TWI412636B - Zno nanorods thin films and fabricated method - Google Patents

Abstract

The invention provides a method to fabricate compact and highly c-axis-oriented ZnO nanorods thin films on silica glass substrates by a simple solution-growth technique. The ZnO seed layer coated substrate is immersed in 0.001 to 0.1 M ZnO precursor solution at 50-100 DEG C /0.5-10 h to grow ZnO nanorods layer. Under the best fabricated parameters, ZnO nanorods thin film can be synthesized. The invention gives a simple solution-growth method for the fabrication of low-cost, low-temperature grown, high density and well optical characteristic ZnO nanorods thin films.

Description

Zinc oxide nano column film and preparation method thereof

This case relates to a zinc oxide nanocolumn film and a preparation method thereof.

Zinc oxide (ZnO) is a direct-gap semiconductor with a band gap of about 3.37 eV at room temperature, which has a large exciton binding energy (60 meV) and a high refractive index (n=2.01 for 550 nm light). ), because of its good optoelectronic properties, it is widely used in light-emitting diodes and solar cells.

The existing zinc oxide film preparation method is a complicated and high-cost technical solution, including chemical vapor deposition (CVD), laser ablation, sputtering or coagulation. The method of sol-gel spin coating, etc.; and the processes of chemical vapor deposition, laser etching or sputtering are carried out under vacuum or high temperature, and the cost is extremely high. Therefore, finding a simple process that is not vacuum, low temperature, and low cost becomes a very important issue. In recent years, a method for preparing a zinc oxide nanocolumn film such as a low temperature solution growth method (Vayssieres et al., J. Phys. Chem. B 2001, 105, 3350) has been used to grow a zinc oxide nanocolumn film. The zinc oxide nanocolumn film is composed of hexagonal nano columns, and there are many unfilled holes between the crystal columns.

Although the prior art already has the aforementioned method for preparing a zinc oxide nanocolumn film such as a low temperature solution growth method, it is disclosed from, for example, academic research (Tak et al., J. Phys. Chem. B 2005, 109, 19263). With regard to the physical properties of the zinc oxide nano-pillar film prepared by the method for preparing the existing zinc oxide nano-pillar film, it is known that the prior art prior to the application of the present application changes the pH, growth temperature, and the like of the growth solution, Growth conditions such as seed layer and zinc ion concentration affect the characteristics of the zinc oxide nano-pillar film, but the prepared zinc oxide nano-pillar film is still not dense and cannot provide high-density zinc oxide nanocrystals with good optical properties. Column film.

On the other hand, a method for preparing a nano-pillar film is also disclosed in U.S. Patent Publication No. 2007/0220713 (US 2007/0220713 A1), but this method also fails to provide a dense nano-pillar film. That is, the prior art documents clearly indicate that there are obvious technical stereotypes or technical obstacles in the prior art, which results in the preparation of such existing zinc oxide nanocolumn thin films and does not provide a highly densified zinc oxide nanocolumn having good optical properties. film.

It can be seen from the above that the disadvantages of the preparation method of the zinc oxide nano-pillar film are: the zinc oxide nano-pillar film which is formed by the method for preparing the zinc oxide nano-pillar film, has many pores inside and is not dense. Therefore, a highly densified zinc oxide nanocolumn film having good optical properties cannot be provided.

In view of the shortcomings of the prior art zinc oxide nano-pillar film preparation method, it is an object of the present invention to provide a zinc oxide nano-pillar film preparation method which can overcome the disadvantages of the prior art and can overcome the disadvantages. The method for preparing a zinc oxide nano-pillar film of the invention is based on a low-temperature solution method, and a high-density zinc oxide nano column having good optical properties such as high c-axis preference is prepared by a simple process, low temperature and low cost. film.

In order to achieve the above object, the technical means adopted by the present invention is that the zinc oxide nano-pillar film preparation method comprises: forming a zinc oxide seed layer on a substrate; and growing in a zinc oxide nano-pillar film growth solution at 50 to a growth temperature of 100 ° C and a growth time of 0.5 to 10 hours, wherein a zinc oxide crystal column layer is grown on the zinc oxide seed layer to obtain a zinc oxide nano-pillar film having a crystal column layer, wherein The zinc oxide nanocolumn film growth solution is an aqueous solution containing hexamethylenetetramine having a zinc ion concentration of 0.001 to 0.1 M.

The method for preparing a zinc oxide nanocolumn film of the invention has the above technical features, and based on the low temperature solution growth method, the zinc oxide naphthalene which grows very dense and has good optical properties is prepared by controlling the growth temperature, the solution concentration and the growth time. The rice column film can indeed achieve the object of the present invention.

Moreover, in the preparation of the zinc oxide nanocolumn film of the present invention, the chemical solution required for growing the zinc oxide nano column can be obtained by simple chemical mixing, and thus, for example, other physical or chemical processes are employed. The film growth method has the method for preparing a zinc oxide nano column film, and the method for preparing the zinc oxide nano column film of the invention has the advantages of simple process, low temperature and low cost.

In addition, the present invention also provides a zinc oxide nanocolumn film having high density and good optical properties by the aforementioned zinc oxide nanocolumn film preparation method.

The method for preparing a zinc oxide nanocolumn film of the present invention uses a specific process parameter such as concentration, temperature or time on the basis of the low temperature solution growth method of Vayssieres et al. to synthesize a highly densified zinc oxide naphthalene having good optical properties. Rice column film. The zinc oxide nanocolumn film of the present invention has relatively good optical properties (for example, zinc oxide nanoparticle obtained after 6 hours of growth), except that the pores are small and the hexagonal crystal columns are fused to each other to exhibit densification properties. The column film has a thickness of about 800 nm, a visible light transmittance of 85%, a refractive index of 1.74, and a bulk density of 0.84.

The invention will be further exemplified by the following examples in conjunction with the drawings. It is to be noted that the examples are intended to be illustrative of the invention and are not intended to limit the scope of the invention in any way.

The method for preparing a zinc oxide nanocolumn film of the present invention comprises a seed layer preparation step and a crystal column layer preparation step.

[Example 1]

This embodiment exemplifies an embodiment in which a seed layer is prepared by a sol-gel method (Sol-gel method).

1. Preparation of a zinc oxide seed layer solution gel solution. First, ethylene glycol monomethyl ether (2-methoxyethanol, 2-MOE, HOC ₂ H ₄ OCH ₃ ), monoethanolamine (MEA, HOC ₂ H ₄ NH ₂ ), and zinc acetate (Zn (CH) ₃ COO) ₂ ), mixed into a mixed solution in a molar ratio of zinc ion (Zn ²⁺ ): ethylene glycol monomethyl ether: monoethanolamine = 1:10 to 40:1. Next, the above mixed solution was stirred for ten hours to obtain a zinc oxide seed layer-soluble gel solution. Further, in addition to the zinc acetate described above, the zinc ion (Zn ²⁺ ) may be provided by a compound such as zinc bromide, zinc chloride, zinc fluoride, zinc iodide, zinc sulfide, zinc sulfate or zinc nitrate.

2. Preparation of a zinc oxide seed layer. Coating the zinc oxide seed layer sol gel solution onto a substrate by spin coating. The substrate may be a glass substrate, and after soft baking for 10 minutes on a hot plate at 100 ° C, sintering at 200 ° C for 10 minutes, and then Annealing at 200 to 800 ° C to form a zinc oxide seed layer. Further, in addition to the glass substrate, a substrate made of quartz material, single crystal germanium material, polycrystalline germanium material or sapphire material, or a soft organic material substrate such as polyethylene terephthalate (PET) may be used. Acrylic, polyimide.

The zinc oxide seed layer formed by the method exemplified in the present embodiment has a crystal grain size of about 5 to 100 nm and a thickness of about 20 to 90 nm.

Further, another specific example of preparing the seed layer by the aforementioned lyotropic method is to anneal the zinc oxide seed layer to 400 ° C to form a zinc oxide seed layer having a grain size of about 20 nm on the substrate. .

As shown in the first (a) to the first (c), in order to grow the densified zinc oxide nano-pillar film, it is necessary to use a seed layer having a grain size of 1 to 100 nm. If the grain size of the seed layer is too large, the surface of the seed layer is not flat enough, which will cause the grown zinc oxide nano column to be too messy to form a densified zinc oxide nano-pillar film. As shown in the first diagram (d), if the grain size of the zinc oxide film annealed at 800 ° C is about 100-150 nm, the grown zinc oxide nano column is very messy, and a dense zinc oxide nano-pillar film cannot be formed.

[Example 2]

This embodiment exemplifies an embodiment in which a seed layer is prepared by sputtering. A zinc oxide seed layer having a crystal grain size of about 20 to 100 nm can be formed on a substrate by sputtering.

Since the sputtering method is well-known in the art, the details of the implementation are well known to those of ordinary skill in the art to which the present invention pertains, and the conventional details are not described herein. The parameters are as follows: substrate material such as: an inorganic substrate of a hard material. Such as: glass, quartz, single crystal germanium, polycrystalline germanium or sapphire, or an organic substrate such as polyethylene terephthalate (PET), acrylic or polyimide.

Substrate temperature: room temperature -600 °C.

1. Gas flow rate: oxygen (O ₂ ) gas flow rate is 30 sccm, and argon (Ar) gas flow rate is 8 sccm.

2. Background pressure: 5 × 10 ^-6 torr.

3. Working pressure: 15mtorr.

4.RF power: 150W.

5. Sputtering time: 5 minutes.

6. Substrate temperature: room temperature to 600 °C.

As shown in the first diagram (e), the crystal grain size of the zinc oxide seed layer formed on a substrate by the method exemplified in the embodiment is about 5 to 50 nm.

Further, another specific example of preparing the seed layer by the sputtering method is to maintain the temperature of the substrate used in the sputtering method at room temperature (RT) to form a crystal on the substrate. A zinc oxide seed layer having a particle size of about 20 nm.

As described above, in order to grow a dense zinc oxide nano-pillar film, it is necessary to use a zinc oxide seed layer having a grain size of 1 to 100 nm. If the crystal grains of the zinc oxide seed layer are too large, zinc oxide crystals are formed. The surface of the seed layer is not flat enough, which will cause the grown zinc oxide nano column to be too messy to form a densified zinc oxide nano-pillar film.

The spin coating method exemplified in the above embodiment and the sputtering method exemplified in the present embodiment have fully explained a feasible method for producing a zinc oxide seed layer. In addition, other methods such as immersion plating, spray coating, metalorganic chemical vapor deposition (MOCVD), laser stripping, etc. can also be used to produce a zinc oxide seed crystal having a grain size of 1 to 100 nm. Floor. In other words, the methods are all suitable for making the zinc oxide seed layer of the present invention.

[Example 3]

The growth of the zinc oxide nano-pillar film can be performed in a multiple-stepwise or one-step process. This embodiment exemplifies an embodiment in which a crystal column layer is prepared by a multi-stage process.

1. Preparation of a zinc oxide nanocolumn film growth solution. The growth solution of the nano-pillar film is zinc nitrate, hexamethylenetetramine (HMT, C ₆ H ₁₂ N ₄ ) and deionized water, molar ratio of zinc ion (Zn ²⁺ ): hexamethylenetetramine : A ratio of deionized water = 0.02 to 2: 0.02 to 2: 1000 to prepare a zinc oxide nano-pillar film growth solution having a zinc ion concentration of 0.001 to 0.1 M. Further, in addition to the zinc nitrate described above, a compound such as zinc bromide, zinc chloride, zinc fluoride, zinc iodide, zinc sulfide, zinc sulfate or zinc acetate may be used to provide the zinc ion (Zn ²⁺ ).

2. Preparation of a zinc oxide crystal column layer in multiple stages. The growth temperature is controlled at 50 to 100 ° C, and the growth time is controlled to 0.5 to 10 hours.

Taking a 75 ° C / 6 hour multi-stage process as an example, the substrate on which the zinc oxide seed layer is formed is placed in a zinc oxide nano-pillar film growth solution that has been heated to 75 ° C for 1.5 hours (that is, the aforementioned growth time of four) After one part, the substrate is taken out and transferred to another bottle of newly prepared zinc oxide nano-pillar film growth solution, and also grown at 75 ° C for 1.5 hours (that is, one quarter of the aforementioned growth time), The substrate is placed in a newly prepared zinc oxide nano-pillar film growth solution to grow it by four times of the growth time, that is, the substrate is divided into four portions to prepare a new zinc oxide nano-pillar film in four portions. After all the growth time in the growth solution, the multi-stage growth of the nano-pillar film is completed, and the zinc oxide seed layer is grown into a zinc oxide crystal column layer to obtain a zinc oxide nano-pillar film with a crystal column layer grown. .

In a more specific embodiment, the zinc oxide seed layer having a grain size of about 20 nm is formed by the above-mentioned sol gel method or sputtering method, and zinc oxide having a zinc ion concentration of 0.05 M is used. The nanocolumn film growth solution was grown at 75 ° C for 6 hours using the above multi-stage process to obtain a zinc oxide nanocolumn film.

Because in the process of growing the nano column, the zinc ion concentration will continue to be consumed. If the concentration of zinc ions is too low, the nano column will tend to grow toward the c-axis, and cannot grow into a densified nano-pillar film. In the present invention, a multi-stage process is used, the purpose of which is to maintain a constant zinc ion concentration while growing a zinc oxide nano column.

On the other hand, in addition to the multi-stage process as described above, it is also necessary to use a machine such as an auto-remediation of zinc ion concentration to automatically replenish the zinc ion concentration to perform a single-stage process in a constant zinc ion concentration. The same is true of the possible embodiments of the present invention.

[Embodiment 4]

This embodiment illustrates an embodiment in which a crystal column layer is prepared by a single-stage process.

1. Preparation of a zinc oxide nanocolumn film growth solution. The growth solution of the nano-pillar film is zinc acetate, hexamethylenetetramine (HMT, C ₆ H ₁₂ N ₄ ) and deionized water, molar ratio of zinc ion (Zn ²⁺ ): hexamethylenetetramine : A ratio of deionized water = 0.02 to 2: 0.02 to 2: 1000 to prepare a zinc oxide nano-pillar film growth solution having a zinc ion concentration of 0.001 to 0.1 M. Further, in addition to the zinc acetate described above, the zinc ion (Zn ²⁺ ) may be provided by a compound such as zinc bromide, zinc chloride, zinc fluoride, zinc iodide, zinc sulfide, zinc sulfate or zinc nitrate.

2. Preparation of a zinc oxide crystal column layer in a single stage. The growth temperature is controlled at 50 to 100 ° C, and the growth time is controlled to 0.5 to 10 hours. The single-stage process illustrated in this embodiment differs from the multi-stage process in that the single-stage process illustrated in this embodiment does not replace the zinc oxide nano-pillar film growth solution, but directly grows in the same bottle of zinc oxide nano-pillar film. In the solution, the substrate on which the zinc oxide seed layer is formed is grown for a set period of time (for example, 6 hours), that is, after the substrate is subjected to a full growth time in a newly prepared zinc oxide nano-pillar film growth solution. The zinc oxide seed layer is grown to form a zinc oxide crystal pillar layer, thereby obtaining a zinc oxide nanocolumn film having a crystal pillar layer.

In a more specific embodiment, the zinc oxide seed layer having a grain size of about 20 nm is formed by the above-mentioned sol gel method or sputtering method, and zinc oxide having a zinc ion concentration of 0.05 M is used. The nanocolumn film growth solution was grown at 75 ° C for 6 hours using the aforementioned single-stage process to obtain a zinc oxide nanocolumn film.

[Embodiment 5]

Example 5 illustrates an embodiment in which various properties of the zinc oxide nano-pillar film produced by the method for preparing a zinc oxide nano-pillar film of the present invention are confirmed by measurement. Thereby, the characteristics and effects of the preparation method of the zinc oxide nanocolumn film of the present invention can be demonstrated.

As shown in the second figure, the scanning electron microscope (SEM) was used to observe the growth temperature, growth time and growth method under the conditions of a zinc ion concentration of 0.05 M and a crystal grain size of about 20 nm. The zinc oxide nano column film shows that the nano column of the zinc oxide nano column film prepared by the method for preparing the zinc oxide nano column film of the invention is very dense. For example, as shown in the second figure (c) and the second figure (d), the zinc oxide nano-pillar film obtained by growing in a multi-stage process at 75 ° C for 6 hours exhibits an extremely high degree of density.

As shown in the third figure, the growth of the zinc oxide nano-pillar film on the seed layer by sputtering is observed by a scanning electron microscope, and it can be seen by referring to the second (c) and second (d) drawings. After the zinc oxide seed layer prepared by the sol-gel method (grain size is about 20 nm) and the zinc oxide seed layer (grain size about 20 nm) prepared by sputtering method, the zinc oxide nano column is grown on the seed layer. The film exhibits similar dense columnar grains.

As shown in the second (c), second (d) and third (a) and third (b), zinc oxide seed layers (grains) are prepared by sol gel or sputtering. The size of the nanometer is about 20nm. The diameter of the nanocolumn is the largest and the length is the smallest under the growth conditions of 75 ° C, 6 hours and multi-stage process. This means that the lateral growth of the crystal column is more active, and the bulk density will increase with the increase. The demand for "densified nanopillar film".

As shown in the fourth figure, the growth time of the single-stage and multi-stage processes is related to the diameter/length of the nano-pillar. The diameter and length of the nano-column of the single-stage process are narrower and longer.

As shown in the fifth figure, the results of XRD analysis show that the nano-pillar film of the zinc oxide grown by the method of the present invention has a high c-axis preference.

As shown in the sixth figure, the zinc oxide nano-pillar film grown in the seed layer at a zinc ion concentration of 0.05 M and a crystal grain size of about 20 nm has good visible light transmittance, especially as shown in the fifth figure. (a) shows that the nano-pillar film obtained under the growth conditions of 75 ° C, 6 hours and multi-stage process has an average visible light transmittance of 85%.

As shown in the seventh figure, the refractive index of the nano-pillar film prepared by the multi-stage process at 3, 4.5, and 6 hours under growth conditions at 75 ° C is 159 nm, 1.705, 1.743, respectively, and the process conditions are known. The film grown for 6 hours has the highest density.

As shown in the eighth figure, the longer the growth time, the larger the bulk density and the refractive index. After six hours of growth, the refractive index reaches 1.743, and the bulk density can reach 0.84.

The zinc oxide nanocolumn film prepared by the method of the present invention was confirmed to have the properties of a dense film after being measured by the above various instruments. Optimized process parameters: the seed layer has a grain size of about 20 nm, a growth solution zinc ion concentration of 0.05 M, a growth temperature of 75 ° C, a growth time of 6 hours, and a multi-stage process. The characteristics of the most dense film obtained were as follows: the thickness of the nano-column film was about 800 nm, the grain size of the seed layer was about 200 nm, the average visible light transmittance was 85%, the refractive index was 1.74, and the bulk density was 0.84. The growth temperature and growth cost required by the invention are low, and no special environment is required, so the process is very simple.

The method for preparing a zinc oxide nanocolumn film of the invention has the above technical features, and based on the low temperature solution growth method, the zinc oxide which grows very dense and has good optical properties is prepared by controlling the growth temperature, the zinc ion concentration and the growth time. The nanocolumn film does indeed achieve the object of the present invention.

Moreover, in the preparation of the zinc oxide nanocolumn film of the present invention, the chemical solution required for growing the zinc oxide nano column can be obtained by simple chemical mixing, and thus, for example, other physical or chemical processes are employed. The film growth method has the method for preparing a zinc oxide nano column film, and the method for preparing the zinc oxide nano column film of the invention has the advantages of simple process, low temperature and low cost.

From the above, it can be seen that the present invention can provide a zinc oxide nano-pillar film having an average visible light transmittance of more than 85% and a bulk density of more than 0.84; in particular, the present invention can provide an average visible light transmittance of more than 85% and bulk density. A zinc oxide nanopillar film having a refractive index greater than 1.74 and greater than 1.74. In other words, the present invention does improve the disadvantages of the prior art and achieves the object of the invention.

The first figure (a) is a seed layer obtained by a sol gel method and sintered at 200 ° C.

The first figure (b) is a seed layer obtained by a sol gel method and sintered at 400 ° C.

The first figure (c) is a seed layer obtained by a sol gel method and sintered at 600 ° C.

The first figure (d) is a seed layer obtained by a sol gel method and sintered at 800 ° C.

The first figure (e) is a seed layer prepared by sputtering.

The second figure (a) is obtained by using a multi-stage process for 1.5 hours at 75 ° C under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the grain size of the seed layer is about 20 nm. A top view scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (b) is obtained by using a multi-stage process for 1.5 hours at 75 ° C under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the grain size of the seed layer is about 20 nm. Side-viewing scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (c) is obtained by growing the multi-stage process at 75 ° C for 6 hours under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the grain size of the seed layer is about 20 nm. A top view scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (d) is obtained by growing the multi-stage process at 75 ° C for 6 hours under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the crystal grain size of the seed layer is about 20 nm. Side-viewing scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (e) is obtained by using a multi-stage process for 1.5 hours at 95 ° C in a zinc oxide nano-pillar film growth solution having a zinc ion concentration of 0.05 M and a seed layer grain size of about 20 nm. A top view scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (f) is obtained by increasing the zinc ion concentration of the zinc oxide nano-pillar film growth solution to 0.05 M and the crystal grain size of the seed layer to about 20 nm at 95 ° C using a multi-stage process for 1.5 hours. Side-viewing scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (g) is obtained by using a single-stage process for 4.5 hours at 75 ° C under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the grain size of the seed layer is about 20 nm. A top view scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (h) is obtained by using a single-stage process for 4.5 hours at 75 ° C under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the grain size of the seed layer is about 20 nm. Side-viewing scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (i) is obtained by growing a single-stage process for 6 hours at 75 ° C in a zinc oxide nano-pillar film growth solution having a zinc ion concentration of 0.05 M and a seed layer grain size of about 20 nm. A top view scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (j) is obtained by using a single-stage process for 6 hours at 75 ° C under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the grain size of the seed layer is about 20 nm. Side-viewing scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (k) is obtained by growing a single-stage process for 6 hours at 75 ° C in a zinc oxide nano-pillar film growth solution having a zinc ion concentration of 0.05 M and a seed layer grain size of about 100 nm. A top view scanning electron micrograph of a zinc oxide nanopillar film.

The second figure (1) is obtained by using a single-stage process for 6 hours at 75 ° C under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the grain size of the seed layer is about 100 nm. Side-viewing scanning electron micrograph of a zinc oxide nanopillar film.

The third figure (a) is used at 75 ° C under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the crystal size of the zinc oxide seed layer prepared by the sputtering method is about 20 nm. A top-view scanning electron micrograph of a zinc oxide nanopillar film obtained by multi-stage process growth for 6 hours.

The third diagram (b) is based on the zinc ion concentration of the zinc oxide nano-pillar film growth solution of 0.05M, and the crystal size of the zinc oxide seed layer prepared by the sputtering method is about 20 nm, and is used at 75 ° C. A side-view scanning electron microscope photograph of a zinc oxide nanocolumn film obtained by multi-stage process growth for 6 hours.

The fourth figure shows the growth temperature, growth time and growth method under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05M and the crystal grain size of the seed layer is about 20 nm. A graph of the average diameter and length of a zinc oxide nanopillar film.

The fifth figure shows the growth temperature, growth time and growth method under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05M and the crystal grain size of the seed layer is about 20 nm. XRD analysis chart of zinc oxide nanocolumn film.

Figure 6 (a) is a multi-stage process of growth of 1.5 to 6 hours at 75 ° C in a zinc oxide nano-pillar film growth solution having a zinc ion concentration of 0.05 M and a seed layer grain size of about 20 nm. The breakthrough spectrum of the different growth time of the obtained zinc oxide nanocolumn film, wherein the vertical axis is the refractive index percentage and the horizontal axis is the wavelength.

The sixth figure (b) is a 1.5- to 6-hour growth in a single-stage process at 75 ° C in a zinc oxide nano-pillar film growth solution having a zinc ion concentration of 0.05 M and a seed layer grain size of about 20 nm. The breakthrough spectrum of the different growth time of the obtained zinc oxide nanocolumn film, wherein the vertical axis is the refractive index percentage and the horizontal axis is the wavelength.

Figure 6 (c) is a single-stage process of 1.5 to 6 hours at 95 ° C in a zinc oxide nano-pillar film growth solution having a zinc ion concentration of 0.05 M and a seed layer grain size of about 20 nm. The breakthrough spectrum of the different growth time of the obtained zinc oxide nanocolumn film, wherein the vertical axis is the refractive index percentage and the horizontal axis is the wavelength.

The seventh figure shows the different growth of the zinc oxide nano-pillar film grown in a multi-stage process under the condition that the zinc ion concentration of the zinc oxide nano-pillar film growth solution is 0.05 M and the crystal grain size of the seed layer is about 20 nm. A graph of the refractive index of time versus wavelength.

The eighth figure shows the growth of zinc oxide naphthalene in a multi-stage process under the conditions of a zinc ion concentration of 0.05 M in a zinc oxide nano-pillar film growth solution, a grain size of the seed layer of about 20 nm, and a growth temperature of 75 ° C. A graph of the bulk density and refractive index of a rice column film.

Claims (11)

A method for preparing a zinc oxide nano-pillar film, comprising: forming a zinc oxide seed layer on a substrate, comprising a plurality of crystal grains, wherein the grain size is 1 to 100 nm; in a zinc oxide nano-pillar film growth solution At a growth temperature of 50 to 100 ° C and a growth time of 0.5 to 10 hours, the zinc oxide seed layer is grown to form a zinc oxide crystal column layer, thereby obtaining a zinc oxide nano column film having a crystal column layer grown thereon. The zinc oxide nano-pillar film growth solution is an aqueous solution having a zinc ion concentration of 0.001-0.1 M and containing hexamethylenetetramine; and the preparation method of the zinc oxide nano-pillar film is selected from the following (A) And the method of group (B) forming the zinc oxide seed layer on the substrate: the method for preparing a zinc oxide nano-pillar film according to (A), which is formed on the substrate by a sol gel method The zinc oxide seed layer is such that the crystal grain size of the zinc oxide seed layer is 5 to 100 nm; and the zinc oxide nano-pillar film preparation method is a spin coating method to form a zinc oxide seed layer The lysate solution is applied to the aforementioned substrate and soft baked at 100 ° C for 10 minutes. Thereafter, sintering at 200 ° C for 10 minutes, and then annealing at 200 to 800 ° C to form the aforementioned zinc oxide seed layer, wherein the zinc oxide seed layer solution gel solution contains zinc ions, ethylene glycol monomethyl ether And a solution of monoethanolamine, and the molar ratio of zinc ion, ethylene glycol monomethyl ether and monoethanolamine is 1:10-40:1; the preparation method of the zinc oxide nanocolumn film is to make zinc oxide seed crystal The annealing temperature of the layer is 400 ° C to form a zinc oxide seed layer having a grain size of about 20 nm on the substrate; and in a zinc oxide nanometer film growth solution having a zinc ion concentration of 0.005 M at 75 ° C The growth temperature is increased by a growth time of 6 hours to cause the zinc oxide seed layer to grow into a zinc oxide crystal column layer; (B) the zinc oxide nano-pillar film preparation method is formed on the substrate by sputtering. The zinc oxide seed layer is such that the crystal grain size of the zinc oxide seed layer is 20 to 100 nm; and the method for preparing the zinc oxide nano-pillar film has an oxygen gas flow rate of 30 sccm and an argon gas flow rate of 8 sccm, background pressure 5 × 10 ^-6 torr, working pressure 15 mtorr, RF power It is 150 W, the substrate temperature is room temperature and the sputtering time is 5 minutes. The method for preparing a zinc oxide nanocolumn film according to claim 1, wherein the proportion of zinc ion, hexamethylenetetramine and water in the zinc oxide nano-pillar film growth solution is 0.02 to 2: 0.02~ 2:1000. The method for preparing a zinc oxide nano-pillar film according to claim 1 is characterized in that the substrate is divided into a plurality of newly prepared zinc oxide nano-pillar film growth solutions for a plurality of growth times, and each part is grown for a plurality of times. The sum total is equal to the aforementioned growth time. The method for preparing a zinc oxide nano-pillar film according to claim 2, wherein the substrate is subjected to a plurality of times of growth time in each of the newly prepared zinc oxide nano-pillar film growth solutions, and each part is grown. The sum total is equal to the aforementioned growth time. The method for preparing a zinc oxide nanocolumn film according to claim 1, wherein the substrate is formed in a newly prepared zinc oxide nanocolumn film. The total growth time in the long solution. The method for preparing a zinc oxide nanocolumn film according to claim 2, wherein the substrate is subjected to a full growth time in a freshly prepared zinc oxide nanocolumn film growth solution. The method for preparing a zinc oxide nano-pillar film according to claim 1, wherein the substrate is subjected to a total growth time in a zinc oxide nano-pillar film growth solution having a constant zinc ion concentration. The method for preparing a zinc oxide nano-pillar film according to claim 2, wherein the substrate is subjected to a total growth time in a zinc oxide nano-pillar film growth solution having a constant zinc ion concentration. The method for preparing a zinc oxide nanocolumn film according to any one of claims 1 to 8, wherein the material of the substrate is selected from the group consisting of glass, quartz, single crystal germanium, polycrystalline germanium, sapphire, and polyethylene terephthalate. a group consisting of glycol esters, acryl and polyimine. The method for preparing a zinc oxide nano-pillar film according to any one of claims 1 to 8, wherein the zinc oxide nano-pillar film growth solution is obtained by selecting free zinc acetate, zinc bromide, zinc chloride, A compound of the group consisting of zinc fluoride, zinc iodide, zinc sulfide, zinc sulfate, and zinc nitrate provides the aforementioned zinc ions. The method for preparing a zinc oxide nanocolumn film according to any one of claims 1 to 8, wherein the zinc oxide seed layer is formed on the substrate by sputtering to form the zinc oxide crystal. The grain size of the seed layer is 20~100 nm; the oxygen gas flow rate is 30 sccm, the argon gas flow rate is 8 sccm, the background pressure is 5×10 ^-6 torr, the working pressure is 15 mtorr, and the RF power is 150 W. The substrate temperature is room temperature and the sputtering time is 5 minutes; and the zinc oxide nano-pillar film is prepared by maintaining the temperature of the substrate at room temperature to form a grain size of 5 to 50 on the substrate. a zinc oxide seed layer of nm; growing in a zinc oxide seed layer at a growth temperature of 75 ° C in a zinc oxide ion concentration of 0.005 M in a growth solution of 75 ° C for a period of 6 hours Column layer.