JP5116016B2 - Method for manufacturing phosphor thin film - Google Patents

Description

  With the development of the information society centered on the Internet in recent years, demand for liquid crystal displays, plasma displays, field emission displays (FED), and flat panel displays (hereinafter referred to as FPD) typified by organic EL has been increasing. Therefore, development of a method for producing the phosphor is an extremely important issue.

  The field emission display (hereinafter referred to as FED) is a display device based on the principle that a phosphor emits light emitted from a flat electron emission source (emitter) in a vacuum. The flat technology enables a bright and high-contrast screen like a CRT on a large flat display. In a cathode ray tube, there is one electron gun that emits electrons at a position that is a few tens to several tens of centimeters away from the light emitting surface. And each emits electrons toward the phosphors on the glass substrate, which are arranged to face each other by several mm. Unlike a cathode ray tube, there is no need for deflection, so it is possible to make a flat display with a thin large screen, and power consumption is about half that of a cathode ray tube display. Along with liquid crystal and PDP (plasma display), it is expected to be a technology for realizing the next generation of large flat-screen TVs / displays.

Among various phosphors, oxide phosphors are stable against electron beams, and thus are expected as phosphors for FED. Conventionally, a red phosphor having Y ₂ O ₃ doped with Eu has been used, but as a red light emitting phosphor for low-speed electron beams, a phosphor based on SrTiO ₃ , which is a complex oxide. Has been developed. (Patent Document 1)
For the production, the phosphor material is fired at 1100 to 1400 ° C. for 1 to 6 hours in an electric furnace to produce fine particles. Further, by changing Sr to Ca, an oxide-based phosphor that has a longer lifetime than a SrTiO ₃ : Pr, Al phosphor and emits light with high brightness even with a low-speed electron beam, and a fluorescent display device have been developed. (Patent Document 2)
However, the conventional phosphor thin film has a problem that it cannot maintain high luminous efficiency due to gas emission by electron beam irradiation because the phosphor film is produced by mixing the obtained fine particles and binder and using screen printing technology. there were. As one of the solutions to such problems, improvement of characteristics has been studied by directly manufacturing rare earth phosphor thin films on glass substrates. However, since the crystallization temperature is usually high, it is fabricated on glass substrates. There was a problem that could not be done. (Non-Patent Document 1)
As a method for producing a certain kind of metal oxide film, metal organic acid salt or organometallic compound M _m R _n (M = Si, Ge, Sn, Pb group 4b elements, Cr, Mo, W Group 6a element, Group 7a element of Mn, Tc, Re: R = CH ₃ , C ₂ H ₅ , alkyl group such as C ₃ H ₇ , C ₄ H ₉ , or CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₃ H ₇ COO ⁻ , C ₄ H ₉ COO ^— or the like, or CO carbonyl group: m and n are integers) or dissolved in a solvent, or the liquid is left on the substrate. A method of producing a metal oxide and a metal oxide thin film using an excimer laser, which is characterized by irradiating an excimer laser in an oxygen atmosphere after being dispersedly coated, is known. (Patent Document 3)

Furthermore, it is a method for producing a metal oxide on a substrate without heat treatment at a high temperature as conventionally known as a coating pyrolysis method, and a metal organic compound (metal organic acid salt, metal acetylacetonate, A metal alkoxide having an organic group having 6 or more carbon atoms) is dissolved in a solvent to form a solution, which is applied to the substrate, dried, and irradiated with laser light having a wavelength of 400 nm or less to form a metal oxide on the substrate. There is known a method for producing a metal oxide characterized by forming a metal oxide. (Patent Document 4)
Here, a metal organic compound is dissolved in a solvent to form a solution, which is applied to a substrate, dried, and then laser light having a wavelength of 400 nm or less, for example, an excimer selected from ArF, KrF, XeCl, XeF, and F ₂ A method for producing a metal oxide is described in which a metal oxide is formed on a substrate by irradiating with a laser, and irradiation with a laser beam having a wavelength of 400 nm or less is performed in a plurality of stages. It is also described that the irradiation is performed with a weak irradiation that does not lead to complete decomposition of the metal organic compound, and then a strong irradiation that can be changed to an oxide. Further, the metal organic compound is two or more kinds of compounds made of different metals, and the obtained metal oxide is a composite metal oxide made of different metals, wherein the metal of the metal organic acid salt is iron, indium, tin, It is also known to be selected from the group consisting of zirconium, cobalt, iron, nickel and lead.

Furthermore, after a precursor coating solution containing raw material components of La, Mn, and Ca, Sr or Ba oxides is applied to the surface of the object to be coated, a thin film formed on the surface of the object to be coated is formed. A complex oxide film (not exhibiting superconductivity) which is crystallized and represented by the composition formula (La _1-x M _x ) MnO _3−δ (M: Ca, Sr, Ba, 0.09 ≦ x ≦ 0.50) In the method for producing a composite oxide film, the wavelength of the precursor coating solution is 360 nm or less with respect to the thin film formed on the surface of the coating object after coating the precursor coating liquid on the surface of the coating object. A method for producing a complex oxide film characterized by irradiating light to crystallize a thin film is known. (See Patent Document 5)
Here, the light source for irradiating the thin film formed on the surface of the object to be coated is an ArF excimer laser, a KrF excimer laser, a XeCl excimer laser, a XeF excimer laser, a triple wave of a YAG laser, or 4 of a YAG laser. A precursor coating solution that is applied to the surface of an object to be coated using double wave light is an alkanolamine coordination compound of La, a carboxylate of Mn, and a metal or alkoxide of M having 1 to 1 carbon atoms. No. 4 is prepared by mixing and reacting in a primary alcohol.

JP-A-8-85788 JP 2005-281507 A Patent No. 2759125 JP 2001-31417 A JP 2000-256862 A Journal of Alloys and Compounds, Volume 374, Issues 1-2, 14 July 2004, Pages 202-206

However, at least an element selected from the group consisting of ABO ₃ , A ₂ BO ₄ , and A ₃ B ₂ O ₇ formed on the substrate, wherein A is Ca, Sr, Ba, B is Ti, Zr. There are no reports on crystal growth by the light irradiation method or fluorescence characteristics of oxide films used one by one. In the manufacturing method of SrTiO ₃ : Pr: Al phosphor, which is a surface phosphor material, it has been baked at a high temperature by a sol-gel method or a solid phase method, and a phosphor thin film has been produced on a substrate by screen printing or the like. Since a high temperature and a lot of time are required, it has been difficult to form a thin film on glass. The present invention enables the formation of a thin film containing SrTiO ₃ : Pr: Al crystallized on a glass or silicon substrate, and the film after laser irradiation is subjected to thermal annealing in an oxidizing atmosphere or UV irradiation in a solution and oxygen atmosphere. By irradiating, a method for producing a phosphor thin film material having high performance is provided.

In order to achieve the above object, the present invention replaces a part of the heat treatment process in the coating pyrolysis method with ultraviolet (laser) irradiation in the production of SrTiO ₃ : Pr: Al. That is, the metal organic compound solution is applied to the support and dried (1), the organic component pyrolysis pre-baking step (2), and the main baking step (3) for conversion into a phosphor thin film. In this case, SrTiO ₃ : Pr: characterized by irradiating with ultraviolet light (laser), in particular with a wavelength of 400 nm or less, in parallel with the step (2) and the step (3) or before the step (2) It is a manufacturing method of a thin film. This enables low-temperature and high-speed film formation of phosphor thin-film materials (significant reduction in heat treatment time), and the patterning required for the element can be achieved by precisely controlling the use of the mask and the irradiation position of ultraviolet light. It can be performed simultaneously with film formation.

That is, according to the present invention, A is an alkaline earth metal element selected from Ca, Sr, and Ba, B is a metal element selected from Ti, Zr, and ABO ₃ , A ₂ BO ₄ , A ₃ B _2. At least one element selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu in the metal oxide represented by the composition formula of O ₇ The added phosphor material , or a thin film of an organometallic salt capable of forming the phosphor material is formed on a substrate and kept at a temperature of 25 to 500 ° C., and the phosphor material or organometallic salt on the substrate The metal oxide phosphor thin film is formed by forming a metal oxide phosphor thin film on a substrate by crystallization while irradiating the thin film with an ultraviolet laser.
Further, the present invention is a common name represented by the composition formula M ₂ [A _n-1 B _n O _{3n + 1} ] (n is a natural number. However, M, A, B, O sites may have defects). In the Dion-Jacobson phase, M used Na, K, Rb, Cs, H, A used Ca, Sr, Ba, La, Lu, and B used at least one element selected from Ti, Zr, Nb, Ta A phosphor material having a composition formula in which at least one of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb is added to a metal oxide , or the phosphor material Form a thin film of organometallic salt that can be formed on the substrate, hold it at a temperature of 25-500 ° C, and crystallize while irradiating the phosphor material on the substrate or the thin film of organometallic salt with an ultraviolet laser Is a method for producing a metal oxide phosphor thin film, comprising forming a metal oxide phosphor thin film on a substrate.
Furthermore, the present invention relates to a so-called Ruddlesden represented by a composition formula M [A _n-1 B _n O _{3n + 1} ] (n is a natural number, but M, A, B, and O sites may have a defect). -Popper phase, M is Na, K, Rb, Cs, H, A is Ca, Sr, Ba, La, Lu, B is a metal using at least one element selected from Ti, Zr, Nb, Ta A phosphor material having a composition formula in which at least one of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb is added to an oxide , or the phosphor material is formed. An organic metal salt thin film can be formed on the substrate, kept at a temperature of 25 to 500 ° C., and crystallized while irradiating the phosphor material on the substrate or the organic metal salt thin film with an ultraviolet laser. A method for producing a metal oxide phosphor thin film is characterized in that a metal oxide phosphor thin film is formed on a substrate by performing.
Furthermore, in the present invention, it is irradiated with ultraviolet lasers to metal oxide phosphor thin film manufactured by the manufacturing method of the metallic oxide phosphor thin film, the fluorescence intensity by increasing the relief of the surface shape increasing be a method for producing a metallic oxide phosphor thin film characterized.
In the present invention, the phosphor material or an organic metal salt, further, Al, Ga, one or more elements selected from In may and early days free.
Furthermore, in the present invention, a thin film of metal oxide or organometallic salt can be produced by any of MBE, vacuum deposition, CVD, and chemical solution methods (coating pyrolysis method, spray method).
In the present invention, the organic compound in the organic metal salt can be selected from β-diketonato, a long-chain alkoxide having 6 or more carbon atoms, and an organic acid salt that may contain halogen.
In the present invention, a pulse laser of 400 nm or less can be used as the ultraviolet laser .
Furthermore, in the present invention, after irradiation with ultraviolet light to the thin film of phosphor material or an organic metal salt, it can be irradiated with ultraviolet Les chromatography THE at a temperature of 200 ° C. to 400 ° C..
In the present invention, after heating a thin film of phosphor material or an organic metal salt at 400 ° C., it can be irradiated with ultraviolet Les chromatography THE at a temperature of 200 ° C. to 400 ° C..
Furthermore, in the present invention, a plurality after irradiation with ultraviolet laser, the fluence 30 mJ / cm ² or more ultraviolet lasers thin film phosphor materials or organic metal salt under conditions consisting of a combination of frequency and fluence ablation does not occur at room temperature Irradiation with a fluence of
In the present invention, oxidation treatment with an oxidizing solution of metal oxide phosphor thin film obtained by ultraviolet laser irradiation, or oxidation treatment by annealing in an oxidizing atmosphere, or in solution and in an oxidizing atmosphere An oxidation treatment using ultraviolet irradiation or an oxidation treatment using oxygen plasma can be performed.
Furthermore, the present invention provides a phosphor material comprising : (Ca _1-xy Sr _x Ba _y ) ₃ (Ti _1-z Zr _z ) ₂ O ₇ (Ca _1-xy Sr _x Ba _y ) ₂ (Ti _1-z Zr _z) a _{O 4, 0 ≦ x + y} ≦ 1,0 ≦ x <1,0 ≦ y ≦ 1,0 ≦ z ≦ 1 metal oxide represented by a set Narushiki as a base material, Ce, Pr, Nd, Sm, Eu, may Gd, Tb, Dy, Ho, Er, Tm, Yb, may include at least one Lu.
In the present invention, the phosphor material may further contain one or more elements selected from Al, Ga, and In.

  The present invention is an invention that enables high luminous efficiency at a low temperature on a glass substrate or a substrate containing silicon and organic, which has been impossible in the past, is suitable for mass production, and the phosphor thin film can obtain excellent luminous efficiency. It is.

A method for producing a phosphor comprising applying a metal organic compound solution forming a phosphor on a support and irradiating ultraviolet light in each step of a drying step, a temporary firing step, and a main firing step. . An example of ultraviolet light used in the present invention is laser light.
Depending on the purpose, it is possible to select in the middle of a predetermined process or before and after each process. Alternatively, a metal organic compound solution can be spin-coated on a substrate and dried at 130 ° C. in a thermostatic chamber for solvent removal, and then the sample can be mounted on a sample holder in a laser chamber and irradiated with laser at room temperature.

In the present invention, ABO ₃ , A ₂ BO ₄ , and A ₃ B ₂ O ₇ (however, A, B, and O sites may be deficient) are used as the metal from which the oxide forms the phosphor material. Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and the like are represented by the composition formula, and oxides using at least one element selected from Ca, Sr, Ba, and B, Ti and Zr. A precursor film may be used in which at least one of Ho, Er, Tm, Yb, and Lu is added, and in addition, one or more of Al, Ga, and In may be added.
It is also effective for a thin film containing a small amount of a conductive material such as In ₂ O ₃ , SnO ₂ , ZnO and metal in advance.
When, for example, a CaCaTiO ₃ : Pr film is produced by irradiating a laser to each of the film coated with a metal organic compound and dried, and the initial fired film, and then applying an appropriate heat treatment to the laser irradiated film The following effects were confirmed.
1. After applying a solution of a metal organic compound that forms a CaTiO ₃ : Pr film on a support, drying, and pre-baking to thermally decompose the organic component in the metal organic compound at 400 ° C., a temperature of 400 ° C. or lower It was found that crystallization was promoted at low temperature by irradiating with laser light.

In the conventional thin film forming method, it is known that the crystallization reaction proceeds at 900 ° C. without being crystallized at 400 ° C. as shown in FIG. 1, but the method for producing the phosphor thin film of the present invention is shown in FIG. As shown in the figure, it was confirmed that thin film crystal growth was possible at room temperature to 400 ° C.
FIG. 3 shows the results of measuring the photoluminescence of the film produced by the coating pyrolysis method and the light irradiation method. As can be seen from the figure, no light emission was observed in the case of heat treatment at 400 ° C., but light was emitted even at room temperature when irradiated with laser. The higher the temperature during laser irradiation, the higher the emission intensity. However, it has been found that the emission intensity increases more than twice by oxidizing the film after laser irradiation (FIG. 4).
Furthermore, the present invention provides an organic substrate, a glass substrate, strontium titanate (SrTiO ₃ ), lanthanum aluminate (LaAlO ₃ ), magnesium oxide (MgO), lanthanum strontium tantalum aluminum oxide ((La _x Sr _1-x ) (Al _x Ta _1-x ) O ₃ ), neodymium gallate (NdGaO ₃ ), yttrium aluminate (YAlO ₃ ) single crystal, aluminum oxide (Al ₂ O ₃ ), yttria stabilized zirconia ((Zr, Y) O ₂ , YSZ) can be used.

Although the specific example of this invention is shown and demonstrated in more detail, this invention is not limited to these Examples.
The substrate used in the examples of the present invention is:
It is a quartz substrate and an alkali-free glass substrate, and the raw material solution is
A 2-ethyl-1 hexanolate Ti solution was used as the strontium 2-ethylhexanoate solution. And praseodymium 2-ethylhexanoate was used. For ultraviolet light irradiation, a KrF excimer laser, an ArF excimer laser, or a XeCl excimer laser was used.

A solution (C1) was prepared by mixing a 2-ethyl hexane calcium acid solution with a 2-ethyl-1 hexanolate Ti solution and praseodymium 2-ethyl hexanoate at a constant ratio.
The C1 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. Thereafter, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz; 5 minutes. The film thus produced showed high emission intensity by ultraviolet excitation only at the irradiated part.

In Example 1, when irradiation was performed at a laser fluence of 100 mJ / cm ² , only the irradiated portion showed high emission intensity by ultraviolet excitation.

In Example 1, when the laser fluence was irradiated at 120 mJ / cm ² , it was found that the surface undulation increased. As a result, the fluorescence intensity by ultraviolet excitation of the irradiated part increased.

  In Example 1, when the number of irradiation repetitions was 50 Hz, only the irradiated part showed high emission intensity by ultraviolet excitation.

  In Example 1, when the number of irradiation repetitions was 10 Hz, only the irradiated portion showed high emission intensity due to ultraviolet excitation.

In Example 1, when the substrate was replaced with quartz and an ITO / glass substrate (with an ITO film provided on the glass substrate) was used, a crystallized CaTiO ₃ : Pr film was obtained at the irradiated portion. In addition, only the irradiated part showed high emission intensity by ultraviolet excitation.

  In Example 1, when the substrate was replaced with quartz and an alkali-free glass substrate was used, only the irradiated portion showed high emission intensity due to ultraviolet excitation.

  In Example 1, since some oxygen vacancies were generated in the phosphor film after laser irradiation, when the oxygen annealing was performed at 500 ° C. for 6 hours, the emission intensity after the treatment increased about 6 times.

  When the calcining temperature performed after spin coating in Example 1 was 25 to 250 ° C., only the irradiated part showed high emission intensity by ultraviolet excitation, but the crystallinity of the film was compared with that of the calcining temperature of 400 ° C. Unfortunately, the increase in emission intensity after oxygen treatment is small. Therefore, the pre-baking temperature is desirably about 400 ° C.

A solution (C2) was prepared by mixing a 2-ethyl hexane calcium acid solution with a 2-ethyl-1 hexanolate Ti solution and praseodymium 2-ethyl hexanoate in a ratio of Ca: Ti: Pr = 1.997: 1: 0.002.
The C2 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. Thereafter, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz; for 5 minutes. As a result, the formation of a Ca ₂ TiO ₄ : Pr film was observed by X-ray diffraction. . In the film thus prepared, only the irradiated part showed high emission intensity by ultraviolet excitation similar to CaTiO ₃ : Pr.

A solution (C3) was prepared by mixing a 2-ethyl hexane calcium acid solution with a 2-ethyl-1 hexanolate Ti solution and praseodymium 2-ethyl hexanoate in a ratio of Ca: Ti: Pr = 2.994: 2: 0.004.
The C3 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. After that, the substrate temperature was kept at 250 ° C., and a 248 nm pulsed laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz for 5 minutes. As a result, X-ray diffraction confirmed the formation of a Ca ₃ Ti ₂ O ₇ : Pr film. It was. The photoluminescence intensity of the irradiated part of the film thus produced was 6 times that of the CaTiO ₃ : Pr film.

A solution (S1) was prepared by mixing 2 ethyl hexane strontium acid solution with 2 ethyl-1 hexanolate Ti solution and praseodymium diethyl hexanoate at a ratio of Sr: Ti Pr = 0.998: 1: 0.002.
The S1 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. Thereafter, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz for 5 minutes. As a result, the formation of a SrTiO ₃ : Pr film was observed by X-ray diffraction. Only the irradiated part emitted light from the film thus prepared.

A solution prepared by mixing 2 ethyl hexane strontium acid solution with 2 ethyl-1 hexanolate Ti solution, praseodymium diethyl hexanoate and aluminum acetylacetonate acid solution in a ratio of Sr: Ti Pr: Al = 1: 1: 0.002: 0.15 (S2) Was made.
The S2 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. After that, the substrate temperature was kept at 250 ° C., and a 248 nm pulsed laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz; 5 minutes. As a result, X-ray diffraction revealed that a SrTiO ₃ : Pr, Al film was formed. . Only the irradiated part emitted light from the film thus prepared.

A solution (S3) was prepared by mixing 2 ethyl hexane strontium acid solution with 2 ethyl-1 hexanolate Ti solution and praseodymium 2 ethyl hexanoate in a ratio of Sr: Ti Pr = 2: 1: 0.002.
The S3 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. After that, the substrate temperature was kept at 250 ° C., and a 248 nm pulsed laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz; 5 minutes. As a result, X-ray diffraction revealed that a Sr ₂ TiO ₄ : Pr film was formed. . Only the irradiated part emitted light from the film thus prepared.

A solution (S4) was prepared by mixing a 2 ethyl hexane strontium acid solution with a 2 ethyl-1 hexanolate Ti solution and praseodymium diethyl ethyl hexanoate at a ratio of Sr: Ti Pr = 3: 2: 0.004.
The S4 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. Thereafter, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz for 5 minutes. As a result, X-ray diffraction confirmed the formation of a Sr ₃ Ti ₂ O ₇ : Pr film. It was. Only the irradiated part emitted light from the film thus prepared.

A solution in which a 2-ethylhexane strontium acid solution, a 2-ethyl-1 hexanolate Ti solution, and praseodymium diethylethylhexanoate are mixed in a ratio of Ca: Sr: Ti Pr = 2: 1: 2: 0.002 to a 2-ethylhexane calcium acid solution (S5) Was made.
The S5 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. After that, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz; 5 minutes. As a result of X-ray diffraction, (Ca, Sr) ₃ Ti ₂ O ₇ : Pr film Generation was confirmed. Moreover, only the irradiated part emitted light about the film | membrane produced in this way.

Spin coating C1 solution on a quartz substrate at 4000 rpm for 10 seconds, irradiating with an ultraviolet lamp at room temperature for 10 minutes, keeping the substrate temperature at 250 ° C., and pulsing a 248 nm pulsed laser in the atmosphere: 80 mJ / cm ² ; 20 Hz; As a result of irradiation for 5 minutes, the formation of a CaTiO ₃ : Pr film was confirmed by X-ray diffraction. Moreover, only the irradiated part emitted light about the film | membrane produced in this way.

In Example 1, room temperature ultraviolet irradiation using an excimer lamp was performed instead of the calcining step, and then a 248 nm pulse laser was irradiated in a room temperature atmosphere at a fluence of 100 mJ / cm ² ; 20 Hz; 5 minutes. The film thus produced showed fluorescence emission by ultraviolet excitation only at the irradiated part.

In Example 1, room temperature ultraviolet irradiation using an excimer lamp was performed instead of the calcining step, and then a 248 nm pulse laser was irradiated in a room temperature atmosphere at a fluence of 100 mJ / cm ² ; 20 Hz; 5 minutes. The film thus produced showed fluorescence emission by ultraviolet excitation only at the irradiated part.

  In Example 19, laser irradiation was performed at a substrate temperature of 250 ° C. The film thus produced showed fluorescence emission by ultraviolet excitation only at the irradiated part, and the intensity thereof was about 5 times higher than that when the substrate temperature was room temperature irradiation.

A solution (C4) was prepared by mixing a 2-ethyl hexane calcium acid solution with a 2-ethyl-1 hexanolate Ti solution and a 2-ethyl hexanoate europium solution at a constant ratio. The C2 solution was spin coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. Thereafter, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 80 mJ / cm ² ; 20 Hz; for 5 minutes. The film produced in this manner showed red amber light emission by ultraviolet excitation only at the irradiated part.

A solution (C5) was prepared by mixing a 2-ethyl hexane calcium acid solution with a 2-ethyl-1 hexanolate Ti solution and a terbium acetate acetone solution at a constant ratio. The C5 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. Thereafter, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 100 mJ / cm ² ; 20 Hz; for 5 minutes. The film thus produced showed fluorescence emission by ultraviolet excitation only at the irradiated part.

2 Ethyl hexanolate Ti solution and 2 ethyl hexanoate praseodymium solution were mixed with potassium ethoxide solution, 2 ethyl hexanoate lanthanum solution in a ratio of K: La: Ti: Pr = 2: 1.994: 3: 0.006. A solution (C6) was prepared. The C6 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. Thereafter, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 100 mJ / cm ² ; 30 Hz; 10 minutes, and then 120 mJ / cm ² ; 30 Hz; 10 minutes. The film thus produced showed red fluorescence emission due to ultraviolet excitation only in the irradiated part.

2 ethyl-1 hexanolate Ti solution and 2 ethylhexanoic acid praseodymium solution were mixed with potassium ethoxide solution, 2 ethylhexanoic acid lanthanum solution at a ratio of K: La: Ti: Pr = 1: 0.998: 1: 0.002. A solution (C7) was prepared. The C7 solution was spin-coated on a quartz substrate at 4000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. Thereafter, the substrate temperature was kept at 250 ° C., and a 248 nm pulse laser was irradiated in the atmosphere at a fluence of 100 mJ / cm ² ; 30 Hz; 10 minutes, and then 120 mJ / cm ² ; 30 Hz; 10 minutes. The film thus produced showed red fluorescence emission due to ultraviolet excitation only in the irradiated part.

(Comparative Example 1)
The C1 solution was spin-coated on a quartz substrate at 3000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. As a result, the generated film did not emit light.

(Comparative Example 2)
The C1 solution was spin-coated on an alkali-free glass at 3000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. As a result, the generated film did not emit light.

(Comparative Example 3)
The C1 solution was spin-coated on an ITO / quartz substrate at 3000 rpm for 10 seconds and heated at 400 ° C. for 10 minutes. As a result, the generated film did not emit light.

XRD pattern of film prepared by heat treatment XRD pattern of the light irradiation film of the present invention PL spectra of films prepared by heat treatment and light irradiation PL spectra of films after laser irradiation and films oxidized after laser irradiation

Claims (14)

A is an alkaline earth metal element selected from Ca, Sr, and Ba, B is a metal element selected from Ti, Zr, and a composition formula of ABO ₃ , A ₂ BO ₄ , and A ₃ B ₂ O ₇ A phosphor material obtained by adding at least one element selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu to the metal oxide represented, Alternatively, a thin film of an organometallic salt capable of forming the phosphor material is formed on the substrate and maintained at a temperature of 25 to 500 ° C., and an ultraviolet laser is applied to the phosphor material or the thin film of the organometallic salt on the substrate. A method for producing a metal oxide phosphor thin film, comprising forming a metal oxide phosphor thin film on a substrate by performing crystallization while irradiating. In the so-called Dion-Jacobson phase represented by the composition formula M ₂ [A _n-1 B _n O _{3n + 1} ] (n is a natural number, but the M, A, B, and O sites may have defects) M is Na, K, Rb, Cs, H, A is Ca, Sr, Ba, La, Lu, B is a metal oxide using at least one element selected from Ti, Zr, Nb, Ta, Ce , Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, a phosphor material having a composition formula , or an organic that can form the phosphor material A thin film of metal salt is formed on the substrate, maintained at a temperature of 25 to 500 ° C., and crystallized while irradiating the phosphor material on the substrate or the thin film of the organic metal salt with an ultraviolet laser. A method for producing a metal oxide phosphor thin film, comprising forming a metal oxide phosphor thin film thereon. In the so-called Ruddlesden-Popper phase represented by the composition formula M [A _n-1 B _n O _{3n + 1} ] (n is a natural number, but M, A, B, and O sites may have defects), M Is Na, K, Rb, Cs, H, A is Ca, Sr, Ba, La, Lu, B is a metal oxide using at least one element selected from Ti, Zr, Nb, Ta, Ce, A phosphor material having a composition formula to which at least one of Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb is added , or an organic metal capable of forming the phosphor material A thin film of salt is formed on the substrate, maintained at a temperature of 25 to 500 ° C., and crystallized while irradiating the phosphor material on the substrate or the thin film of the organometallic salt with an ultraviolet laser. A method for producing a metal oxide phosphor thin film, comprising forming a metal oxide phosphor thin film on the substrate. Irradiated with ultraviolet lasers to metal oxide phosphor thin film manufactured by the manufacturing method of the metallic oxide phosphor thin film as claimed in any one of claims 1 to 3, to increase the relief of the surface shape method for producing a metallic oxide phosphor thin film characterized by increasing the fluorescence intensity Te. Phosphor material or an organic metal salt, further, Al, Ga, metal oxide described in any one of claims 1 to 3, characterized in Monodea Rukoto containing one or more elements selected from In Method for manufacturing a phosphor thin film. Any thin film phosphor materials or organic metal salt, MBE, vacuum evaporation, CVD, chemical solution method (coating thermal decomposition method, a spraying method) according to claim 1, characterized in that produced by any one of the 5 A method for producing a metal oxide phosphor thin film according to claim 1 . Organic compounds in the organic metal salts, beta-diketonate alkoxide having 6 or more long chain carbon, claims 1 to 3, which is a type which is also selected from a good organic acid salt include halogen, 5,6 either A method for producing a metal oxide phosphor thin film according to item 1 . Metal oxide phosphor manufacturing method of a thin film as claimed in any one of claims 1-3 ultraviolet laser is less pulsed laser 400 nm. After irradiation with ultraviolet light to the thin film of phosphor material or an organic metal salt, according to claim 1, characterized in that irradiating ultraviolet Les chromatography THE at a temperature of 200 ° C. to 400 ° C., the first term or 8 A method for producing the described metal oxide phosphor thin film. After heating a thin film of phosphor material or an organic metal salt at 400 ° C., as described in any one of claims 1 to 3, characterized in that irradiating ultraviolet Les chromatography THE at a temperature of 200 ° C. to 400 ° C. A method for producing a metal oxide phosphor thin film. After irradiation with ultraviolet laser thin films of phosphor material or an organic metal salt under conditions consisting of a combination of frequency and fluence ablation does not occur at room temperature, to irradiate the fluence 30 mJ / cm ² or more ultraviolet lasers in multiple fluence method for producing a gold genus oxide phosphor thin film according to any one of claims 1～3,8 characterized. In the manufacturing method described in any one of claims 1～3,5～10, a metal oxide phosphor thin film obtained by ultraviolet laser irradiation oxidation treatment with the oxidizing solution, or, in an oxidizing atmosphere oxidation treatment by heat treatment, or oxidation treatment with UV irradiation in solution and in an oxidizing atmosphere, or metallic oxide phosphor manufacturing method of a thin film, which comprises oxidation treatment using oxygen plasma. The phosphor material is (Ca _{1 -xy} Sr _x Ba _y ) ₃ (Ti _{1 -z} Zr _z ) ₂ O ₇ (Ca _{1 -xy} Sr _x Ba _y ) ₂ (Ti _{1 -z} Zr _z ) O ₄ , 0 ≦ x + a y ≦ 1,0 ≦ x <1,0 ≦ y ≦ 1,0 ≦ z ≦ 1 set metal oxide represented by Narushiki as a base material, Ce, Pr, Nd, Sm , Eu, gd, Tb, Dy, Ho, Er, Tm, Yb, method for producing a metal oxide phosphor thin film according to claim 1 element selected from the herd consisting of Lu is Ru der those being at least one additive. Phosphor material, further, Al, Ga, method for producing a metal oxide phosphor thin film according to claim 13, characterized in that it is intended to include one or more elements selected from In.

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