WO2004096949A1 - 酸化亜鉛蛍光体とその製造法及び発光装置 - Google Patents
酸化亜鉛蛍光体とその製造法及び発光装置 Download PDFInfo
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- WO2004096949A1 WO2004096949A1 PCT/JP2004/006402 JP2004006402W WO2004096949A1 WO 2004096949 A1 WO2004096949 A1 WO 2004096949A1 JP 2004006402 W JP2004006402 W JP 2004006402W WO 2004096949 A1 WO2004096949 A1 WO 2004096949A1
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- zinc oxide
- phosphor
- light
- emitting device
- oxide phosphor
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/621—Chalcogenides
- C09K11/623—Chalcogenides with zinc or cadmium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J63/00—Cathode-ray or electron-stream lamps
- H01J63/02—Details, e.g. electrode, gas filling, shape of vessel
- H01J63/04—Vessels provided with luminescent coatings; Selection of materials for the coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to a zinc oxide phosphor, a method for producing the same, and a light emitting device.
- the present invention is characterized by being relatively inexpensive and resource-stable, providing a fluorescent paint using zinc oxide obtained in a stable manner, or a broad visible light-emitting spectrum used in light-emitting devices. And a method for producing the same, and a light emitting device m using the zinc oxide phosphor.
- Characteristic control by adding impurities to zinc oxide is realized by adding any of group III elements such as aluminum, indium and gallium, or alkali metal elements such as sodium and lithium.
- group III elements such as aluminum, indium and gallium, or alkali metal elements such as sodium and lithium.
- the addition of these additives is described as Equations 3 and 4, where Equation 3 provides conductivity by the addition of a Group III element represented by X, and Equation 4 represents the alkali represented by Z. It shows suppression of conductivity by addition of a metal element. (Equation 3)
- the effect of additives to ZnO is typically art that you introduce either donor or Akuseputa, even the zinc oxide based composition to provide a green light, in principle, Zni + x 0 , Or a composition as given by ⁇ - ⁇ ⁇ ⁇ ⁇ , that is, zinc oxide which has been introduced with a donor.
- the present invention is based on the simultaneous addition of an m-group element that causes the formation of a donor level and an alkali metal element that causes the formation of an acceptor level in zinc oxide. It is different from the conventional technology because it controls the optical characteristics.
- Patent Literature 2 relates to a zinc oxide paint that gives a yellow color.
- the invention described in Patent Document 2 discloses a composition of a paint that looks yellow when illuminated with sunlight or white light represented by general illumination, and a method for producing the same. That is, the present invention relates to a zinc oxide-based composition that gives a yellow reflection spectrum.
- Patent Document 2 does not show anything about light emission when a yellow paint is irradiated with particle beams or electromagnetic waves, and the present invention and the present invention have different purposes and effects. The emitted light cannot be achieved by the technique disclosed in Patent Document 2.
- Yttrium aluminum garnet which is a phosphor that emits yellowish light and to which cellium is added, may be mentioned.
- Non-Patent Document 1 shows the state of light emission.
- the phosphor has been used in the manufacture of a semiconductor device that emits white light by being combined with a nitride semiconductor LED.
- Patent Document 3 discloses the composition.
- the zinc oxide-based composition according to the present invention emits visible light using an emission line of a lanthanide element and emits only a specific wavelength. This is not a method for producing a zinc oxide-based composition which has a broad light emission band and which generates a continuous light emission spectrum as represented by a so-called incandescent lamp. Therefore, the object of the present invention and the effects obtained therefrom cannot be achieved by the technique disclosed in Patent Document 3.
- Patent Document 2 Japanese Patent Publication No. 0'6_070190
- Patent Document 3 JP 08-236275 A
- Non-Patent Document 1 T. Tamura, T. Setoraoto, and T. Taguchi, Journal of Luminescence, 87-89, 1180, (2000) Disclosure of the Invention
- the luminescence of the zinc oxide-based composition of interest in the present invention is a subject that has already been physically studied.
- Schermel and Twingel Solid State Communications, Vol. 8, p. 1559, 1970 shows that at cryogenic temperatures, yellow luminescence is obtained from zinc oxide-based compositions.
- the strongest value of the intensity of the light emitting spectrum is observed in the wavelength range of 550 to 600 nanometers, and the tail on the short wavelength side extends to wavelengths of 400 nanometers or less, and the long wavelength Zinc oxide phosphor characterized in that the side skirt has a continuous spectrum extending over 800 nm or longer. It is the realization of. That is, an effective energy level for realizing the light emission is introduced into the zinc oxide-based composition.
- the problem to be solved by the present invention is to reduce the probability of non-radiative transition and increase luminous efficiency.
- Pure zinc oxide is a semiconductor with a band gap of about 3.3 eV, and pure zinc oxide gives about 380 nanometers of ultraviolet light emission.
- the introduction of the defect gives a blue-green emission having an emission intensity peak at about 520 nm.
- the defect introduced in this way has an energy that is not blue or green and emits a yellowish visible luminescence when excited by a particle beam or an electromagnetic wave having an energy exceeding the band gap. You need to have a state.
- the present inventors have conducted research to achieve light emission by a donor-acceptor pair, that is, light emission by a bond between an electron possessed by a donor and a hole possessed by an acceptor. As a result, aluminum, gallium, and indium were selected.
- the maximum value of the intensity of the emission spectrum at room temperature is observed in the wavelength range of 550 to 600 nm, and the tail on the short wavelength side extends to 400 nm or less.
- a zinc oxide phosphor characterized by having a continuous spectrum extending over a long wavelength of 800 nm or more at the long wavelength side has been found.
- the zinc oxide phosphor which has a yellowish color corresponding to .47, is a phosphor that emits yellow-white light at room temperature.
- the reason why the coordinate values of the color system are spread is that the emission of the phosphor according to the present invention has an afterglow characteristic, and the excitation method or the excitation is continuous or pulsed. Depending on the conditions such as whether or not the excitation method is such that the afterglow is remarkably observed, it means that the width of the appearance of light emission is wide.
- the present invention by adjusting the concentration of hydrogen introduced into the zinc oxide phosphor, only the defects or impurities that give useful visible light emission in the zinc oxide phosphor are activated to give a non-radiative transition. By inactivating visible light emission, its function as a phosphor is improved.
- the zinc oxide phosphor As a zinc oxide phosphor that reduces the probability of non-radiative transition, the zinc oxide phosphor, which is characterized by emission of visible light, has a defect that causes non-radiative transitions formed in the phosphor. Having a surface layer in which hydrogen is dissolved in a solid solution whose concentration is adjusted so as not to inactivate and to inactivate defects that cause radiative transition, or in the phosphor over the entire crystal particle. A zinc oxide containing hydrogen whose concentration is adjusted so as to inactivate the defects that cause the formed non-radiative transition and to inactivate the defects that cause the force and radiative transition. Phosphors are available.
- there is no particular limitation on the method of adding hydrogen as long as the method can introduce hydrogen into zinc oxide.
- an object of the present invention is to excite a zinc oxide phosphor and extract light therefrom.
- the zinc oxide phosphor provided by the present invention can obtain light emission by electromagnetic waves or particle beams exceeding the band gap energy of zinc oxide.
- the methods include (1) irradiating the zinc oxide phosphor with an electromagnetic wave having a wavelength of 375 nm or less to excite the emission, and (2) irradiating the zinc oxide phosphor with an electron beam.
- the emission of the phosphor is excited, and a device that obtains visible light is obtained by any of the following four methods.
- a display panel for displaying information and images can be obtained by arranging the devices for obtaining visible light in a desired pattern.
- FIG. 1 is a schematic diagram of a light emitting device by ultraviolet excitation according to the present invention.
- FIG. 2 A 3 Figure is a schematic view of a light emitting device by electron beam excitation of the present invention is a schematic diagram showing an embodiment fitted with a color filter to the light emitting device according to the ultraviolet excitation of the. Present invention.
- FIG. 4 is a schematic diagram showing a state in which a color filter is attached to a light emitting device excited by an electron beam according to the present invention.
- FIG. 5 shows the emission spectrum of the zinc oxide phosphor according to the present invention, which is produced by the electron beam excitation of the phosphor produced in Example 1 and the phosphor of the comparative example.
- FIG. 1 is a schematic diagram of a light emitting device by ultraviolet excitation according to the present invention.
- FIG. 2 A 3 Figure is a schematic view of a light emitting device by electron beam excitation of the present invention is a schematic diagram showing an embodiment fitted with a color filter to the light emitting device according
- FIG. 6 shows the zinc oxide phosphor according to the present invention, which is the phosphor produced in Example 1 and the phosphor obtained by adding hydrogen to the phosphor of Example 1 produced in Example 2. This is a light emission spectrum by linear excitation.
- FIG. 7 shows a light-emitting spectrum of the zinc oxide phosphor according to the present invention, which is produced by the electron beam excitation of the phosphor produced in Example 1 and the phosphor produced in Example 3.
- the zinc oxide phosphor targeted by the present invention gives a yellowish emission by visual observation at least when excited by a particle beam or an electromagnetic wave having an energy exceeding the bandgap energy of the composition. That is, the strongest value of the intensity of the light-emitting spectrum at room temperature is observed in the wavelength range of 550 to 600 nm, and the tail on the short wavelength side is equal to or less than 400 nm.
- a zinc oxide phosphor characterized in that the tail on the long wavelength side is a continuous spectrum extending over a long wavelength of 800 nm or more, irrespective of its production method.
- the zinc oxide phosphor targeted by the present invention is the zinc oxide-based composition, and a defect that causes non-radiative transition formed in the phosphor to further increase the luminous efficiency.
- Oxidation characterized by containing hydrogen whose concentration has been adjusted so as to inactivate the defects that cause the formed non-radiative transition and not to inactivate the defects that cause the radiative transition. It is a zinc phosphor.
- a zinc oxide phosphor characterized by having a yellowish color corresponding to a range of from 0.5 to 0.47, and y 0.44 to 0.47, and emitting light thereof.
- the concentration of the phosphor that causes non-radiative transitions formed in the phosphor is inactivated, and the concentration is adjusted so as not to inactivate defects that cause radiative transitions.
- It has a surface layer in which the adjusted hydrogen is dissolved, or inactivates defects that cause non-radiative transitions formed in the phosphor throughout the particles, and does not cause defects that cause radiative transitions. It contains hydrogen whose concentration has been adjusted so as not to be activated It is a zinc phosphor.
- the composition of the zinc oxide used for producing the zinc oxide phosphor of the present invention includes at least one of inorganic salts or oxides containing aluminum, gallium, and indium, and lithium and sodium. It is zinc oxide to which at least one kind of inorganic salts or oxides is added.
- the concentration of these additives in zinc oxide is determined by its solid solubility limit.
- the solid solution limit of these additives in zinc oxide changes depending on the environment in which the zinc oxide phosphor is placed, that is, the heat treatment temperature and oxygen partial pressure in producing the solid solution.
- the maximum value of the amount of impurities added for controlling the emission wavelength is defined by the solid solution limit.
- the solid solution limit depends on the temperature and oxygen partial pressure when synthesizing the material and cannot be specified unconditionally, but the maximum value of the concentration of aluminum, indium and gallium is 300 For PPM, sodium and lithium, it is around 1000 ppm.
- the minimum for obtaining a certain high luminous efficiency is more than 500 ppm for aluminum, gallium and indium, and more than 100 ppm for lithium and sodium. Since these impurities become the source of light emission, the higher the concentration, the better the light emission.However, the method of emitting light by irradiating an electron beam reduces the luminous efficiency if the electrical resistance becomes too high. Therefore, it is necessary to adjust the addition amount of lithium and sodium.
- the initial composition for producing the solid solution is determined by taking into account the heat treatment temperature and atmosphere during the production of the solid solution, as well as the vaporization and evaporation of the raw materials during the process of producing the solid solution. There is a need to.
- the maximum value of the intensity of the light emission spectrum is observed in the wavelength range of 550 to 600 nm, and the tail on the short wavelength side extends to the wavelength of 400 nm or less,
- the bottom of the long wavelength side is a continuous spectrum extending over a wavelength of 800 nm or more
- aluminum, gallium, and indium were used. This shows that it is effective to obtain zinc oxide containing at least one of them and at least one of lithium and sodium, which is a total of two or more additives. Need to be optimized during manufacturing.
- the present invention is directed to ultraviolet rays and electromagnetic waves having shorter wavelengths or electron beams.
- the maximum value of the intensity of the emission spectrum at room temperature is observed in the wavelength range of 550 to 600 nanometers, and the tail on the short wavelength side is wavelength 400 nanometers.
- One of the simple methods for producing a zinc oxide phosphor characterized in that it has a continuous spectrum extending down to the At least one of alkali metal elements mainly composed of zinc oxide and causing the formation of an acceptor level, and at least one type of element of group IV causing the formation of a donor level.
- a zinc oxide-based composition characterized by containing the following subcomponents:
- One of the production methods is, in particular, at least one of inorganic salts or oxides containing aluminum, gallium and indium, and at least one of inorganic salts or oxides containing lithium and sodium.
- the method is characterized in that zinc oxide to which the above additive is added is heat-treated at a high temperature sufficient for the additive to form a solid solution in the zinc oxide crystal.
- As the raw material of H [group elements, oxides (Al203, Ga 2 03, ⁇ etc. 2 .theta.3) is convenient to be used.
- Heat treatment must be performed at a temperature sufficient to form a donor level and an acceptor one level that sufficiently react with zinc oxide and contribute to light emission in the zinc oxide-based composition.
- a commercially available powdered reagent, Li2C03, and a commercially available powdered reagent, A1203 are added to a generally available powdered reagent, zinc oxide, and heat treated
- a heat treatment apparatus that does not limit the heating mechanism, it is desirable to perform heat treatment in the range of 800 ° C. to 110 ° C. for 3 hours to 12 hours. Since the heat treatment conditions depend on the additive material and the particle size of the zinc oxide material as the main component, the heat treatment temperature and heat treatment time depend on the form of the raw material used in the production. Need to be adjusted.
- the heat treatment atmosphere is not particularly limited. However, it is preferable to perform the heat treatment in an oxygen atmosphere except for the purpose of obtaining a light-emitting material having low electric resistance.
- the alkali metal element has a high vapor pressure, and tends to evaporate and be lost particularly when the temperature is increased.Therefore, the temperature is such that the additive reacts with zinc oxide as the main component, and the alkali metal evaporates. It is also possible to adopt a method in which heating is performed once at a temperature at which the temperature does not become noticeable, the reaction is started, calcined, and then heat treatment is performed at a higher temperature.
- This calcination depends on the raw materials to be used. If raw materials having a high decomposition temperature have to be used, the calcination must be performed at a higher temperature.
- the calcination temperature is preferably set to 800 ° C. to 100 ° C.
- One of the other simple manufacturing methods is to use a solution (UC1, NaCl) containing zinc oxide powder containing at least one metal element that causes the formation of one-level acceptor in zinc oxide.
- Aqueous solution or a solution obtained by diluting it with alcohol) and a solution containing at least one group III element that causes the formation of donor levels in zinc oxide such as an aqueous solution of Al (NO 3) 3 or an alcohol
- a diluted solution the mixture obtained by drying and mixing, or kneading and drying is subjected to a heat treatment and reacted.
- the process of kneading and drying, or the process of drying and mixing is not particularly limited. However, even if the order is appropriately changed depending on the amount of the solution to be added, the influence on the entire manufacturing process can be ignored. Drying and mixing may be performed simultaneously.
- the drying conditions are as follows: In the heat treatment performed after the drying, if the evaporation of volatile components (such as water) is not so hindered as to hinder the reaction and the recovery of the product, particularly the drying process
- the temperature and atmosphere are not limited. As a result, a method that can achieve a state in which the main component and the added alkali metal and group m element are well mixed does not particularly give a remarkable difference in the characteristics of the product.
- auxiliary components such as lithium and aluminum react sufficiently with zinc oxide, which is a main component, and the zinc oxide-based composition has donor levels and ceptor levels that contribute to light emission. It must be heat treated at a temperature sufficient to form.
- the temperature may be 800 ° C to 11 ° C. It is desirable to carry out a heat treatment in the range of 00 ° C for 3 hours to 12 hours.
- the heat treatment conditions depend on the additive material and the particle size of the zinc oxide raw material, which is the main component, and therefore, in the production, it is necessary to adjust the heat treatment temperature and heat treatment time according to the form of the raw material used. is there.
- the heat treatment atmosphere is not particularly limited, but it is preferable to perform the heat treatment in an oxygen atmosphere except for the purpose of obtaining a light-emitting material exhibiting an electrically low resistance.
- the alkali metal element has a high vapor pressure and is easily evaporated and lost particularly when the temperature is raised. Therefore, the temperature at which the additive reacts with zinc oxide as the main component is a temperature at which the alkali metal evaporates. There is no harm in using a method in which the reaction is started by heating to a temperature that does not become remarkable and then heat-treated at a higher temperature.
- the heat treatment when the heat treatment is performed at an excessively high temperature or an excessively low oxygen partial pressure, evaporation of zinc oxide as a main component, or an alkali metal element or a group I element as a subcomponent becomes remarkable, Since the luminescent material comprising the zinc oxide-based composition according to the present invention may not have desired characteristics, it is desirable to perform the heat treatment at a temperature and an atmosphere under such conditions that the composition does not significantly change due to evaporation.
- the method shown here is an example of a simple method, and whether or not to carry out this method is not a necessary matter in the present invention.
- the mixture is used.
- the luminous efficiency may be improved.
- the oxygen partial pressure needs to be adjusted according to the characteristics (here, luminous efficiency and electrical resistivity) required of the product. As the oxygen partial pressure increases, the electrical resistance of the product also increases. Therefore, it is necessary to adjust the oxygen partial pressure so that a product having desired characteristics is obtained.
- the production in the oxygen atmosphere is not always necessary in the present invention.
- improvement of the luminous efficiency may be recognized by subjecting the la composition to a heat treatment in an atmosphere containing oxygen as a main component. Therefore, in the final step of the production of the composition, annealing the composition in a gas containing oxygen as a main component may be effective in improving luminous efficiency.
- the annealing treatment here is carried out after the above-mentioned manufacturing process.
- Zinc oxide which is the main component, is added to any of the in-group elements, aluminum, gallium, and indium, which are sub-components.
- the annealing treatment here is for changing the amount and state of defects, it is desirable to perform the annealing at the most effective temperature between 400 ° C. and 110 ° C. That is, the concentration and state of the defect species such as oxygen vacancies in the zinc oxide are affected by both the temperature and the oxygen partial pressure, so that the desired characteristics (here, luminous efficiency and electrical conductivity) or It is necessary to adjust the temperature and atmosphere so that characteristics similar to those can be obtained. In general, oxygen vacancies tend to decrease when the temperature is low and the oxygen partial pressure is high. If it becomes lower, the diffusion coefficient of ions in the solid decreases, and longer treatment is required. Further, the sufficient annealing time depends on the size of the zinc oxide-based composition to be produced.
- the annealing condition that can obtain the effect in a finite time is 800 ° C to 110 ° C.
- heating is performed for 1 to 10 hours, and then the temperature is lowered to room temperature in the same atmosphere for 3 to 6 hours. It is necessary to examine the processing conditions depending on the shape and density of the product, and to find the optimum conditions.
- annealing in an oxygen atmosphere is not essentially necessary in the present invention.
- the most typical method of hydrogenation is a method using plasma. It is also possible to add hydrogen to the phosphor by heat treatment with flowing hydrogen gas.1 When zinc oxide is heated in a reducing atmosphere with hydrogen, evaporation of zinc oxide or defects in zinc oxide The concentration may increase, and depending on the degree of reduction, the luminous efficiency of the zinc oxide phosphor to be manufactured by the present invention may be impaired. By using a plasma that can supply atomic hydrogen, hydrogen can be added without causing significant evaporation or reduction of the phosphor due to its high chemical reactivity.
- the hydrogenation treatment of the present invention is intended to suppress the non-radiative transition by changing the state of defects that reduce the high rate of the target light emission without changing the state of the additive that causes the target light emission. is there. Also, depending on the phosphor manufacturing conditions, the concentration of defects that cause a non-radiative transition may be low. In such a case, even if hydrogen is added, improvement in luminous efficiency cannot be expected. That is, the hydrogenation according to the present invention is not always necessary for improving the function of the phosphor, but should be performed as necessary.
- Optimizing the processing conditions means, for example, changing the input power for generating plasma or the distance between the plasma flame and the phosphor to be treated, to obtain several types of hydrogenated phosphors. It is implemented by manufacturing and evaluating its light emission spectrum. It is possible to optimize the conditions by obtaining hydrogenation treatment conditions that give the best emission spectrum under the given excitation conditions.
- a light emitting device using the zinc oxide phosphor of the present invention wherein the light emission is excited by irradiating the zinc oxide phosphor with an electromagnetic wave having a wavelength of not more than 37.5 nm.
- the device By forming the device, a device utilizing the light emission of the phosphor is formed.
- a light emitting device that emits light is formed by applying a sufficient intensity of excitation to the phosphor using a general ultraviolet light source as an excitation source.
- the ultraviolet light source includes a discharge tube or a solid-state ultraviolet light emitting element. That is, it is also possible to apply a phosphor to the inside of the discharge tube and use ultraviolet light emitted by the discharge as a light source.
- FIG. 1 shows a schematic diagram of the light emitting device. This is an example of a light emitting device in which a fluorescent tube (14) that emits general ultraviolet light is installed behind a glass substrate (13) coated with the zinc oxide phosphor (12) of the present invention.
- the light emitting device can be used for stimulating human vision or as an exposure device for stimulating light-responsive objects.
- the excitation intensity is stronger than the range appropriate for the phosphor.
- the phosphor may emit band-edge light, that is, ultraviolet light, and its excitation intensity needs to be adjusted according to the luminous efficiency of the phosphor.
- the fluorescent tube which is an ultraviolet light source
- a pulsed ultraviolet light source composed of a combination of a Q-switch Nd: YVO pulse laser and a nonlinear optical crystal that emits a fourth harmonic.
- a light emitting device corresponds to this.
- the pulse light source using the Q switch Nd: YVO has a power density 100 times or more higher than that of the ultraviolet light source using a fluorescent tube.
- a light-emitting device using the zinc oxide phosphor of the present invention is characterized in that the light emission of the phosphor is excited by irradiating the zinc oxide phosphor with an electron beam. You.
- thermoelectrons and field emitters electrons generated from various electron beam sources, including thermoelectrons and field emitters, are accelerated and irradiated to the phosphor to have sufficient energy to form sufficient electron-hole pairs in the phosphor.
- light is emitted.
- the mechanism for generating the electron beam is not particularly limited, and the electron beam generated by thermionic or electric field radiation is generally available. That is, (1) a mechanism for generating an electron beam with an appropriate irradiation intensity is included, and (2) a kinetic energy sufficient to generate electron-hole pairs in the zinc oxide phosphor. (3) Poured into the phosphor by electron beam irradiation An electrode (ground electrode) for discharging the charge is provided to prevent the accumulated charge from accumulating in the phosphor and causing a charge-up state. (4) The emitted fluorescent light illuminates the target place Any device provided with a light extraction port made of a light transmissive material that enables light emission is a light emitting device encompassed by the present invention. In particular, when an electron beam generating mechanism that extracts an electron beam by an electric field is provided, it is possible to use a common mechanism for the electron beam generating mechanism and the mechanism for accelerating the electron beam.
- FIG. 2 shows a schematic diagram of the light emitting device.
- thermionic beam source (1), electron beam accelerating electrode (3), grounding (5), focusing mirror (6), light extraction window (7), and phosphor (8) are vacuum
- the light emitting device is installed inside the package (9), and connected to a power supply for thermionic emission (2) and a power supply for electron beam acceleration (4) prepared outside the package.
- the light emitting device connected to the source (1) and the electron beam accelerating electrode (3) is constructed.
- the phosphor (8) is irradiated with an electron beam from the thermionic beam source (1) to extract light through the light extraction window 7.
- the device shown here is an example of a light emitting device configuration, and the condenser mirror (6) is not an essential component.
- the vacuum package (9) transparent, the light extraction window (7) may not be necessary, and is essentially a device that can irradiate the phosphor with an electron beam.
- this light emitting device it is possible to use the light emitting device for stimulating human vision and to use the light emitting device as an exposure device for applying a light stimulus to a light-responsive object.
- a light emitting device using the zinc oxide phosphor of the present invention wherein the light emitting device comprises A light emitting device characterized in that a fluorescent material is used to excite the phosphor by using a probe beam, and a broad spectrum obtained by exciting the zinc oxide phosphor with an electron beam or ultraviolet rays.
- a power filter By emitting light through a power filter, it is possible to obtain a light emitting device characterized in that only light in a limited wavelength range is extracted out of the device and used.
- FIG. 3 shows a schematic diagram of the light emitting device.
- a light-emitting device that emits red-orange light by attaching a general color filter (31) that absorbs light with a wavelength shorter than 600 nm to the light-emitting device shown in Fig. 1.
- This light-emitting device can be used for stimulating human vision and as an exposure device for stimulating light-responsive objects.
- FIG. 4 shows a schematic diagram of the light emitting device.
- the light emitting device shown in Fig. 2 is equipped with a general color filter (2 1) that absorbs light with a wavelength shorter than 600 nm, thereby emitting red-orange light. It is an example of a light emitting device.
- Atomic ratio of gallium to lithium is 1 / 1,000 and lithium is 1 / 10,000 in terms of atomic ratio to zinc, compared to a commercially available 99.99% pure zinc oxide powder reagent.
- Gallium oxide powder and lithium carbonate powder are mixed, and the mixed powder is placed in alumina porcelain, set in an electric furnace, which is a general heating device, and placed in an oxygen atmosphere supplied from a commercially available oxygen gas cylinder.
- the reaction was carried out at 800 ° C. for 3 hours.
- lithium carbonate as a lithium source was decomposed, and carbon dioxide gas was vaporized and desorbed. Note that the amount of lithium added was reduced so as not to increase the resistance.
- a 1 ton load was applied to the reaction product obtained here, and it was molded into a pellet having a diameter of 10 mm and a thickness of 3 mm.
- the molded product was put back into the alumina porcelain, and was used as a general heating device. It was placed in a furnace and fired at 110 ° C. in an oxygen atmosphere, whereby a zinc oxide-based yarn in which gallium and lithium were dissolved was obtained.
- the zinc oxide-based composition obtained by the above method is irradiated with light having a wavelength of about 355 nanometers or about 245 nanometers, the light emitted from the composition is visually observed. Upon observation, yellowish emission was confirmed, confirming that the desired phosphor was produced. When a conventional zinc oxide phosphor having a zinc-rich composition was observed in the same manner, blue-green light emission was visually confirmed.
- the above zinc oxide-based composition is irradiated with an electron beam accelerated to 5 kiloelectron volts, and the light generated by this excitation is separated by a commercially available general spectroscope to obtain a commercially available general light.
- the light was detected by a CCD detector, and the emission spectrum was recorded. As a result, the spectrum as shown in Fig. 5 was obtained.
- the zinc oxide-based composition according to the present invention shown by the thin line shows an It contains an alkali metal element that causes the formation of a level and an nr-group element that causes the formation of a donor level, and emits light with the strongest value at about 2.0 electron ports (wavelength: about 600 nm). ing.
- FIG. 5A is a diagram in which the light emitting spectrum of the phosphor according to the present invention is rewritten with the vertical axis on a logarithmic scale. As can be seen here, an extremely broad emission spectrum has been obtained. These two spectra are the results of measurement under the same measurement conditions using the same spectrometer and photodetector. These are the results obtained under possible experimental conditions.
- a comparison of the spectrum with a conventional zinc oxide phosphor that emits blue-green color indicates that the zinc oxide-based composition obtained by adding a donor and an axceptor at the same time gives a broader visible light emission and a spectrum close to white. Torr.
- Example 2
- Example 1 With respect to the zinc oxide phosphor obtained in Example 1 described above, plasma generated by a plasma generator as described in Japanese Patent No. 2920207 shown above, that is, Irradiation of inductively coupled plasma obtained by applying radio waves to a mixed gas of hydrogen gas and Ar gas was performed to produce a phosphor in which hydrogen was introduced into a zinc oxide phosphor.
- the dumbbell oxide phosphor used in this treatment was a pellet having a diameter of about 8 millimeters and a thickness of about 2 millimeters, and the plasma irradiation time was 5 minutes.
- FIG. 6 shows the result of evaluating the emission spectrum of the phosphor obtained after the introduction of hydrogen by this plasma treatment by the same electron beam excitation method as in Example 1 above. .
- the pattern shown by the thick line is the phosphor before the hydrogen introduction treatment, and the thin line is the spectrum after the hydrogen introduction treatment.
- the luminous efficiency was improved by introducing hydrogen into the dumbbell oxide phosphor by the treatment using hydrogen plasma. Phosphor was produced.
- Example 1 The zinc oxide phosphor obtained in Example 1 was annealed at 110 ° C. for 6 hours in an oxygen atmosphere.
- Fig. 7 shows the emission spectrum of the phosphor before annealing (thick line) and that of the annealed product (thin line) under irradiation of an electron beam accelerated to 5 kE.
- the spectra were obtained using the same equipment and under the same measurement conditions, and their comparisons are possible.
- the higher intensity is the emission spectrum of the phosphor annealed in oxygen gas. That is, phosphors having higher luminous efficiency were produced by annealing in oxygen.
- annealing has the function of restoring the luminous efficiency of a phosphor whose luminous efficiency has been reduced for some reason, and its effect on the phosphor that originally exhibits high luminous efficiency. was limited.
- the zinc oxide phosphor of the present invention comprises an ultraviolet ray and an electromagnetic wave having a shorter wavelength or an electron beam. It is used as a light-emitting device that is excited by light and is used to stimulate human vision, such as traffic signals and display panels, and light-responsive objects, such as light sources for printing photos and reading devices. On the other hand, it can be used as an exposure device for applying a light stimulus, or used as a fluorescent paint.
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Description
Claims
Priority Applications (3)
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US10/554,724 US7535162B2 (en) | 2003-04-30 | 2004-04-30 | Zinc oxide phosphor, process for producing the same and light emitting device |
JP2005505959A JP4635184B2 (ja) | 2003-04-30 | 2004-04-30 | 酸化亜鉛蛍光体とその製造法及び発光装置 |
EP04730742.6A EP1630218B1 (en) | 2003-04-30 | 2004-04-30 | Zinc oxide phosphor and process for producing the same |
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JP2003124743 | 2003-04-30 | ||
JP2003-124743 | 2003-04-30 |
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WO2004096949A1 true WO2004096949A1 (ja) | 2004-11-11 |
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PCT/JP2004/006402 WO2004096949A1 (ja) | 2003-04-30 | 2004-04-30 | 酸化亜鉛蛍光体とその製造法及び発光装置 |
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US (1) | US7535162B2 (ja) |
EP (1) | EP1630218B1 (ja) |
JP (1) | JP4635184B2 (ja) |
KR (1) | KR100666663B1 (ja) |
WO (1) | WO2004096949A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100509998C (zh) * | 2005-11-26 | 2009-07-08 | 中国科学院合肥物质科学研究院 | 具有紫外发光性能的氧化锌纳米片薄膜材料及其制备方法 |
JP2009286856A (ja) * | 2008-05-27 | 2009-12-10 | Fukuda Crystal Laboratory | シンチレータ材料とその製造方法、及び、電離放射線検出器 |
WO2013046511A1 (ja) * | 2011-09-27 | 2013-04-04 | パナソニック株式会社 | 紫外発光蛍光体材料の製造方法 |
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JP4994235B2 (ja) * | 2005-08-09 | 2012-08-08 | スタンレー電気株式会社 | ZnO結晶とその成長方法、及び発光素子の製造方法 |
EP2480626A4 (en) * | 2009-09-21 | 2013-04-03 | Univ Georgia | NEAR-FROSTED PHOSPHERE WITH AN ALKALI GALLAT MATRIX |
WO2011035292A2 (en) | 2009-09-21 | 2011-03-24 | University Of Georgia Research Foundation, Inc. | Near infrared doped phosphors having a zinc, germanium, gallate matrix |
CN102660264B (zh) * | 2012-04-17 | 2014-06-04 | 绍兴文理学院 | 一种近紫外光激发白光LED用ZnO基荧光粉材料及其制备方法 |
RU2520892C2 (ru) * | 2012-07-06 | 2014-06-27 | Министерство образования и науки Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Норильский индустриальный институт" (ФГБОУ ВПО "НИИ") | Способ обработки цинкооксидных люминофоров |
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- 2004-04-30 JP JP2005505959A patent/JP4635184B2/ja not_active Expired - Fee Related
- 2004-04-30 KR KR1020057015493A patent/KR100666663B1/ko not_active IP Right Cessation
- 2004-04-30 EP EP04730742.6A patent/EP1630218B1/en not_active Expired - Fee Related
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CN100509998C (zh) * | 2005-11-26 | 2009-07-08 | 中国科学院合肥物质科学研究院 | 具有紫外发光性能的氧化锌纳米片薄膜材料及其制备方法 |
JP2009286856A (ja) * | 2008-05-27 | 2009-12-10 | Fukuda Crystal Laboratory | シンチレータ材料とその製造方法、及び、電離放射線検出器 |
WO2013046511A1 (ja) * | 2011-09-27 | 2013-04-04 | パナソニック株式会社 | 紫外発光蛍光体材料の製造方法 |
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Also Published As
Publication number | Publication date |
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US7535162B2 (en) | 2009-05-19 |
EP1630218A1 (en) | 2006-03-01 |
JP4635184B2 (ja) | 2011-02-16 |
EP1630218A4 (en) | 2009-04-29 |
JPWO2004096949A1 (ja) | 2006-07-13 |
KR100666663B1 (ko) | 2007-01-09 |
US20070158615A1 (en) | 2007-07-12 |
EP1630218B1 (en) | 2014-08-20 |
KR20050100698A (ko) | 2005-10-19 |
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