JP2006199876A - Aluminum nitride-based fluorescent substance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aluminum nitride-based fluorescent substance having good fluorescence characteristics on an industrial scale. <P>SOLUTION: This aluminum nitride-based fluorescent substance contains at least one kind of a transition element and a rare earth element and further contains aluminum, wherein an aluminum-based component which does not combine with nitrogen is contained in an amount of ≤1 wt.%. The method for producing the aluminum nitride-based fluorescent substance comprises subjecting a raw material containing at least one kind of the transition element and the rare earth element and further containing the aluminum to nitriding synthesis in an atmosphere containing nitrogen, and then firing the synthesized material at a temperature higher than 1,050°C in an atmosphere containing the nitrogen. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel aluminum nitride phosphor and a method for producing the same.

  In addition to various display devices such as a fluorescent display tube (VFD), a field emission display (FED), a cathode ray tube (CRT), and a plasma display panel (PDP), phosphors are widely used in light emitting elements such as white light emitting diodes (LEDs). in use.

  In these light emitting elements, the light emitting part is composed of a phosphor coating film containing a phosphor. The phosphor coating film can be obtained by coating a powdered phosphor together with a binder. This makes it easy to form a light emitting portion on a large-area substrate or in a planar shape having a complicated shape.

  These phosphor coating films are manufactured by coating and molding a powdered phosphor together with a binder mainly on a glass or plastic film substrate.

  Conventionally, various types of phosphor coating films, such as silicate phosphors, phosphate phosphors, aluminate phosphors, oxide phosphors and sulfide phosphors, are used depending on the application and desired emission color. A phosphor (fluorescent compound) is used.

  These phosphors are composed of an emission center and a host crystal. The emission center is excited by an excitation source having high energy such as an electron beam or ultraviolet rays to emit visible light, but energy absorption by the host crystal also occurs at the same time, and the conversion efficiency to visible light is usually as low as about 30%.

  In recent years, fluorescent coating films for displays and the like are required to emit fluorescent light with higher brightness. In particular, for a phosphor coating film for PDP whose screen size is increasing, a method using powdered phosphor as a paint has become the mainstream because of ease of processing. For this reason, it is necessary to form a phosphor coating film with high brightness from these phosphors.

  However, when the applied energy is increased, the energy absorbed by the host crystal is also increased, causing damage due to destruction of the structure of the phosphor and the like, resulting in a decrease in the luminance of the phosphor.

  As a phosphor capable of exhibiting sufficiently high luminance and long life characteristics, for example, a phosphor containing zinc sulfide as a base material and containing an activator and a coactivator (for example, Patent Document 1), sulfide-based or oxide-based A powder phosphor (for example, Patent Document 2) is known.

  However, these phosphors inevitably release sulfur, sulfide gas, oxygen, etc. when their structure is destroyed, and corrode or deteriorate peripheral parts such as electron sources and filaments used in display devices. Cause.

  Further, as phosphors other than sulfide or oxide, there are gallium nitride phosphors (for example, Patent Document 3 and Patent Document 4).

  However, although the gallium nitride phosphor does not release sulfur, sulfide gas, oxygen, etc., it can only obtain the same brightness as the sulfide or oxide phosphor even when the applied energy is increased. The raw material is expensive. In addition, the forbidden band width of gallium nitride is about 3.4 eV, and high luminous efficiency cannot be expected particularly for vacuum ultraviolet light excitation used for PDP.

  On the other hand, an aluminum nitride-based phosphor obtained by doping aluminum nitride with a luminescent center impurity element has a large forbidden band width of about 6.2 eV, and has high luminous efficiency against ultraviolet light excitation in the vacuum ultraviolet region. It is advantageous in that it has high mechanical and chemical stability and does not deteriorate even when strongly excited, and high brightness can be obtained. In addition, aluminum nitride is abundant in resources, is not toxic and corrosive, and is composed of elements that are highly compatible with the ecosystem.

  As a method for producing such a material, for example, a method of treating Al—Mn mixed powder at 1000 ° C. and 1000 psi (about 7 MPa) in a nitrogen atmosphere is known (for example, Non-Patent Document 1).

  However, since the above method requires a high-pressure atmosphere, it is not suitable for production on an industrial scale in terms of safety and cost.

  In addition, a method of doping an aluminum nitride powder with an emission center impurity element by thermal diffusion (for example, Non-Patent Document 2) has also been proposed.

However, the doping amount of the luminescent center impurity element required for obtaining sufficient light emission intensity is usually 0.1 atomic% or more, but such amount cannot be doped by thermal diffusion. is there. In order to increase the doping amount, there is a method (for example, Non-Patent Document 2) in which MnCl ₂ is added to expensive (NH ₄ ) ₃ AlF ₆ and reacted in a toxic NH ₃ atmosphere. It is not a suitable method for production.

For this reason, the present situation is that aluminum nitride is only used for producing a thermoluminescent material (for example, Patent Document 5) on an industrial scale.
Japanese Patent Laid-Open No. 8-183954 JP-A-9-260060 JP 2002-309249 A JP 2002-356676 A JP-A-5-263075 J. electrochemical society 109 (11) 1962 Czechoslovakia J. Physics B, vol. 22 (1972), 847

  Accordingly, a main object of the present invention is to provide an aluminum nitride phosphor having good fluorescence characteristics on an industrial scale.

  As a result of intensive studies in view of the problems of the prior art, the present inventor has found that an aluminum nitride-based phosphor manufactured by a specific process can achieve the above object, and has completed the present invention.

  That is, the present invention relates to the following aluminum nitride phosphor and a method for producing the same.

  1. An aluminum nitride-based phosphor containing 1% by weight or less of an aluminum-based component that contains at least one of a transition element and a rare earth element and an aluminum-based component and is not bonded to nitrogen.

  2. Item 2. The aluminum nitride-based phosphor according to Item 1, further containing at least one boron group element selected from boron, gallium, indium, and thallium.

  3. Item 3. The aluminum nitride phosphor according to Item 1 or 2, which is a powder having an average particle size of 100 µm or less.

  4). A film-like phosphor obtained from a paint containing the aluminum nitride-based phosphor according to any one of Items 1 to 3.

  5. 5. A plasma display panel using the film-like phosphor according to item 4 as a light emitting part.

6). A method for producing an aluminum nitride phosphor,
(1) a first step of nitriding a raw material containing at least one of a transition element and a rare earth element and an aluminum component in an atmosphere containing nitrogen;
(2) a second step of firing the reaction product obtained in the first step at a temperature exceeding 1050 ° C. in a nitrogen-containing atmosphere;
The manufacturing method of the aluminum nitride type fluorescent substance containing this.

  7). Item 7. The method according to Item 6, wherein an alloy or compound containing at least one of a transition element and a rare earth element and aluminum is used as a part or all of the raw material in the first step.

  8). Item 8. The method according to Item 6 or 7, wherein the raw material in the first step further contains at least one boron group element selected from boron, gallium, indium, and thallium.

  9. Item 9. The production method according to any one of Items 6 to 8, wherein the firing temperature in the second step is 1100 to 2000 ° C.

  The phosphor obtained by the present invention has a high emission intensity equal to or exceeding that of conventional phosphors, and also has characteristics (high thermal conductivity, etc.) of aluminum nitride because the matrix is made of aluminum nitride. Combined, overall, it can exhibit properties superior to conventional materials.

  In addition, according to the production method of the present invention, the aluminum nitride phosphor of the present invention can be produced, so that the film-like phosphor can be provided on an industrial scale.

1. Aluminum nitride-based phosphor The aluminum nitride-based phosphor of the present invention contains at least one of transition elements and rare earth elements (hereinafter collectively referred to as “second element”) and an aluminum component, and The aluminum-based component not bonded to nitrogen is 1% by weight or less.

  As the second element, at least one of a transition element and a rare earth element is used. These types are not limited and can be appropriately selected according to desired fluorescence characteristics and the like. In the present invention, as the transition element, at least one of Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Ag, and Zn is particularly preferable. As the rare earth element, at least one of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb is particularly preferable.

  The content of the second element is not particularly limited and can be appropriately set according to desired fluorescence characteristics and the like, but is generally about 0.01 to 10 atomic% (particularly 0.05 to 5 atomic%). What should I do? Moreover, the structure which some or all of the 2nd element dissolved in the aluminum nitride base body may be sufficient. The solid solution amount of the second element with respect to the aluminum nitride matrix is not particularly limited, and may be appropriately adjusted so that desired fluorescence characteristics can be obtained.

  In the phosphor of the present invention, the remainder other than the second element and the third element basically consists of an aluminum-based component. That is, it is basically composed of aluminum nitride and metal aluminum. At this time, the aluminum-based component not bonded to nitrogen is 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight or less in the total aluminum nitride phosphor. By setting the aluminum-based component not bonded to nitrogen to 1% by weight or less, excellent light emission intensity can be obtained. Note that the lower limit of the aluminum-based component that is not bonded to nitrogen is generally about 0.001% by weight.

  The phosphor of the present invention further contains at least one boron group element selected from boron, gallium, indium and thallium (hereinafter also referred to as “third element”) for the purpose of increasing the emission intensity. May be. The content of the third element is not particularly limited, and is usually about 0.05 to 10 atomic% (particularly 0.1 to 5 atomic%). By setting to such a range, better emission intensity and the like can be obtained.

  Although the form of the phosphor of the present invention is not limited, it is usually preferable to be in a powder form. In this case, the average particle size of the powder is generally about 0.5 to 100 μm, and particularly preferably 1 to 50 μm. By setting within such a range, more excellent surface characteristics, dispersion characteristics, and the like can be obtained. In addition, adjustment of a particle size can be implemented using a well-known grinding | pulverization method, a classification method, etc.

  The phosphor of the present invention can be used for the same applications as conventional phosphors, and can be suitably used for production of a film-like phosphor. For example, a film-like phosphor can be formed by applying a paste containing the phosphor of the present invention and a resin binder to a substrate. The resulting film-like phosphor can be used as a light emitting element such as a fluorescent display tube (VFD), a field emission display (FED), a cathode ray tube (CRT), a plasma display panel (PDP), and a white light emitting diode (LED). It can be widely used for the light emitting element.

2. Manufacturing method of aluminum nitride phosphor The manufacturing method of the present invention is a manufacturing method of an aluminum nitride phosphor,
(1) a first step of nitriding a raw material containing at least one of a transition element and a rare earth element and an aluminum component in an atmosphere containing nitrogen;
(2) including a second step of firing the reaction product obtained in the first step at a temperature exceeding 1050 ° C. in a nitrogen-containing atmosphere.
(1) First Step In the first step, a raw material containing at least one of a transition element and a rare earth element and an aluminum component is nitrided in an atmosphere containing nitrogen.

As the raw material, one containing at least one kind of transition element and rare earth element and an aluminum component is used.

  As the transition element, at least one of Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Ag, and Zn is particularly preferable. As the rare earth element, at least one of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb is particularly preferable.

  Furthermore, the present invention may contain at least one boron group element selected from boron, gallium, indium and thallium (ie, a third element) for the purpose of increasing the emission intensity.

  The raw material only needs to contain a second element (third element as required) and an aluminum component. The second element simple substance, aluminum simple substance (metallic aluminum), and a mixture containing the third element simple substance as necessary Besides, a part or all of the raw material may be an alloy or compound containing any of these.

  Examples of the alloys or compounds include inorganic acid salts (nitrates, sulfates, carbonates, chlorides, etc.), organic acid salts (acetates, oxalates, etc.), oxides, nitrides, carbides, boron Compounds, metal organic compounds, etc. are used. In addition, the alloy in this invention is the concept containing an intermetallic compound. Among these, oxides can be preferably used as the second element and / or the third element.

  As an aluminum component, it can also be used with the form of the alloy or compound containing this besides the aluminum simple substance as mentioned above. In particular, in the present invention, it is desirable to use metallic aluminum. Metal aluminum is not particularly limited, and commercially available products can also be used. Moreover, the thing by well-known manufacturing methods, such as an atomizing method and a shred method, can also be used.

  The purity of the metallic aluminum is not particularly limited, but generally it is preferably 99% or more, more preferably 99.9% or more. Although there is no limitation on the upper limit value of purity, it may be usually about 99.999%.

  What is necessary is just to determine suitably the ratio of the 2nd element (3rd element as needed) in a raw material according to the kind of 2nd element to be used, the composition of the target product, etc. Generally, the content may be set so as to be the content described in the phosphor of the present invention.

  The form of the raw material used in the present invention is not limited, but it is particularly desirable to use it in powder form. In this case, the average particle diameter of the raw material is usually about 100 μm or less, preferably 50 μm or less. In particular, the average particle size of the aluminum powder is usually 1 to 100 μm, preferably 5 to 50 μm. By setting the average particle size of the aluminum powder within the above range, it is possible to more surely perform uniform dispersion of the second element serving as the emission center in the obtained aluminum nitride phosphor.

  In addition, the average particle size of the powder of the second element and the third element (in the case of the compound of the second element and the third element, the powder of the compound) is usually 50 μm or less, particularly 20 μm or less, and further 5 μm or less. preferable. When the average particle size of the second element and the third element is 50 μm or less, more excellent dispersibility can be obtained, which contributes to the improvement of the fluorescence characteristics. The lower limit of the average particle size of the powder of the second element and the third element is not particularly limited, but it is usually about 0.01 μm that is used industrially.

Nitriding treatment The raw material (particularly metallic aluminum) is nitrided in an atmosphere containing nitrogen. By this treatment, aluminum nitride is synthesized, and at the same time, part or all of the second element (and also the third element) serving as the emission center is dissolved in the crystal lattice of aluminum nitride. Note that the amount of solid solution of the second element or the third element in aluminum nitride is extremely small in a chemical reaction in a general thermal equilibrium state. In order to increase the solid solution amount of the second element or the third element, it is necessary to 1) make the reaction temperature as high as possible, for example, 2000 ° C. or more, and 2) make the reaction time as short as possible, for example, 20 minutes or less.

  The nitriding synthesis method of the present invention is not particularly limited, and a known method can be adopted. In particular, a reaction process (for example, combustion synthesis reaction, plasma heating synthesis reaction, high-frequency induction heating synthesis reaction, etc.) that has a high reaction temperature and can be rapidly heated and cooled can be suitably used. Among these, a combustion synthesis reaction that does not require a large facility is more preferable. Hereinafter, combustion synthesis will be described as a representative example.

  The reaction conditions and operation procedures for combustion synthesis may be the same as those for known combustion synthesis reactions. For example, a raw material is placed in a high-pressure nitrogen gas atmosphere and ignited, or a combustion reaction is started by heating a part of the raw material in an atmospheric pressure nitrogen gas atmosphere, and the reaction is continued by supplying nitrogen gas. Can be completed.

In the combustion synthesis reaction, the normal combustion reaction part instantaneously becomes a high temperature of 2500 ° C. or higher, and aluminum nitride is synthesized there, and at the same time, a part or all of the second element or the third element serving as the luminescent center is a lattice of aluminum nitride. Dissolve inside.
After that, the part where combustion synthesis is completed is rapidly cooled to near room temperature, so that part or all of the second or third element that becomes the luminescence center is in solid solution (in some cases, a large amount of solid solution up to a non-equilibrium state). ) Obtained.

  The nitrogen gas concentration in the atmosphere is preferably 20% by volume or more (particularly 50% by volume or more), and the gas pressure at high pressure is preferably about 0.2 to 3 MPa. Within this range, an appropriate reaction rate can be secured, and safety management is also preferable.

For the purpose of adjusting the reaction temperature, commercially available aluminum nitride (powder) or the aluminum nitride phosphor according to the present invention (powder) can also be added to the raw material.
(2) Second Step In the second step, the reaction product obtained in the first step is baked at a temperature exceeding 1050 ° C. in a nitrogen-containing atmosphere.

  Since the reaction product is a high-temperature and short-time reaction, a large amount of aluminum-based components that are not bonded to nitrogen are usually present. These aluminum-based components generally include 1) unreacted metallic aluminum in the raw material, 2) decomposition of the reaction product (nitriding reaction product) (atmospheric pressure nitrogen atmosphere, aluminum nitride is around 2500 ° C. It is composed of metallic aluminum deposited by decomposition. When an aluminum-based component that is not bonded to nitrogen is present in the aluminum nitride-based phosphor, the crystallinity of the aluminum nitride is reduced and a part of the incident excitation energy and light emission is absorbed, resulting in phosphor emission. Causes the characteristics to deteriorate significantly. Therefore, in the present invention, the aluminum-based component that is not bonded to nitrogen in the reaction product is reduced by baking the reaction product obtained in the first step in an atmosphere containing nitrogen.

  The reaction product used for high-temperature baking can be used as a lump after synthesis, but preferably after pulverizing the reaction product, the average particle size is about 1 to 100 μm, preferably 5 to 5 by classification or the like. Adjust to about 50 μm to make a powder. The pulverization may be performed by a known method, and may be performed by either dry pulverization or wet pulverization using an organic solvent or the like as a dispersion medium.

  The firing atmosphere is a nitrogen-containing atmosphere. At this time, the nitrogen gas concentration is preferably 20% by volume or more, and particularly preferably 50% by volume or more.

  The firing temperature is usually in the range exceeding 1050 ° C, particularly 1100 to 2000 ° C, preferably 1200 to 1900 ° C, and most preferably 1300 to 1800 ° C. By firing within such a range, it is possible to realize a more excellent emission intensity. When the processing temperature is 1050 ° C. or less, the nitriding of the aluminum-based component is insufficient, and when the processing temperature is too high, the luminescent center element dissolved in the aluminum nitride lattice may reprecipitate or evaporate, There is a risk of lowering the amount of solution.

  The firing time can be set as appropriate depending on the firing temperature, the size of the reaction product, and the like, but it may be usually about 10 minutes to 10 hours. By setting within this range, better emission intensity can be obtained.

  Through the above-described steps, the aluminum nitride phosphor of the present invention is obtained. When producing a phosphor coating film from the aluminum nitride phosphor of the present invention, a phosphor coating film can be produced by molding a mixture containing an aluminum nitride phosphor. More specifically, for example, the phosphor powder of the present invention may be used, mixed with a resin binder or the like to prepare a paste, and the paste may be applied or printed on a substrate so as to have a desired pattern. .

  Hereinafter, examples and comparative examples will be shown to clarify the features of the present invention. However, the present invention is not limited to these examples.

  Each physical property in the present invention was measured as follows.

<X-ray diffraction measurement>
It was measured by powder X-ray diffraction method. The X-rays used were Cu Kα rays, and the tube voltage and tube current were set to 35 kV and 20 mA, respectively.

<Analysis of the amount of aluminum components not bonded to nitrogen>
1 g of the powder sample was put into a container containing a NaOH (20 wt%) aqueous solution and decomposed, and the amount of aluminum-based components not bonded to nitrogen was calculated from the amount of generated hydrogen gas. For example, in accordance with the following calculation formula (1), the amount of aluminum-based components not bonded to nitrogen was calculated from the amount of hydrogen gas detected by a commercially available hydrogen concentration meter.

Formula 2Al + 6H ₂ O = 2Al (OH) ₃ + 3H ₂ (1)
<Transition element / rare earth element content>
It was measured by ICP emission spectroscopy or flame analysis.

<Luminescent characteristics>
It was measured by the cathodoluminescence (CL) method. The acceleration voltage and current density of the electron beam were 5 kV and about 10 μA / cm ² , respectively, and the measurement was performed at room temperature (25 ° C.).

Comparative Example 1
Aluminum powder (average particle size 40 μm) and MnO ₂ powder (average particle size 5 μm) were mixed in a mortar for 10 minutes to obtain a uniform mixed powder. In this case, the ratio of aluminum and Mn was Al: Mn = 99.4 atomic%: 0.6 atomic%. 40 g of the obtained mixed powder was placed in the center of a 10 cm × 20 cm graphite plate, and this graphite plate was placed in a reaction vessel. As a combustion reaction ignition source, a carbon ribbon heater is brought into contact with one end of the mixed powder, degassed to 50 Pa, nitrogen gas is introduced, and when the internal pressure of the container reaches 0.8 MPa, 2. The combustion synthesis reaction was started by energizing at 25 KW for 15 seconds and igniting.

  After the completion of the combustion reaction, the synthesized reaction product was pulverized by a vibration mill, and a powdered aluminum nitride phosphor (average particle size 8 μm) was obtained by pulverization and sieving. The Mn content in the aluminum nitride phosphor was 0.6 atomic%.

  The obtained aluminum nitride phosphor was subjected to X-ray diffraction measurement, and the crystalline phases of metallic aluminum and aluminum nitride were confirmed. The X-ray diffraction pattern is shown in FIG. Further, when the obtained aluminum nitride phosphor was irradiated with an electron beam, light emission with a center wavelength of about 600 nm (orange near red) was slightly observed. The emission spectrum is shown in FIG. The emission spectrum of the obtained aluminum nitride phosphor is shown in Table 1 with the emission intensity at the center wavelength as a relative value of 1. The aluminum-based component that is not bonded to nitrogen in the obtained aluminum nitride phosphor was analyzed by the method described above, and the results are shown in Table 1.

Examples 1-3
Synthesis and pulverization were performed in the same manner as in Comparative Example 1 to obtain a powdered aluminum nitride-based phosphor (average particle size 8 μm).

  The obtained pulverized product was filled in a boron nitride crucible and introduced into a graphite high temperature furnace. After deaeration to 20 Pa, nitrogen gas replacement was performed. Firing was performed at 1300 ° C., 1500 ° C., and 1700 ° C. for 3 hours in a nitrogen gas flow of 5 liters / minute, and Example 1, Example 2, and Example 3 were obtained, respectively. The Mn content in the aluminum nitride phosphor was 0.5 atomic% in all Examples 1 to 3. The obtained aluminum nitride phosphors of Examples 1 to 3 were subjected to X-ray diffraction measurement, and only the crystal phase of aluminum nitride was confirmed. The X-ray diffraction pattern is shown in FIG.

  When the obtained aluminum nitride phosphors of Examples 1 to 3 were irradiated with an electron beam, light emission with a center wavelength of about 600 nm (orange near red) was observed. The emission spectrum is shown in FIG. With respect to the emission spectra of the obtained aluminum nitride phosphors of Examples 1 to 3, the relative emission intensity at the center wavelength was measured and shown in Table 1. The aluminum-based component not bonded to nitrogen in the obtained aluminum nitride-based phosphor was analyzed by the method described above, and the results are shown in Table 1.

Comparative Example 2
Aluminium powder (average particle diameter 40 μm) and Eu ₂ O ₃ powder (average particle diameter 1 μm) were used and mixed so that the ratio of aluminum to Eu was Al: Eu = 97 atomic%: 3 atomic%. In the same manner as in Comparative Example 1, a powdered aluminum nitride phosphor (average particle size 8 μm) was produced. The Eu content in the obtained aluminum nitride phosphor was 3 atomic%.

  When the obtained aluminum nitride phosphor was irradiated with an electron beam, light emission with a center wavelength of about 530 nm (green) was observed, and the light emission intensity is shown in Table 2 as relative value 1. The aluminum-based component that is not bonded to nitrogen in the obtained aluminum nitride-based phosphor was analyzed by the method described above, and the results are shown in Table 2.

Example 4
Synthesis and pulverization were performed in the same manner as in Comparative Example 2 to obtain a powdered aluminum nitride-based phosphor (average particle size 8 μm).

  The obtained pulverized product was fired in an atmosphere containing nitrogen in the same manner as in Example 2 to obtain an aluminum nitride phosphor. The Eu content in the aluminum nitride phosphor was 3 atomic%.

When the obtained aluminum nitride phosphor was irradiated with an electron beam, light emission with a central wavelength of about 530 nm (green) was observed, and the relative value of the emission intensity is shown in Table 2. Nitrogen in the obtained aluminum nitride phosphor The aluminum-based component not bonded to was analyzed by the above-described method, and the results are shown in Table 2.

It is a X-ray-diffraction pattern figure of the fluorescent substance obtained by the comparative example 1 and Examples 1-3. It is a spectrum figure of the fluorescent substance obtained by the comparative example 1 and Examples 1-3.

Claims (9)

An aluminum nitride-based phosphor containing 1% by weight or less of an aluminum-based component that contains at least one of a transition element and a rare earth element and an aluminum-based component and is not bonded to nitrogen. The aluminum nitride based phosphor according to claim 1, further comprising at least one boron group element selected from boron, gallium, indium and thallium. The aluminum nitride based phosphor according to claim 1 or 2, which is a powder having an average particle size of 100 µm or less. A film-like phosphor obtained from a paint containing the aluminum nitride phosphor according to any one of claims 1 to 3. A plasma display panel using the film-like phosphor according to claim 4 as a light emitting part. A method for producing an aluminum nitride phosphor,
(1) a first step of nitriding a raw material containing at least one of a transition element and a rare earth element and an aluminum component in an atmosphere containing nitrogen;
(2) a second step of firing the reaction product obtained in the first step at a temperature exceeding 1050 ° C. in a nitrogen-containing atmosphere;
The manufacturing method of the aluminum nitride type fluorescent substance containing this. The manufacturing method of Claim 6 using the alloy or compound containing at least 1 sort (s) of a transition element and rare earth elements, and aluminum as a part or all of the raw material of a 1st process. The manufacturing method according to claim 6 or 7, wherein the raw material in the first step further contains at least one boron group element selected from boron, gallium, indium, and thallium. The manufacturing method in any one of Claims 6-8 whose calcination temperature of a 2nd process is 1100-2000 degreeC.

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