TWI323298B - Method for producing highly arrayed alox-zno nanorods - Google Patents

Description

1323298 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for preparing a highly array-arranged alumina-zinc oxide composite nanowire, in particular to produce an alumina-zinc oxide naphthalene having blue light characteristics. Low temperature process of rice noodles. [Prior Art] Since zinc oxide is a direct energy gap semiconductor with a wide energy gap (about 3.37 eV) and a high exciton binding energy (about 60 meV), it can be self-issued by doping into appropriate elements. The three primary colors, and the advantages of low material prices, are very suitable as luminescent materials and ultraviolet lasers. However, due to the excessive problems of its material properties, its luminescent properties have become difficult to control. Therefore, many recent studies in the scientific community have focused on how to stably control the luminescence of zinc oxide, such as World Patent Organization No. WO20041 1 4422. The prior art, such as U.S. Patent Publication No. US20030523 No. 8 and Japanese Patent No. JP7262801. In contrast, at present, the aluminum doping into the oxygenated zinc nanowire or the nanorod can be roughly divided into two major systems. The first is the physical method 'in addition to the hydrothermal method, which has its advantages and disadvantages. In terms of physical processes such as MOCVD, PVD and Vapor-liquid-solic UVLS, there are quite a few studies and reports, but they all must have high energy (temperature) and special process environment. In order to react and form, on the other hand, it is a synthetic reaction involving a liquid phase solution. Most of it involves a lower energy transfer process such as hydrolysis and hydration, so it can react at a lower temperature. However, this method cannot The alumina-zinc oxide composite nanowire with high brightness blue 5 1323298 light nature is produced, so it is impossible to have significant industrial price. Therefore, in the preparation of the alumina-zinc oxide composite nanowire or the nanorod, the above-mentioned improvement space exists. [Summary of the Invention]

In view of the prior art in the preparation of alumina-zinc oxide composite nanowires or nanorods, the main object of the present invention is to disclose that it can be applied to any substrate such as plastic, ruthenium or oxide at low temperatures. The process of producing a highly array-arranged alumina-zinc oxide (ZnO) nanowire or nanocolumn can be used to complete the alumina-zinc oxide nanowire which has superior characteristics over the prior art and is excited by light. The optical spectrum (PL) further shows that the invention can effectively reduce the essential ultraviolet region signal (UV peak @ 377 nm) after rapid annealing treatment, so that the optical properties of the zinc oxide nanowire are improved, and the radiation is very good. Strong blue light. The second object of the present invention is to disclose that the alumina-zinc oxide nanowire which can be produced by the low-temperature aqueous solution process has surface defect characteristics, and can be applied by using other ions such as manganese, magnesium, and plasma. Such as green light, red light and other spectrum of light. Briefly, the present invention is combined with the simple liquid phase solution method, and is combined with an aqueous solution degumming method for alumina on a zinc oxide nanowire or a nanorod to form a composite nanomaterial and has a high Brightness and high purity blue light characteristics. [Embodiment] - First, a zinc oxide film was deposited on a germanium substrate by a radio frequency magnetron plating machine, and the target was zinc oxide having a purity of 99.99%. The substrate is first cleaned by a general semiconductor program and then placed in a cavity. The best sputtering conditions are substrate temperature 50-C, AC 6 1323298 power 50W, sputtering pressure 10mTorr, and sputtering time 40 minutes. Thereafter, the ruthenium substrate covered with the zinc oxide film was placed in a glass bottle containing 0.005 M aqueous solution of nitrate (Zn(N03)2 6H20) and hexamethylenetetracarboxylic acid (C6H, 2N4, HMT), followed by maintenance in an oven. 5, 1 hour growth of zinc oxide

Nano line. The substrate was then taken out, rinsed with water and dried at room temperature, and as expected, grown in a line of zinc oxide nanowires. In the second step, the alumina degumming solution is prepared. First, add 1.5 g of A1(N03)3 to l〇ml of deionized water, then add ammonia water to control the crucible to 1 〇, shake and mix evenly to produce solidification. Then, the solidified body is centrifugally washed several times, and then added to 100 ml of water, and the pH is adjusted to 6.0 to 7.0 by adding dilute ΗΝ〇3, and the dissolving solution is prepared. In the third step, the previous zinc oxide nanowire is added to the degumming solution and allowed to stand for a few seconds to produce the A10x-Zn0 composite nanowire. In order to more clearly show the various stages of the present invention, please refer to FIG. It is a scanning electron micrograph (SEM) of a zinc oxide nanowire placed in a degumming solution of different pH 。. Figure 1 (a) shows the zinc oxide nanowires which are not placed in the degumming solution. Figure 1 (b) shows the zinc oxide nanowire placed in a degumming solution between pH = 4 and 6. The figure shows the case where the zinc oxide nanowire is eroded and polymerized, and has been converted into nanoparticle. (as shown), it is approximately 10-20 nm in diameter. Figure 1 (c) is to place the zinc oxide nanowire in the degumming solution between pH 6.0 and 7.0, as shown in the figure, so that the aluminum oxide film can be attached to the highly arrayed zinc oxide nanowire or The column of nanometers is on the surface and perpendicular to the substrate. Next, please refer to Figure 2, which is an alumina film attached to a zinc oxide nanowire. 7 1323298

A high-resolution transmissive electron micrograph of the cross-section, from which it can be seen that the diameter of the zinc oxide nanowire is about 20 nm, and the thickness of the oxidized film attached to it is about 7 nm, which is an electron microscope of the zinc oxide nanowire. The periodic structure and the diffraction pattern can be judged that this is a high-crystal single crystal nanowire with a growth direction of [0002], and the aluminum oxide film layer has an amorphous phase structure and covers the entire zinc oxide nanowire. Moreover, there is no structure that destroys the original zinc oxide nanowire. Elemental analysis (EDS) was performed on the zinc oxide nanowire and the aluminum oxide thin film layer, respectively. The elemental analysis of the zinc oxide nanowire has only a very weak aluminum signal. However, elemental analysis of the thin film layer reveals a small amount of zinc oxide signal. However, the aluminum signal is very obvious, so it can be obtained. It is known that the film layer is a non-metered aluminum oxide film. Next, please refer to Figure 3, which is Fourier transform infrared spectroscopy (Fourier

Transform Infrared Spectroscopy (FTIR map), the key points represented by the important peaks, are shown on the graph. Among them, aluminum ions easily form A1-OH2+ in an acidic aqueous solution, and the ion group is easy to attract each other with Ν03· 馨 in an aqueous solution, and NO, the ion group is easily adsorbed on the surface of the zinc oxide material in an aqueous solution, so under an acidic solution 'Easy to form a layer of aluminum oxide film, but in an acidic solution (PH <6)' has a very strong nitrate ion signal, and when the zinc oxide nanowire is placed in this PH solution, it will be rotted * Eclipse, so, by the results of SEM (Fig. 1(b)), there is no way to see the complete - zinc oxide nanowire. However, when the zinc oxide nanowire was placed at a pH of 6 to 7, it was found to be less likely to be corroded, so that a highly array-arranged A10x-Zn0 composite nanowire was formed. While PH=8~9, the aluminum ion is easily shaped into an ion group of A1-OH, and it is not easy to form a film adsorbed on the zinc oxide nanowire.

Next, Fig. 4 to Fig. 6 illustrate how to find the operating conditions for the rapid annealing heat treatment of the optimum atmosphere, and at the same time, Fig. 4 is a photoluminescence spectrum of the zinc oxide nanowire grown by the aqueous solution method. It can be seen that when the As-grown ZnO nanorods are not heat treated, the intrinsic characteristic light (380 nm) is rather weak, while the peak in the green band (550 nm) is stronger. However, when subjected to oxygen heat treatment at 600 ° C, the essential light wave band becomes very strong and sharp, while the green light band is almost absent. But did not see any band of blue light. Figure 5 and Figure 6 show that the A10x-Zn0 nanowire is held at 200, 400, 600, 800 °C for 20 minutes under nitrogen and oxygen, and after rapid annealing heat treatment, it is directly taken out and cooled to room temperature. Photonescence spectrum. It can be seen from the figure that whether it is treated under nitrogen or oxygen, it can be seen that the zinc oxide has an intrinsic luminescence of 3.78~3 8 2 nm, which indicates the structure of zinc oxide even after heat treatment. It has not changed, and the green-yellow light (in the band around 550 nm) emitted by the oxygen vacancy of the zinc oxide nanowire is also due to the ZnO nanowire through eight 10) [coating and heat treatment) , obviously drops, weak to almost invisible, greatly improving optical quality. However, under nitrogen treatment (Fig. 5), it can be seen that when the A10x-ZnO nanowire has a heat treatment temperature above 200 °C, a weak blue light signal (450 nm) can be seen. Under the oxygen treatment, as shown in Figure 6, it can be found that the 9 1323298 A10x-Zn0 nanowire is under oxygen. As the heat treatment temperature increases, the blue-band signal (450 nm) gradually increases, and at 600 ° C, it is obvious. And very sharp blue peaks. This means that under this heat treatment temperature condition, A10x has reacted with the ZnO nanowire to emit this strong blue light. It also proves that we successfully use the low temperature aqueous solution process, supplemented by the atmosphere rapid annealing heat treatment, and grow out to emit Alumina-zinc oxide composite nanowires with blue-light characteristics and a highly directional array of nanostructures.

In summary, the present invention is synthesized by a simple chemical solution, and is combined with an aluminum ion degumming aqueous solution and subjected to rapid annealing heat treatment to prepare an aluminum oxide-zinc oxide composite nanowire structure having blue light characteristics. The alumina-zinc oxide composite nanowire or nanorod can further develop a blue ZnO nanocomponent to be applied to a field-type light-emitting device of high power and high purity light. Therefore, the present invention has considerable innovation and progress, and is also highly industrially applicable, so please grant a patent. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a) to Fig. 1 (c) are scanning electron micrographs (SEM) of the process of the present invention. Figure 2 is a high resolution transmission electron microscope image of the present invention. Fig. 3 is a Fourier transforming infrared spectroscopy (FTIR) of the present invention. - Figure 4 is a Photoluminescence spectrum of a zinc oxide nanowire grown by an aqueous solution method. Figure 5 and Figure 6 show the photon excitation light of the present invention respectively.

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Claims (1)

Yueqiang (3⁄4正本'' ________ί X. Patent application scope: 1. A method for preparing a highly array-arranged alumina-zinc oxide composite nanowire comprising the following steps: (1) plating a zinc oxide film a polymer or a substrate of ruthenium, placed in a metal salt-based chemical degumming solution containing Ζn ions, and grown at a low temperature to form a zinc oxide nanowire or a nano column, thereby making a nanowire or a nanocolumn Standing upright on the substrate; (2) placing the zinc oxide nanowire or nano column in a degumming solution containing Α1 ions, and then rapidly annealing and heat treatment in different atmospheres to prepare a highly array type Arranged alumina-zinc oxide composite nanowire or nanorod. 2. Preparation method of high-array-arranged alumina-zinc oxide composite nanowire as claimed in claim 1 The nanowire is subjected to rapid atmosphere heat treatment annealing to reduce the visible light radiation intensity of the zinc oxide nanowire, thereby improving optical properties and producing intense blue light properties, which have a wavelength of about 450 nm. A method for preparing a highly array-arranged alumina-zinc oxide composite nanowire according to claim 1, wherein the substrate may be a ruthenium substrate, a plastic, a metal, a glass, an oxide, a ruthenium to a V, and a II to VI. 4. A method for preparing a highly array-arranged alumina-zinc oxide composite nanowire according to claim 1, wherein the metal salt chemical solution containing Ζη ions may be zinc nitrate (Ζη(Ν〇) 3)2·6Η2〇), zinc chloride or zinc acetate. 12 132329.8 IC 9 5. A method for preparing a highly array-arranged alumina-oxygen-zinc composite nanowire according to the scope of claim i, wherein The optimum temperature for the zinc oxide nanowire or nano-column process is 55 ° C to 95 ° C. 6. High-array array of alumina-oxygen, zinc-zinc composite nanowires as in Patent Application No. 1. The preparation method, wherein the zinc oxide nanowire or the nanometer column has a growth time of from 1 minute to 100 hours. 7. A highly array-arranged alumina-zinc oxide composite nanoparticle as in the scope of claim 1 Method for preparing a wire, The zinc oxide nanowire or the nanometer column can have a growth angle of 0 to 90 degrees with respect to the substrate. 8. A highly array-arranged alumina-zinc oxide composite nanowire as in the scope of claim 1 The preparation method, wherein the zinc oxide nanowire or nano column, the diameter may be from 10 nm to 1 〇〇〇nm, and the length may be 10 to 100 times the diameter. 9. As in the scope of claim 1 A method for preparing a highly array-arranged alumina-zinc oxide composite nanowire, wherein the aqueous solution contains an A1 Φ metal ion chemical solution, which may be Al(N〇〇3, Al(CH3COO)3 or A1C1 3 0 1 0 The method for preparing a highly array-arranged alumina-zinc oxide composite nanowire according to claim 1, wherein the atmosphere heat treatment temperature is 400 ° C to 800 ° C, and the atmosphere may be N 2 , 〇 2, H 2 /N2 or vacuum. 1, 1 . A method for preparing a highly array-arranged alumina-zinc oxide composite nanowire as claimed in claim 1, wherein the aqueous solution soaking treatment time can be from 1 second to 10 hours. 13 1323298 12, as in the application of the patent paradigm _ 1 high array of oxidized Ming · zinc oxide composite nanowire preparation method 'in which the nanowire growth method and individual processes, can also use other Ions, such as: Mg, Mn, Ga, 'Ge, etc., emit different spectra, which can be green or red. 14