TWI385117B - Production Method of ZnO Nanometer Structure by Liquid Chromatography - Google Patents

Description

Method for manufacturing zinc oxide nanostructure by liquid phase deposition method

The invention relates to a manufacturing method for growing a zinc oxide nanostructure by using a liquid phase deposition method, which has a simplified overall growth structure and can be applied to a solar cell, a gas sensor, a UV light sensor, a photonic crystal, an LED, an optical waveguide. In terms of other aspects, the overall growth system is beneficial to the development of optoelectronic components.

Driven by the development of semiconductors, the size of nanomaterials is becoming a hot trend in the much-anticipated future; and nanotechnology is the use of nanomaterials as various dimensions to assemble their structures into the required structures, and how to use them. This unique nature, overcoming the problems faced by traditional processes, is currently the focus of attention.

Zinc oxide belongs to the hexagonal system (HCP) P63mc symmetrical wurtzite tructure, and its lattice constant is a=3.2539A, c=5.2098A, etc., and the length-to-minor axis ratio is 1.602, which is close to perfect 1.633. Asymmetric crystal structure, with non-metered crystal defects in the structure; zinc oxide has excellent thermal stability, melting point is 1975 ° C, and exciton binding energy is about 60 meV, which is direct Direct bandgap semiconductor, with a gap of about 3.37 eV, is a wide band n-type semiconductor; in terms of functionality, it has high light transmittance, high refractive index, and high voltage, acousto-optic, electro-optical and nonlinear optical coefficients. It has excellent properties in dielectric, piezoelectric, pyroelectric, acousto-optic and electro-optic, and can be widely used in solar cells, gas sensors, UV sensors, photonic crystals, LEDs, and light. In terms of waveguides, etc., it is a highly functional multifunctional material, so in materials There is great potential for development.

There are many methods for synthesizing one-dimensional zinc oxide (ZnO) structures. The most common ones are chemical vapor deposition (CVD), thermal evaporation, and molecular beam epitaxy (Molecular beam). Epitaxy, MBE), physical vapor deposition (PVD), and sputtering.

However, the above methods generally have the following problems: 1. process high temperature; 2. special equipment (high vacuum); 3. complicated experimental procedures; 4. strict experimental conditions; 5. high cost.

Based on this, the inventor of this case has in-depth discussion on the above-mentioned problems of nano growth technology, and he has made improvements and innovations. After years of painstaking research, he finally succeeded in research and development of a liquid crystal deposition method for the growth of zinc oxide nanostructures. method.

The main object of the present invention is to provide a method for manufacturing a zinc oxide nanostructure by liquid phase deposition method, which can obtain a one-dimensional zinc oxide nanocolumn array which has both quality and aspect ratio and is easy to handle length and uniaxial growth. As a result, the zinc oxide nano-pillar array is deposited on a different substrate on a zinc oxide buffer layer, or a seed layer. To good quality standards, the photoelectric components will be better rendered through nanocrystallization.

A second object of the present invention is to provide a system for growing a zinc oxide semiconductor into a one-dimensional nanostructure by liquid phase deposition, in which heterogeneous nucleation is used for heterogeneous nucleation and subsequent crystal growth on a specific substrate. A zinc oxide single crystal nano column having a quality and aspect ratio is formed by forming a homogeneous nucleation reaction by using a zinc oxide buffer layer to solve the interface contact problem and occurring in a supersaturated solution having a low degree of saturation.

The invention provides a method for manufacturing a zinc oxide nanostructure by liquid phase deposition method which is designed for the above purpose, and at least comprises: providing a substrate; depositing a zinc oxide buffer layer on the substrate in a supersaturated solution; A zinc oxide nano column is synthesized from a zinc oxide buffer layer, and the surface of the substrate is used as a heterogeneous nucleation of the zinc oxide nano column; the zinc oxide nano column is grown on the surface of one of the zinc oxide buffer layers. In a super-saturated supersaturated solution, nanocrystals are formed on a specific substrate by means of heterogeneous nucleation, and the key factors of the crystal growth are controlled by the concentration and concentration of the saturated solution in the hydrolysis and precipitation of the metal ions and their complexes. Temperature, ligand, pH, ion tension, etc. are all related. Finally, a one-dimensional zinc oxide nanocolumn array with both quality and aspect ratio, easy to manipulate length and uniaxial growth is obtained.

The method for manufacturing a zinc oxide nanostructure by liquid phase deposition method designed by the present invention, in a super-saturated supersaturated solution, using a heterogeneous nucleation method on a specific substrate (different substrates and materials) Nano-crystals are formed on the surface, and the key factors of crystallization are controlled by the hydrolysis and precipitation of metal ions (Cation) and its complexes, and the concentration of saturated solution, Temperature, ligand, pH value, ionic strength, etc., all of which are related to the quality and aspect ratio, and easy to control the length and uniaxial growth. Dimensional zinc oxide nanopillar array.

Referring to FIG. 1 again, the method for manufacturing the zinc oxide nanostructure by liquid phase deposition method of the present invention is as follows. The detailed composition thereof mainly includes: providing zinc by using zinc salt (Zinc Nitrate Hexahydrate, Zinc Acetate) ²⁺ ions, an alkaline buffer (sodium hydroxide NaOH, ammonia NH ₃ , urotropine HMTA) provides OH ^- , and substrate 1 reacts in a supersaturated solution to form a zinc oxide complex.

A layer of zinc oxide buffer layer is formed on the substrate 1 by a coating spin coater (shown in FIG. 3) or a sputtering RF magnetic controlled sputtering system (shown in FIG. 4). When the zinc oxide nano column is grown, a homogeneous nucleation reaction occurs, which reduces the interface problem and the effect as a seed layer.

The constant temperature oven (8) and the electromagnetic heating stirrer (81) are used to provide the growth energy of the zinc oxide nano column for heating or stirring, and different results are also produced under different parameters, such as different temperatures, stirring speed, heating time, etc. It will affect the morphology, growth rate and crystal direction of zinc oxide nano-pillars.

Finally, the high temperature furnace (4) is used for annealing heat treatment to reduce the occurrence of defects in the zinc oxide nano column, and the recrystallization also makes the crystal face structure more obvious.

Furthermore, the present invention uses the liquid crystal deposition method to grow the zinc oxide nanostructure, and has the technical features. The next step is to use the various instruments and experimental conditions to be explained: the basic process is as follows (eg Figure 1): The substrate 1 is cut into small pieces, and then the test piece is subjected to a basic cleaning process, such as acetone (10 min) → two-stage water (10 min) → methanol (10 min) → two-stage water ( 10 min)→ After drying with nitrogen (as in Figure 1A), a zinc oxide buffer layer is formed on the substrate 1 by coating method 2 or sputtering method (as shown in Fig. 1). B), after the substrate test piece 3 forming the zinc oxide buffer layer is placed in the high temperature furnace 4 to anneal to make the surface morphology more uniform (C in FIG. 1), and the zinc salt-containing solution and the alkaline solution 6 are disposed at the same time. And after mixing the ratio of the zinc salt-containing solution and the alkaline solution 6 (for example, the concentration ratio of 1:10 ^-3 to 40), the mixture is uniformly stirred (as shown in FIG. 1D), and a zinc oxide buffer layer is formed after annealing. 5 on the test strip configured proportions supersaturated solution (as shown in one of E) (such as the range of 1:10 to 40 ^-3 concentration ratio); after dissolution of the sealing 7 Provide energy for growth at different times (0.3~48 hr), stirring rate (0~20 rpm) and temperature (60~95 °C) (heating and stirring for constant temperature oven 8 heating or electromagnetic heating stirrer 81) As shown in Fig. 1 (F)), after a solution reaction time (0.3~48hr), take out the test piece 9 and take it into deionized water to stand and rinse (G in Figure 1). After an hour, it is naturally dried, and finally placed in a high temperature furnace 4 to remove residual solution, and to reduce defects and crystallize, that is, to complete the growth of the nanostructure 10; after using various analytical instruments (such as X- Ray diffraction (XRD) high-resolution X-ray diffractometer, scanning electron microscopy (SEM) scanning electron microscope, and micro-Raman spectroscopy (μRS) micro-Raman spectrometer, photoluminescence (PL) spectrum optical fluorescence spectrometer, transmission Electron microscope (TEM) transmission electron microscope) analysis of measurement results.

Therefore, the growth framework of the present invention mainly utilizes the growth and precipitation of metal ions and their complexes to form zinc oxide crystals (as shown in FIG. 2), and further promotes a method for manufacturing a one-dimensional nanostructure.

Please refer to FIG. 3 and FIG. 4 together. Since the present invention uses a coating machine and a radio frequency magnetic controlled sputtering system to respectively apply a coating method and a sputtering method to form a layer on the substrate 1 during the experiment. When the zinc oxide buffer layer is grown, the coating method is to immerse the substrate 1 in a solution at a fixed rate by using the pulling method 211 (as shown in FIG. 3), and to drop the solution into the solution pattern 212 with the inclined substrate 1, and to apply the solution as a dropper. The substrate 1 is dropped on the substrate 1 by a spin coating method 213, and the solution dropped on the substrate 1 is dispersed on the substrate 1 by centrifugation on the principle of centrifugal force, and the zinc hydroxide film is further flattened several times, and finally the temperature is high. Furnace annealing recrystallization and removal of residual solution, and finally forming a zinc oxide film sputtering method and using an ionizing gas to bombard the atoms on the surface of the target, using a momentum transfer (momentum transfer) The surface atoms are sputtered onto the surface of the target and rushed toward the surface of the opposite substrate 1 to form a coating, as shown in Figure 4(S), to form a homogeneous nucleation using a zinc oxide buffer layer. Improve interface issues. Further, in the above, the coating method and the sputtering method are all known conditions.

The above-mentioned growth principle mainly utilizes the hydrolysis and precipitation relationship of metal ions and their complexes. In the growth mechanism of synthetic zinc oxide nano columns, the following three methods are used to achieve the purpose of uniaxial growth:

(1) The molecules in the supersaturated solution are easily adsorbed on the plane of the zinc oxide which is just growing, in order to form a complete crystal plane, to achieve the effect of stabilizing the crystal structure.

(2) The surface energy of zinc oxide nano-pillars is related to the size. When the microstructure is thin enough, it will be beneficial to the growth of the crystal surface of the zinc oxide nano-pillar, but when the size is larger than a certain level After that, the growth of the zinc oxide nano-pillar is restricted in a kinetically locked-in manner.

(3) At the initial stage of deposition, the monolayer atoms on the surface of the crystal can escape the thermodynamic constraints and freely switch to the crystallographic direction of the zinc oxide nano-pillar to facilitate the uniaxial growth mechanism; plus the use of zinc oxide buffer layer synthesis Zinc oxide nano-pillars, the inherent surface roughness of the original film substrate material, can be used as a heterogeneous nucleation of zinc oxide nano-pillars, providing a good growth environment and adding high-order oxidation. The aspect of the high orientation ZnO nanorod-array.

In summary, the present invention is not only innovative in terms of space type, but also can enhance the above-mentioned multiple functions compared with conventional articles, and should fully comply with the statutory invention patent requirements of novelty and progressiveness, and apply for it according to law, and invites you to apply for it. Approved this invention patent application, in order to invent invention, to the sense of virtue.

1‧‧‧Substrate

2‧‧‧ Coating method

21‧‧‧ Sputtering

211‧‧‧Tira way

212‧‧‧Sloping substrate into solution

213‧‧‧Rot coating

3‧‧‧Test strips forming a zinc oxide buffer layer

4‧‧‧High temperature furnace

5‧‧‧Test piece for forming zinc oxide buffer layer after annealing

6‧‧‧Zinc salt solution and a certain proportion of alkaline solution

7‧‧‧Seal the solution of the test piece

8‧‧‧ fixed temperature oven

81‧‧‧Electromagnetic heating stirrer

9‧‧‧ Growing unannealed test strips

10‧‧‧Attenuated test strips

A‧‧‧Basic cleaning process: acetone (10 min) → two-stage water (10 min) → methanol (10 min)→second water (10 min)→nitrogen blow drying

B‧‧‧Formation of zinc oxide buffer layer

C‧‧‧ Annealing

D‧‧‧ blending ratio of zinc-containing salt solution and alkaline solution

E‧‧‧Place the test piece into the reaction solution

F‧‧‧heating or stirring

Rest and rinse in G‧‧‧DI water

S‧‧‧ surface atoms sputter the surface of the target

1 is a structural diagram of a manufacturing method for growing a zinc oxide nanostructure by a liquid deposition method according to the present invention; FIG. 2 is a schematic diagram of a growth process of a zinc oxide crystal by a liquid deposition method according to the present invention; Schematic diagram of coating deposition; Figure 4 is a schematic diagram of the deposition of the buffer layer applied by the present invention by magnetron sputtering.

1‧‧‧Substrate

2‧‧‧ Coating method

21‧‧‧ Sputtering

3‧‧‧Test strips forming a zinc oxide buffer layer

4‧‧‧High temperature furnace

5‧‧‧Test piece for forming zinc oxide buffer layer after annealing

6‧‧‧Zinc salt solution and a certain proportion of alkaline solution

7‧‧‧Seal the solution of the test piece

8‧‧‧ fixed temperature oven

81‧‧‧Electromagnetic heating stirrer

9‧‧‧ Growing unannealed test strips

10‧‧‧Attenuated test strips

Claims (8)

A method for manufacturing a zinc oxide nanostructure by using a liquid phase deposition method, comprising at least: providing a substrate, providing a Zn ²⁺ ion by using a zinc salt, and providing an OH ^{- by} an alkaline buffer to react the substrate in a supersaturated solution; a zinc oxide complex; forming a zinc oxide buffer layer on the substrate by a coating method or a sputtering method; and synthesizing a zinc oxide nano column by a zinc oxide buffer layer to make the surface of the substrate serve as zinc oxide naphthalene Heterogeneous nucleation of the rice column; growing a zinc oxide nano column on the surface of one of the zinc oxide buffer layers; using heating or stirring to provide the growth energy of the zinc oxide nano column; and annealing the heat treatment to reduce the defect of the zinc oxide nano column The generation, and recrystallization also make the crystal face structure more obvious. The application of the application of paragraph 1 patentable scope of the method of producing a zinc oxide nano structures grown by liquid phase deposition, wherein the heterogeneous nucleation takes place in a low degree of supersaturation of the supersaturated solution, and a buffer layer of zinc oxide solution A homogenous nucleation reaction is formed by the interface contact problem to grow a zinc oxide nano column having both quality and aspect ratio. The manufacturing method of zinc oxide nano-structures grown by liquid deposition of the first item of the scope of patent applications, wherein the coating method is the use of pull mode at a fixed rate immersing the substrate in a supersaturated solution, or to the solution with The substrate was tilted at an angle, and the solution dropped on the substrate was dispersed on the substrate by centrifugation on the principle of centrifugal force, and the zinc hydroxide film formed by repeating it several times was made flatter. The manufacturing method of zinc oxide nano-structures grown by liquid deposition of the first item of the scope of the patent application, the coating method wherein a layer of zinc oxide buffer layer on a substrate, the substrate after forming the buffer layer discharge test piece Annealing into a high temperature furnace results in a more uniform surface morphology. The application of the application of paragraph 1 patentable scope of the method of producing a zinc oxide nano structures grown by liquid phase deposition, wherein the substrate is formed a buffer layer while the test strip disposed zinc salt solution and an alkaline solution, by formulation containing After the ratio of the zinc salt solution and the alkaline solution is sufficiently stirred, the test piece which forms the zinc oxide buffer layer after annealing is placed in a solution of a proper ratio to provide energy for growth at different times, stirring rates and temperatures. After a solution reaction time, the test piece is taken out, placed in deionized water, allowed to stand and rinsed, and then naturally dried after several hours, and finally placed in a high temperature furnace to remove residual solution, reduce defects and improve crystallization, that is, Complete the growth of the nanostructure. The manufacturing method of zinc oxide nano-structures grown by liquid deposition of the first item of the scope of the patent application, wherein the sputtering method and the use of the ionized gas atoms to induce bombard the target surface by momentum transfer surface The atom sputters the surface of the substrate and rushes toward the surface of the opposite substrate to form a plating film. Finally, the buffer layer is used to obtain the homogenous nucleation of the interface, that is, the growth buffer layer is completed. The manufacturing method of zinc oxide nano-structures grown by liquid deposition of the first item of the scope of the patent application, wherein the sputtering a layer of zinc oxide buffer layer on a substrate, the substrate after forming the buffer layer discharge test piece Annealing into a high temperature furnace results in a more uniform surface morphology. The application of the application of paragraph 1 patentable scope of the method of producing a zinc oxide nano structures grown by liquid phase deposition, wherein the substrate is formed a buffer layer while the test strip disposed zinc salt solution and an alkaline solution, by formulation containing After the ratio of the zinc salt solution and the alkaline solution is sufficiently stirred, the test piece which forms the zinc oxide buffer layer after annealing is placed in a solution of a proper ratio to provide energy for growth at different times, stirring rates and temperatures. After a solution reaction time, the test piece is taken out, placed in deionized water, allowed to stand and rinsed, and then naturally dried after several hours, and finally placed in a high temperature furnace to remove residual solution, reduce defects and improve crystallization, that is, Complete the growth of the nanostructure.