TW201038716A - Inorganic phosphor material and dispersion-type electroluminescence device - Google Patents

Abstract

An inorganic phosphor material is provided, the inorganic phosphor material including: a base material which is a mixed crystal including at least one or two or more compounds, the compounds being selected from compounds containing at least one element belonging to group XII and at least one element belonging to group XVI of the Periodic Table, wherein the base material contains at least one element selected from elements belonging to group XIII of the Periodic Table, Cu, and Mn.

Description

201038716 VI. Description of the Invention: [Technical Field] The present invention relates to a dispersion type electroluminescence device and an inorganic phosphorus material which can be used for the production of the dispersion type electroluminescence device. [Prior Art] A material that emits light by externally imparted energy (such as light, electricity, pressure, heat, electron beam, etc.) and phosphorus-containing organic materials have been used in Braun for their light-emitting characteristics and stability. Tubes, fluorescent lamps, electroluminescent (EL) devices, etc. In recent years, inorganic phosphorus as a color conversion material for LEDs and low-speed electron beam excited phosphorus in PDP have been actively studied. A phenomenon in which light is emitted by applying an electric field to phosphorus is called electroluminescence (EL), and an emitting light device using this phenomenon is called an electroluminescence (EL) device. The EL device includes two types of a dispersion type EL device in which phosphorus particles are dispersed in a binder having a high dielectric constant to form an emission layer, and a film type EL device in which a phosphor film is sandwiched between dielectric layers. In both types, since the dispersion type EL device does not use a high temperature program in manufacturing, the device is characterized in that plastic can be used as a substrate to form a flexible device, and can be manufactured without using a relatively simple and inexpensive procedure of the vacuum apparatus. Further, the dispersion type EL device made of phosphor particles may have a thickness of several millimeters or less, and it has many advantages such as a light source emitted from the surface, a small heat generation, and good light emission efficiency, so that the dispersion type EL device is expected to have Various uses, such as road signs, various indoor and outdoor lighting, light sources for flat panel displays (such as liquid crystal displays), and light sources for large-area advertising lighting. When a decentralized EL device is used as a light source for backlighting and illumination, the light color of 201038716 is preferably white, but 尙 is only known to emit only white light. It is therefore necessary to combine some illuminating colors. For example, white light emission can be obtained by a combination of blue-green emission-red emission, and blue emission-yellow emission. However, the phosphorus currently used in the dispersion type EL device is still free of ZnS:Cu, C1 (showing blue-green emission), and phosphorus having few red emission (emission peak wavelength: 60 nm or higher). Therefore, the prior art has been tested to emit blue-green light ZnS: Cu, C1 phosphorus, and an organic compound that emits red light by absorbing the luminescent color of ZnS:Cu, C1 phosphor, and added to the light-emitting layer. Light emission to obtain white emission (JP-A-2_78188 and JP-A-2006-156358, the term "JP-A" as used herein means "unexamined Japanese patent application"). However, due to the added organic compound, these EL devices are in a colored state even when they are not emitted. Therefore, although an electric field is applied to obtain white emission, this technique is not suitable for general illumination use due to the appearance when it is not illuminated. On the other hand, a red-emitting phosphor material in a thin film type inorganic EL has conventionally been known only as a material such as ZnGa2S4:Mn, Ba2ZnS3:Mn (JP-A-55-147584, JP-A-2005- 1 62948, and Journal of Vacuum). Science & Technology' Vol. 10, p. 789 (1 973)). SUMMARY OF THE INVENTION However, the inventors applied these materials to the dispersion type inorganic EL, and the red emission was not obtained by applying an electric field. This is caused by the difference in the structure of the film type and the dispersion type. In the thin film type inorganic EL., an electron energy emission from the interface between the light-emitting layer and the insulating layer and an electron accelerated by the electric field (thermoelectric 201038716) excite the emission center to emit light when an electric field is applied. On the other hand, in a dispersion-type inorganic EL, an electron generating source (for example, needle crystal of Cu2S) exists in a stack of phosphor particles, and emits electrons and holes from the source due to application of an electric field, and is The precursor and acceptor energy levels are recombined to capture and emit light; or the recombination energy emits light into the excitation energy of other emission centers present in the particle. Therefore, it is believed that even if the phosphorus of the thin film type inorganic EL (source without electron generation) is directly turned to the dispersed inorganic EL, no electron excitation emission center is generated, so that emission cannot be obtained. It is therefore an object of the present invention to obtain a red light-emitting dispersion type electroluminescent device' and another object to obtain an inorganic phosphor material which can be used in the manufacture of such a dispersion type electroluminescent device. As a result of the intensive test, the inventors have discovered a novel inorganic phosphorus material by adding at least one element selected from the group consisting of Group XIII, Cu and Mn to an element containing at least one group belonging to the group of the periodic table and at least A compound belonging to the element of Group XVI, and in the case of an alternating current dispersion type device, the ultraviolet light is emitted and the light emitted by the red light is emitted. The present invention has thus been completed, i.e., the present invention has been completed by the following elements. (1) An inorganic phosphorus material comprising: a material 'which is a mixed crystal comprising at least one or two or more compounds' selected from the group consisting of at least one element belonging to Group XII of the periodic table and at least one species A compound belonging to the element of Group XVI, wherein the base material contains at least one element selected from the group consisting of the lanthanum of the periodic table, Cu and Μη. (1) The inorganic phosphorus material according to (1), wherein the element selected from the group consisting of the elements of the group XIII is Ab Ga 〇 (3), the inorganic phosphorus material as described in (1) or (2), The inorganic phosphorus material particles, wherein the total number of particles relative to the total number of phosphorus particles is 2% or more, each having 10 or more stacked bodies having an interval of 5 nm or less. (4) The inorganic phosphorus material according to (3), wherein the phosphorus particles have an average particle size of 20 μm or less, and a smaller particle size variation coefficient. (5) A dispersion type electroluminescence device comprising: a light-emitting layer; and an inorganic phosphorus material as described in any one of (1) to (4) in the light-emitting layer. [Embodiment] The present invention will be described in detail below. Inorganic material: The inorganic phosphorus material according to the present invention is an inorganic phosphorus material having mixed crystals as a material, which comprises at least one or two or more selected from the group consisting of less than one element belonging to Group XII of the periodic table and at least one species A compound of a compound of a group of elements, and the base material contains at least one element belonging to Group 111 of the Periodic Table, and Cu and Μη. Incidentally, in some cases, it will be used as the inorganic phosphorus material of the present invention, and at least one of the χπ-group elements of the periodic table and at least one or the phosphorus of the phosphorus is contained in the base material of the XVI species. The compound of the group XVI element of 201038716 is described as "Group 11 _xv; [Group Compound", which term is a description commonly used by those skilled in the art to which the present invention pertains. Examples of the elements belonging to the group ΧΠ of the periodic table of the basic material of the inorganic phosphorus material of the present invention include Zn, Cd and Hg, and preferably Zn or Cd is used. Examples of elements belonging to Group XVI of the Periodic Table include 〇, s, Se, Te, and Po, and preferably s, Se or Te. As examples of the basic material, ZnS, ZnSe, ZnSSe, ZnTe, CdS, CdSe, CdTe, or the like is used. It is preferred to use ZnS, ZnSe and ZnSSe, and more preferably ZnS. The inorganic phosphorus material of the present invention contains at least one element selected from the group consisting of the first group of the periodic table, and Cu and Mn, by which an inorganic phosphorus material exhibiting emission of a red region can be obtained when the material is used in a dispersion type electroluminescent device. For example, phosphorus containing Μη in ZnS usually has an emission peak wavelength near 580 nm in the orange region. On the contrary, the emission peak wavelength of the inorganic phosphorus material of the present invention shows a red region emission longer than that of the orange region, so that it is preferably used as a phosphorus of a dispersion-type inorganic EL for red emission. The light emission of Μη is transferred by the (3d5) electrons in the 3d orbital domain of Μη2 + (referred to as d-d transfer) and 3d is the outermost layer of Mn2 + ions, so that it is strongly affected by the crystal field. It is assumed that the ionic bond property of the crystal is increased by adding an element belonging to Group XIII (e.g., Al, Ga, etc.) to ZnS, and the intensity of the crystal field around Mn2+ is increased. As a result, the excitation energy level is lowered and the emission wavelength becomes long. The thin film type inorganic EL system is based on the above mourning test ZnGa2S4:Mii as a red emitting phosphor material. However, in the case of the dispersed inorganic EL, since the source of electron generation is further required in the particle, even if the direct light is not available to the household. For example, in the case where the basic material is ZnS in the phosphorus of the dispersed inorganic EL, the crystal structure includes the hexagonal system, and the difference in the application of the heat and stress conversion crystallization system, and the Cu2S which becomes the source of electron generation can be stably divided. On the other hand, since crystallization of ZnGa2S4 is only a four-step process such as ZnS, and even if doped with Cu, there is no source of electrons. Therefore, the dispersed inorganic EL cannot contain the elements of Group XIII of the periodic table and the elements of Cu and Mn in the basic material of the phosphorus particles according to the present invention, and in the case of the inorganic EL, a light having a red region having a large emission peak wavelength can be obtained. Inorganic phosphorous material emitted. Further, in the case of forming a difference in the base material, it is preferable to obtain a red light having an emission peak wavelength of 600 nm or more. The addition of the elements belonging to Group XIII of the periodic table to the basic or doping method is not limited, and any one of the parties may be used to form the phosphorus particles, and the elements may be mixed in the form of a metal salt if it may be melted, sublimed or reacted under baking conditions. , the basic material of the crystalline form of matter. Further, the element may be borrowed from the solution, and the aqueous solution is stirred and added to the suspension of the base material to be evaporated and then baked. As for the compound composition, examples thereof include oxides, sulfides, oxysulfide halides, nitrates, and nitrides, and in the case of these compounds, ZnGa2S4:Mn, a stack of crystals in the system and the cubic system is present. In the stacking system, it cannot exist in the particles to obtain light emission. One less method selected from the group consisting of light-emitting materials for dispersing a 600 nm or more inorganic EL colorable region (for example, it may be in a basic material, or may be a mixture of metal salt water, and The solvent may be any compound, oxalate or the like, and particularly preferably used for the sulfide, oxide and halide of -8-201038716. The doping amount per base material of the molar is preferably from 1χ10·3 to 5X10·1. The ear, and more preferably 5x10·3 to ΙχΙΟ-1 Mo. The preferred embodiment of the element of the inorganic phosphorus material of the present invention belonging to Group XIII of the periodic table includes B, A, Ga, In, and T1, and Preferably, Al, Ga and In are used. When the phosphor particles of the present invention are doped with Cu and Μη, a method similar to the method of doping the basic material of the present invention with an element belonging to Group XIII of the periodic table may also be used. The doping amount is preferably ΙχΙΟ·4 to 1×l〇 2 mol per mol of the basic material of the moir, and more preferably 5×l (T4 to 5×10 −3 mol. The doping amount of Μη is preferably per basic material of the moule. ΙχΙΟ·3 to 1x10〃莫耳, and more preferably 5x1 0·3 to 5x1 (Γ2 moles. Phosphorus of the present invention The particles are phosphorus particles, and the particles of 20% or more in terms of the number of particles of all particles are preferably particles having 10 or more intervals of 5 nm or less, and more preferably 10 or more. Or a plurality of particles having a difference of 5 nm or less are 30% or more. The "stacking" used herein means a twin plane and a phase interface. In the case of ZnS, these crystal planes usually become Plane faults on the {111} plane. The general description of the stack is detailed in B. Henderson's Lattice Defect's Chapters 1 and 7, translated by Masao Dohyama & Marquen Co., Ltd. In the case of ZnS, the stack difference Described in Andrew C. Weight and Ian VF Viney, Philosophical Mag. B, 2001 1, Vol. 81, No. 3, pp. 279-297. Lamination is observed when etching phosphorus particles with an acid such as hydrochloric acid. Appearing -9-201038716 is evaluated on the base structure of the particle side (particle surface). The stacking system exists at the interface of the layer structure and appears as a strip on the surface due to etching. This layer structure has all particles and can be SEM Clearly counted with TEM. In the material crushing and vertical stacking When leaving, the layer structure can also be clearly observed by TEM. For example, the phosphorus particles can be pulverized by stirring and the particle fragments can be observed by TEM. The interval and number of the difference can be directly observed. The stacked particles of the present invention are 10 or more. Particles with a spacing of 5 nm or less. Regarding the planar spacing of the lamination, fine structures are currently known. When observing the TEM image of the particle fragments of the pulverized inorganic phosphorus material of the present invention, it was observed that a particle containing 1 〇 or more of a difference of 5 nm or less was observed. Preferably, the inorganic phosphorus material of the present invention has a plane stack of 10 or more, more preferably 15 or more, and still more preferably 18 or more spacer densities of up to 5 nm or less. particle. The average particle size of the particles constituting the phosphorus particles is preferably 20 μm or less, more preferably 18 μm or less, and is preferably 50 nm or more. This is the reason why the stack density is preferably high. The coefficient of variation of the particle size of the present invention can be calculated by the equation (standard deviation of the volume-accumulated particle size distribution + average particle size of the volume cumulative X100 (%)), and the coefficient of variation is preferably 40% or less, more preferably 38% or It is smaller, and is preferably 15% or more. From the point of view of manufacture, the coefficient of variation for this range is preferred. The volume of each particle is converted into a sphere and the particle size is expressed by a sphere or the like. It can measure the particle size from the photo of the particle, or can optically measure the distribution, or can calculate the distribution from the precipitation rate. The average granularity here is the median size. The stack difference in the phosphor particles of the inorganic phosphorus material of the present invention is spontaneously produced by baking - -10-201038716, but it is preferred to carry out the baking twice and appropriately select the first baking and the second baking. The conditions make the phosphorus fine particles contain more stacking. In addition, the difference in the density of the phosphor particles can be substantially increased by applying a specific range of impact force to the particles, preferably the baked particles (intermediate phosphor particles) obtained by the first baking. Does not destroy particles. Examples of a method which can be suitably used for applying an impact force to phosphor particles include a method of bringing particles into contact, a method of mixing particles in the presence of a sphere (such as alumina) (by a ball mill), a method of accelerating particles and ^ A method of colliding with each other, a method of irradiating particles by ultrasonic waves, a method of applying hydrostatic pressure to particles, and a method of generating instantaneous pressure by sudden shock of explosion. The method of impacting the phosphorus particles is preferably a method using a ball mill. The method of using a ball mill will be described below as an example. The container and the ball which can be suitably used for the ball mill are glass, alumina, chromium oxide, etc., but regarding the contamination by the ball, alumina and chromium oxide are superior to others. The diameter of the ball used is suitably in the range of 0.01 to 10 mm, preferably 0.05 to 1 mm. Selecting the optimum diameter of the ball allows the ball to be easily separated from the intermediate phosphor particles after treatment, even allowing the intermediate phosphor particles to easily avoid crushing and uniform stress. It is also advantageous to mix two or more balls of different diameters because this mixing imparts a uniform stress to the intermediate phosphor particles. A suitable ratio of the mixed intermediate phosphorus to the sphere is in the range of 1 part by mass of the intermediate phosphorus of 1 to 100 parts by mass, preferably 2 to 20 parts by mass. A suitable loading ratio of the ball-intermediate phosphorus mixture is in the range of 10 to 60% by volume for the container. It appropriately selects the number of revolutions of the ball mill in accordance with the outer diameter of the container. -11- 201038716 The appropriate linear velocity during rotation is in the range of 1-500 cm/sec, preferably 10-100 cm/sec, and the number of revolutions is adjusted to impart a semicircle to the ball-intermediate phosphorus mixture in the vessel. It is appropriate to operate and to make the tilt angle of the rotating ball within the range of 5-45 degrees. Although depending on the conditions (including the number of revolutions), the proper operation time of the ball mill is in the range of 1 minute to 24 hours, preferably 10 minutes to 3 hours. It is preferred to appropriately combine these conditions by the brightness and life of the EL phosphor. The above is a method of operating a ball mill under dry conditions. On the other hand, in the case of operating the ball mill under wet conditions, an organic solvent (e.g., an alcohol and a ketone) can be used in addition to water. Although the optimum amount of solvent is just enough to fill the inter-ball space, it is appropriate to add a solvent up to 1 to 10 times the volume of the load to enhance the flow force of the mixture. Optimizing the amount of solvent added maintains the flow force of the mixture and tends to apply uniform stress. In order to enhance the flow of the mixture, a surfactant, water glass or the like may be added as a dispersing agent. It is also preferred that the other conditions employed in operating the wet ball mill are within the same range as operating a dry ball mill. In the case where stress is applied by the ball, a device for forcibly stirring the ball with a pusher, a rotor or the like, a device for vibrating the container, or the like may be used. The probability of generating a stacking force by only the impact force is low, and the stacking is caused at a high density by further performing subsequent combustion. The method applicable to the formation of the inorganic phosphorus material of the present invention can be the same as the baking method (solid phase method) widely used in the field, except that it includes a procedure for introducing a large number of stacks. In the case of taking zinc sulfide, a fine particle powder (referred to as a coarse powder) having a particle diameter of 10 to 50 -12 to 201038716 m is prepared by a liquid phase method, and a primary particle is mixed as an impurity of a primary particle activator, and the obtained The particles are subjected to a first high temperature of from 900 ° C to 1,300 ° C for a period of from 1 minute to 1 hour, thereby obtaining particles. The alkaline earth metal and excess activator and co-activator are removed by ion-cleaning by the first baking to become particles of the intermediate phosphor powder. The procedure for introducing the stack is used more frequently during this period. Then the middle so baked is obtained. Compared to the first baking, the second baking is carried out by heating (annealing) at a lower temperature of ° ° ° to 800X for 30 minutes to a shorter time. EL device: Hereinafter, a dispersion type electric device (hereinafter referred to as an EL device of the present invention in some cases) using the inorganic phosphorus material of the present invention will be described. The dispersion type EL device using the inorganic phosphorus material of the present invention has a light-emitting layer of an inorganic phosphorus material between a pair of opposed electrodes (one of which is a transparent electrode). In order to prevent the dielectric tile of the EL device

The purpose of the electric field is to concentrate the light-emitting layer, and it is preferable to dispose the dielectric layer and the barrier layer between the light-emitting layer and the electrode. Next, a sub-EL device using the inorganic phosphorus material of the present invention will be described below. The dispersion type electroluminescent device (preferably an AC sub-assembly) of the present invention comprises at least one dielectric layer, a phosphor layer, and an electrode therebetween, and one of the electrodes is usually a transparent electrode. Transparent electrode: . It will be called a flux placed in the roasting of the people. The water is replaced by an alkali metal or a suitable phosphor powder. The light-emitting device at 500 hours has, for example, a solution containing the present invention and an anti-layer (such as a dispersive inorganic type EL). The surface resistivity of the transparent electrode suitably used in the present invention is preferably 10 ohm/□ or less, more preferably 0.01 to 10 ohm/□, and particularly preferably 0.01 to 1 ohm/ □ The surface resistivity of the transparent electrode can be measured according to the method described in JIS K6911. The transparent electrode is formed on a glass or plastic substrate, and it preferably contains tin oxide. As for the glass, although a typical glass (such as a non-alkali) can be used. Glass or soda lime glass), which preferably uses glass having high heat resistance and high flatness. As for the plastic substrate, a transparent film such as polyethylene terephthalate or ethyl naphthalate may be advantageously used. Or a cellulose triacetate base. A transparent conductive material (such as indium tin oxide (ITO), tin oxide or zinc oxide) may be deposited on any of these substrates, and a film may be formed by evaporation, coating, printing, or the like. In the case where the surface layer of the transparent electrode is mainly tin oxide, it is advantageous for enhancing durability. The deposition amount of the transparent conductive material as a component of the transparent electrode is preferably from 100% to 1% by mass of the transparent electrode, Preferably, it is 70% to 5 mass%, and further preferably 40% to 10% by mass. The method for preparing the transparent electrode may be a vapor phase method such as sputtering or vacuum evaporation, or may be coated or screen printed. The ITO or tin oxide in a slurry state is formed into a film and heated entirely, or may be formed into a film by laser heating. The transparent electrode used in the EL device of the present invention may use any conventional transparent electrode material. Examples include oxides (such as tin-doped tin oxide, antimony-doped tin oxide, zinc-doped tin oxide, fluorine-doped tin oxide, and oxygen-Il 4 - 201038716 zinc), with a thin silver layer sandwiched between high refractive layers. Multi-layer structure, and conjugated polymers (such as polyaniline and polypyrrole). In order to further reduce the resistance, it is appropriate to improve the current-carrying property by arranging a mesh or strip-shaped metal thin wire (such as a lattice or comb-shaped metal thin wire). . Suitable embodiments of the wire metal or alloy include copper, silver, aluminum, and nickel. The metal wires have any thickness, but the thickness thereof preferably ranges from about 0.5 micrometers to 20 micrometers. The metal fine wires are preferably 50 micrometers. Pitch to 400 microns, especially at a pitch of 1 〇〇 to 300 μm. Since the light transmittance is reduced by the arrangement of thin metal wires, it is important to minimize this reduction, and the light transmittance is ensured. A range of 80% to less than 100% is advantageous. The metal fine wire mesh may be adhered to the transparent conductive film, or a metal oxide or the like may be coated or deposited on the film by evaporation or etching by a mask in advance. The metal thin wires may be formed on the metal oxide film prepared in advance. On the other hand, although the formation method is different from the above, the transparent electrode suitable for the present invention can be formed by laminating a metal oxide and a metal thin film having an average thickness of 100 nm or less instead of the metal thin wire. As the metal used for the metal film, those having high corrosion resistance and excellent metallicity and ductility (e.g., Au, In, Sn, Cu, and Ni) are suitable, but the usable metals are not particularly limited to these metals. It is preferred to achieve high light transmittance for this metal film, particularly 70% or higher, particularly preferably 80% or higher. The wavelength defining the light transmittance is 550 nm. The light transmittance can be measured by using an interference filter for extracting 550 nm of monochromatic light and an integrated light amount recorder for a typical white light source of 201038716, or by a spectroscopic measuring device. Back Electrode: Any conductive material can be used as the back electrode provided on the opaque side. The conductive material for the back electrode may be appropriately selected from metals (e.g., gold, silver, uranium, copper, iron, and indium) or graphite depending on the form of the device to be fabricated, the temperature of the process, and the like. It is important that the material selected has a high thermal conductivity, which is preferably a thermal conductivity of 2.0 watts/cm or higher. In order to ensure high heat dissipation to the periphery of the EL device and high current carrying capacity, it is also appropriate to use a metal sheet or a wire mesh. Light-emitting layer (phosphorus layer): In the dispersion type electroluminescence device of the present invention, it is preferred that the light-emitting layer contains an inorganic phosphorus material. In the case of producing an AC dispersion type EL device from the inorganic phosphorus material of the present invention, the phosphorus layer is formed by dispersing particles in an organic dispersion medium and coating the resulting dispersion. As the organic dispersion medium, an organic polymeric material or an organic solvent having a high boiling temperature can be used, but an organic binder mainly comprising an organic polymeric material is preferable. The organic binder is preferably a material having a high dielectric constant. Examples of such materials include fluoropolymer compounds (e.g., polymerized compounds containing fluoroethylene or monochlorodifluoroethane as polymerized units), cyano-ethylated hydroxyl groups (e.g., cyanoethyl water-soluble polysaccharides, Cyanoethyl cellulose), polyvinyl alcohol (cyanoethyl polyvinyl alcohol), and resin (for example, phenol resin, polyethylene, polypropylene, polystyrene-based resin, polyoxyl resin, ring 201038716 oxyresin And the fluoroethylene vinyl resin)' and preferably the light-emitting layer contains all or a part thereof as an organic binder. The dielectric constant can also be adjusted by appropriately mixing these binders with fine particles having a 咼 dielectric constant such as BaTi03 and SrTi〇3. Preferably, the blending ratio of the binder to the light-emitting particles is determined such that the content of the light-emitting particles in the phosphor layer is from 30 to 90% by mass of the total solid content. /〇 ‘and more preferably 60 to 85% by mass. As the binder, it is preferred to use a cyanoethylated hydroxyl group in an amount of 20% by mass or more and more preferably 50% or more, based on the entire organic dispersion medium in the light-emitting particle layer. Polymeric compound. The thickness of the phosphor layer thus obtained is preferably 1 μm or more and 200 μm or less' and more preferably 3 μm or more and 100 μm or less. It is also preferred to use the inorganic phosphorus material of the present invention covered with a non-light emitting shell comprising an oxide, a sulfide or a nitride, as shown in JP-A-2004-1377492. Dielectric layer: The AC dispersion type inorganic EL device of the present invention preferably has a dielectric layer on the opposite side of the transparent electrode to the phosphor layer. The dielectric layer can be formed of any material as long as it has a high dielectric constant and insulating properties, and a high dielectric breakdown voltage. The material is selected from the group consisting of metal oxides and nitrides, for example, Ti02, BaTiO3, SrTi〇3, PbTi〇3, KNb〇3, PbNb〇3, Ta2〇3, BaTa2〇6, LiTa03, Y203, Al2〇3, Zr 〇 2, AlON, ZnS, and the like. It may be provided as a thin film crystal layer, or may be used as a film having a particle structure, or may be combined. -17- 201038716 Process: In the AC dispersion type EL device of the present invention, the phosphor layer and the dielectric layer are preferably dissolved in a solvent by a forming material, and are spin-coated, dip-coated, bar-coated, or The resulting coating liquid is applied by spraying. It is particularly preferable to use a method of not selecting - a printing surface (such as screen printing), and a method of continuous coating (such as a slip coating method). These coating methods are preferably prepared by adding a suitable organic solvent to the constituent materials of the phosphor layer and the dielectric layer. As the organic solvent to be preferably used, dichloromethane, chloroform, ketone, acetonitrile, methyl ethyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, toluene, and xylene are exemplified. It is particularly preferable to form a phosphor layer by continuously coating a coating film having a dry coating thickness of 5 μm or more and 50 μm or less. The layers applied to the support are preferably formed by a continuous process of at least coating to dryness. This drying procedure is divided into a fixed rate drying procedure until the coating film is dried and cured, and a reduced rate drying procedure to reduce residual solvent in the coating film. The drying procedure preferably performs a fixed rate drying procedure at a temperature sufficient to dry the solvent, followed by a reduced rate drying procedure. As for the method of appropriately performing the fixed rate drying process, it is preferred to divide the drying chamber through which the support is divided into a plurality of zones, and to gradually increase the drying temperature after the coating process is terminated. Seal = It is preferred to finally treat the dispersion type EL device of the present invention to exclude the influence of humidity and oxygen from the external environment with a sealing film. Details of the sealing are disclosed in JP-A-2007-1 2466, paragraphs [0050] to [005 5]. Embodiment-1 S - 201038716 The present invention is described in detail with reference to the embodiments. However, the invention is in no way limited by it

Q Example 1 25 parts of zinc sulfide (ZnS) particles, gallium sulfide in terms of Ga in terms of 5xl·2·mol/mol, and copper sulfide in an amount of 9×10 _4 mol/mole in terms of Cu And dry powder of manganese sulfide converted to 3x10 _2 mol/mol according to Μη, as a flux, each of zinc, MgCl2 and ammonium chloride (NH3C1), and 10% by mass of phosphorus powder The amount of magnesium oxide powder was placed in an aluminoxane, baked at 1,150 °c for 2 hours (first baking), and then the temperature was lowered. A 15 mm φ glass bottle was filled with 5 g of baked particles and 20 g of 1 mm φ aluminoxane, and subjected to ball milling at 10 rpm for 20 minutes. The alumina spheres were then separated from the intermediate phosphor particles by a 100 mesh screen. Further, 5 g of ZnO and 0.25 g of sulfur were added to prepare a dry powder, and the dry powder was again placed in an alumina crucible and baked at 700 ° C for 6 hours (second baking). The baked particles were again pulverized, dispersed in H20 at 40 ° C, and precipitated. Wash the particles after removing the supernatant. Then, an aqueous solution of 5% by mass of hydrochloric acid was added thereto to carry out dispersion, precipitation, removal of the supernatant, removal of unnecessary salts, and drying. Further, 10% by mass of the KCN aqueous solution was heated at 70 ° C to exclude oxides (e.g., ZnO) from the surface of the particles. Then, a surface layer of 10% by mass based on the entire particles was removed by etching with 0.1 N hydrochloric acid. The small particles are separated from the particles thus obtained by screening. The phosphor particles thus obtained were observed by an electron microscope and the particle size of 500 particles was examined, and the average particle size was 19 μm and the coefficient of variation of the particle size was 38%. -19- 201038716 Further, phosphorus particles are honed in a crucible and particle fragments having a thickness of 0.2 μm or less are taken out. Observation of the fragments by an electron microscope at an accelerating voltage of 200 volts revealed that 25% of the observed particle fragments (the number of particles) contained a portion having 10 or more plane differences of 5 nm or less. (Table 1 below shows the frequency (% of particles) containing high density stack). An AC dispersion type inorganic EL device was produced from the inorganic phosphorus material prepared as above. The structural outline of this AC dispersion type inorganic EL device is shown in Fig. 1. The first layer and the second layer are sequentially coated on the aluminum electrode (back electrode) (7) having a thickness of 70 μm in the form of a coating liquid of each layer. In addition, in the nitrogen atmosphere, indium tin oxide (3) was sputtered to form a transparent electrode of a thickness of 40 nm of polyethylene terephthalate (thickness: 75 μm) (2) by 190 ° C hot roll pressure bonding aluminum The electrode (7) is such that the transparent electrode (3) side (conductive side) faces the aluminum electrode (7) ' side, and the second layer of the transparent electrode (3) and the phosphor layer (5) are connected to each other. The amount of each layer shown below is the mass per square meter of the EL device. First layer: dielectric layer (6) (layer thickness: 30 nm) Cyanoethyl water-soluble polysaccharide 14.0 g

G cyanoethyl polyvinyl alcohol 10.0 g barium titanate particles (average equivalent spherical diameter: 0.05 μm) 100.0 g second layer: phosphorus layer (5) (layer thickness: 55 nm) Cyanoethyl water-soluble polysaccharide 1 8.0 g of cyanoethyl polyvinyl alcohol 12.0 g or more prepared inorganic phosphorus material (4) 120.0 g by adjusting the viscosity of the coating liquid for forming each layer by adding dimethylformamide, and after coating The layer was dried at H0 ° C for 10 hours. -20- 201038716 As described above, the film (2) having the transparent electrode (3) is pressure-bonded to the thus obtained coated material and the electrode terminals (thickness) of the aluminum electrode (7) and the transparent electrode (3) are respectively thick A 60-micron aluminum plate was wired and the two electrodes were sealed with a sealing film (trifluoropolyvinyl chloride, thickness: 200 μm) (1, 8) to produce an AC dispersion type. Inorganic EL device. Example 2 An inorganic phosphorus material was produced in the same manner as in Example 1, except that gallium sulfide was replaced with aluminum sulfide.实施 Example 3 An inorganic phosphorus material was produced in the same manner as in Example 1, except that gallium sulfide was replaced with indium sulfide. Example 4' An inorganic phosphorus material was produced in the same manner as in Example 1, except that gallium sulfide was replaced with boron sulfide. Example 5 ^ An inorganic phosphorus material was produced in the same manner as in Example 1, except that gallium sulfide was replaced with ruthenium sulfide. Example 6 An inorganic phosphorus material was produced in the same manner as above except that the ball milling time was changed to 60 minutes. Observation of the material by an electron microscope in a similar manner revealed that 32% of the particles contained a portion having 10 or more plane overlaps of 5 nm or less. Example 7 An inorganic phosphorus material was produced in the same manner as above except that the time for baking the first -21 - 201038716 was changed to 6 hours. The electron micrograph was observed to have an average particle size of 29 μm and a particle size variation coefficient of 43 %. Comparative Example 1 An inorganic phosphorus material gallium was produced in the same manner as above except that no vulcanization was added. Comparative Example 2 An inorganic phosphorus material was produced in the same manner as above except that copper sulfide was not added.

Comparative Example 3 An inorganic phosphorus material was produced in the same manner as above except that no vulcanization was added. The results of the emission wavelength and the emission intensity obtained by applying an AC electric field of 1 kHz and 100 V to each device made of the obtained phosphorus are shown in Table 1. The E L emission intensity shows the relative intensity of the emission intensity of Example 取 of 1 。.

-22- 201038716 〇ο I撇EL emission intensity 〇ο in ON 00 Os 1 〇EL emission wavelength (nano) (N v〇ON 634 604 芝 620 623 580 not emitted 513 particle size variation coefficient (%) 〇〇cn Os m 00 cn 00 CO a\ ΓΛ ro $ On m in cn Average particle size (micron) Os 宕00 00 C\ (N 〇\ c\ m - m _ _ Η boat &~> Platinum from {m (Ν CM CN <N (N CO (N (N m N CN 蚺 蚺 u 蚺璀 蚺璀 蚺璀 蚺璀 P P P P P P P P P P P 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 丨Ίι — 201038716 In Examples 1 to 7, the emission wavelength of Mn2+ was biased to the longer side due to the addition of the XIII element, and In the case of a dispersion type EL device, emission of a red region of 600 nm or higher is displayed. Specifically, in Embodiment 6, since the stress application time of the ball mill is extended, the high-density lamination frequency becomes high so that the interval is 5 nm. Or a smaller plane overlap of 1 〇 or more, and can increase the EL emission intensity. The factor is assumed to be that Cu2S, which is a source of electron generation, may be present as the stacking difference increases. In Example 7, the baking time was longer than that of Example 1 to grow larger particles, and the particle size distribution was also broadened. The surface area becomes smaller as the particle size increases, so that it is believed that the area of the emitted light becomes smaller and the emission intensity decreases. On the other hand, Comparative Example 1 containing no element of Group XIII emits a yellow-orange emission of 580 nm, which can be caused by The hetero ZnS was observed with Μη. In Comparative Example 2 in which Cu was not added, EL did not show emission. It was considered that Cu2S which is a source of electron generation was not present. Further, Comparative Example 3 in which Μη was not added was added. Chlorine (for example, NaCl and MgCl2) as a flux is doped into ZnS to form a DA pair of Cu and C1, and the result is blue-green emission. Industrial Applicability As described above, a display of a dispersion-type inorganic EL device can be obtained according to the present invention. An inorganic phosphor material that emits red light. This inorganic phosphor material can be used for the production of a dispersion-type inorganic EL device that exhibits white emission not only showing erythrescence emission but also combining other phosphors showing blue-green EL emission.

According to the inorganic phosphorus material of the present invention, a dispersion type EL device which emits red light can be obtained. Further, in combination with the inorganic phosphorus material of the present invention and the conventional disc which exhibits the emission of the cyan EL-24-201038716, a white light-emitting type EL device which can be used for illumination purposes can be obtained. The present application is based on a Japanese patent application No. JP 2009-075192 filed on March 25, 2009, the entire disclosure of which is hereby incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the structural outline of a dispersion type inorganic EL device manufactured in Examples and Comparative Examples, wherein 1 and 8 represent a sealing film, 2 represents a ruthenium film (PET), and 3 represents oxidation. Indium tin (transparent electrode), 4 denotes an inorganic phosphorus material, 5 denotes a phosphorus layer, 6 denotes a dielectric layer, and 7 denotes an aluminum electrode. [Main component symbol description] 1,8 sealing film 2 film base 3 indium tin oxide 4 ", machine phosphorus material 5 phosphorus layer 6 dielectric layer 7 aluminum electrode -25-

Claims (1)

201038716 VII. Patent application scope: 1. An inorganic phosphorus material, comprising: - a basic material comprising mixed crystals comprising at least one or two or more compounds - the compound is selected from the group consisting of at least one belonging to the periodic table An element of Group XII and at least one compound belonging to the element of Group XVI, wherein the base material contains at least one element selected from the group consisting of Groups XIU of the Periodic Table, Cu and Mn. 2. The inorganic phosphorus material according to item 1 of the patent application, wherein the element selected from the group consisting of the elements of the group XIII is Ga or Ga. 3. In the case of the inorganic phosphorus material of claim 1 or 2, the inorganic material is a pitiful particle, wherein the total number of particles relative to the phosphorus particles is 20% or more based on the number of particles, each having 1 or more Particles with a spacing of 5 nanometers or less. 4. The inorganic phosphorus material according to claim 3, wherein the phosphorus particles have an average particle size of 20 microns or less, and a particle size variation coefficient of 4% by mole. A dispersion type electroluminescence device comprising: a light-emitting layer; and an inorganic phosphorus material as in the first aspect of the patent application in the light-emitting layer. -26-