryl)-4-(4-carboxyl styrene thiazolinyl)-2,5-two octane-iso oxygen base benzene, 1,4-two (4-carboxyl styrene thiazolinyl)-2,5-two hot alkoxy benzenes.
3. preparation method according to claim 1 is characterized in that: the concentration of the organic solution of described functional organic molecule is 1 * 10
-6-1 * 10
-4Mol/L.
4. preparation method according to claim 3 is characterized in that: the concentration of the organic solution of described functional organic molecule is 1 * 10
-4Mol/L.
5. preparation method according to claim 1 is characterized in that: the solvent of described organic solution is methyl alcohol or ethanol or tetrahydrofuran (THF).
6. preparation method according to claim 5 is characterized in that: the solvent of described organic solution is a methyl alcohol.
7. according to the arbitrary described preparation method of claim 1-6, it is characterized in that: the used time of described immersion is 12-96h.
8. preparation method according to claim 7 is characterized in that: the used time of described immersion is 48h.
9. according to the arbitrary described preparation method of claim 1-6, it is characterized in that the used leacheate of described drip washing is methyl alcohol, ethanol or tetrahydrofuran (THF).
10. preparation method according to claim 9 is characterized in that, the used leacheate of described drip washing is a methyl alcohol.
11. the nanometic zinc oxide rod array of the finishing functional organic molecule that the arbitrary described preparation method of claim 1-10 obtains.
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| CN102034610A (en) * | 2010-09-21 | 2011-04-27 | 上海大学 | Semiconductor zinc oxide thin film surface modification method |
| CN104986794B (en) * | 2015-07-10 | 2016-08-24 | 常州市宏硕电子有限公司 | Nano zine oxide and production technology thereof |
| CN106000471B (en) * | 2016-06-03 | 2018-05-01 | 河南大学 | A kind of zinc oxide-porphyrin core-shell nano rod composite material and preparation method thereof |
| CN106732781B (en) * | 2016-11-11 | 2019-02-22 | 福州大学 | Tetraploid rice/zinc oxide composite membrane nano material primary reconstruction preparation method |
| CN113740389B (en) * | 2021-08-25 | 2023-10-13 | 温州大学 | Zinc oxide nanorod-based field emission hydrogen sensor and preparation method and application thereof |
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