WO2021100839A1 - Élément électroluminescent fluorescent et son procédé de production - Google Patents

Élément électroluminescent fluorescent et son procédé de production Download PDF

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Publication number
WO2021100839A1
WO2021100839A1 PCT/JP2020/043306 JP2020043306W WO2021100839A1 WO 2021100839 A1 WO2021100839 A1 WO 2021100839A1 JP 2020043306 W JP2020043306 W JP 2020043306W WO 2021100839 A1 WO2021100839 A1 WO 2021100839A1
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binder
phosphor
light emitting
fluorescent light
emitting element
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PCT/JP2020/043306
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English (en)
Japanese (ja)
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井上　正樹
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ウシオ電機株式会社
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Priority to JP2021558463A priority Critical patent/JP7363919B2/ja
Publication of WO2021100839A1 publication Critical patent/WO2021100839A1/fr

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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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements

Definitions

  • the present invention relates to a fluorescent light emitting device containing a phosphor and a method for manufacturing the same.
  • a fluorescence light source device that includes an excitation light source composed of a semiconductor laser element and a fluorescence light emitting element containing a phosphor and irradiates the phosphor with light (laser light) emitted from the excitation light source to generate fluorescence.
  • the fluorescence generated by such a fluorescence light source device is used as, for example, a light source for a projector.
  • Patent Document 1 discloses a fluorescent light emitting element composed of a YAG (yttrium aluminum garnet) phosphor and a binder made of alumina (Al 2 O 3).
  • Patent Document 2 discloses a fluorescent light emitting device including a phosphor represented by a composition formula of La 3 Si 6 N 11 called an LSN phosphor and a binder made of a fluoride inorganic material such as CaF 2. Has been done.
  • the fluorescent light emitting element is generally used as a fluorescent plate obtained by forming a mixture of a phosphor and a binder into a plate shape and then sintering the mixture.
  • a fluorescent light emitting element containing a YAG phosphor and a binder made of alumina as described in Patent Document 1
  • the difference between the refractive index of the phosphor and the binder is small (about 0.08). Therefore, among the light (fluorescence) generated by the phosphor, the light traveling in a direction substantially parallel to the main surface of the fluorescent plate has many components that travel in the same direction as it is. As a result, by the time it is taken out from the main surface of the fluorescent plate, it has an spread in the surface direction, and the spot diameter of the fluorescence becomes large.
  • the difference in refractive index between the two is about 0.61, so that the phosphor composed of YAG
  • the value of the refractive index difference is larger than that of the combination of binders made of alumina.
  • the fluorescence on the extraction surface side is higher than that of the fluorescence emitting element containing the phosphor composed of YAG and the binder composed of alumina.
  • the spot diameter can be reduced, and a high-brightness fluorescent light source can be realized.
  • excitation light such as blue laser light is incident from an excitation light source composed of a semiconductor laser element or the like, and the phosphor is excited by the excitation light to generate excitation light. Extracts fluorescence of different wavelengths.
  • the temperature of the fluorescence light emitting element rises. Resulting in.
  • the fluoride inorganic material such as CaF 2 described in Patent Document 2 has a lower thermal conductivity than alumina.
  • the thermal conductivity of CaF 2 is 9.7 [W / m ⁇ K]
  • the thermal conductivity of BaF 2 is 11.7 [W / m ⁇ K]
  • the thermal conductivity of alumina is Is 40.0 [W / m ⁇ K]. Therefore, when using a fluorescent plate using CaF 2 as a binder, it is necessary to take measures to suppress an increase in temperature, for example, by rotating the fluorescent plate itself or blowing wind from a fan.
  • the fluoride inorganic material has a considerably larger coefficient of thermal expansion than the LSN phosphor. More specifically, the coefficient of thermal expansion of the LSN phosphor is 5 ppm, whereas the coefficient of thermal expansion of CaF 2 is 18.9 ppm, and the coefficient of thermal expansion of BaF 2 is 18.1 ppm. That is, there is a difference of 13 ppm in the coefficient of thermal expansion between the LSN phosphor and the fluoride inorganic material. Therefore, when cooled to room temperature after the completion of the sintering treatment, the fluorescent plate may be cracked due to the difference in the coefficient of thermal expansion between the two.
  • the proportion of the phosphor to be introduced is lower than that of a fluorescent light emitting element using alumina as a binder from the viewpoint of preventing cracking. There is no choice but to do this, which can be a factor in lowering the fluorescence intensity.
  • the present inventor relates to a fluorescent light emitting element having a binder made of an oxide such as alumina instead of a fluoride inorganic material such as CaF 2 because of its high thermal conductivity and easy sintering. Diligent research was conducted. As a result, a fluorescent light emitting device capable of further increasing the luminous efficiency (internal quantum efficiency) has been realized.
  • An object of the present invention is to provide a fluorescent light emitting element having a higher internal quantum efficiency than the conventional one, while using a binder made of an oxide.
  • the fluorescent light emitting device is A binder containing oxide particles with a particle size on the order of submicrons, It is characterized by having a Ce-activated nitride phosphor dispersed in the binder.
  • the relative density refers to the ratio of the apparent density of the sintered body to the theoretical density.
  • the low relative density means that many pores are contained inside, and this is because the heat exhausting property of the entire fluorescent light emitting element is lowered in such a state.
  • the reason for this is that when the LSN phosphor is placed in a high temperature environment, some nitrogen atoms contained in the LSN phosphor are desorbed and oxygen atoms contained in alumina are taken in. It is presumed that this is due to the formation of La oxide represented by a composition formula different from that of La 3 Si 6 N 11, which reduced the content of LSN phosphor contained in the fluorescent light emitting element.
  • this phenomenon occurs when the phosphor contains a nitrogen atom and the binder contains an oxide, in other words, a nitride phosphor other than the LSN phosphor and a binder composed of an oxide other than alumina. It is considered that this may occur during the manufacture of the fluorescent light emitting element containing the oxide.
  • the binder may be a material (mixture, spinel structure) containing MgO or Al 2 O 3 and MgO in addition to alumina.
  • the sintering start temperature can be lowered as compared with the oxide particles having a particle size of about several microns.
  • the phosphor and the binder can be sintered at a temperature at which nitrogen atoms are not easily desorbed from the nitride phosphor such as the LSN phosphor, and the nitride phosphor is oxidized containing the constituent atoms of the phosphor.
  • the rate of change to a substance for example, La oxide
  • alumina when used as the binder, it is more preferable because it can secure high heat exhausting property and increase the content of the nitride phosphor in the fluorescent light emitting element.
  • the particle size of the oxide particles constituting the binder for example, it can be measured by obtaining the shortest and longest averages of the oxide particles having a shape close to a circle appearing on the SEM image.
  • the particle size of the oxide particles is preferably 100 nm or more and 900 nm or less, and more preferably 400 nm or more and 800 nm or less.
  • ⁇ -alumina becomes more stable than ⁇ -alumina as the particle size becomes smaller. Therefore, conventionally, ⁇ -alumina having a particle size of less than 100 nm is produced. Was technically difficult.
  • ⁇ -alumina is known to transfer to ⁇ -alumina at a temperature close to 1000 ° C.
  • ⁇ -alumina is used as the alumina particles constituting the binder and mixed with the particles of the LSN phosphor and subjected to the sintering treatment, ⁇ -alumina is transferred to ⁇ -alumina in the sintering process.
  • ⁇ -alumina has a higher density than ⁇ -alumina, when a mixture of phosphor particles and ⁇ -alumina particles is placed at a high temperature, ⁇ -alumina is transferred to ⁇ -alumina and at the same time. , Many pores of more than 40% are generated inside.
  • alumina which is a material having high thermal conductivity, is used for the binder, the manufactured fluorescent light emitting element may not be able to secure sufficiently high heat exhaust property. From this point of view, it is preferable to use ⁇ -alumina as the binder material.
  • the lower limit of the particle size of the alumina particles is preferably 100 nm or more, and more preferably 400 nm or more for reasons of manufacturing technology.
  • the particle size of the alumina particles is 1 ⁇ m or more, the sintering start temperature becomes high, and there is a possibility that the temperature environment is such that nitrogen atoms contained in the LSN phosphor are easily desorbed during the sintering process.
  • the upper limit of the particle size of the alumina particles is preferably 900 nm or less, more preferably 800 nm or less.
  • the fluorescent light emitting element has a binder having a concave-convex shape having a particle size on the order of submicrons, the effect of scattering the incident excitation light can be obtained. Therefore, when the excitation light is blue light and the fluorescence is yellow light, the intensity of the white light obtained as the combined light of the excitation light and the fluorescence can be increased.
  • the chemical formula of the diffraction intensity I 30.9 which is the signal derived from La 3 Si 6 N 11 in the XRD spectrum
  • the intensity of the diffraction intensity I 29.4 which is the signal derived from La 2 Si 6 N 8 O 3 in the XRD spectrum.
  • the content of La oxide defined by La 2 Si 6 N 8 O 3 can be suppressed to a low level, and the content of LSN phosphor defined by La 3 Si 6 N 11 is low. Since it is high, a fluorescent light emitting device having high internal quantum efficiency can be realized.
  • the fluorescent light emitting element is The relative density is 80.4% or more and 99.5% or less.
  • the mass ratio of the binder to the total mass of the phosphor and the binder may be 50% by mass or more and 70% by mass or less.
  • the relative density depends on the number of pores generated in the sintering process.
  • the relative density is 80.4% or more and 99.5% or less, a large difference in refractive index is generated between the phosphor and the pores and between the binder and the pores.
  • Fluorescence that has progressed in a direction substantially parallel to the surface of the fluorescent plate can be efficiently directed to the surface of the fluorescent plate (light extraction surface). As a result, a fluorescent light emitting element having high brightness can be realized.
  • volume ratio of the binder that is, the content of oxide particles to 50% by mass or more and 70% by mass or less, it is possible to further improve the internal quantum efficiency.
  • the method for manufacturing a fluorescent light emitting device is as follows.
  • the step (b) of molding the mixture obtained in the step (a) and It is characterized by having a step (c) of sintering the molded product obtained in the step (b) at a temperature of 1050 ° C. or higher and 1200 ° C. or lower.
  • a fluorescent light emitting device having high heat dissipation and internal quantum efficiency is realized.
  • FIG. 1 is a drawing schematically showing a configuration of a fluorescence light source device of one embodiment including a fluorescence light emitting element.
  • the fluorescence light source device 1 shown in FIG. 1 includes an excitation light source 2, a dichroic mirror 3, and a fluorescence light emitting element 10.
  • the excitation light source 2 includes, for example, a semiconductor laser device that emits light in a blue region having a wavelength of 445 nm or more and 465 nm or less.
  • the excitation light source 2 may be provided with an optical system such as a collimating lens, if necessary.
  • the fluorescent light emitting element 10 includes a phosphor 16 and a binder 17 described later (see FIG. 3).
  • the excitation light 21 emitted from the excitation light source 2 irradiates the fluorescence light emitting element 10
  • the phosphor 16 contained in the fluorescence light emitting element 10 is excited, and the fluorescence 22 is emitted from the fluorescence light emitting element 10.
  • the fluorescence 22 is light having a longer wavelength than the excitation light 21, and has, for example, a wavelength of 470 nm or more and 700 nm or less.
  • the dichroic mirror 3 is configured to transmit the excitation light 21 emitted from the excitation light source 2 and reflect the fluorescence 22 emitted from the fluorescence light emitting element 10.
  • the dichroic mirror 3 is arranged so that the mirror surface is inclined at an angle of 45 ° with respect to the incident angle of the excitation light 21, for example. With such a configuration, the fluorescence 22 is taken out of the fluorescence light source device 1 and is incident on, for example, an optical system in a subsequent stage (not shown).
  • the fluorescent light emitting element 10 has a high heat exhaust property because it contains a binder having a high thermal conductivity. Therefore, the fluorescent light emitting element 10 does not need to be installed on a separate rotating wheel or the like for cooling, and can be fixedly installed at a predetermined position of the device.
  • FIG. 2 is a cross-sectional view schematically showing an example of the configuration of the fluorescent light emitting element 10.
  • the fluorescent light emitting element 10 has a substrate 11, a bonding layer 12, a reflective layer 13, and a fluorescent plate 14.
  • the substrate 11 is provided to exhaust the heat generated by the fluorescent plate 14.
  • the substrate 11 is made of, for example, a material having a thermal conductivity of 90 [W / m ⁇ K] or more, specifically 230 to 400 [W / m ⁇ K]. Examples of such materials include Cu, copper compounds (MoCu, CuW, etc.), Al, AlN, and the like.
  • the thickness of the substrate 11 is, for example, 0.5 mm to 5 mm. Further, from the viewpoint of heat exhaustability and the like, the area on the surface of the substrate 11 is preferably larger than the area of the fluorescent plate 14.
  • the bonding layer 12 is a layer for bonding the substrate 11 and the fluorescent plate 14, and is made of, for example, a solder material. From the viewpoint of heat dissipation and the like, it is preferable to use a material having a thermal conductivity of 40 [W / m ⁇ K] or more as the material constituting the bonding layer 12. More specifically, for example, cream solder, Sn-Ag-Cu-based solder, Au-Sn-based solder, etc., in which a material such as Sn or Pb is mixed with flux or other impurities to form a cream-like (paste-like) form. Can be used.
  • the thickness of the bonding layer 12 is, for example, 20 ⁇ m to 200 ⁇ m.
  • the reflective layer 13 is formed on the surface of the fluorescent plate 14 on the substrate 11 side.
  • the reflection layer 13 is provided to reflect the fluorescence 22 that has progressed to the side opposite to the light extraction surface 14a (the substrate 11 side) among the fluorescence 22 generated by the fluorescence plate 14 and guide the fluorescence 22 to the light extraction surface 14a.
  • the reflective layer 13 can be composed of, for example, a metal film such as Al or Ag, or an antireflection film in which a dielectric multilayer film is formed on the metal film.
  • the surface of the fluorescent plate 14 on the substrate 11 side, more specifically, the reflective layer 13 and the fluorescent plate 14 A metal film made of, for example, a Ni / Pt / Au film or a Ni / Au film formed by vapor deposition may be formed between the two.
  • the fluorescent plate 14 is formed on the upper layer of the reflective layer 13.
  • the fluorescent plate 14 emits fluorescence 22 when the excitation light 21 emitted from the excitation light source 2 is incident.
  • the fluorescent plate 14 shows a rectangular flat plate-like structure when viewed from a direction orthogonal to the surface of the substrate 11.
  • the thickness of the fluorescent plate 14 is, for example, 0.05 mm to 1 mm.
  • FIG. 3 is a cross-sectional view schematically showing the configuration of the fluorescent plate 14.
  • the fluorescent plate 14 shown in FIG. 3 includes a phosphor 16, a binder 17, and pores 18. Further, as shown in FIG. 2, the fluorescent plate 14 has a moth-eye structure 15 which has been subjected to fine unevenness processing on a surface located on the opposite side of the substrate 11, that is, on the light extraction surface 14a side. However, it is arbitrary whether or not the fluorescent light emitting device 10 of the present invention has the moth-eye structure 15 on the light extraction surface 14a side.
  • the phosphor 16 is made of a Ce-activated nitride phosphor.
  • the phosphor 16 is composed of an LSN phosphor in which Ce is activated and represented by the composition formula La 3 Si 6 N 11 or (La, Y) 3 Si 6 N 11.
  • the phosphor 16 is in the form of particles and is dispersed in the binder 17.
  • the particle size of the phosphor 16 is 30 ⁇ m or less, preferably 25 ⁇ m or less, more preferably 20 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • the lower limit of the particle size of the phosphor 16 is not particularly specified, but is generally 1 ⁇ m or more.
  • the binder 17 is made of alumina (Al 2 O 3 ), and more specifically, of ⁇ -alumina.
  • the fluorescent plate 14 is a sintered body of alumina particles having a particle size on the order of submicrons, which is a constituent material of the binder 17, and particles of an LSN phosphor, which is a constituent material of the phosphor 16.
  • the pores 18 contained in the fluorescent plate 14 are generated in the process of sintering.
  • the binder 17 may be composed of an oxide material (for example, MgO or the like) other than Al 2 O 3 , or may be composed of Al 2 O 3 and Mg O.
  • FIG. 4 is an SEM photograph of a cross section of the fluorescent screen 14, and the right photograph is an enlarged photograph of region (a) of the left photograph.
  • the alumina particles constituting the binder 17 remain to the extent that they can be confirmed.
  • the alumina particles have a particle size on the order of submicrons, preferably 100 nm or more and 900 nm or less, and more preferably 400 nm or more and 800 nm or less.
  • the alumina particles remaining after sintering exhibit a submicron-order uneven shape in the fluorescent plate 14.
  • the mass ratio of the binder 17 contained in the fluorescent plate 14 is preferably 30% by mass or more and 70% by mass or less, and more preferably 50% by mass or more and 90% by mass or less.
  • the mass ratio of the binder 17 contained in the fluorescent plate 14 refers to the ratio of the mass of the binder 17 to the total mass of the phosphor 16 and the binder 17.
  • the sintering treatment is performed by heating in a state where the particles of the LSN phosphor constituting the phosphor 16 and the particles of alumina constituting the binder 17 are mixed.
  • the mass ratio of the binder 17 is substantially equal to the mass ratio of the alumina particles to the mixture of the LSN phosphor particles and the alumina particles at the time of manufacture.
  • the relative density of the fluorescent plate 14 is preferably 80.4% or more and 99.5% or less.
  • the relative density is the ratio of the apparent density to the theoretical density of the sintered body, that is, the fluorescent plate 14, and is based on, for example, JIS R 1634 (method for measuring the sintered body density and open porosity of fine ceramics). It can be measured by the method described above.
  • the fluorescent plate 14 includes pores 18 having a content of 0.5% or more and 19.6% or less. By including the pores 18 within the above range as compared with the case where the fluorescent plate 14 does not contain the pores 18 at all, that is, when the relative density is 100%, the phosphor 16 or the binder 17 and the pores 18 are combined. Since the difference in refractive index is generated at the interface between the two, it becomes easy to refract the fluorescence generated in the fluorescent plate 14 toward the light extraction surface 14a.
  • the ratio of strength I 30.4 , I 30.4 / I 30.9, is 7.5% or less. This point will be described later with reference to Examples after explaining the method for manufacturing the fluorescent plate 14.
  • Step S1 Oxide particles with a particle size on the order of submicrons (here, alumina particles) and Ce-activated nitride phosphor particles (here, LSN phosphor particles) are prepared, and these are mixed to form a mixed powder. obtain.
  • alumina used as the binder, it is preferable that the alumina particles are ⁇ -alumina.
  • the mass ratio of the particles (oxide particles) of the binder constituent material to the mixed powder is 30% by mass or more and 70% by mass or less, and more preferably 50% by mass or more and 90% by mass or less. It is as follows.
  • a method for obtaining a mixed powder a method using a dry mixing method such as a ball mill or a V blender, or a ball mill, a homogenizer, an ultrasonic homogenizer, after adding a predetermined solvent to alumina particles and phosphor particles to form a slurry state, After mixing using a wet mixing method using a twin-screw kneader or the like, a method of volatilizing the solvent of the obtained slurry at a predetermined temperature can be adopted.
  • a dry mixing method such as a ball mill or a V blender, or a ball mill
  • a homogenizer an ultrasonic homogenizer
  • Step S1 corresponds to step (a).
  • Step S2 The mixed powder obtained in step S1 is formed into a plate shape under pressure.
  • a molding method a method such as uniaxial mold molding or cold hydrostatic pressure molding can be used.
  • This step S2 corresponds to the step (b).
  • Step S3 The molded product obtained in step S2 is sintered. Specifically, the molded product is installed in a predetermined furnace or heating device and heated to a temperature required for sintering. In this step S3, sintering is performed at a temperature of 1050 ° C. or higher and 1200 ° C. or lower. Since the oxide particles contained in the mixed powder in step S1 are particles having a particle size on the order of submicrons, sufficient sintering can be performed even at a temperature of 1200 ° C. or lower.
  • the atmosphere at the time of sintering can be an atmospheric atmosphere, an N 2 atmosphere, or an Ar atmosphere.
  • This step S3 corresponds to the step (c).
  • Step S4 If necessary, the obtained sintered body is subjected to hot isostatic pressing (HIP). Depending on the conditions of pressure processing, the content of the pores 18 contained in the fluorescent plate 14 can be controlled within a certain width. After that, by performing an etching treatment on one surface, a fluorescent plate 14 including a moth-eye structure 15 having a fine uneven shape is generated.
  • HIP hot isostatic pressing
  • the obtained fluorescent plate 14 has a reflective layer 13 formed on the surface opposite to the light extraction surface 14a, and is fixed to the substrate 11 via the bonding layer 12.
  • the mass ratio of the oxide particles prepared in step S1 and the temperature of the sintering process executed in step S3 (hereinafter referred to as “sintering temperature”) are different, and the other conditions are common to steps S1 to S4.
  • the fluorescent plate 14 was obtained by executing the above.
  • alumina particles were adopted as the oxide particles, and La 3 Si 6 N 11 particles were adopted as the nitride phosphor particles.
  • the results of measuring the relative density and the internal quantum efficiency of each fluorescent screen 14 are shown in Table 1 and FIGS. 5 to 6.
  • the dimensions of all the fluorescent plates 14 were the same: length ⁇ width ⁇ thickness 3 mm ⁇ 3 mm ⁇ 0.13 mm.
  • FIG. 5 is a graph of the relationship between the sintering temperature and the relative density
  • FIG. 6 is a graph of the relationship between the sintering temperature and the internal quantum efficiency.
  • FIGS. 5 and 6 also show the results of a fluorescent plate obtained by molding and sintering only the particles of the LSN phosphor without containing the alumina particles.
  • each phosphor 16 For the relative density of each phosphor 16, a value measured by a method based on the above JIS R 1634 (measurement method of sintered body density and open porosity of fine ceramics) was used.
  • the internal quantum efficiency of each phosphor 16 was measured by a method based on JIS R 1697 (an internal quantum efficiency absolute measurement method using an integrating sphere of a phosphor for a white light emitting diode).
  • the internal quantum efficiency tends to decrease. More specifically, when the alumina content is 30% by mass, the internal quantum efficiency is highest when the sintering temperature is 1150 ° C., and the sintering temperature is raised to 1200 ° C., 1250 ° C., and 1300 ° C. It can be seen that the internal quantum efficiency is gradually decreasing. This tendency is also confirmed when the content ratio of alumina is 50% by mass, 70% by mass, and 90% by mass. In particular, when the sintering temperature was 1250 ° C. and 1300 ° C., it was confirmed that the internal quantum efficiency was lower than that of the conventional fluorescent plate made of YAG phosphor and alumina binder regardless of the content ratio of alumina.
  • the fluorescent light emitting element 10 is actually mounted, a step of cutting and polishing the sintered body is required, but if the relative density of 80% or more is not shown, the sintered body will be damaged when the step is executed. There is a risk. Therefore, it is difficult to realize the fluorescent light emitting element 10 by itself of the LSN phosphor.
  • FIG. 7 shows the fluorescent plate of Example 1 (sintering temperature 1050 ° C.), the fluorescent plate of Example 2 (sintering temperature 1150 ° C.), the fluorescent plate of Example 3 (sintering temperature 1200 ° C.), and the fluorescent plate of Comparative Example 1 (sintering temperature 1200 ° C.). It is a figure which shows the XRD spectrum obtained by the X-ray diffraction method about the sintering temperature (1250 ° C.). In each of the Examples and Comparative Examples, the content of alumina contained in the fluorescent plate was 70% by mass.
  • FIG. 7 for reference, is a constituent material of the phosphor 16 La 3 Si 6 N 11, and La 3 Si 6 N 11 is La 2 Si 6 sought to be obtained by the oxidized N
  • the XRD spectrum of 8 O 3 is also shown.
  • Table 2 shows the measurement results for each fluorescent plate obtained under each of the five types of sintering temperatures of 1050 ° C, 1150 ° C, 1200 ° C, 1250 ° C, and 1300 ° C. There is.
  • the amount of the nitride phosphor is obtained by desorbing the nitrogen atom derived from the nitride phosphor and reacting with the oxygen derived from the binder to generate an oxide of a material different from the constituent material of the phosphor. Is considered to decrease and the internal quantum efficiency decreases.
  • the sintering temperature is set to a lower temperature than before in the sintering step in step S3. It becomes possible. As a result, the amount of oxidation of the nitride phosphor material, that is, the amount of La 3 Si 6 N 11 changing to La 2 Si 6 N 8 O 3 in this example is suppressed, and high internal quantum efficiency is realized. Will be done.
  • step S3 From the viewpoint of making it more difficult to desorb nitrogen atoms contained in the nitride phosphor, it is preferable to carry out the sintering step in step S3 in a nitrogen atmosphere or an argon atmosphere, and nitriding of oxide particles such as alumina is preferable. From the viewpoint of prevention, it is more preferable to carry out in an argon atmosphere under a pressurized environment.
  • the alumina particles used in step S1 are ⁇ -alumina from the viewpoint of preventing the formation of many pores in the fluorescent plate 14 due to the transfer of alumina in the sintering process. It is preferable to have it.
  • Fluorescent light source device 2 Excited light source 3: Dycroic mirror 10: Fluorescent light emitting element 11: Substrate 12: Bonding layer 13: Reflective layer 14: Fluorescent plate 14a: Light extraction surface 15: Moss eye structure 16: Fluorescent material 17: Binder 18: Pore 21: Excitation light 22: Fluorescence

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Abstract

L'invention concerne un élément électroluminescent fluorescent qui utilise un liant qui comprend un oxyde mais a toujours un rendement quantique interne plus élevé que les éléments électroluminescents fluorescents classiques.　L'invention concerne un élément électroluminescent fluorescent qui comprend : un liant comprenant des particules d'oxyde qui ont un diamètre de particule d'ordre submicronique ; et un luminophore de nitrure activé par Ce dispersé dans le liant.
PCT/JP2020/043306 2019-11-22 2020-11-20 Élément électroluminescent fluorescent et son procédé de production WO2021100839A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023190866A1 (fr) * 2022-03-31 2023-10-05 京セラ株式会社 Plaque au phosphore

Citations (6)

* Cited by examiner, † Cited by third party
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