KR20110057257A - Method for producing metal oxide thin film - Google Patents

Abstract

(Problem) In the manufacturing method of the metal oxide film obtained from the thin film manufacturing process using a metal organic compound, by heating, ultraviolet irradiation, or a plasma irradiation using the metal oxide nanoparticle solution and the metal organic compound solution containing metal oxide nanoparticles, An object of the present invention is to provide a method for efficiently producing a phosphor thin film such as Y ₂ O ₃ : Eu or CaTiO ₃ : Pr directly to an organic material substrate or a glass substrate.
(Solution) In the method for producing a metal oxide thin film using the chemical solution method, after applying the metal oxide nanoparticle solution to the support in advance, a metal oxide thin film is formed by firing or laser irradiation, and the metal oxide thin film phase A precursor solution containing a metal was applied to the metal, and the metal and the metal oxide were simultaneously used by using at least one or a plurality of steps of (1) heat treatment step, (2) plasma irradiation step, and (3) ultraviolet irradiation step. A method for producing a metal oxide thin film, characterized in that to remove other materials to form a metal-containing metal oxide thin film.

Description

Method for producing metal oxide thin film {METHOD FOR PRODUCING METAL OXIDE THIN FILM}

The present invention relates to a method for producing a metal oxide thin film containing metal on an organic substrate or a glass substrate with low energy.

Metal oxides are stable in the atmosphere and exhibit magnetic, semiconducting, dielectric, superconducting, or optical properties by controlling the crystal structure, metal composition, and oxygen irregularity. It is becoming.

For example, conductivity control is possible by controlling elemental substitutions or oxygen vacancies with different valences as in semiconductors, but since oxides such as ITO are in the visible region and exhibit transparency, they are used in applications such as liquid crystals and solar cells. Has been supporting.

For these conductors, perovskite oxides such as lead titanate, which exhibit high dielectric properties and dielectric properties, have been conventionally used in capacitors, sensors, and the like, and have been developed to develop nonvolatile memories for better integration of LSIs as thin films become thinner. have.

Similarly, even in the case of a material having a perovskite flexible structure, high-temperature superconducting oxides are being promoted for practical use in next-generation devices, current collectors, filter applications, and the like as their thicknesses are reduced. Thus, since metal oxide has many functions, development of various thin film manufacturing methods has been performed until now.

Among various thin film production methods, the chemical solution method is expected as a low-cost manufacturing process of a metal oxide thin film because it does not use a vacuum device and can control the composition of a solution strictly.

The chemical solution method uses a method of calcining a gel film obtained by a hydrolysis reaction of a metal alkoxide, a metal organic acid salt, a metal acetylacetonate, or the like as a precursor film, and thermal decomposition reaction of the organic compound and crystal growth by thermal equilibrium reaction. Metal organic decomposition (MOD) or applied pyrolysis.

Since MOD or coating pyrolysis method uses stable organometallic compounds in the air, the long-term stability of the raw material solution is excellent, whereas the pyrolysis process of the organic components of the raw material is required compared to the sol-gel method using the metal alkoxide. There is a problem with the substrate heat treatment.

For this reason, there existed a problem that it cannot manufacture into a current silicon device (refer nonpatent literature 1 and nonpatent literature 2).

In order to solve such a problem, a metal organic compound (metal organic acid salt, metal acetylacetonate, organic group having 6 or more carbon atoms) is produced by a method for producing a metal oxide on a substrate without heat treatment under a high temperature, which is conventionally known as coating pyrolysis. A metal oxide having a metal alkoxide) is dissolved in a solvent to form a solution, coated on a substrate, dried, and irradiated with a laser beam having a wavelength of 400 nm or less to form a metal oxide on the substrate. See Patent Document 1).

In this case, the metal organic compound is dissolved in a solvent to form a solution, which is applied to a substrate, followed by drying, and a laser beam having a wavelength of 400 nm or less, for example, an excimer laser selected from ArF, KrF, XeCl, XeF, and F ₂ . A method for producing a metal oxide is described, wherein a metal oxide is formed on a substrate by irradiation with a light. The irradiation with a laser beam having a wavelength of 400 nm or less is performed in a plurality of stages, and the irradiation of the first stage is carried out to completely It is also described to carry out by weak irradiation of the degree which cannot reach decomposition, and to perform strong irradiation which can be changed to oxide next.

In addition, the metal organic compound is a two or more compound composed of different metals, the metal oxide obtained is a composite metal oxide composed of different metals, and the metal of the metal organic acid salt is iron, indium, tin, zirconium, cobalt, iron, nickel, or lead. It is also known that it is selected from the group which consists of. Moreover, the low temperature production method of the La _1-x Sr _x MnO ₃ thin film for infrared sensor bolometer thin films is also known (refer patent document 2).

Moreover, after apply | coating the film | membrane which mixed the metal organic compound raw material uniformly to a support body, perovskite-related phosphor oxide thin film, SrTIO ₃ Pr, Al (patent document 3), and 200 nm or less at low temperature by the method of irradiating an ultraviolet-ray. A method for producing a Y ₂ O ₃ : Eu phosphor thin film in which Eu of crystallization and luminescence center ions is dissolved in Y ₂ O ₃ by irradiation with ultraviolet rays is disclosed (Patent Document 4).

Also, the generation of the alignment film of the metal oxide (BaTiO _3, etc.) containing Ba and Ti on the metal having a (111) crystal plane on the base material film is known (Patent Document 5).

However, in the manufacturing method of the metal oxide film obtained by the thin film manufacturing process using a metal organic compound, although it was effective as a method of manufacturing a high brightness oxide fluorescent substance on a silicon or a glass substrate, since high intensity laser beam needs to be irradiated for crystal growth, It became clear that it is difficult to manufacture directly on an organic substrate.

Japanese Laid-Open Patent Publication 2001-031417 Japanese Laid-Open Patent Publication 2002-284529 Japanese Laid-Open Patent Publication 2008-044803 Japanese Unexamined Patent Publication 2008-075073 Japanese Laid-Open Patent Publication 2008-028381

 Mizuta Susumu, Toshima Kumakai, "Synthesis of Superconducting Thin Films by Organic Acid Coating Pyrolysis", Industrial Materials, 35 (454), 78-79 (1987).  Mizuta Susumu, Toshima Kumagai, Manabe Takaaki, `` Synthesis of Superconducting Films by Coating Pyrolysis '', Japanese Chemical Society, 1997, 11-23 (1997)

As described above, the present invention relates to a method for producing a metal oxide film obtained in a thin film production process using a metal organic compound, wherein heating, ultraviolet irradiation or plasma is performed using a metal oxide nanoparticle solution and a metal organic compound solution containing metal oxide nanoparticles. by irradiation, organic material (for example PET) in the substrate, Y ₂ O _3: to provide a process for preparing a phosphor thin film, such as Pr directly: Eu or CaTiO _3.

Moreover, when manufacturing on a glass substrate, it is a subject to provide the method which can manufacture the high brightness fluorescent substance thin film by irradiating the conventional low laser energy in which the fluorescent substance is not produced | generated even if a laser irradiates the film | membrane which used a metal organic compound as a precursor. Shall be.

In order to achieve the above object, specifically, the following invention is provided.

1) In the method for producing a metal oxide thin film using the chemical solution method, after applying the metal oxide nanoparticle solution to the support in advance, a metal oxide thin film is formed by firing or laser irradiation, and on this metal oxide thin film A precursor solution containing a metal is applied, and at the same time, at least one of the (1) heat treatment step, (2) plasma irradiation step, and (3) ultraviolet irradiation step or a plurality of steps is used to obtain a metal and a metal oxide. Removing the substance to form a metal-containing metal oxide thin film.

2) Metal oxide nanoparticles having a single metal composition and crystal structure and a crystal structure equivalent to that of the nanoparticles, and a metal oxide nano having a dissimilar metal composition by a heating step or an ultraviolet irradiation step in which the support is not decomposed or melted. A thin film made of particles is formed on a support, and a precursor solution containing a metal is applied onto the thin film of these metal oxide nanoparticles, which is (1) heat treatment step, (2) plasma irradiation step, (3) A method for producing a metal oxide thin film, wherein a metal-containing metal oxide thin film is formed by removing a substance other than the metal and the metal oxide by simultaneously using at least one or a plurality of processes in the ultraviolet irradiation step.

3) The method for producing a metal oxide thin film according to claim 1 or 2, wherein the precursor solution is a metal oxide nanoparticle solution or a metal organic compound solution.

Moreover, this invention provides the following invention.

4) A method for producing a metal oxide thin film using the chemical solution method, wherein a precursor solution containing a metal oxide nanoparticle solution and a metal organic compound is applied to a support, followed by (1) heat treatment step and (2) plasma irradiation. A method of producing a metal oxide thin film, characterized in that a metal oxide thin film containing a metal is produced by removing an organic substance by simultaneously using at least one of the step and (3) ultraviolet irradiation step.

5) The method for producing a metal oxide thin film according to the above 4), wherein the metal composition ratio of the metal oxide nanoparticle solution in the precursor solution and the metal composition ratio of the metal organic compound are the same.

6) The manufacturing method of metal oxide thin film as described in said 4) or 5) comprised from the metal organic compound containing metal different from the metal which comprises the metal oxide nanoparticle of the said precursor solution.

Moreover, this invention provides the following invention.

7) The method for producing a thin film according to any one of 1) to 6), wherein the ultraviolet ray is irradiated without drying the precursor film containing the solvent.

8) The manufacturing method of the thin film as described in any one of said 1) -7) WHEREIN: The ultraviolet laser irradiation is carried out after ultraviolet irradiation by an ultraviolet lamp, The manufacturing method of the metal oxide thin film characterized by the above-mentioned.

9) The metal oxide nanoparticles according to any one of 1) to 8) above, wherein the metal oxide nanoparticles are prepared by heating and / or ultraviolet irradiation with a raw material solution selected from any one of metal organic acid salts and β diketonate or metal alkoxide. The manufacturing method of the metal oxide thin film of description.

10) The method for producing a metal oxide thin film according to any one of 1) to 9) above, wherein the metal organic compound solution is selected from any one of a metal organic acid salt and β diketonate or a metal alkoxide.

Moreover, this invention provides the following invention.

11) Metal oxides using precursor solutions containing metal oxide nanoparticles having perovskite structure, ilmenite structure, tungsten bronze structure, spinel, pyroclaw structure, rutile structure, anatase structure, fluorite structure The method for producing a metal oxide thin film according to any one of 1) to 10) above, wherein the nanoparticles are formed.

12) The oxide nanoparticle is an insulator composite metal oxide, and any one of the above 1) to 11) characterized in that a precursor solution obtained by mixing a metal organic compound solution containing a metal different from the valence of the constituent metal of the insulator metal oxide is used. The manufacturing method of the metal oxide thin film of Claim 1.

13) A precursor in which metal oxide nanoparticles of the parent material of the phosphor material are mixed with a metal organic compound containing at least one of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. A method for producing the metal oxide thin film according to any one of 1) to 12) above, wherein a solution is used.

14) The method for producing a metal oxide thin film according to any one of 1 to 11, wherein the oxide nanoparticles are AVO ₃ (A = Cs, Rb).

By irradiating plasma or ultraviolet light with or after heating in a temperature range in which the support is not decomposed, it becomes possible to carry out crystal growth, densification and doping of dissimilar metals of the target metal oxide thin film. As a result, the process time can be significantly shortened at a low temperature of the metal oxide thin film material, and the patterning required for the device can be performed simultaneously with the film formation.

As an organic raw material of the precursor used by the process of this invention, a metal organic acid salt, (beta) diketonate, the metal alkoxide which does not produce a hydrolysis reaction, etc. can be used. Specific examples thereof include metal acetates, metal 2 ethylhexanates, metal acetylacetonates, and metal naphthenates, which are absorbed by ultraviolet rays and are not dissolved in a solvent or in which a hydrolysis reaction does not proceed in the atmosphere. If it is a metal organic compound, it can use without a restriction | limiting in particular.

In addition, the metal oxide nanoparticles have a desired metal composition, or in a metal composition of a dissimilar metal having a different valence for expressing conductivity or a parent material without addition of emission center ions for fluorescence, If the particle size is about 1 to 100 nm, preferably about 1 to 30 nm, there is no particular limitation, and CVD, hydrothermal synthesis, solvent thermal synthesis, thermal decomposition, a method of irradiating ultraviolet laser to metal organic compounds, etc. can be used. Can be.

These metal oxide nanoparticles and metal organic compounds can be uniformly dispersed using an organic solvent. The solvent is preferably methanol, ethanol, propanol, butanol, hexanol, heptanol, ethyl acetate, butyl acetate, toluene, xylene, benzene, acetylacetonate, ethylene glycol and the like. The uniformly dispersed solution is not limited to a method of coating on a substrate such as spincoat, spray, inkjet, etc., and may be selected according to the purpose.

There is no restriction | limiting in particular about the metal oxide which can be manufactured by this method, A metal having a perovskite structure, a ilmenite structure, a tungsten bronze structure, a spinel, a pyrochlore structure, a rutile structure, an anatase structure, a fluorite structure An oxide film can be produced. For example, PbTiO ₃ , Pb (Ti, Zr) O ₃ , SrBi ₂ Ta ₂ O ₉ , BiFeO ₃ , Bi ₄ Ti ₃ O ₁₂ as a ferroelectric material, BaTiO ₃ , LiNbO ₃ , KTaO ₃ as a dielectric material. And SrTiO ₃ can be produced.

In addition, the conductive material is a composite oxide of _{A 1- x B x MnO 3 (} A = Pr, Nd, La, Sm, B = Ca, Sr, Ba), La 1 - x Sr x CoO 3, SrRuO 3, LaNiO ₃ , La-doped SrTiO ₃ , Nb-doped SrTiO ₃ , superconducting materials and the like are possible.

In the phosphor material, the oxide is represented by a metal composition of ABO ₃ , A ₂ BO ₄ , A ₃ B ₂ O ₇ (wherein A, B, O sites may have a defect) as a metal forming the phosphor material, and A Ca, Sr, Ba, B is Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu is used for the oxide using at least one element selected from Ti, Zr At least one may be added, and in addition to this, one or more of Al, Ga, and In may be added.

It is also effective for thin films containing trace amounts of conductive materials such as In ₂ O ₃ , SnO ₂ , ZnO, and metals in advance.

The support is a glass substrate, a glass substrate, strontium titanate (SrTIO _3), lanthanum aluminate (LaAlO _3), magnesium (MgO), lanthanum strontium oxide, tantalum aluminum _{((La x Sr 1 -x)} (Al x Ta 1- oxide _x ) O ₃ ), neodymium hydrate (NdGaO ₃ ), yttrium aluminate (YAlO ₃ ) single crystal, aluminum oxide (Al ₂ O ₃ ), yttria stabilized zirconia ((Zr, Y) O ₂ , YSZ) substrate 1 type etc. can be used.

In the present invention, it is preferable to use a metal oxide nanoparticle solution containing a metal organic compound after forming a thin film using a desired metal oxide nanoparticle solution or a heterogeneous metal oxide having the same crystal structure on the support. It is effective for reducing the energy of ultraviolet rays to be irradiated.

In the preparation of the present thin film, the substrate is produced by plasma irradiation or ultraviolet irradiation at room temperature on an organic substrate, and in a support such as other glass, the support is not deteriorated if it is in the range of 25 to 600 ° C. to achieve the above object. It can be produced by producing a thin film by ultraviolet lamp, laser and plasma irradiation simultaneously with substrate heating.

The heating method is not particularly limited as long as the support and the electrode are not decomposed or deteriorated. Various heating methods such as an electric furnace, an infrared heating furnace, and microwave heating can be used. As the ultraviolet light source, any one of a lamp of 400 nm or less and a pulse laser can be used.

The ultraviolet wavelength, light intensity, repetition rate (pulse or continuous) substrate temperature, and atmosphere in the step 2 are appropriately selected depending on the type of thin film to be subjected. Although the ultraviolet wavelength is not specifically limited, 400 nm or less is preferable and pulsed laser light or lamp light may be sufficient.

The light source used for light irradiation may be either an ultraviolet laser or an ultraviolet lamp, but an ultraviolet laser XeF (351 nm), XeCl (308 nm), KrF (248 nm), ArF (193 nm) It is preferable to use an excimer laser such as F2 (157 nm), a YAG laser (fourth harmonic: 266 nm), and an Ar ion laser (second harmonic: 257 nm).

Since the transmittance of the optical material decreases as the wavelength is shortened, a KrF (248 nm) laser is suitable as a light source for applying a refractive optical system using a lens. Plasma irradiation can be irradiated in any gas of atmospheric pressure, nitrogen, and oxygen as long as there is no heating effect.

The present invention can produce a thin film on a substrate containing organic, which has not been possible by low temperature and low energy ultraviolet radiation, and thus has an excellent effect of producing a metal oxide thin film which has high production efficiency and is suitable for mass production.

A method of applying metal oxide nanoparticles onto a support and irradiating plasma or ultraviolet light, wherein the nanoparticles have the same crystal structure or the same crystal structure as the parent material forming, for example, a phosphor on the support before applying the metal organic compound. It is a manufacturing method of the metal oxide thin film which irradiates a plasma and an ultraviolet-ray after forming a particle thin film and apply | coating the metal organic compound solution which may contain the target metal oxide nanoparticle solution or metal oxide nanoparticle solution after that. As ultraviolet light used by this invention, a laser beam is mentioned, for example.

According to the objective, it can select during the predetermined process, or before and after each process. In addition, after spin coating a solution of an organic compound of a metal to a substrate, drying at 130 ° C. in an incubator for solvent removal, or irradiating an ultraviolet lamp, the sample is placed in a sample holder in a laser chamber, and the atmosphere is controlled to control the room temperature to Laser irradiation at 500 degreeC can also be carried out.

After applying the metal oxide nanoparticles to the support, a thin film is formed by firing or laser irradiation. Then, laser irradiation is performed to each of the film | membrane which apply | coated and dried the metal organic compound, and this main baking initial film.

For example, when the SnO ₂ : Eu (Europium) film was produced, the following effects were confirmed. Orange photoluminescence by applying a solution obtained by mixing Eu organic acid salt to SnO ₂ nanoparticles on a glass substrate on a support, irradiating an ultraviolet lamp and irradiating an ArF laser at a temperature of room temperature to 400 ° C. or lower after drying. Was found to be observed.

This phenomenon can be considered to be due to the promotion of crystal growth of the parent material SnO _{2 and} the solid solution of europium ion as the emission center by ultraviolet irradiation.

Moreover, in the conventional SnO ₂ : Eu thin film formation method, it is known that the crystallization reaction and the solid solution reaction of the luminescent center atoms proceed in the heat treatment at 1000 ° C. or higher. It was confirmed that the solid solution reaction of the reaction and the emission center atom proceeded.

Further, CaTiO _3: Pr (praseodymium) nanoparticle film, PET (polyester terephthalate ethylene) and then applied to the support construction, by irradiating a UV lamp and irradiated with a laser beam at 25 ℃, was observed in the red photoluminescence.

In the conventional CaTiO ₃ : Pr thin film formation method, it is known that the crystallization reaction and the solid solution reaction of the luminescent center atoms proceed in the heat treatment at 900 ° C. or higher. Confirmed.

Example

EMBODIMENT OF THE INVENTION Hereinafter, the characteristic of this invention is demonstrated in detail based on an Example. In addition, the following description is made to facilitate the understanding of the present invention, but is not limited thereto. That is, modifications, embodiments, and other examples based on the technical spirit of the present invention are included in the present invention.

example As the substrate used in the embodiment of the present invention, an alkali free glass substrate, a glass substrate with ITO, and a PET substrate were used. It goes without saying that other substrate materials can be used. The following raw material solution was used as a metal organic compound raw material solution. Precursor solutions other than those shown below will be described in the respective Examples and Comparative Examples.

(Raw material solution 1-1)

A raw material solution in which 2 ethyl-1 hexanolate titanium (Ti) solution and 2-ethylhexanoate praseodymium (Pr) solution are mixed with 2 calcium hexanoate solution in a predetermined composition ratio.

(Raw material solution 1-2): (replacement raw material solution of raw material solution 1)

Instead of praseodymium (Pr) in the raw material solution 1-1, 2-ethylhexanoic acid of each metal of Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, which is a rare earth metal, was prepared , A raw material solution mixed with a 2 ethyl hexanoate solution and a 2 ethyl-1 hexanolate titanium solution.

(Raw Solution 1-3): (Alternative Raw Material Solution of Raw Material Solution 1)

A barium diethylhexanoate solution was used as a substitute for the 2 calcium hexanoate solution, and the other was made a raw material solution equivalent to the raw material solution 1-1 and the raw material solution 1-2.

(Raw Solution 1-4): (Alternative Raw Material Solution of Raw Material Solution 1)

A 2 strontium hexanate solution was used as a substitute for the 2 calcium hexanoate solution, and the other was used as a raw material solution equivalent to the raw material solution 1-1 and the raw material solution 1-2.

(Raw Solution 1-5): (Alternative Solution of Raw Material Solution 1)

2 ethyl zirconium zirconium (Zr) solution is used as a substitute for the 2 ethyl-1 hexanolate titanium (Ti) solution of the raw material solution 1-1, and the other is equivalent to the raw material solution 1-1 and the raw material solution 1-2. It was set as the raw material solution.

(Raw material solution 2-1)

CaTiO ₃ : Pr nanoparticle powder was prepared using the raw material solution 1 by the following method. The stock solution was placed in a crucible and heated at 200 ° C. to remove the solvent. Then, it baked preliminarily for 300 degreeC and 6 hours, and then baked for 500 degreeC and 12 hours. The resulting powder was dispersed in a mixed solvent of ethanol: ethylene glycol. In other words, this is CaTiO _3: manufactured by one, and dispersed again in a solvent to this powder Pr nano particles powder was a precursor solution.

(Raw Solution 2-2): (Alternative Raw Material Solution of Raw Material Solution 2)

Instead of praseodymium (Pr) in the raw material solution 2-1, mixed particle powders of CaTiO ₃ with metals of Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb as rare earth metals were prepared. And this mixed particle powder was made into the precursor solution disperse | distributed to the solvent again.

(Raw solution 2-3)

In the preparation of CaTiO ₃ : Pr nanoparticle powder of raw material solution 2-1, the final firing temperature is 900 ° C. It baked for 12 hours. The resulting powder was dispersed in a mixed solvent of ethanol: ethylene glycol.

(Raw material solution 2-4): (Ca ₃ Ti ₂ O ₇ : Pr nanoparticle solution)

The same operation was performed except having made metal composition ratio Ca: Ti = 3: 2 at the time of manufacture of raw material solution 2-1.

(Raw material solution 2-5): (Ca ₃ Ti ₂ O ₇ : Pr nanoparticle solution)

The same operation was performed except having made metal composition ratio Ca: Ti = 3: 2 at the time of manufacture of raw material solution 2-3.

(Raw solution 2-6)

The RbVO ₃ particles were mixed with SYM-RbO ₃ solution and VO ₂ solution of Corkdo Chemical at a predetermined ratio, and then calcined at 400 ° C for 1 hour, and then 700 ° C. Calcined at 30 minutes. The resulting powder was dispersed in a mixed solvent of ethylene glycol.

(Raw solution 2-7)

RbVO ₃ particles contain Rv ₂ CO ₃ and V ₂ O ₅ Mixed at a predetermined ratio, firing temperature: 700 ℃ It was calcined for 30 minutes at . The powder pulverized the product was dispersed in a mixed solvent of ethylene glycol.

(Raw solution 3)

Raw material solution 1-1 or raw material solution 1-2, and raw material solution 2-1 or raw material solution 2-2 were mixed at a predetermined ratio.

(Raw solution 4)

BaTiO ₃ nanoparticle solution was used as the solution of Nikol.

(Raw solution 5)

2% Eu-EMOD solution (made by Kododo Chemical Co., Ltd.) was mixed with the tin oxide nanoparticle solution (made by Mitsubishi Material).

(Ultraviolet light irradiation)

Ultraviolet light irradiation used 172 nm, 222 nm excimer lamps, and ArF, KrF, and XeCl excimer lasers.

(Example 1-1)

BaTiO ₃ nanoparticle solution (raw material solution 4) was spin-coated to a glass substrate with ITO. After drying at 200 ℃, followed by firing at 500 ℃, it was produced in the BaTiO ₃ / ITO / glass substrate.

The substrate was coated with raw material solution 1 (2 ethyl-1 hexanolate titanium solution and 2-ethylhexanoate praseodymium solution on 2 calcium hexanoate solution), and irradiated with a 20 mJ / cm2 KrF laser at 50 Hz for 2 minutes. It was.

About the irradiation part, photoluminescence was measured with the excitation light of 320 nm using Shimadzu UV5300, and light emission of 615 nm (red) was observed. As a result, the existence of the CaTiO ₃ thin film containing praseodymium was confirmed by low energy laser irradiation.

(Example 1-2)

In addition, 2-ethylhexanoic acid of each element of Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb is prepared instead of praseodymium (Pr) as an alternative solution of raw material solution 1, Even in the case of mixing with 2 ethyl-1 hexanolate titanium solution in 2 ethyl hexanoate solution, the presence of CaTiO ₃ thin films containing these rare earth metals was confirmed by the same operation.

(Example 1-3)

BaTiO ₃ nanoparticle solution (raw material solution 4) was spin coated onto a PET substrate. After drying at 100 ℃, by treatment with an ultraviolet lamp of 172 ㎚, to prepare a BaTiO ₃ / PET substrate.

The substrate was coated with raw material solution 1 (2 ethyl-1 hexanolate titanium solution and 2-ethylhexanoate praseodymium solution on 2 calcium hexanoate solution), and then irradiated with a 40 mJ / cm2 KrF laser at 5 kV for 5 minutes. It was. About the irradiation part, photoluminescence was measured with the excitation light of 320 nm using Shimadzu UV5300, and light emission of 615 nm (red) was observed. As a result, the existence of the CaTiO ₃ thin film containing praseodymium was confirmed by low energy laser irradiation.

(Comparative Example 1-1)

After coating the raw material solution 1 on the glass substrate (ITO (100 nm) / glass substrate) with ITO without the support layer (BaTiO ₃ nanoparticles) used in Example 1, a KrF laser of 20 mJ / cm 2 was Irradiation was carried out at 50 kPa for 2 minutes. As a result of measuring photoluminescence with 320 nm excitation light with Shimadzu UV5300, no emission of 615 nm (red) was observed in the irradiated part.

Thus, when the support layer manufactured from the nanoparticles of an oxide does not exist, it turned out that a predetermined characteristic cannot be acquired even if the raw material solution 1 is used by low energy laser irradiation. From Example 1 and Comparative Example, it can be seen that the presence of the support layer produced from the nanoparticles of the oxide is important.

(Comparative Example 1-2)

ITO without the support layer (BaTiO ₃ nanoparticles) used in Example 1 After coating raw material solution 1-1 on the attached glass substrate (ITO (100 nm) / glass substrate), the 20 mJ / cm <2> KrF laser was irradiated at 50 Hz for 2 minutes. As a result of measuring photoluminescence with 320 nm excitation light with Shimadzu UV5300, no emission of 615 nm (red) was observed in the irradiated part.

Also in this case, when the support layer made from the nanoparticles of the oxide does not exist in the same manner as in Comparative Example 1-1, the predetermined characteristics could not be obtained even when the raw material solution 1 was used in the low energy laser irradiation.

(Example 2-1)

Example 1 The raw material solution 2-1 was used instead of the raw material solution 1 used by the method. Other conditions were the same as in Example 1. Thereby, photoluminescence of 615 nm (red) was observed similarly to Example 1. As a result, the existence of the CaTiO ₃ phosphor thin film containing praseodymium was confirmed by low energy laser irradiation.

(Example 2-2)

Example 2-1 The raw material solution 2-2 was used instead of the raw material solution 2-1 used by the method. Other conditions were the same as in Example 1-1. Thereby, photoluminescence of 615 nm (red) was observed similarly to Example 1-1. As a result, the existence of the CaTiO ₃ phosphor thin film containing praseodymium was confirmed by low energy laser irradiation.

(Example 2-3)

Example 2-1 The raw material solution 2-3 was used instead of the raw material solution 2-1 used by the method. Other conditions were the same as in Example 1-1. Thereby, photoluminescence of 615 nm (red) was observed similarly to Example 1-1. As a result, the existence of the CaTiO ₃ phosphor thin film containing praseodymium was confirmed by low energy laser irradiation.

(Example 2-4)

Example 2-1 The raw material solution 2-4 was used instead of the raw material solution 2-1 used by the method. Other conditions were the same as in Example 1-1. As a result, a photoluminescence of 615 nm (red) was observed . As a result, the existence of the CaTiO ₃ phosphor thin film containing praseodymium was confirmed by low energy laser irradiation.

(Example 2-5)

Example 2-1 The raw material solution 2-5 was used instead of the raw material solution 2-1 used by the method. Other conditions were the same as in Example 1-1. The photoluminescence was measured with the Shimadzu UV5300 by 350 nm excitation light with respect to the irradiation part, and white photoluminescence was observed. The film showed a transmittance of 80% in the visible region (550 ㎚). As a result, the presence of the RbVO ₃ transparent phosphor film was confirmed by low energy laser irradiation.

(Example 2-6)

Example 2-1 The raw material solution 2-6 was used instead of the raw material solution 2-1 used by the method. Other conditions were the same as in Example 1-1. The photoluminescence was measured with the Shimadzu UV5300 by 350 nm excitation light with respect to the irradiation part, and white photoluminescence was observed. Moreover, the transmittance | permeability of a membrane showed 80% in the visible region (550 nm). As a result, the presence of the RbVO ₃ transparent phosphor film was confirmed by low energy laser irradiation.

(Example 2-7)

Example 2-1 The raw material solution 2-7 was used instead of the raw material solution 2-1 used in the method. Other conditions were the same as in Example 1-1. The photoluminescence was measured with the Shimadzu UV5300 by 350 nm excitation light with respect to the irradiation part, and white photoluminescence was observed. Moreover, the transmittance | permeability of a membrane showed 80% in the visible region (550 nm). As a result, the presence of the RbVO ₃ transparent phosphor film was confirmed by low energy laser irradiation.

(Example 2-8)

BaTiO ₃ nanoparticle solution (raw material solution 4) was spin coated onto a PET substrate. After drying at 100 ℃, by treatment with an ultraviolet lamp of 172 ㎚, to prepare a BaTiO ₃ / PET substrate.

After coating raw material solution 2-1 on this board | substrate, the 40 mJ / cm <2> KrF laser was irradiated with 5 Hz for 5 minutes. About the irradiation part, photoluminescence was measured with the excitation light of 320 nm using Shimadzu UV5300, and light emission of 615 nm (red) was observed. As a result, the existence of the CaTiO ₃ thin film containing praseodymium was confirmed by low energy laser irradiation.

(Example 2-9)

BaTiO ₃ nanoparticle solution (raw material solution 4) was spin coated onto a PET substrate. 100 ℃ After drying at, a treatment with the ultraviolet lamp 172 ㎚, to prepare a BaTiO ₃ / PET substrate.

example After coating raw material solution 2-1 on the board | substrate, the ultraviolet lamp of 172 nm was irradiated for 2 minutes. About the irradiation part, photoluminescence was measured with the excitation light of 320 nm using Shimadzu UV5300, and light emission of 615 nm (red) was observed. As a result, the presence of a CaTiO ₃ thin film containing praseodymium was confirmed by ultraviolet lamp irradiation.

(Example 3-1)

Example 1 In the method, raw material solution 3 was used instead of raw material solution 1-1. The intensity | strength of the photoluminescence of 615 nm (red) increased. In the case where the metal organic compound solution and the metal oxide nanoparticle solution are further contained in the solution in which the raw material solution 1-1 and the raw material solution 2-1 are mixed, that is, the precursor solution, the CaTiO ₃ phosphor thin film containing praseodymium is further formed. Validity was confirmed.

(Example 3-2)

When the raw material solution 1-1 or the raw material solution 1-2, and the raw material solution 2-1 or the raw material solution 2-2 were arbitrarily combined instead of the said Example 3-1, the same result as the above was obtained.

That is, even in the case of containing each metal element of Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb instead of praseodymium (Pr), it is more effective for forming a CaTiO ₃ phosphor thin film. Could confirm.

(Example 4)

In Example 2-1, a BaTiO ₃ / ITO / glass substrate was used as the substrate in the same manner as in Example 1-1. In Example 4, a glass substrate with ITO was used, and a CaTiO ₃ : Pr nanoparticle solution ( Raw material solution 2-1) was spin-coated to the glass substrate with ITO. After drying at 100 ° C, a 20 mJ / cm 2 KrF laser was irradiated with 50 kPa for 2 minutes.

About the irradiation part, photoluminescence was measured with the excitation light of 320 nm using Shimadzu UV5300, and light emission was observed at 615 nm (red).

In this way, also be used as a glass substrate, a precursor solution containing a metal oxide nano-particles was found to be valid for the formation of a thin film phosphor CaTiO _3.

(Example 5)

A CaTiO ₃ : Pr nanoparticle solution (raw material solution 2-1) was spin coated onto a PET substrate. After drying at 100 degreeC, the ultraviolet-ray lamp of 222 nm was irradiated. The irradiation part measured photoluminescence with 320 nm excitation light, and light emission was observed at 615 nm (red).

With this Similarly, even if the precursor solution containing the metal oxide nanoparticles is used on a PET substrate as it is, it is effective to form a CaTiO ₃ phosphor thin film by irradiating an ultraviolet lamp. I could confirm it.

(Example 5-1)

A CaTiO ₃ : Pr nanoparticle solution (raw material solution 2-1) was spin coated onto a PET substrate. 100 ℃ After drying, the 222 nm ultraviolet ray lamp was irradiated.

Subsequently, an ultraviolet lamp of 172 nm was irradiated. The irradiation part measured photoluminescence with 320 nm excitation light, and light emission was observed at 615 nm (red).

Thus, even when the precursor solution containing metal oxide nanoparticles was used for a PET substrate as it is, it was confirmed that it is effective for forming a CaTiO ₃ phosphor thin film by irradiating an ultraviolet lamp.

(Example 5-2)

A CaTiO ₃ : Pr nanoparticle solution (raw material solution 2-2) was spin coated onto a PET substrate. 100 ℃ After drying, the 222 nm ultraviolet ray lamp was irradiated. The irradiation part measured photoluminescence with 320 nm excitation light, and light emission was observed at 615 nm (red). In addition, the transmittance | permeability of the membrane showed 80% in the visible region (550 nm). As described above, even if the precursor solution containing the metal oxide nanoparticles is used in the PET substrate as it is, it is effective to form a CaTiO ₃ : Pr phosphor thin film by irradiating an ultraviolet lamp. I could confirm it.

(Example 5-3)

A CaTiO ₃ : Pr nanoparticle solution (raw material solution 2-3) was spin coated onto a PET substrate. 100 ℃ After drying, the 222 nm ultraviolet ray lamp was irradiated. The irradiation part measured photoluminescence with 320 nm excitation light, and light emission was observed at 615 nm (red). In addition, the transmittance | permeability of the membrane showed 80% in the visible region (550 nm). As described above, even when the precursor solution containing the metal oxide nanoparticles was used as it is on the PET substrate, it was confirmed that it was effective in forming a CaTiO ₃ : Pr phosphor thin film by irradiating an ultraviolet lamp.

(Example 5-4)

A Ca ₃ Ti ₂ O ₇ : Pr nanoparticle solution (raw material solution 2-4) was spin coated onto a PET substrate. 100 ℃ After drying, the 222 nm ultraviolet ray lamp was irradiated. The irradiation part measured photoluminescence with 320 nm excitation light, and light emission was observed at 615 nm (red). In addition, the transmittance | permeability of the membrane showed 80% in the visible region (550 nm). As described above, even when the precursor solution containing the metal oxide nanoparticles was used as it is on the PET substrate, it was confirmed that it was effective in forming a CaTiO ₃ : Pr phosphor thin film by irradiating an ultraviolet lamp.

(Example 5-5)

An RbVO ₃ particle solution (raw material solution 2-5) was spin coated onto a PET substrate. 100 ℃ After drying, the 222 nm ultraviolet ray lamp was irradiated. As a result of measuring the photoluminescence with 350 nm excitation light, the irradiation part observed white light emission. Moreover, the transmittance | permeability of a membrane showed 80% in the visible region (550 nm). As described above, even when the precursor solution containing the metal oxide nanoparticles was used as it is on the PET substrate, it was confirmed that the film was effective in forming the RbVO ₃ transparent phosphor thin film by irradiating an ultraviolet lamp.

(Example 5-6)

An RbVO ₃ particle solution (raw material solution 2-6) was spin coated onto a PET substrate. 100 ℃ After drying, the 222 nm ultraviolet ray lamp was irradiated. As a result of measuring the photoluminescence with 350 nm excitation light, the irradiation part observed white light emission. In addition, the transmittance | permeability of the membrane showed 80% in the visible region (550 nm). As described above, even when the precursor solution containing the metal oxide nanoparticles was used as it is on the PET substrate, it was confirmed that the film was effective in forming the RbVO ₃ transparent phosphor thin film by irradiating an ultraviolet lamp.

(Example 6)

A CaTiO ₃ : Pr nanoparticle solution (raw material solution 2-1) was spin coated onto a PET substrate. 100 ℃ After drying, the plasma was irradiated. The irradiation part measured photoluminescence with 320 nm excitation light, and light emission was observed at 615 nm (red). In this way, by also investigating the plasma with the precursor solution containing the metal nano-particles as the PET substrate, and confirmed that the effective formation of a thin film phosphor CaTiO _3.

(Example 7)

2 (raw material solution 1-3) containing a barium ethyl hexanoate solution was spin-coated to a PET substrate, irradiated with a 222 nm ultraviolet lamp to form BaTiO ₃ nanoparticles, and then CaTiO ₃ : Pr nano The particle solution (raw material solution 2-1) was made into spin coat. After drying at 100 ° C, a 20 mJ / cm 2 KrF laser was irradiated with 50 kPa for 2 minutes. As a result of measuring photoluminescence with an excitation light of 320 nm, light emission was observed at 615 nm (red).

In this case, the same result even if a method of preparing a SrTiO ₃ nanoparticles was obtained by using the raw material solutions 1 to 4 of 2-ethylhexanoic acid, strontium solution.

(Comparative Example 2)

After coating the PET substrate with the organometallic compound raw material solution 1, a 20 mJ / cm 2 KrF laser was irradiated at 50 kPa for 2 minutes, and the PET substrate was decomposed by photoreaction. Moreover, as a result of measuring the photoluminescence with the 320 nm excitation light, no irradiation was observed. In this regard, at least the presence of oxide nanoparticles on the substrate is required. I could confirm it.

(Example 8)

The raw material solution 3-1 was coated on the glass substrate. This raw material solution 3-1 mixes raw material solution 1-1 and raw material solution 2-1 by predetermined ratio.

That is, the raw material solution 1-1: 2 calcium hexanoate solution and the raw material solution 2-1 phosphorus mixed with 2 ethyl-1 hexanolate titanium (Ti) solution and 2-ethylhexanoate praseodymium (Pr) solution CaTiO _3: the precursor solution composed of a solution of Pr nanoparticle powder.

After irradiating an 172 nm excimer lamp to the coated film, photoluminescence was measured by the excitation light of 320 nm, and light emission was observed at 615 nm (red). The same result was obtained when raw material solution 1-2 or raw material solution 2-2 was used as a precursor solution.

(Comparative Example 3)

The raw material solution 3-1 was coated on the glass substrate. The photoluminescence was measured with the excitation light of 320 nm for the film | membrane after coating, and light emission was not observed. In contrast with Example 9, it was found that the phosphor could not be formed because the excimer lamp of 172 nm was not irradiated.

(Comparative Example 4)

When the 172 nm excimer lamp was irradiated to the film | membrane which coated the raw material solution 1-1 on the glass substrate, photoluminescence was measured with the excitation light of 320 nm, and luminescence was not observed.

Thus, when the nanoparticles of an oxide do not exist, it turned out that a predetermined characteristic cannot be acquired even if raw material solution 1-1 is used with the 172 nm excimer lamp. From the above examples and comparative examples it can be seen that it is important to prepare from a solution containing nanoparticles of oxide.

(Example 9)

A mixture of an organic metal compound solution containing Eu on SnO ₂ nanoparticles was applied to a glass substrate to the substrate. The 80 mJ / cm <2> ArF laser was irradiated at 10 Hz for 2 minutes at 300 degreeC. The irradiation part measured photoluminescence with 320 nm excitation light, and light emission was observed at 590 nm.

(Example 10)

A precursor solution for forming BaTiO ₃ nanoparticles on a Pt-attached SiO ₂ substrate, comprising mixing a Ba2 ethylhexanoate solution with a metal composition of 1: 1 and a metal organic compound solution containing Ti-2 ethyl-hexanolate Was applied to the substrate. The BaTiO ₃ film | membrane produced | generated when the ArF laser of 80 mJ / cm <2> irradiated at 10 Hz for 2 minutes at room temperature.

As mentioned above, this invention uses the precursor solution containing a metal oxide nanoparticle and an organometallic compound, and also manufactures which has the same crystal structure as fluorescent substance material which is a target metal oxide as a base material, and has low laser irradiation energy. The metal oxide thin film can be produced at a low temperature, and the metal oxide thin film can be produced on an organic substrate such as a PET substrate by ultraviolet laser, lamp, or plasma irradiation, and thus it is useful for the production of high efficiency devices by thinning.

Claims (14)

A method of producing a metal oxide thin film using the chemical solution method, wherein a metal oxide nanoparticle solution is applied to a support in advance, and then a metal oxide thin film is formed by firing or laser irradiation, and the metal is contained on the metal oxide thin film. A precursor solution is applied and the material is removed by using at least one of the (1) heat treatment step, (2) plasma irradiation step, and (3) ultraviolet irradiation step or a plurality of steps simultaneously. A metal oxide thin film production method characterized by forming a metal-containing metal oxide thin film. By a heating process or an ultraviolet irradiation process in which the support is not decomposed or melted, the metal oxide nanoparticles having one metal composition and crystal structure and the crystal structure equivalent to the nanoparticles, and also as metal oxide nanoparticles of different metal composition A thin film is formed on a support, and a precursor solution containing a metal is applied onto a thin film of these metal oxide nanoparticles, which is subjected to (1) heat treatment step, (2) plasma irradiation step, and (3) ultraviolet irradiation. A method for producing a metal oxide thin film, characterized in that a metal-containing metal oxide thin film is formed by removing materials other than metal and metal oxide by simultaneously using at least one or a plurality of processes. The method according to claim 1 or 2,
The precursor solution is a method for producing a metal oxide thin film, characterized in that the metal oxide nanoparticle solution or metal organic compound solution. A method for producing a metal oxide thin film using the chemical solution method, comprising: (1) heat treatment step, (2) plasma irradiation step, after applying a precursor solution containing a metal oxide nanoparticle solution and a metal organic compound to a support; 3) A method for producing a metal oxide thin film, characterized in that a metal oxide thin film containing a metal is produced by removing an organic substance by simultaneously using at least one or a plurality of processes of ultraviolet irradiation. The method of claim 4, wherein
The metal composition ratio of the metal oxide nanoparticle solution in the said precursor solution and the metal composition ratio of a metal organic compound are the same, The manufacturing method of the metal oxide thin film characterized by the above-mentioned. The method according to claim 4 or 5,
A method for producing a metal oxide thin film, comprising a metal organic compound containing a metal different from the metal constituting the metal oxide nanoparticles of the precursor solution. The method according to any one of claims 1 to 6,
A method for producing a metal oxide thin film, which comprises irradiating ultraviolet rays without drying the precursor film containing the solvent. The method according to any one of claims 1 to 7,
Irradiating an ultraviolet laser after ultraviolet irradiation by an ultraviolet lamp, The manufacturing method of the metal oxide thin film characterized by the above-mentioned. The method according to any one of claims 1 to 8,
The metal oxide nanoparticles are prepared by heating and or irradiating ultraviolet light with a raw material solution selected from a metal organic acid salt and β diketonate or a metal alkoxide. The method according to any one of claims 1 to 9,
The metal organic compound solution is selected from a metal organic acid salt and β diketonate or metal alkoxide. The method according to any one of claims 1 to 10,
Metal oxide nanoparticles using a precursor solution comprising metal oxide nanoparticles having perovskite structure, ilmenite structure, tungsten bronze structure, spinel, pyroclaw structure, rutile structure, anatase structure, fluorite structure Method for producing a metal oxide thin film, characterized in that to form a. The method according to any one of claims 1 to 11,
The oxide nanoparticle is an insulator composite metal oxide, and a precursor solution obtained by mixing a valence of a constituent metal of an insulator metal oxide with a metal organic compound solution containing a different metal is used. The method according to any one of claims 1 to 12,
A precursor solution containing a metal organic compound containing at least one of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb is used as the metal oxide nanoparticle of the parent material of the phosphor material. Method for producing a metal oxide thin film, characterized in that. The method according to any one of claims 1 to 11,
The oxide nanoparticles are AVO ₃ (A = Cs, Rb), wherein the metal oxide thin film is produced.