KR100914449B1 - Manufacturing method of nanoporous TiO2-VrO2 hybrid thin film with adjustable band gap - Google Patents

Abstract

The present invention relates to a method for manufacturing a TiO ₂ -ZrO ₂ hybrid thin film in which band gap energy is controlled using a sol-gel method and nano-sized micropores are formed. In detail, the preparation method of the present invention is a mixed solution by mixing 15 to 25 parts by weight of a stabilizer for lowering the activity of the zirconium precursor, 70 to 90 parts by weight of alcohol and 60 to 100 parts by weight of titanium precursor with respect to 100 parts by weight of zirconium precursor. Preparing a; (b) preparing a zirconium-titanium precursor solution by adding 20 to 30 parts by weight of acid and 250 to 400 parts by weight of an organic polymer alcohol solution of 10 to 20% by weight based on 100 parts by weight of zirconium precursor to the mixed solution; And (c) coating the zirconium-titanium precursor solution on a substrate, followed by drying and heat treatment.

Porous thin film, metal oxide, high dielectric constant, band gap, hybrid thin film

Description

Fabrication Method of Nano-porous TiO2-ZrO2 Hybrid Thin Film Having Controlled Band Gap Energy

The present invention relates to a method for manufacturing a TiO ₂ -ZrO ₂ hybrid thin film in which band gap energy is controlled using a sol-gel method and nano-sized micropores are formed. will be.

Although metal oxides have similar crystal structures, they have various characteristics such as conductors, semiconductors, nonconductors, superconductors, piezoelectrics, ferroelectrics, ferromagnetic materials, magnetoresistance, and nonlinear optical properties. Due to these characteristics, research on metal oxide thin films is being conducted in various fields such as optoelectronic devices, photocatalysts, and electronic devices.

In particular, the high-K gate oxide film of a metal oxide semiconductor field-effect transistor (MOSFET) used in logic circuits or displays as the scale down of the device is increased for high integration, high performance, and low power of the electronic device, The use of DRAM (Dynamic Random Access Memory) as a cell capacitor is expected, and interest in TiO ₂ thin films actively being used as photoanode of dye-sensitized solar cells is increasing. have.

Conventional techniques for producing oxide thin films include e-beam evaporation, sputtering, chemical vapor deposition (CVD), and sol-gel methods. The most practical method is the sol-gel method, by coating a liquid metal precursor sol simply on the substrate to produce a thin film, easy to control the composition, to form a homogeneous film, The low heat treatment temperature to obtain the final oxide thin film, large area is possible, and does not use expensive equipment. This sol-gel method is applied to various fields in combination with the latest nanochemical technology. The sol-gel method using surfacant-templating routes using aggregates of surfactants as structural derivatives has been spotlighted as a new technology for forming nanopores in metal oxide thin films. In particular, the TiO ₂ thin film having nano pores is expected to be utilized as a photoanode of a dye-sensitized solar cell because the specific surface area of the dye-coated thin film can be increased to obtain a large photoelectric current.

As a conventional technique for preparing a TiO ₂ thin film using a sol-gel method, Korean Patent Laid-Open Publication No. 2003-0054616 discloses that a sol is dissolved by dissolving titanium tetraisopropoxide, a titanium precursor, in alcohol and then adding hydrochloric acid. A technique of preparing a carrier coated with a titanium oxide film by supporting a carrier in a prepared and prepared titanium precursor sol and then performing heat treatment is described.

Korean Patent Publication No. 2005-0114563 uses alkyltrimethylammonium bromide or alkyltriethylammonium bromide as a surfactant as a structural derivative, and uses titanium isopropoxide as a titanium precursor. A method for synthesizing mesoporous TiO ₂ using a sol-gel method under acidic conditions using sulfuric acid is described. Hexachloroplatonic acid (H ₂ PtCl as a precursor of transition metal (platinum) to the pores of the synthesized mesoporous TiO ₂ is described. o ₆ 6H ₂ o) to have the method of impregnating the platinum nano-particle concentration by using the impregnation method used is described.

Korean Patent No. 10-0607171 uses poly (ethylene oxide) ₁₀₆ -block-poly (propylene oxide) ₇₀ -block-poly (ethylene oxide) ₁₀₆ as a surfactant, which is a structural derivative. Titanium isopropoxide or titanium ethoxide is used, and the nanoporous alumina thin film used as a template is modified with an organic material, and the modified nanoporous alumina thin film is immersed in the precursor solution to gel the inside of the nanoporous channel. After the derivation of the nanoporous alumina thin film containing the obtained gelling reactant, and then calcined with hydrochloric acid to remove the organic template material and the nanoporous alumina thin film is described a method for producing mesoporous titanium oxide nanofibers. .

US Patent Publication No. 2005-0239644 describes a method for preparing a titanium oxide thin film on a flexible substrate using polyglycol or octadexylamine as a surfactant as a structural derivative and n-butyl titanate as a titanium precursor. It is.

However, the research on the composite metal oxide thin film composed of two or more metals to control the characteristics of the oxide thin film is insignificant, and furthermore, the composite metal oxide thin film having a single phase by atomically mixing two or more metals. And there is almost no research on the characteristics control such as the dielectric constant, band gap energy control of the metal oxide thin film using the same.

An object of the present invention for solving the above problems is to control the band gap energy (sol-gel) method is added to the templating agent (templating agent) and nano-sized micropores It is to provide a method for producing the formed TiO ₂ -ZrO ₂ hybrid thin film.

According to the present invention, a method for preparing a nanoporous TiO ₂ -ZrO ₂ hybrid thin film in which the bandgap energy is controlled is 15 to 25 parts by weight of a stabilizer for lowering the activity of the zirconium precursor with respect to 100 parts by weight of zirconium precursor, and 70 to 70 alcohol. Preparing a mixed solution by mixing 90 parts by weight and 60 to 100 parts by weight of the titanium precursor; (b) preparing a zirconium-titanium precursor solution by adding 20 to 30 parts by weight of acid and 250 to 400 parts by weight of an organic polymer alcohol solution of 10 to 20% by weight based on 100 parts by weight of zirconium precursor to the mixed solution; And (c) coating the zirconium-titanium precursor solution on a substrate, followed by drying and heat treatment.

According to the above-described manufacturing method, a zirconium precursor and a titanium precursor are mixed and dissolved to prepare a mixed solution, and then, an acid and an organic polymer alcohol solution are added to the substrate in a state in which the zirconium precursor and the titanium precursor are atomically evenly mixed. After coating in the form of a film on the surface, drying and heat treatment are performed to obtain a composite oxide thin film of a hybrid state (hybrid) of the zirconium and oxygen-bonded titanium combined with oxygen and at the same time, the organic polymer By removing it, a TiO ₂ -ZrO ₂ hybrid composite oxide thin film having nano-sized pores evenly formed in the thin film can be obtained.

The zirconium precursor is preferably zirconium alkoxide, and the titanium precursor is preferably titanium alkoxide.

Zirconium precursors, especially zirconium alkoxides have a high reaction activity, there is a high risk of uneven gelation when the acid is added, it is preferable to add acetylacetone as a stabilizer to lower the activity of the zirconium precursor to prevent this.

The organic polymer alcohol solution is a solution in which a structural derivative which is a surfactant is dissolved in alcohol, and the organic polymer is an ethylene oxide based block copolymer. The ethylene oxide based block copolymer is preferably polyethylene oxide-polypropylene oxide block copolymer or polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer, and more preferably polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer. desirable.

The alcohol used in the mixed solution or the alcohol used in the organic polymer alcohol solution is preferably methanol, ethanol, isopropyl alcohol, butanol, or a mixture thereof, and more preferably butanol.

The acid is hydrochloric acid, sulfuric acid, nitric acid, formic acid, or a mixed acid thereof, preferably hydrochloric acid. The acid may be high purity or low purity acid, and the weight part to which acid is added is weight part converted into pure acid.

Since the substrate is a physical support layer on which the coating film is formed, the material and the shape of the substrate are not limited, but depending on the application, the substrate may be a glass substrate, a substrate on which a transparent electrode is formed, a semiconductor substrate, or a ceramic substrate. An electric / magnetic / optical device using the semiconductor process may be formed.

15 to 25 parts by weight of a stabilizer for lowering the activity of the zirconium precursor with respect to 100 parts by weight of the zirconium precursor in the step of preparing the mixed solution of step (a) to prevent the formation of gels based on the zirconium precursor when the acid is added Is suitably added in weight parts, and the alcohol is preferably added in an amount of 70 to 90 parts by weight in order to secure the coating property following. In addition, since the activity of the zirconium precursor is determined according to the addition amount of the stabilizer, the composition of the composite metal oxide finally obtained by adjusting the addition amount of the stabilizer can also be adjusted.

In this case, the zirconium precursor, the stabilizer and the alcohol are mixed and stirred, and then a titanium precursor is added to prepare the mixed solution. At this time, the amount of the titanium precursor added on the basis of the zirconium precursor affects the composition of the TiO ₂ -ZrO ₂ hybrid composite oxide thin film to be finally produced, the zirconium combined with oxygen and the titanium combined with oxygen In order to obtain an evenly mixed phase, it is preferable that 60 to 100 parts by weight of the titanium precursor is added based on 100 parts by weight of the zirconium precursor.

In the step of preparing the zirconium-titanium precursor solution of step (b), 20 to 30 parts by weight of acid is slowly added to the mixed solution of step (a) with respect to 100 parts by weight of the zirconium precursor, followed by 10 to 20% by weight. 250 to 400 parts by weight of an organic polymer alcohol solution is preferably added and stirred for 2 to 5 hours. 20 to 30 parts by weight of acid, 25 to 80 parts by weight of organic polymer and 200 to 360 parts by weight of alcohol are added to the zirconium-titanium precursor solution based on 100 parts by weight of zirconium.

In this case, as described above, the acid is added first, followed by the addition of the organic polymer alcohol solution. The zirconium precursor or the titanium precursor must first be converted into an oligomer state through a polycondensation reaction to facilitate the induction of nanostructure by the organic polymer. For it is done. When the added acid is less than 20 to 30 parts by weight, it is difficult to grow into oligomers for inducing nanostructures, and in more cases, the gelation reaction tends to occur.

When 10 to 20% by weight of the organic polymer alcohol solution, which is a structural inducing agent, is added to 250 parts by weight or less in the acid-containing mixed solution, to obtain uniform connectivity of nano pores in the thin film after thin film coating. It is difficult, when added in more than 360 parts by weight, the mechanical strength of the thin film is reduced by excessive pore formation, there is a disadvantage that a thin film of uniform thickness is difficult to manufacture.

In the method for preparing a nanoporous TiO ₂ -ZrO ₂ hybrid thin film of which the bandgap energy of the present invention is controlled as described above, all steps except the drying and heat treatment steps of step (c) are preferably performed at room temperature. Drying is preferably carried out at a temperature of 60 to 90 ℃. Preferably, the heat treatment is performed at 400 to 500 ° C., and the heat treatment temperature removes the organic polymer to form nano pores of uniform size and simultaneously nucleates and grows TiO ₂ nanocrystals and ZrO ₂ nanocrystals. It is a condition suitable for producing a single-phase composite oxide thin film in which TiO ₂ and ZrO ₂ are atomically uniformly mixed.

After the step (b), it may further comprise the step of filtering the zirconium-titanium precursor solution using a filter of 0.1 to 0.2 ㎛ size.

The coating of step (c) is preferably a spin coating.

The TiO ₂ -ZrO ₂ hybrid thin film manufactured using the above-described method of the present invention is a porous composite oxide thin film in which nanopores of a single phase are formed, and the single phase is Ti combined with oxygen and Zr combined with oxygen. It has an amorphous feature with this short range order. In addition, the TiO ₂ -ZrO ₂ hybrid thin film is characterized by having a controlled bandgap energy, the bandgap energy is characterized by more than the crystalline TiO ₂ bandgap energy or less than the crystalline ZrO ₂ bandgap energy. The band gap energy is controlled by the mixing ratio of the zirconium precursor and the titanium precursor and the amount of the stabilizer added.

The method for preparing a nanoporous TiO ₂ -ZrO ₂ hybrid thin film in which the bandgap energy is controlled according to the present invention prepares a single phase composite metal oxide thin film having uniform nano pores and atomically mixed with Ti and Zr. There is an advantage that can be, by controlling the mixing ratio of the Ti precursor and Zr precursor has the advantage of controlling the band gap energy of the composite metal oxide thin film. In addition, since the sol-gel method is used, there is an advantage of being manufactured through a simple process and low temperature heat treatment using a low cost coating equipment. The TiO ₂ —ZrO ₂ hybrid thin film manufactured by using the manufacturing method of the present invention may be used as a gate oxide film of a transistor, and may be used as a photoanode of a dye-sensitized solar cell.

Hereinafter, a method of manufacturing a nanoporous TiO ₂ -ZrO ₂ hybrid thin film in which the bandgap energy of the present invention is controlled will be described in detail. The following embodiments are provided as examples to ensure that the spirit of the invention to those skilled in the art can fully convey.

(Example 1)

1.1 g of zirconium alkoxide (Zr (OC ₄ H ₉ ) ₄ , Sigma-Aldrich, 333948) was dissolved in 0.78 g of normal butanol (n-butanol, Duksan, Pure Chemical, 71-36-3) and then acetylacetone , Jun sei chemical, 11010-0380) and then stirred for 5 minutes. 0.78 g of titanium alkoxide (Ti (OC ₄ H ₉ ) ₄ , Sigma-Aldrich, 244112) was added to the prepared solution so that an element ratio of zirconium: titanium was 1: 1, and the mixture was stirred for 5 minutes to prepare a mixed solution. . 0.8 g of 35 wt% hydrochloric acid (HCl) was slowly added to the mixed solution under stirring.

0.57 g of polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer (EO ₂₀ PO ₇₀ EO ₂₀ , BASF, Pluronic P123) was added to 3 g of normal butanol (n-butanol, Duksan, Pure Chemical, 71-36-3) After stirring for 30 minutes, 3.57 g of an organic polymer alcohol solution was prepared.

The zirconium-titanium precursor solution was prepared by adding 3.57 g of the organic polymer alcohol solution to the mixed solution to which the hydrochloric acid was added and stirring for 3 hours. The agitation was carried out using a magnetic bar.

After the prepared zirconium-titanium precursor solution was filtered using a 0.2 μm filter, the filtered solution was spin-coated on a silicon substrate (1-30 Ωcm, 525 nm thickness) at a rotational speed of 2000 rpm. The coated substrate was dried at 80 ° C. for 1 hour, and then heat-treated at 450 ° C. under a vacuum of 1.3 Pa for 1 hour to prepare a porous composite oxide thin film.

(Comparative Example 1)

Single Metal Oxide Thin Film Using Titanium Precursor

1.57 g of titanium alkoxide (Ti (OC ₄ H ₉ ) ₄ , Sigma-Aldrich, 244112) was dissolved in 1 g of normal butanol (n-butanol, Duksan, Pure Chemical, 71-36-3), followed by 35% by weight of hydrochloric acid. 0.8 g (HCl) was added slowly with stirring.

0.57 g of polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer (EO ₂₀ PO ₇₀ EO ₂₀ , BASF, Pluronic P123) was added to 3 g of normal butanol (n-butanol, Duksan, Pure Chemical, 71-36-3) After stirring for 30 minutes, 3.57 g of an organic polymer alcohol solution was prepared. 3.57 g of the organic polymer alcohol solution was added to the acid-added solution, followed by stirring for 3 hours to prepare a titanium precursor solution.

A titanium oxide thin film was manufactured in the same manner as in Example 1, except that the titanium precursor solution was used instead of the zirconium-titanium precursor solution.

(Comparative Example 2)

Single Metal Oxide Thin Film Using Zirconium Precursor

2.2 g of zirconium alkoxide (Zr (OC ₄ H ₉ ) ₄ , Sigma-Aldrich, 333948) was dissolved in 0.56 g of normal butanol (n-butanol, Duksan, Pure Chemical, 71-36-3), and then acetylacetone , Jun sei chemical, 11010-0380) and then stirred for 5 minutes. 0.8 g of 35% by weight hydrochloric acid (HCl) was slowly added to the solution to which acetylacetone was added while stirring.

0.57 g of polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer (EO ₂₀ PO ₇₀ EO ₂₀ , BASF, Pluronic P123) was added to 3 g of normal butanol (n-butanol, Duksan, Pure Chemical, 71-36-3) After stirring for 30 minutes, 3.57 g of an organic polymer alcohol solution was prepared. The zirconium precursor solution was prepared by adding 3.57 g of the organic polymer alcohol solution to the acid-added solution and stirring for 3 hours.

A zirconium oxide thin film was manufactured in the same manner as in Example 1, except that the zirconium precursor solution was used instead of the zirconium-titanium precursor solution.

1 is a high magnification scanning electron microscope (Field-emission Scanning Electron Microscopy) of Example 1 (FIG. 1A), Comparative Example 1 (FIG. 1B), and Comparative Example 2 (FIG. 1C). In the examples and all comparative examples it can be seen that the pores having a size of 5 ~ 10 nm is formed in a uniform distribution, the pores are not regularly arranged.

FIG. 2 shows X-ray diffraction results of Example 1 (TiO ₂ -ZrO ₂ hybrid in FIG.), Comparative Example 1 (TiO ₂ in FIG.), And Comparative Example 2 (ZrO ₂ ). X-ray diffraction evaluation was performed under the conditions of 20-60 degrees 2θ, scan rate of 2 degrees per minute, Cu Kα, 40 kV. In the X-ray diffraction results of FIG. This is due to the (311) surface of the formed silicon substrate.

In some cases to prepare a Ti precursor alone or zirconium precursor single metal oxide thin film from the result of the second crystal (in the case of the titanium precursor anatase structure, in the case of the Zr precursor tetra polygonal structure) the metal, but the oxide thin film is produced having, TiO ₂ - X-ray results of the ZrO ₂ hybrid thin film can be seen that the result of the amorphous phase having only a typical short-range regularity. Accordingly, it can be seen that an amorphous TiO ₂ -ZrO ₂ hybrid thin film in which TiO ₂ grains, ZrO2 grains, or crystal grains in which TiO ₂ -ZrO ₂ forms a solid solution is not formed is produced. have.

Table 1 below shows the results of X-ray photoelectron spectroscopy (XPS) of Example 1 (sample TiO ₂ -ZrO ₂ hybrid), Comparative Example 1 (sample TiO ₂ ) and Comparative Example 2 (sample ZrO ₂ ). As can be seen in Table 1 below, in the case of Example 1, both Ti and Zr were detected, although the zirconium-titanium precursor solution was prepared such that the element ratio of zirconium: titanium in Example 1 was 1: 1. The composite oxide thin film can be seen that Zr has a value more than twice as large as Ti. Through this, it can be seen that the composition of the final composite oxide thin film is controlled by the amount of the stabilizer added to the solution in which the zirconium precursor is dissolved and the amount of the titanium precursor added.

Table 1

3 shows the results of spectroscopic ellipsometry of Example 1 (TiO ₂ -ZrO ₂ hybrid in FIG.), Comparative Example 1 (TiO _{2 in} FIG.), And Comparative Example 2 (ZrO ₂ ). The left Y axis of FIG. 3A is a refractive index n, and the right Y axis is an extinction coefficient k. FIG. 3 (b) is a Tauc plot calculated based on the absorbance coefficient measurement result of FIG. 3 (a). The thickness of the TiO ₂ -ZrO ₂ hybrid thin film of Example 1 was 131 nm, the thickness of the TiO ₂ thin film of Comparative Example 1 was 192 nm, and the thickness of the ZrO ₂ thin film of Comparative Example 2 was 112 nm. As can be seen from the refractive index measurement graph of FIG. 3 (a), the TiO ₂ -ZrO ₂ hybrid thin film of the present invention has a refractive index of 1.85, which is a value between 1.78 of the refractive index of the TiO ₂ thin film of Comparative Example 1 and 1.87 of the ZrO ₂ thin film of Comparative Example 2 Has The refractive indices of the thin films prepared in Comparative Example 1 and Comparative Example have a smaller value than the known refractive index (the refractive index of the anatase structure TiO ₂ is 2.49 to 2.66 and the refractive index of the tetragonal structure ZrO ₂ is 2.12). This difference can be interpreted as the effect of nanopores formed on the thin film by removing the organic polymer as a structural derivative by the heat treatment. In addition, based on the degree of peak broadening of each diffraction pick of Figure 2 using the Scherrer formular (Scherrer formular) to calculate the grain size of Comparative Examples 2 to 3, and compared with the high magnification SEM picture As a result, it can be seen that the grains of Sunano are distributed on the amorphous matrix, which may affect the refractive index of the oxide thin film prepared in Comparative Examples 1 to 2.

Figure 3 (b) is a tau plot shown on the basis of the extinction coefficient results of Figure 3 (a) to determine the band gap energy of Example 1 and Comparative Examples 2 to 3, as can be seen in Figure 3 (b) The TiO ₂ -ZrO ₂ hybrid thin film of the present invention has a band gap energy of 3.61, which is a value between 3.43 eV of the bandgap energy of the TiO ₂ thin film of Comparative Example 1 and 5.34 eV of the bandgap energy of the ZrO ₂ thin film of Comparative Example 2 have.

As described above, the present invention has been described by specific matters and limited embodiments, such as specific materials. However, the present invention is provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments. Various modifications and variations can be made by those skilled in the art to which the invention pertains.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all the things that are equivalent to or equivalent to the scope of the claims as well as the claims to be described later belong to the scope of the present invention. will be.

1 is a high magnification scanning electron microscope (Field-emission Scanning Electron Microscopy) of Example 1 (FIG. 1A), Comparative Example 1 (FIG. 1B), and Comparative Example 2 (FIG. 1C),

FIG. 2 shows X-ray diffraction results of Example 1 (TiO ₂ -ZrO ₂ hybrid in FIG. 1), Comparative Example 1 (TiO _{2 in} FIG.), And Comparative Example 2 (ZrO ₂ ),

FIG. 3 is a spectroscopic ellipsometry measurement result of Example 1 (TiO ₂ -ZrO ₂ hybrid of FIG. 1), Comparative Example 1 (TiO _{2 of} FIG.) And Comparative Example 2 (ZrO ₂ ), and of FIG. The left Y-axis is the refractive index (n), the right Y-axis is the extinction coefficient (k), Figure 3 (b) is a tau plot (Tauc) calculated based on the absorption coefficient measurement results of Figure 3 (a) plot).

Claims (11)

(a) preparing a mixed solution by mixing 15 to 25 parts by weight of a stabilizer for lowering the activity of the zirconium precursor, 70 to 90 parts by weight of alcohol and 60 to 100 parts by weight of the titanium precursor with respect to 100 parts by weight of zirconium precursor; (b) preparing a zirconium-titanium precursor solution by adding 20 to 30 parts by weight of acid and 250 to 400 parts by weight of an organic polymer alcohol solution of 10 to 20% by weight based on 100 parts by weight of zirconium precursor to the mixed solution; And (c) coating the zirconium-titanium precursor solution on a substrate, followed by drying and heat treatment to prepare a nanoporous TiO ₂ -ZrO ₂ hybrid thin film in which an amorphous band gap energy is controlled; Method for producing a nanoporous TiO ₂ -ZrO ₂ hybrid thin film is controlled bandgap energy is carried out, including. delete The method of claim 1, The bandgap energy of the control nanoporous TiO ₂ -ZrO ₂ hybrid thin film of the band gap energy of crystalline TiO ₂ band gap energy than the band gap energy to the crystalline ZrO ₂ has an energy band gap adjusting nanoporous TiO _2, characterized in that not more than -ZrO ₂ hybrid thin film manufacturing method. The method of claim 3, wherein The bandgap energy is controlled by the mixing ratio of the zirconium precursor and the titanium precursor, characterized in that the bandgap energy controlled nanoporous TiO ₂ -ZrO ₂ hybrid thin film manufacturing method. The method of claim 1, wherein step (a) And mixing the zirconium precursor, the stabilizer, and the alcohol, followed by adding a titanium precursor, to prepare a bandgap energy-controlled nanoporous TiO ₂ -ZrO ₂ hybrid thin film. The method of claim 1, wherein step (b) The method of manufacturing a nanoporous TiO ₂ -ZrO ₂ hybrid thin film having a bandgap energy controlled by adding an acid to the mixed solution and then stirring, followed by adding the organic polymer alcohol solution. The method of claim 1, The zirconium precursor is a zirconium alkoxide, the titanium precursor is a method for producing a bandgap energy-controlled nanopore TiO ₂ -ZrO ₂ hybrid thin film, characterized in that the titanium alkoxide. The method of claim 7, wherein The stabilizing agent is a method of producing a nanopore TiO ₂ -ZrO ₂ hybrid thin film having a band gap energy controlled, characterized in that acetylacetone. The method of claim 1, The organic polymer alcohol solution is a method for producing a bandgap energy-controlled nanoporous TiO ₂ -ZrO ₂ hybrid thin film, characterized in that the ethylene oxide based block copolymer is a solution dissolved in alcohol. The method of claim 9, The ethylene oxide-based block copolymer is a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer, characterized in that the bandgap energy controlled nanoporous TiO ₂ -ZrO ₂ hybrid thin film manufacturing method. The process of claim 1, wherein The heat treatment is a method for producing a nanopore TiO ₂ -ZrO ₂ hybrid thin film with a band gap energy, characterized in that performed at 400 to 500 ℃.

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