WO2023167306A1 - コンポジットセラミックス、蛍光体素子、レーザー照明装置、およびコンポジットセラミックスの製造方法 - Google Patents
コンポジットセラミックス、蛍光体素子、レーザー照明装置、およびコンポジットセラミックスの製造方法 Download PDFInfo
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- WO2023167306A1 WO2023167306A1 PCT/JP2023/007928 JP2023007928W WO2023167306A1 WO 2023167306 A1 WO2023167306 A1 WO 2023167306A1 JP 2023007928 W JP2023007928 W JP 2023007928W WO 2023167306 A1 WO2023167306 A1 WO 2023167306A1
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Definitions
- the present disclosure relates to composite ceramics containing a garnet-based phosphor component, a nitride-based phosphor component, and a matrix component, a phosphor element and a laser illumination device having the same, and a method for manufacturing the composite ceramics.
- Laser lighting devices are more energy efficient, compact, and brighter than other lighting devices, and have already begun to be put into practical use as lighting devices for projectors and automobile headlights. Also, in the home lighting market, replacement of existing LED (light emitting diode) lighting devices and fluorescent lamps with laser lighting devices is expected, and the laser lighting market is expected to expand rapidly in the future.
- LED light emitting diode
- Patent Document 1 discloses, as composite ceramics, ceramics containing a phosphor phase made of YAG containing Ce, a matrix phase made of at least one of Al 2 O 3 and AlN, and impurities within a predetermined range. A composite is disclosed.
- Patent Document 2 As a composite ceramic, a fluorescent substance molded body is produced by sintering a mixture of AlN powder and phosphor powder by a discharge plasma sintering method, melting the AlN powder, and then cooling it. is disclosed.
- the red phosphor means a phosphor that emits red to orange light.
- Patent Document 2 discloses that a nitride-based phosphor may be used as the phosphor powder.
- a composite ceramic according to one aspect of the present disclosure is a composite ceramic made of a sintered body containing a garnet phosphor component, a nitride phosphor component, and a matrix component, , the matrix component is at least one selected from the group consisting of MgO and Al 2 O 3 , the content of the matrix component is in the range of 31 wt% or more and 95 wt% or less of the total components, and the matrix component surrounds the garnet-based phosphor component and the nitride-based phosphor component and is sintered.
- a phosphor element according to one aspect of the present disclosure includes composite ceramics according to one aspect of the present disclosure, and a base material for fixing the composite ceramics.
- a laser illumination device includes a phosphor element according to one aspect of the present disclosure, and a laser light source that irradiates the composite ceramics in the phosphor element with excitation light. and a condensing member condensing light output from the composite ceramics in the phosphor element.
- a method for manufacturing a composite ceramic mixes a first raw material powder containing a garnet-based phosphor component, a nitride-based phosphor component, and a matrix component.
- a composite ceramic containing a red phosphor for laser illumination which can be produced relatively easily, a phosphor element and a laser illumination device including the same, and the It is possible to provide a method for producing such composite ceramics.
- FIG. 1 is a cross-sectional view showing an example of the structure of composite ceramics according to Embodiment 1.
- FIG. 3 is a flow chart showing an example of a method for manufacturing composite ceramics according to Embodiment 1.
- FIG. FIG. 5 is a cross-sectional view showing an example of the structure of composite ceramics according to Embodiment 2;
- FIG. 10 is a cross-sectional view showing an example of the structure of composite ceramics according to Embodiment 3;
- FIG. 10 is a cross-sectional view showing an example of the structure of composite ceramics according to Embodiment 4;
- FIG. 10 is a diagram showing a composite ceramic having one main surface provided with an antireflection coating film according to Embodiment 5;
- FIG. 11 is a cross-sectional view showing an example of a phosphor element according to Embodiment 5; 8 is a flow chart showing an example of a method for manufacturing the phosphor element shown in FIG. 7.
- FIG. FIG. 12 is a cross-sectional view showing an example of a laser illumination device according to Embodiment 6; 3 is a ternary diagram showing the contents of nitride-based phosphor components, matrix components, and garnet-based phosphor components in Examples 1 to 5 and Comparative Examples 1 to 5.
- FIG. 1 is a diagram showing an XRD pattern of composite ceramics obtained in Example 1.
- FIG. 1 is a graph showing laser power dependence of fluorescence power of composite ceramics obtained in Example 1.
- FIG. 1 is a diagram showing fluorescence spectra of composite ceramics obtained in Example 1.
- FIG. FIG. 10 is a diagram showing an example of a SEM image of composite ceramics obtained in Example 2; 3 is a diagram showing an XRD pattern of composite ceramics obtained in Example 2.
- FIG. FIG. 4 is a graph showing laser power dependence of the fluorescence power of composite ceramics obtained in Example 2.
- FIG. 4 is a diagram showing fluorescence spectra of composite ceramics obtained in Example 2.
- FIG. 10 is a graph showing laser power dependence of the fluorescence power of composite ceramics obtained in Example 3.
- FIG. 10 is a diagram showing fluorescence spectra of composite ceramics obtained in Example 3; 4 is a graph showing laser power dependence of fluorescence power of composite ceramics obtained in Comparative Example 1.
- FIG. 2 is a diagram showing fluorescence spectra of composite ceramics obtained in Comparative Example 1.
- FIG. 10 is a ternary diagram showing the contents of nitride-based phosphor components, matrix components, and garnet-based phosphor components in Examples 6 and 7 and Comparative Examples 6 to 9.
- FIG. 10 is a diagram showing laser power dependence of the fluorescence power of composite ceramics obtained in Example 6.
- FIG. 10 is a diagram showing fluorescence spectra of composite ceramics obtained in Example 6;
- FIG. 10 is a graph showing laser power dependence of fluorescence power of composite ceramics obtained in Examples 6 and 7.
- FIG. 3 is a ternary diagram showing the contents of nitride-based phosphor components, matrix components, and garnet-based phosphor components in Examples 8-12 and Comparative Examples 10-13.
- FIG. 3 is a ternary diagram showing the contents of nitride-based phosphor components, matrix components, and garnet-based phosphor components in Examples 13-18 and Comparative Examples 14-17.
- FIG. 10 is a diagram showing fluorescence power characteristics before and after annealing in composite ceramics of Reference Example 12;
- FIG. 13 is a diagram showing fluorescence power characteristics before and after annealing in composite ceramics of Reference Example 13;
- FIG. 10 is a diagram showing excitation light power durability of a phosphor element made of the composite ceramics of Example 18;
- FIG. 4 is a diagram showing fluorescence power characteristics due to continuous irradiation of laser light;
- FIG. 1 is a cross-sectional view showing an example of the structure of a composite ceramic 1 according to this embodiment.
- the composite ceramic 1 according to this embodiment is a multi-wavelength luminescent ceramic composite made of a sintered body containing phosphor components having two or more emission wavelengths and a matrix component.
- the composite ceramic 1 shown in FIG. 1 includes a garnet-based phosphor component 2, a nitride-based phosphor component 3, and a matrix component 4, and the matrix component 4 includes the garnet-based phosphor component 2 and the nitride-based phosphor. It has a sintered structure surrounding component 3.
- the composite ceramic 1 has a sea-island structure in which the garnet-based phosphor component 2 and the nitride-based phosphor component 3 are mixed in islands in the matrix component 4 . That is, the composite ceramic 1 has a structure in which the garnet-based phosphor component 2 and the nitride-based phosphor component 3 are dispersed like islands in a relatively continuous sea-like matrix component 4 . A matrix component 4 is filled between the garnet phosphor component 2 and the nitride phosphor component 3 .
- the garnet-based phosphor component 2, the nitride-based phosphor component 3, and the matrix component 4 are adhered to each other.
- the composite ceramic 1 comprises at least three phases of a first phosphor phase comprising a garnet phosphor component 2, a second phosphor phase comprising a nitride phosphor component 3, and a matrix phase comprising a matrix component 4. have phases.
- the composite ceramic 1 has a structure in which at least the above three phases are mixed and phases adjacent to each other are fixed.
- the structure in which at least the above three phases are mixed and the phases adjacent to each other are fixed means that the above three phases are not solid-dissolved, but are separated into regions of each phase in the solid, and the phases adjacent to each other are separated. A sticking structure is shown. It also includes the case where sintering aids or impurities are present at grain boundaries. Alternatively, even if there is a slight denatured phase or a melted phase between grains, if it basically has a solid three-phase structure, it is considered a composite ceramic.
- Composite ceramics 1 excludes joints in which three or more phases are simply directly joined, and compositions in which at least the three phases are solidified by at least one of inorganic glass and organic binder.
- the garnet-based phosphor component 2 indicates a phosphor having a garnet crystal structure.
- the garnet-based phosphor component 2 is a phosphor having a large refractive index and excellent fluorescence characteristics, and emits yellowish to greenish yellowish fluorescence, for example, by blue excitation light.
- the light that does not contribute to the excitation among the excitation light is scattered and transmitted. Therefore, the garnet-based phosphor component 2 outputs blue scattered light and yellowish fluorescence.
- the garnet-based phosphor component 2 has excellent heat resistance, and can suppress deterioration even when irradiated with, for example, a high-power excitation light LD (laser diode).
- a high-power excitation light LD laser diode
- a YAG (yttrium-aluminum-garnet)-based phosphor can be used as the garnet-based phosphor component 2.
- the YAG-based phosphor indicates a phosphor that can be attributed to the crystal structure of the YAG phosphor.
- YAG phosphors examples include (Ce, Y) 3 Al 5 O 12 , (Ce, Lu) 3 Al 5 O 12 , (Ce, Lu, Y) 3 Al 5 O 12 , (Ce, Lu, Y ) 3 (Al, Ga) 5 O 12 .
- the YAG phosphor as the garnet phosphor component 2 in the composite ceramic 1, it is possible to easily realize the composite ceramic 1 that outputs yellowish to greenish yellow fluorescence.
- the composite ceramics 1 contains the YAG-based phosphor as the garnet-based phosphor component 2, the composite ceramics 1 having more excellent fluorescence characteristics can be obtained.
- the nitride-based phosphor component 3 indicates a phosphor containing nitrogen.
- Specific examples of the nitride phosphor component 3 include at least one phosphor selected from the group consisting of nitride phosphors and oxynitride phosphors.
- the nitride-based phosphor component 3 is a red-based phosphor that emits red-to-orange red-based fluorescence with excellent fluorescence properties. For example, it emits red-based fluorescence with blue excitation light. In addition, the light that does not contribute to the excitation among the excitation light is scattered and transmitted. Therefore, the nitride phosphor component 3 outputs blue scattered light and red fluorescence.
- the composite ceramic 1 contains the nitride-based phosphor component 3, the composite ceramic 1 having more excellent fluorescence characteristics can be obtained.
- nitride-based phosphor component 3 examples include Sr 2 Si 5 N 8 , (Sr, Ba) 2 Si 5 N 8 , (Ca, Sr, Ba) at least one nitride phosphor selected from the group consisting of 2Si5N8 .
- these nitride phosphors may be referred to as nitride phosphor (A).
- Eu and Ce are activators and are doped in the crystal.
- nitride- based phosphor component 3 for example, Eu:Sr2Si5N8, Eu:(Sr,Ba)2Si5N8 , Eu : ( Ca , Sr , Ba) 2Si5 N 8 , Ce: Sr 2 Si 5 N 8 , Ce: (Sr, Ba) 2 Si 5 N 8 , Ce: (Ca, Sr, Ba) Si 5 N 8 , (Eu, Ce): Sr 2 Si 5 N 8 , (Eu, Ce): (Sr, Ba) 2 Si 5 N 8 , (Eu, Ce): (Ca, Sr, Ba) 2 Si 5 N 8 and other nitride phosphors (A).
- the composite ceramic 1 that emits stable reddish fluorescence can be produced.
- nitride phosphors At least one of part of Si and part of N in the above composition formula may be substituted.
- Si When part of Si is substituted, Si is substituted with Al.
- N is replaced with O when part of N is replaced.
- the nitride-based phosphor component 3 is Sr 2 Si 5 N 8 , (Sr, Ba) 2 Si 5 N 8 , or (Ca, Sr, Ba) 2 Si 5 N 8 , in which part of Si is Al It may be a nitride phosphor in which N is substituted with or an oxynitride phosphor in which a part of N is replaced with O. Further, an oxynitride phosphor in which part of Si is replaced with Al and part of N is replaced with O may be used. As an example, for example, for example, (Sr, Ba) 2 (Si, Al) 5 N 8 , (Sr, Ba) 2 (Si, Al) 5 (N, O ) 8 and the like.
- nitride-based phosphor component 3 By including at least one of such a nitride phosphor and an oxynitride phosphor as the nitride-based phosphor component 3 in the composite ceramic 1, a more reliable composite ceramic 1 can be realized.
- the nitride-based phosphor component 3 is, for example, at least one nitride phosphor selected from the group consisting of CaAlSiN 3 and (Ca, Sr)AlSiN 3 activated with at least one element of Eu and Ce, respectively. It can be a body.
- these nitride phosphors may be referred to as nitride phosphor (B).
- Eu and Ce are activators and are doped in the crystal.
- the nitride-based phosphor component 3 includes, for example, Eu:CaAlSiN 3 , Eu:(Ca,Sr)AlSiN 3 , Ce:CaAlSiN 3 , Ce:(Ca,Sr)AlSiN 3 , (Eu, Ce ): CaAlSiN 3 , (Eu, Ce): (Ca, Sr) AlSiN 3 and other nitride phosphors (B).
- the nitride-based phosphor component 3 in addition to the nitride phosphor (A) and the nitride phosphor (B), for example, Ce-activated (La, Y) 3 Si 6 N 11 , etc. There may be.
- the nitride-based phosphor component 3 is (La) 3 Si 6 N 11, (La, Y) 3 Si 6 N 11 , (La, Y) 3 Si 6 N 11, (La, At least one nitride-based phosphor component selected from the group consisting of Y, Lu) 3 Si 6 N 11 can be mentioned.
- the nitride phosphor component 3 is selected from the group consisting of (La) 3 Si 6 N 11, (La, Y) 3 Si 6 N 11, and (La, Y, Lu) 3 Si 6 N 11 .
- At least one nitride-based phosphor component also referred to as "La 3 Si 6 N 11 -based phosphor component"
- each nitride-based phosphor component activated with at least one element of Eu and Ce be.
- these nitride phosphors may be referred to as "nitride phosphor (C)".
- Eu and Ce are activators and are doped in the crystal.
- nitride phosphors (A), nitride phosphors (B) and nitride phosphors (C), and nitride phosphors other than these nitride phosphors (A) and nitride phosphors (B) are , may be used separately, or may be used together as long as they do not dissolve or react with each other.
- Matrix component 4 is at least one selected from the group consisting of MgO (magnesium oxide) and Al 2 O 3 (aluminum oxide).
- the matrix component 4 may be MgO, Al 2 O 3 , or a mixture of MgO and Al 2 O 3 .
- the composite ceramic 1 according to this embodiment has an excitation light power resistance of 0.5 kW/cm 2 or more.
- the composite ceramic 1 according to the present embodiment is a composite ceramic for low color temperature, which has a high fluorescence power with respect to the excitation light power, can withstand laser excitation, and has a high excitation light power resistance. Therefore, according to this embodiment, it is possible to realize a phosphor element for a laser that is practical and does not saturate fluorescence even at relatively high power.
- the upper limit is not particularly limited.
- the upper limit of the pumping light power resistance is 100 kW/cm 2 from the pumping light power resistance (laser power resistance) of a laser light source or various optical components that can be practically used. Therefore, the excitation light power resistance of the composite ceramic 1 according to the present embodiment is preferably 0.5 kW/cm 2 or more, more preferably 1 kW/cm 2 or more, and still more preferably 3 kW/cm 2 or more, and 100 kW/cm 2 or more. It is desirable to be within the range of cm 2 or less.
- the excitation light power tolerance indicates a value at which fluorescence power is saturated with respect to excitation light power (specifically, laser excitation light power) per 1 cm 2 .
- the excitation light power resistance can be measured by a phosphor evaluation device equipped with a laser light source, an integrating sphere, and a spectroscope.
- the content of the matrix component 4 in the composite ceramics 1 is within the range of 31 wt % or more and 95 wt % or less of the total components in the composite ceramics 1 .
- the composite ceramic 1 is a composite ceramic made of a sintered body containing the garnet phosphor component 2, the nitride phosphor component 3, and the matrix component 4, and the matrix component 4 is at least one selected from the group consisting of MgO and Al 2 O 3 , the content of matrix component 4 is in the range of 31 wt % or more and 95 wt % or less of all components, and matrix component 4 is garnet The phosphor component 2 and the nitride phosphor component 3 are surrounded and sintered.
- the content of the matrix component 4 in the composite ceramics 1 is set closer to the upper limit within the above range. Therefore, the content of the matrix component 4 in the composite ceramics 1 is more preferably 45 wt % or more, more preferably 60 wt % or more.
- the content of the matrix component 4 in the composite ceramic 1 is in the range of 31 wt% or more and 95 wt% or less of the total components, and is in the range of 31 wt% or more and 90 wt% or less of the total components. more preferred.
- the total content of the garnet-based phosphor component 2 and the nitride-based phosphor component 3 in the composite ceramics 1 is preferably in the range of 5 wt % or more and 69 wt % or less of all components in the composite ceramics 1 .
- the matrix component 4 surrounds the garnet-based phosphor component 2 and the nitride-based phosphor component 3 and is sintered to form the composite ceramic 1 having a structure in which adjacent phases adhere to each other. Obtainable.
- the respective contents of the garnet-based phosphor component 2 and the nitride-based phosphor component 3 in the composite ceramic 1 may be appropriately set so that the total content of these components falls within the above range, and is particularly limited. isn't it.
- the garnet-based phosphor component 2 emits yellow fluorescence or green fluorescence with blue excitation light, as described above.
- the nitride phosphor component 3 emits red fluorescence when exposed to blue excitation light.
- these phosphors scatter and transmit the light that did not contribute to the excitation among the excitation light. Therefore, when the composite ceramics 1 is irradiated with blue excitation light, the composite ceramics 1 outputs reddish bulb-colored light in which blue scattered light, yellowish fluorescence, and reddish fluorescence are mixed. be.
- the content of the garnet-based phosphor component 2 in the composite ceramics 1 is preferably in the range of 2 wt% or more and 65 wt% or less of the total components in the composite ceramics 1, and is in the range of 2 wt% or more and 59 wt% or less. It is more preferable to be in the range of 4 wt % or more and 59 wt % or less.
- the content of the nitride-based phosphor component 3 in the composite ceramic 1 is preferably in the range of 2 wt% or more and 65 wt% or less of all the components in the composite ceramic 1, and is in the range of 2 wt% or more and 59 wt% or less. more preferably within the range of 4 wt % or more and 59 wt % or less.
- the light bulb also contains red to orange red fluorescence, which is particularly suitable for home lighting devices, projector lighting devices, automobile headlights, outdoor lighting, and particularly remote lighting devices. Color emission spectra can be obtained.
- the content of the nitride-based phosphor component 3 in the composite ceramic 1 increases, the fluorescence power tends to saturate with respect to the excitation light power. Therefore, by reducing the content of the nitride-based phosphor component 3 in the composite ceramic 1, it is possible to further improve the excitation light power resistance. Therefore, the content of the nitride-based phosphor component 3 in the composite ceramic 1 is preferably set at the lower limit within the above range. Therefore, the content of the nitride-based phosphor component 3 in the composite ceramic 1 is more preferably 60 wt % or less, more preferably 40 wt % or less.
- the composite ceramic 1 is shown in FIGS.
- the contents of the nitride-based phosphor component 3, the matrix component 4, and the garnet-based phosphor component 2 are within the range surrounded by straight lines connecting points A to D below. is particularly preferred.
- the content of nitride phosphor component 3 is 59 wt%
- the content of matrix component 4 is 31 wt%
- the content of garnet phosphor component 2 is 10 wt%. shows the point where
- Point B indicates a point where the content of nitride phosphor component 3 is 8 wt %, the content of matrix component 4 is 90 wt %, and the content of garnet phosphor component 2 is 2 wt %. .
- Point C indicates a point where the content of nitride phosphor component 3 is 2 wt %, the content of matrix component 4 is 90 wt %, and the content of garnet phosphor component 2 is 8 wt %. .
- Point D indicates a point where the content of nitride phosphor component 3 is 10 wt %, the content of matrix component 4 is 31 wt %, and the content of garnet phosphor component 2 is 59 wt %. .
- a composite ceramic 1 for a low color temperature which has a high fluorescence power relative to the excitation light power, can withstand laser excitation, and has a high excitation light power resistance.
- the particle size of the garnet-based phosphor component 2 and the nitride-based phosphor component 3 contained in the composite ceramics 1 is determined according to the types of the garnet-based phosphor component 2 and the nitride-based phosphor component 3 to obtain desired light emission. It may be appropriately set so that a spectrum can be obtained. Therefore, the particle sizes of the garnet-based phosphor component 2 and the nitride-based phosphor component 3 are not particularly limited.
- the raw material powder used as the raw material of the garnet phosphor component 2 (in other words, the garnet phosphor component before sintering) has a number average particle diameter within the range of 3 ⁇ m or more and 50 ⁇ m or less. It is preferably used.
- the raw material powder of the garnet-based phosphor component 2 has a number-average particle diameter within the above range, it hardly reacts with the matrix component 4 and the nitride-based phosphor component 3 .
- the raw material powder used as the raw material for the nitride phosphor component 3 (in other words, the garnet phosphor component before sintering) has a number average particle size of 3 ⁇ m or more and 50 ⁇ m or less. Powder is preferably used. When the number average particle diameter of the raw material powder of the nitride phosphor component 3 is within the above range, it hardly reacts with the matrix component 4 and the garnet phosphor component 2 .
- the number average particle diameter of these raw material powders may be a value measured by a scanning electron microscope (SEM). specifications may be used.
- the number average particle size of the garnet-based phosphor component 2 contained per unit volume of the composite ceramic 1 is preferably in the range of 3 ⁇ m or more and 50 ⁇ m or less, for example.
- the number average particle size of the nitride-based phosphor component 3 contained per unit volume of the composite ceramic 1 is preferably in the range of 3 ⁇ m or more and 50 ⁇ m or less, for example. It is ideal that these phosphor particles have the size of primary particles, but they may have the size of secondary particles in which several primary particles are adhered.
- the matrix component 4 surrounds the garnet-based phosphor component 2 and the nitride-based phosphor component 3 and is sintered. Therefore, the number average particle size of the raw material powder used as the raw material of the matrix component 4 (in other words, the matrix component before sintering) is the same as that of each of the raw material powders of the garnet phosphor component 2 and the nitride phosphor component 3. It is preferably smaller than the number average particle size. On the other hand, if the particle size of the raw material powder is too small, there is a problem of cost or hygroscopicity.
- the raw material powder used as the raw material of the matrix component 4 preferably has a number average particle diameter within the range of 0.01 ⁇ m or more and 1 ⁇ m or less.
- the number average particle size of the matrix component 4 is preferably smaller than the number average particle size of the garnet phosphor component 2 and the nitride phosphor component 3 from the viewpoint of reactivity.
- the raw material powder of the matrix component 4 may also undergo grain growth due to sintering depending on the sintering method.
- the number average particle size of the matrix component 4 contained per unit volume of the composite ceramic 1 is preferably in the range of 0.01 ⁇ m or more and 10 ⁇ m or less.
- the sintering temperature can be further lowered, making it easier to manufacture the composite ceramic containing the red phosphor. In addition, it can be produced in a wide composition range.
- the matrix component 4 enters the gap between the garnet phosphor component 2 and the nitride phosphor component 3 . Thereby, a sintered body having a dense structure can be obtained.
- the matrix component 4 surrounds the garnet phosphor component 2 and the nitride phosphor component 3 and is sintered to form a mutually A composite ceramic 1 having a structure in which adjacent phases are fixed can be obtained.
- the structure of the composite ceramic 1 can optimize the phase structure of
- the number average particle diameter of the garnet phosphor component 2, the number average particle diameter of the nitride phosphor component 3, and the number average particle diameter of the matrix component 4 can be measured by SEM. Also, the number average particle size of other components described later can be similarly measured by SEM.
- particle size means the particle size when the component to be measured is a true sphere.
- the garnet phosphor component 2, the nitride phosphor component 3, the matrix component 4, and their raw material powders are all desirably spherical.
- the garnet phosphor component 2, the nitride phosphor component 3, the matrix component 4, and their raw material powders do not necessarily have a true spherical shape.
- the garnet phosphor component 2, nitride phosphor component 3, and matrix component 4 contained in the composite ceramic 1 are also roughly spherical.
- the garnet phosphor component 2, the nitride phosphor component 3, and the matrix component 4 contained in the composite ceramic 1 are also irregular. Particles of angular shape are obtained. Moreover, depending on the sintering method, the sintering may cause grain growth of these raw material powders to change the shape.
- the "particle size" means the particle size when converted to a true sphere with the same volume.
- the composite ceramics 1 may further contain a sintering aid.
- Raw material powder used as a raw material for the garnet-based phosphor component 2, raw material powder used as a raw material for the nitride-based phosphor component 3, and raw material powder used as a raw material for the matrix component 4 (first raw material powder) contains a sintering aid, the composite ceramic 1 also contains a sintering aid.
- the sintering aid used in the composite ceramics 1 include at least one selected from the group consisting of Si3N4 , SiO2 , CaO, MgO, ZnO, Y2O3 , LiF and AlF3 .
- the matrix component 4 is MgO
- MgO is excluded from the sintering aid.
- MgO can be used as a sintering aid when the matrix component is Al 2 O 3 only.
- the matrix component 4 is Al 2 O 3
- at least one sintering aid selected from the group consisting of Si 3 N 4 , SiO 2 , CaO, MgO, ZnO, Y 2 O 3 , LiF and AlF 3 agent is used.
- the matrix component 4 contains at least MgO among MgO and Al2O3
- at least one selected from the group consisting of Si3N4 , SiO2 , CaO , ZnO, Y2O3 , LiF and AlF3 of sintering aids are used.
- the sintering temperature can be further lowered, making it easier to produce the composite ceramics 1 . Moreover, this can further reduce the risk of deteriorating the performance of the phosphor.
- the content of the sintering aid in the first raw material powder and the composite ceramic 1 made of the first raw material powder is within the range of 0.05 wt % or more and 10 wt % or less in order not to deteriorate the phosphor characteristics. Preferably.
- the number average particle diameter of the sintering aid contained per unit volume of the composite ceramic 1 should be in the range of 0.01 ⁇ m or more and 1 ⁇ m or less, since the effect of the sintering aid is likely to be exhibited. is preferred.
- the sintering aid is very fine and in a very small amount compared to the garnet-based phosphor component 2, nitride-based phosphor component 3, and matrix component 4, and its illustration is omitted.
- the thickness of the composite ceramics 1 is not particularly limited, it is preferably in the range of, for example, 10 ⁇ m or more and 10 mm or less when used for a phosphor element of a laser lighting device.
- the composite ceramics 1 When the thickness of the composite ceramics 1 is 10 mm or less, the composite ceramics 1 is not too thick and has excellent heat dissipation properties. Patterns can be controlled. Moreover, since the thickness of the composite ceramics 1 is 10 ⁇ m or more, the composite ceramics 1 is not too thin, and the strength for applying the composite ceramics 1 to a phosphor element can be maintained.
- excitation light emitted from an excitation light source such as a laser light source can be transmitted.
- the composite ceramics 1 have a high light scattering property. If fluorescence or excitation light generated in the composite ceramic propagates in the lateral direction of the phosphor element, the beam emitted from the phosphor element will be blurred.
- the composite ceramic 1 having a linear transmittance of 0.01% or more and 20% or less for light with a wavelength of 450 nm at a thickness of 100 ⁇ m.
- a value measured using a spectrophotometer equipped with an integrating sphere or a laser light source and a light receiver having an aperture can be used.
- a phosphor element using a composite ceramic having such a light transmittance reduces light propagating laterally to the main surface of the phosphor element inside the phosphor element, eliminates blurring of the beam diameter, and is effective for laser illumination. It is advantageous as a phosphor element for
- the object color of the composite ceramic 1 can be expressed in the L * a * b * color system.
- L * above is the lightness
- a * above is the chromaticity between red and green
- b * above is the chromaticity between yellow and blue.
- saturation is represented by the square root of the sum of the squares of a * and b * .
- the object color of the composite ceramics 1 is preferably represented within an appropriate range in the L * a * b * color system from the viewpoint of increasing the fluorescence power of the composite ceramics.
- the object color in the L * a * b * color system can be measured with a known colorimeter. Further, the object color in the L * a * b * color system can be adjusted by the annealing treatment described later.
- the internal quantum efficiency of the composite ceramics 1 is preferably 70% or more and preferably 95% or less.
- FIG. 2 is a flow chart showing an example of a method for manufacturing the composite ceramics 1 according to this embodiment.
- the manufacturing method of the composite ceramics 1 according to this embodiment includes at least the following steps S1 to S4.
- a first raw material powder containing a garnet phosphor component 2, a nitride phosphor component 3, and a matrix component 4 is mixed (step S1 , mixing step).
- mixing the first raw material powder means mixing each component contained in the first raw material powder.
- the first raw material powder may contain the sintering aid.
- Dry mixing is used to mix the first raw material powder.
- any mixer may be used as long as powder mixing by a dry method is possible.
- step S2 first raw material powder accommodating step.
- step S3 the first raw material powder accommodated in the mold is sintered (step S3, sintering step).
- SPS discharge plasma sintering
- hot press method is used for sintering the first raw material powder.
- the SPS method and the hot press method are types of solid compression sintering methods, in which the first raw material powder accommodated in the mold is press-molded while being heated.
- the molded body is sintered by pulse electric heating while press-molding with mechanical pressure.
- electromagnetic energy due to pulse current, self-heating of the molded body, discharge plasma energy generated between each component, etc. are combined for sintering.
- the compact can be sintered.
- the SPS method it is possible to sinter by heating to a high temperature in a short period of time while applying mechanical pressure. can be sintered into a sintered body in which each component contained in is bonded at high density and substantially uniformly. In addition, since the SPS method requires a short sintering time, grain growth of each component can be suppressed.
- the hot press method sintering is performed in a pressurized atmosphere as in the SPS method.
- the sintering time is longer than that of the SPS method.
- the hot press method is excellent in mass productivity.
- a high-speed sintering method can also be used for sintering the first raw material powder.
- the sintering temperature in the sintering step is preferably 1000°C or higher and 2000°C or lower. By setting the sintering temperature to 2000 ° C. or less, the sintering temperature is not too high, and it is possible to suppress the formation of oxides and the solid solution of the above components to form new compounds. Without losing the characteristics of each component.
- the sintering temperature is not too low, and the primary particles of the above components are likely to be in a bonded state.
- the components described above are mixed without solid solution, and a structure in which adjacent phases adhere to each other is likely to be formed. For this reason, for example, it becomes easy to obtain the composite ceramics 1 that has a sufficient processing strength as a bulk body and that outputs a suitable incandescent fluorescent light.
- the sintering time in the sintering step is not particularly limited, and may be any time from 5 minutes to 20 hours, for example.
- step S4 mold release step
- the method for manufacturing the composite ceramics 1 may further include an annealing step (step S5) for annealing the sintered body obtained in the sintering step after the releasing step.
- the annealing temperature is preferably 800°C or higher and 1500°C or lower, for example.
- the annealing time is not particularly limited, and may be any time from 5 minutes to 20 hours, for example.
- Annealing is preferably performed in a reducing atmosphere such as an N2 atmosphere or an H2 and N2 atmosphere (for example, an ammonia-containing gas).
- a reducing atmosphere such as an N2 atmosphere or an H2 and N2 atmosphere (for example, an ammonia-containing gas).
- a heat treatment process such as an annealing process may be performed in a reducing atmosphere or an inert gas atmosphere during the manufacturing process.
- the heat treatment step is effective from the viewpoint of developing a better body color of the composite ceramic 1, and may be performed at any time during the manufacturing process as long as such an effect can be obtained.
- the heat treatment step is preferably the above annealing treatment, and the treatment temperature in the heat treatment step may be the same as the above annealing temperature.
- the heat treatment step may be performed between two suitable steps among the above steps, unlike the annealing treatment.
- the method for manufacturing the composite ceramics 1 may further include a cutting/polishing step (step S6) in which at least one of cutting and polishing is applied to the sintered body.
- the size of the composite ceramics 1 is not particularly limited, and the sintered body taken out from the mold in the mold release process can be used as the composite ceramics 1 as it is. However, in order to make the composite ceramics 1 of a predetermined size, the obtained sintered body may be subjected to at least one of cutting and polishing as described above.
- the method of cutting the sintered body is not particularly limited, and for example, the sintered body may be sliced (cut) with a wire saw or the like.
- a thin composite ceramic 1 can be obtained by cutting the sintered body.
- the thin composite ceramics 1 may be manufactured without cutting by using a thin mold or by adjusting the amount of the first raw material powder contained in the mold.
- the method for polishing the sintered body is not particularly limited.
- the surface of the sintered body may be polished by rotating the polishing unit while discharging the polishing liquid from the discharge unit of the polishing apparatus.
- the thickness of the sintered body can be reduced while the surface can be made smooth. Therefore, the composite ceramic 1 having a thin thickness and a smooth surface can be obtained by performing polishing.
- the present embodiment is not limited to this. Only one of the annealing process and the cutting/polishing process may be performed. Also, the annealing step may be performed after the cutting/polishing step.
- FIG. 3 is a cross-sectional view showing an example of the structure of the composite ceramics 11 according to this embodiment.
- the composite ceramic 11 according to this embodiment has the same configuration as the composite ceramic 1 according to Embodiment 1, except that it further contains a light scattering component 12.
- the light scattering component 12 may be a light scatterer having a refractive index higher than that of the matrix component 4 by 0.21 or more.
- the composite ceramic further contains the light scattering component 12 in addition to the garnet phosphor component 2, the nitride phosphor component 3, and the matrix component 4, the sum of the matrix component 4 and the light scattering component 12 is From the point of view described below, the content is preferably 31 wt % or more and 95 wt % or less of the total components.
- the composite ceramics 11 which is excellent in light scattering properties and capable of efficiently extracting the generated fluorescence and excitation light to the outside.
- the light scattering component 12 includes, for example, at least one selected from the group consisting of AlN, cBN, SiC, AlN--SiC solid solution, and diamond. These light-scattering components are particularly excellent in light-scattering properties and can be suitably used as the light-scattering component 12 .
- the upper limit of the refractive index difference between the light scattering component 12 used in this embodiment and the matrix component 4 is not particularly limited. However, among MgO and Al 2 O 3 used for the matrix component 4, the refractive index of Al 2 O 3 having a low refractive index is 1.63. , the refractive index of SiC, which has the highest refractive index, is about 2.72. Therefore, when the above-exemplified light scattering component is used as the light scattering component 12, the maximum difference in refractive index between the light scattering component 12 and the matrix component 4 is 1.1.
- the number average particle diameter of the light scattering component 12 contained per unit volume of the composite ceramic 1 is preferably 0.25 ⁇ m or more and 40 ⁇ m or less, more preferably 0.5 ⁇ m or more and 20 ⁇ m or less.
- the number average particle size of the light scattering component 12 may be a value measured by SEM, or may be a specification described in a statement of delivery or a catalog. When the number average particle size of the light scattering component 12 is within the above range, light scattering is maximized by Mie scattering.
- the maximum light scattering effect can be obtained.
- the first raw material powder contains the raw material powder serving as the raw material of the light scattering component 12, so that the composite ceramics 11 can emit light. It contains a scattered component 12 . Therefore, the composite ceramics 11 can be manufactured by mixing the first raw material powder, which further contains the raw material powder of the light scattering component 12, in the mixing step (step S1).
- the composite ceramics 11 may also contain the sintering aid.
- FIG. 4 is a cross-sectional view showing an example of the structure of the composite ceramics 21 according to this embodiment.
- the composite ceramics 21 according to this embodiment has a laminated structure including a first ceramics layer 22 and a second ceramics layer 23 .
- the first ceramics layer 22 shown in FIG. 4 has the same configuration as the composite ceramics 1 according to the first embodiment.
- the second ceramic layer 23 is made of at least one selected from the group consisting of MgO and Al 2 O 3 and is bonded to one main surface of the first ceramic layer 22 .
- the second ceramic layer 23 having the above-described configuration is bonded onto the first ceramic layer 22, burning of the surface of the composite ceramic is suppressed even when strongly excited by laser light. can do. Therefore, according to the present embodiment, it is possible to provide the composite ceramic 12 capable of suppressing deterioration of the surface due to such scorching.
- the thickness of the first ceramics layer 22 is not particularly limited, and can be set to the same thickness as the composite ceramics 1 according to the first embodiment, for example.
- the thickness of the second ceramics layer 23 is not particularly limited, the second ceramics layer 23 does not contain a fluorescent component and does not contribute to fluorescence emission. It is desirable to be formed thinner than one ceramic layer 22 .
- the thickness of the second ceramics layer 23 is, for example, 30 ⁇ m or less.
- the thickness of the second ceramics layer 23 is desirably 1 ⁇ m or more, for example.
- the method of manufacturing the composite ceramics 21 is the same as the method of manufacturing the composite ceramics 1 according to the first embodiment, except for the following points.
- the method for manufacturing the composite ceramics 21 includes a step of accommodating a second raw material powder containing at least one selected from the group consisting of MgO and Al 2 O 3 and containing a second raw material powder less than the first raw material powder in a molding die. Including more.
- the first raw material powder and the second raw material powder accommodated in the molding die are sintered.
- a sintered body is formed in which the sintered body of the first raw material powder and the sintered body of the second raw material powder, which is thinner than the first raw material powder, are joined together.
- the composite ceramics 21 can be manufactured.
- the second raw powder containing step may be performed after the first raw powder containing step (step S2) (that is, between steps S2 and S3), and the first raw powder containing step ( It may be performed before step S2) (that is, between steps S1 and S2).
- the second raw powder containing step be performed twice before the first raw powder containing step and after the first raw powder containing step.
- the step of accommodating the second raw material powder is performed twice before and after the step of accommodating the first raw material powder
- the second ceramic layer 23 is formed with the first ceramic layer 22 interposed therebetween after the mold release step (step S4).
- the second ceramic layer 23 on one main surface of the first ceramic layer 22 may be removed by grinding, polishing, or the like. Said removal may be performed in said cutting/polishing step.
- the sintered body is sliced (cut) so that one main surface of the first ceramic layer 22 has a second ceramic layer 23 on one main surface.
- a plurality of composite ceramics 21 having ceramic layers 23 formed thereon may be manufactured.
- the annealing process (step S5) may be performed as necessary.
- the composite ceramics 21 may also contain the sintering aid.
- the case where the first ceramic layer 22 has the same configuration as the composite ceramic 1 according to Embodiment 1 is illustrated as an example, but this embodiment is limited to this. not a thing
- the first ceramics layer 22 may have the same configuration as the composite ceramics 11 according to the second embodiment.
- FIG. 5 is a cross-sectional view showing an example of the structure of the composite ceramics 31 according to this embodiment.
- the composite ceramic 31 according to the present embodiment has, for example, the same configuration as the composite ceramic 1 according to the first embodiment, except that unevenness 31a is formed on one main surface. are doing.
- the method for manufacturing the composite ceramics 21 is the same as the method for manufacturing the composite ceramics 1 according to Embodiment 1, except that it further includes an unevenness forming step of forming unevennesses 31a on one main surface of the sintered body. is.
- the unevenness 31a is a dicer groove.
- this embodiment is not limited to this.
- the unevenness 31a may be formed by a dicer or laser processing, or the unevenness 31a may be formed by roughening the main surface by polishing.
- the composite ceramic 31 having the unevenness 31a formed on one main surface can scatter and efficiently extract the fluorescence or excitation light generated inside. be able to.
- the height of the unevenness 31a on the surface is not particularly limited as long as it can scatter the fluorescence or excitation light generated inside, as described above.
- FIG. 5 shows an example in which the composite ceramics 31 has a structure in which unevenness 31 a is formed on one main surface of the composite ceramics 1 .
- the composite ceramics 31 according to this embodiment may have a structure in which one main surface of the composite ceramics 11 is formed with irregularities 31a.
- the composite ceramics 31 according to the present embodiment has a structure in which irregularities 31a are formed on the main surface of the second ceramics layer 23 of the composite ceramics 21 opposite to the first ceramics layer 22. good too.
- FIG. 6 shows a composite ceramic 1 provided with an AR (anti-reflection) coating film 41 on one main surface according to this embodiment.
- the AR coating film 41 is provided on the main surface of the composite ceramics 1, so that when the composite ceramics 1 is used as a phosphor element for laser illumination, excitation light is emitted on the irradiation surface of the excitation light. Light can be prevented from being reflected. Thereby, the loss of light when the excitation light is absorbed by the composite ceramics 1 can be reduced. Furthermore, fluorescence or scattered light generated in the phosphor of the composite ceramics 1 can be effectively extracted.
- a dielectric multilayer film such as SiO 2 , TiO 2 , Si 3 N 4 is used. These can be formed by a film forming method such as ion beam vapor deposition or sputtering.
- composite ceramics provided with the AR coating film 41 in this way may be referred to as composite ceramics with an AR coating film.
- Composite ceramics with an AR coating film that has been AR-coated in this manner is suitably used, for example, as a phosphor element for laser illumination.
- the excitation light power resistance (device reliability) of the phosphor device is preferably 0.5 kW/cm 2 or more, more preferably 3 kW/cm 2 or more, from the viewpoint of laser illumination applications.
- the excitation light power resistance of the phosphor element is preferably as high as possible, the upper limit may be set from the viewpoint of obtaining a sufficient effect in the application of laser illumination.
- the element reliability of the phosphor element can be determined in the same manner as that of the composite ceramics described above, and can be adjusted in the same manner.
- FIG. 7 is a cross-sectional view showing an example of the phosphor element 50 according to this embodiment.
- the phosphor element 50 shown in FIG. 7 includes the composite ceramics 1 provided with the AR coating film 41, the substrate 51, the adhesive layer 52, and the mirror 53 shown in FIG.
- the base material 51 is a supporting member that supports the composite ceramics 1 .
- Composite ceramics 1 is fixed on substrate 51 .
- the base material 51 is not particularly limited as long as the composite ceramics 1 can be fixed.
- the base material 51 includes metals such as SUS, Al, Cu, Mo, Ag, W, and the like. When the base material 51 is made of these metals, it can suitably reflect excitation light emitted from an excitation light source such as a laser light source.
- the phosphor element 50 having excellent thermal conductivity can be obtained.
- substrate 51 is not limited to such a non-transmissive substrate.
- substrate 51 may be a transmissive substrate such as, for example, monocrystalline sapphire or polycrystalline alumina, denoted Al 2 O 3 .
- the composite ceramic 1 is fixed to the base material 51 so that the AR coat film 41 is positioned on the main surface opposite to the base material 51, as shown in FIG.
- the mirror 53 is a reflector (mirror body) that reflects the light transmitted through the composite ceramics 1 .
- the mirror 53 is provided on the main surface of the composite ceramics 1 on the substrate 51 side.
- the main surface of the composite ceramic 1 on the substrate 51 side may be referred to as the "back main surface”
- the main surface on the opposite side of the substrate 51 may be referred to as the "front main surface”.
- the mirror 53 is provided on the back main surface side of the composite ceramics 1, and the AR coat film 41 is provided on the front main surface side of the composite ceramics.
- the mirror 53 is provided on the back main surface side of the composite ceramics 1 in this way, when the excitation light is applied to the front main surface side of the composite ceramics 1, the light transmitted through the composite ceramics 1 is reflected by the mirror 53. can be reflected. Thereby, the utilization efficiency of light can be improved.
- the mirror 53 is not particularly limited as long as it can reflect the light transmitted through the composite ceramics 1.
- a silver-based mirror containing silver or a silver alloy, which is a specular reflection positive material, is preferably used.
- the adhesive layer 52 is a layer that bonds the composite ceramics 1 provided with the mirror 53 and the base material 51 .
- the adhesive material used for the adhesive layer 52 is not particularly limited as long as it can adhere the composite ceramics 1 provided with the mirror 53 and the base material 51 .
- Examples of the adhesive material include silver-based or silver-alloy based inorganic adhesives.
- FIG. 8 is a flow chart showing an example of a method for manufacturing the phosphor element 50 shown in FIG.
- a cutting step (step S11) of cutting the sintered body, and a back main surface of the sintered body A back main surface polishing step (step S12) is performed.
- the cutting/grinding step is not essential.
- step S13 a film of the mirror 53 is formed on the back main surface of the sintered body (step S13, mirror film forming process).
- step S13 mirror film forming process
- the substrate 51 is prepared (step S21, substrate preparation step).
- step S13 the base material 51 and the mirror-equipped composite ceramics obtained in step S13 are bonded together with an adhesive material forming the adhesive layer 52 (step S14, bonding step).
- step S15 front main surface polishing step
- step S16 AR coat film formation step
- the front main surface polishing process is performed after the bonding process, but the present embodiment is not limited to this.
- the front and main surface polishing step may be performed before the bonding step.
- the phosphor element 50 is not limited to the structure shown in FIG.
- the phosphor element 50 may include, for example, the composite ceramics 1 and a substrate 51 to which the composite ceramics 1 is fixed.
- the composite ceramics 1 instead of the composite ceramics 1, the composite ceramics 11, the composite ceramics 21, or the composite ceramics 31 may be provided. Composite ceramics obtained by combining them may also be used.
- composite ceramics can be suitably used for phosphor elements for laser illumination (in other words, phosphor elements for laser illumination devices).
- the laser illumination device includes a phosphor element, a laser light source that irradiates excitation light to the composite ceramics in the phosphor element, and a condensing member that collects the light output from the composite ceramics in the phosphor element ( (first condensing member).
- FIG. 9 is a cross-sectional view showing an example of a laser illumination device 60 according to this embodiment.
- a laser illumination device 60 shown in FIG. 9 includes, for example, a phosphor element 50 shown in FIG. 8 as an example of the phosphor element.
- a laser illumination device 60 shown in FIG. 9 includes a laser light source 61 as the laser light source and a lens 63 as the first condensing member.
- the laser illumination device 60 shown in FIG. 9 includes a lens 62 as a second condensing member for condensing the excitation light output from the laser light source 61 .
- the laser light source 61 irradiates the composite ceramics 1 in the phosphor element 50 with the excitation light L1 as the first light through the lens 62 .
- the excitation light L1 output from the laser light source 61 is condensed by the lens 62, and the lens 62
- the composite ceramics 1 in the phosphor element 50 is irradiated with the light from above.
- the composite ceramic 1 absorbs at least part of the excitation light L1' and outputs second light including light with a wavelength different from the excitation light L1' (that is, light with a wavelength different from the excitation light L1).
- the garnet phosphor component 2 described above emits, for example, yellow fluorescence Y by the blue light that is the excitation light L1
- the nitride phosphor component 3 emits red fluorescence by the blue light that is the excitation light L1. Emit R.
- these phosphors scatter the blue light that does not contribute to the excitation in the blue light that is the excitation light L1, and transmits the blue light as scattered blue light B. As shown in FIG.
- the phosphor element 50 may include the composite ceramics according to the present disclosure and the substrate 51 as described in the fifth embodiment.
- the composite ceramic may be the composite ceramic described in any one of Embodiments 1 to 4, or may be a composite ceramic obtained by combining them.
- the laser light source 61 is not particularly limited as long as it can irradiate the excitation light L1.
- a blue semiconductor LD LD: laser diode
- irradiates blue light as the excitation light L1 as described above can be cited. be done.
- the phosphor element 50 When the phosphor element 50 includes the mirror 53 as described above, or when the base material 51 is a non-transmissive base material that does not transmit the excitation light L1, the phosphor element 50 is positioned on the side of the emitted light of the laser light source 61. It is arranged so that the composite ceramics 1 is positioned.
- the substrate 51 is a transmissive substrate and does not have a reflector such as the mirror 53 on the back main surface side of the composite ceramics 1, the side of the substrate 51 opposite to the fixed surface of the composite ceramics 1
- the excitation light L1 is irradiated from the surface of .
- the second light is emitted from the front main surface side of the composite ceramics 1 .
- both the first light collecting member and the second light collecting member are lenses
- these condensing members may be lenses or mirrors.
- the above-described La 3 Si 6 N 11 phosphor component (nitride phosphor (C)) is used instead of the garnet phosphor component as long as the effects of the present invention can be obtained. may have.
- the "nitride phosphor component” may be selected from nitride phosphor components other than La 3 Si 6 N 11 phosphor components.
- the composite ceramic of Embodiment 7 is a sintered body containing a La 3 Si 6 N 11 phosphor component, a nitride phosphor component other than the La 3 Si 6 N 11 phosphor component, and a matrix component.
- the matrix component is at least one selected from the group consisting of MgO and Al 2 O 3 , and the content of the matrix component is in the range of 31 wt% or more and 95 wt% or less of all components and the matrix component may be sintered surrounding the La 3 Si 6 N 11 based phosphor component and the nitride based phosphor component.
- the composite ceramics of Embodiment 7 are configured, manufactured, and used in the same manner as the composite ceramics of the above-described embodiments except that the above-described La 3 Si 6 N 11 -based phosphor component is used instead of the garnet-based phosphor component.
- the composite ceramics uses the La 3 Si 6 N 11 -based phosphor component instead of the garnet-based phosphor component, which is advantageous from the viewpoint of easier production of the composite ceramics.
- the composite ceramics in the embodiment of the present invention have substantially only the La 3 Si 6 N 11 -based phosphor component (nitride phosphor (C)) as the phosphor component within the range where the effects of the present invention can be obtained.
- the composite ceramics of Embodiment 8 is a composite ceramics composed of a sintered body substantially containing only a La 3 Si 6 N 11 based phosphor component and a matrix component, the matrix component being Al 2 O 3 , At least one component selected from the group consisting of a mixture of Al 2 O 3 and MgO, and MgAlO 2 , and the content of the matrix component is within the range of 31 wt % or more and 95 wt % or less of the total components.
- the matrix component may be sintered surrounding the La 3 Si 6 N 11 based phosphor component based phosphor.
- the content of the matrix component and the content of the nitride phosphor (C) are appropriately set from the viewpoint of providing a composite ceramic for low color temperature with high resistance to fluorescence power and excitation light power. obtain.
- the composite ceramics of Embodiment 8 are configured in the same manner as the composite ceramics of the above-described embodiments except that the La 3 Si 6 N 11 -based phosphor component is used instead of the garnet-based phosphor component and the nitride-based phosphor component, manufactured and available.
- the composite ceramics is advantageous from the viewpoint of easier production of the composite ceramics, because the phosphor component substantially consists of only the La 3 Si 6 N 11 -based phosphor component.
- a first aspect of the present invention is a composite ceramic comprising a sintered body containing a garnet-based phosphor component, a nitride-based phosphor component, and a matrix component, wherein the matrix component is MgO and Al2O . 3 , the content of the matrix component is in the range of 31 wt% or more and 95 wt% or less of the total components, and the matrix component comprises the garnet phosphor component and the nitriding It is characterized by being sintered while surrounding the physical phosphor component.
- a second aspect of the present invention is characterized in that, in the first aspect, the matrix component contained per unit volume of the composite ceramic has a number average particle size of 0.01 ⁇ m or more and 10 ⁇ m or less. do.
- a third aspect of the present invention is the second aspect, wherein the garnet-based phosphor component is (Ce, Y) 3 Al 5 O 12 , (Ce, Lu) 3 Al 5 O 12 , (Ce, Lu, Y ) 3 Al 5 O 12 and (Ce, Lu, Y) 3 (Al, Ga) 5 O 12 .
- a fourth aspect of the present invention is Sr 2 Si according to any one of the first to third aspects, wherein the nitride-based phosphor component is activated with at least one of Eu and Ce, respectively. 5N8 , ( Sr , Ba ) 2Si5N8 , and ( Ca,Sr,Ba) 2Si5N8 .
- a fifth aspect of the present invention is the fourth aspect, wherein at least one of a portion of the Si and a portion of the N is substituted, and a portion of the Si is substituted, the Si is substituted with Al, and when part of N is substituted with O, N is substituted with O.
- a sixth aspect of the present invention is any one of the first to fifth aspects, wherein the nitride-based phosphor component is CaAlSiN 3 and CaAlSiN 3 and It is characterized by containing at least one selected from the group consisting of (Ca, Sr) AlSiN3 .
- a seventh aspect of the present invention is any one of the first to sixth aspects, wherein the total content of the nitride-based phosphor component, the matrix component, and the garnet-based phosphor component is 100 wt%
- the contents of the nitride phosphor component, the matrix component, and the garnet phosphor component are a point A where the content of the nitride-based phosphor component is 59 wt%, the content of the matrix component is 31 wt%, and the content of the garnet-based phosphor component is 10 wt%; a point B where the content of the nitride-based phosphor component is 8 wt%, the content of the matrix component is 90 wt%, and the content of the garnet-based phosphor component is 2 wt%; a point C where the content of the nitride-based phosphor component is 2 wt%, the content of the matrix component is 90 wt%, and the content of
- An eighth aspect of the present invention is any one of the first to seventh aspects, further comprising a light scattering component having a refractive index higher than that of the matrix component by 0.21 or more, wherein the matrix component and the light scattering component The total content of the components is 31 wt% or more and 95 wt% or less of all components.
- a ninth aspect of the present invention in the eighth aspect, is characterized in that the light scattering component is at least one selected from the group consisting of AlN, cBN, SiC, AlN-SiC solid solution, and diamond.
- a tenth aspect of the present invention is the eighth aspect or the ninth aspect, wherein the light scattering component contained per unit volume of the composite ceramic has a number average particle size of 0.25 ⁇ m or more and 40 ⁇ m or less. It is characterized by
- the linear transmittance of light with a wavelength of 450 nm at a thickness of 100 ⁇ m is 0.01% or more and 20% or less. characterized by
- a twelfth aspect of the present invention in any one of the first to eleventh aspects, further comprises a sintering aid, the sintering aid comprising:
- the matrix component is Al 2 O 3 , it is at least one selected from the group consisting of Si 3 N 4 , SiO 2 , CaO, MgO, ZnO and Y 2 O 3
- the matrix component contains at least MgO among MgO and Al 2 O 3
- it is at least one selected from the group consisting of Si 3 N 4 , SiO 2 , CaO, ZnO and Y 2 O 3 .
- a thirteenth aspect of the present invention is any one of the first aspect to the twelfth aspect, wherein a layer composed of at least one selected from the group consisting of MgO and Al 2 O 3 is bonded to one main surface. It is characterized by having a stacked laminated structure.
- a fourteenth aspect of the present invention is characterized in that, in any one of the first to thirteenth aspects, the excitation light power resistance is 0.5 kW/cm 2 or more.
- a fifteenth aspect of the present invention is characterized in that, in any one of the first to fourteenth aspects, unevenness is formed on one main surface.
- a sixteenth aspect of the present invention is a phosphor element comprising the composite ceramics according to any one of the first to fifteenth aspects, and a substrate for fixing the composite ceramics. be.
- a seventeenth aspect of the present invention is the phosphor element of the sixteenth aspect, a laser light source for irradiating the composite ceramics in the phosphor element with excitation light, and the composite ceramics in the phosphor element. and a condensing member for condensing the light.
- An eighteenth aspect of the present invention is a mixing step of mixing a first raw material powder containing a garnet-based phosphor component, a nitride-based phosphor component, and a matrix component, and molding the mixed first raw material powder.
- a second raw material powder made of at least one selected from the group consisting of MgO and Al 2 O 3 and less than the first raw material powder is added to the molding die.
- the first raw material powder and the second raw material powder contained in the mold are sintered to obtain the first raw material powder
- a sintered body is formed by bonding a sintered body and a sintered body of the second raw material powder, which is thinner than the first raw material powder.
- a 20th aspect of the present invention in the 18th aspect or the 19th aspect, further comprises a cutting/polishing step of performing at least one of cutting and polishing the sintered body. do.
- a twenty-first aspect of the present invention in any one of the eighteenth to twentieth aspects, is characterized by further comprising an unevenness forming step of forming unevenness on one main surface of the sintered body.
- a twenty-second aspect of the present invention is characterized in that, in the twenty-first aspect, the unevenness is formed by a dicer, laser processing, or polishing in the unevenness forming step.
- the nitride-based phosphor component is (La) 3 Si 6 N 11 (La) 3 Si 6 N 11 ( It is characterized by containing at least one selected from the group consisting of La, Y) 3 Si 6 N 11 and (La, Y, Lu) 3 Si 6 N 11 .
- a twenty-fourth aspect of the present invention is characterized in that, in the fourteenth aspect, the excitation light power resistance is 1 kW/cm 2 or more.
- a twenty-sixth aspect of the present invention is any one of the first to fifteenth aspects and the twenty-third to twenty-fifth aspects, wherein the internal quantum efficiency is 70% or more and 95% It is characterized by the following.
- the excitation light power resistance is 0.5 kW/cm 2 or more.
- the phosphor element according to claim 16 wherein the thirty-first aspect of the present invention is the sixteenth aspect, wherein the excitation light power resistance is 3 kW/cm 2 or more.
- a thirty-second aspect of the present invention is, in any one of the eighteenth to twenty-second aspects, the step of heat-treating the sintered body in a reducing atmosphere or an inert gas atmosphere during the manufacturing process. characterized by further comprising
- a thirty-third aspect of the present invention in the thirty-second aspect, is characterized in that the step of heat-treating is a step of heat-treating the sintered body in an ammonia-containing gas.
- a thirty-fourth aspect of the present invention is a sintered phosphor comprising a La 3 Si 6 N 11 -based phosphor component, a nitride-based phosphor component other than the La 3 Si 6 N 11 -based phosphor component, and a matrix component.
- a composite ceramic consisting of a body, wherein the matrix component is at least one selected from the group consisting of MgO and Al 2 O 3 , and the content of the matrix component is 31 wt% or more and 95 wt% or less of the total components. within the range, wherein the matrix component is sintered surrounding the La 3 Si 6 N 11 phosphor component and the nitride phosphor component.
- the thirty-fourth aspect has the features of any one of the second to fifteenth aspects and the twenty-third to twenty-ninth aspects as long as the effect of the aspect can be obtained. It can contain more.
- a thirty-fifth aspect of the present invention is a composite ceramic comprising a sintered body substantially containing only a La 3 Si 6 N 11 -based phosphor component and a matrix component, wherein the matrix component is Al 2 O 3 , a mixture of Al 2 O 3 and MgO, and MgAlO 2 , and the content of the matrix component is 31 wt % or more and 95 wt % or less of the total components. and the matrix component is sintered surrounding the La 3 Si 6 N 11 based phosphor component based phosphor.
- the thirty-fifth aspect has the features of any one of the second to fifteenth aspects and the twenty-third to twenty-ninth aspects described above within the range in which the effect of the aspect can be obtained. It can contain more.
- Example 1 As shown in FIG. 10, in Example 1, the contents of YAG as a garnet-based phosphor component, Sr 2 Si 5 N 8 as a nitride-based phosphor component, and Al 2 O 3 as a matrix component were However, each raw material powder was mixed so as to be 25 wt %, 25 wt %, and 50 wt %, respectively.
- this raw material powder was filled into a mold and sintered at 1350°C for 3 minutes in a nitrogen atmosphere using the SPS method to produce composite ceramics.
- the laser power dependence of the fluorescence power of the resulting composite ceramics was measured using a phosphor evaluation device equipped with a laser light source, an integrating sphere, and a spectroscope.
- the excitation laser beam in the laser light source had a diameter of 1 mm, an excitation laser wavelength of 450 nm, and a continuous excitation laser beam. The results are shown in FIG. Arrows in FIG. 12 indicate saturation points of fluorescence.
- the obtained composite ceramics was irradiated with excitation light from a laser light source, and the fluorescence spectrum of the beam output from the composite ceramics through a lens was measured using a fluorescence spectroscope. More specifically, using a spectroscope manufactured by Ocean Photonics Co., Ltd., the emission spectrum was measured under room temperature conditions with the excitation wavelength fixed at 441 nm. The results are shown in FIG.
- Example 2 As shown in FIG . 10, in Example 2, each raw material powder was mixed so that the contents of YAG, Sr2Si5N8 , and Al2O3 were 15 wt%, 15 wt%, and 70 wt%, respectively. Mixed. Except for this point, in Example 2, the same operation as in Example 1 was performed to produce a composite ceramic.
- Example 2 the same phosphor evaluation device as in Example 1 was used to measure the laser power dependence of the fluorescence power of the obtained composite ceramics. The results are shown in FIG.
- Example 2 Using the same device as in Example 1, the fluorescence spectrum of the beam output from the composite ceramics through the lens was measured using the same fluorescence spectrometer as in Example 1. The results are shown in FIG.
- Example 3 As shown in FIG. 10, in Example 3, each raw material powder was mixed so that the contents of YAG, Sr2Si5N8 , and Al2O3 were 5 wt%, 5 wt%, and 90 wt % , respectively. Mixed and sintered at 1300°C. Except for this point, in Example 3, the same operation as in Example 1 was performed to produce a composite ceramic.
- Example 2 the same phosphor evaluation device as in Example 1 was used to measure the laser power dependence of the fluorescence power of the obtained composite ceramics. The results are shown in FIG.
- Example 2 the fluorescence spectrum of the beam output from the composite ceramics through the lens was measured using the same fluorescence spectrometer as in Example 1. The results are shown in FIG.
- Comparative Example 1 As shown in FIG. 10, in Comparative Example 1, only Sr 2 Si 5 N 8 was filled in the mold and sintered at 1800°C. Except for this point, in Comparative Example 1, the same operation as in Example 1 was performed to produce a composite ceramic for comparison.
- Example 2 the same phosphor evaluation device as in Example 1 was used to measure the laser power dependence of the fluorescence power of the obtained composite ceramics. This result is shown in FIG.
- Example 2 Using the same device as in Example 1, the fluorescence spectrum of the beam output from the composite ceramics through the lens was measured using the same fluorescence spectrometer as in Example 1. The results are shown in FIG.
- Comparative Example 2 As shown in FIG. 10, it is a binary composite ceramic of Sr 2 Si 5 N 8 red phosphor and Al 2 O 3 .
- Example 4 As shown in FIG. 10, an attempt was made to produce composite ceramics in the same manner as in Example 1, except that the contents of YAG, Sr 2 Si 5 N 8 and Al 2 O 3 were changed to 15 wt%, 65 wt% and 20 wt%, respectively. However, the sintered body was cracked or broken, and no composite was obtained, so the characteristics could not be evaluated. The reason for this is thought to be that sintering was not successful because it contained a large amount of YAG phosphor particles and Sr 2 Si 5 N 8 phosphor particles having a large particle size.
- Example 5 A study was conducted in the same manner as in Example 5 except for the contents of YAG, Sr 2 Si 5 N 8 and Al 2 O 3 . The state of cracking and breakage was the same as in Comparative Example 4.
- Table 1 shows the laser power dependency and the peak wavelength of the output beam in the composite ceramics of Examples 4 and 5.
- Example 6 As shown in FIG. 22, in Example 6 , MgO was used instead of Al2O3 , and the contents of YAG, Sr2Si5N8 , and MgO were 15 wt% , 15 wt%, and 70 wt%, respectively. %, and sintered at 1300°C. Except for this point, in Example 6, the same operation as in Example 1 was performed to produce a composite ceramic.
- Example 2 the same phosphor evaluation device as in Example 1 was used to measure the laser power dependence of the fluorescence power of the obtained composite ceramics. The results are shown in FIG.
- Example 2 Using the same device as in Example 1, the fluorescence spectrum of the beam output from the composite ceramics through the lens was measured using the same fluorescence spectrometer as in Example 1. The results are shown in FIG.
- Example 7 As shown in FIG. 22, in Example 7, about 10% of MgO was changed to AlN as a light scattering component, and the contents of YAG, Sr2Si5N8 , MgO, and AlN were each 15 wt. %, 15 wt %, 63 wt %, and 7 wt %. Except for this point, in Example 7, the same operation as in Example 1 was performed to produce a composite ceramic.
- Example 6 the same phosphor evaluation device as in Example 1 was used to measure the laser power dependence of the fluorescence power of the obtained composite ceramics. This result is shown in FIG. 25 together with the laser power dependency of the fluorescence power of the composite ceramics obtained in Example 6.
- Comparative Example 6 is a composite ceramic consisting of a binary system of Sr 2 Si 5 N 8 and MgO.
- Comparative Example 7 As shown in FIG. 22, it is a binary composite ceramic made of YAG and MgO.
- Example 8 As shown in FIG. 22, an attempt was made to produce composite ceramics in the same manner as in Example 6 except that the contents of YAG, Sr 2 Si 5 N 8 and MgO were changed to 65 wt %, 15 wt % and 20 wt %, respectively. , the sintered body crumbled or cracked, and a composite ceramic was not obtained.
- the SEM image shown in FIG. 14 is a backscattered electron image of the composite ceramic shown in Example 1, in which the portions composed of heavy elements appear white and the portions composed of light elements appear dark. Moreover, the shape of each component is a shape corresponding to the shape of the raw material particles. From the results shown in FIG . 14, the obtained composite ceramic contains YAG, Sr2Si5N8 , and Al2O3 , and Al2O3 surrounds YAG and Sr2Si5N8 . It was confirmed that it was sintered.
- the nitride-based phosphor component Sr 2 Si 5 N 8 is an oxide matrix component such as Al 2 O 3 I was able to confirm that there were still some left.
- the nitride phosphor has low excitation light power resistance (laser power resistance), and the garnet phosphor component and the matrix component are low. It can be seen that the pumping light power resistance is greatly improved by the addition.
- the fluorescent power was improved by about 10% or more by including, for example, AlN having a high refractive index as a light scattering component as part of the matrix component.
- Example 9 As shown in FIG. 26, composite ceramics were produced in the same manner as in Example 1 except that the contents of YAG, (BaSr) 2 Si 5 N 8 and Al 2 O 3 were 20 wt %, 10 wt % and 70 wt %, respectively. manufactured. Also, in the same manner as in Example 1, the laser power dependency of the fluorescence power of the obtained composite ceramics was measured.
- Example 10 As shown in FIG. 26, composite ceramics were produced in the same manner as in Example 1, except that the contents of YAG, (BaSr) 2 Si 5 N 8 , and Al 2 O 3 were 25 wt %, 5 wt %, and 70 wt %, respectively. manufactured. Also, in the same manner as in Example 1, the laser power dependency of the fluorescence power of the obtained composite ceramics was measured.
- Example 11 As shown in FIG. 26, composite ceramics were produced in the same manner as in Example 1, except that the contents of YAG, (BaSr) 2 Si 5 N 8 , and Al 2 O 3 were 8 wt %, 2 wt %, and 90 wt %, respectively. manufactured. Also, in the same manner as in Example 1, the laser power dependency of the fluorescence power of the obtained composite ceramics was measured.
- Example 12 As shown in FIG. 26, composite ceramics were produced in the same manner as in Example 1, except that the contents of YAG, (BaSr) 2 Si 5 N 8 , and Al 2 O 3 were 35 wt %, 33 wt %, and 32 wt %, respectively. manufactured.
- Example 13 As shown in FIG. 26, a composite ceramic was produced in the same manner as in Example 8 except that the contents of YAG, (BaSr) 2 Si 5 N 8 and Al 2 O 3 were 30 wt %, 0 wt % and 70 wt %, respectively. manufactured.
- Table 2 shows the laser power dependency and the peak wavelength of the output beam in the composite ceramics of Examples 8-12 and Comparative Examples 10-13.
- Example 13 As shown in FIG. 27, composite ceramics were produced in the same manner as in Example 1 except that the contents of YAG, (CaAl)SiN 3 and Al 2 O 3 were 15 wt %, 15 wt % and 70 wt %, respectively.
- Example 14 As shown in FIG. 27, composite ceramics were produced in the same manner as in Example 1 except that the contents of YAG, (CaAl)SiN 3 and Al 2 O 3 were 20 wt %, 10 wt % and 70 wt %, respectively.
- Example 15 As shown in FIG. 27, composite ceramics were produced in the same manner as in Example 1 except that the contents of YAG, (CaAl)SiN 3 and Al 2 O 3 were 25 wt %, 5 wt % and 70 wt %, respectively.
- Example 16 As shown in FIG. 27, composite ceramics were produced in the same manner as in Example 1 except that the contents of YAG, (CaAl)SiN 3 and Al 2 O 3 were 25 wt %, 25 wt % and 50 wt %, respectively.
- Example 17 As shown in FIG. 27, composite ceramics were produced in the same manner as in Example 1 except that the contents of YAG, (CaAl)SiN 3 and Al 2 O 3 were 35 wt %, 33 wt % and 32 wt %, respectively.
- Example 18 As shown in FIG. 27, composite ceramics were produced in the same manner as in Example 1 except that the contents of YAG, (CaAl)SiN 3 and Al 2 O 3 were 10 wt %, 5 wt % and 85 wt %, respectively.
- a composite ceramic was produced in the same manner as in Example 11 , except that the contents of YAG, (CaAl) SiN3 and ( LaY ) 3Si6N11 , and Al2O3 were 25 wt %, respectively, and 5 wt% and 70 wt% in total. manufactured.
- a composite ceramic was prepared in the same manner as in Example 11 , except that the contents of YAG, (CaAl) SiN3 and ( LaY ) 3Si6N11 , and Al2O3 were 30 wt %, respectively, and 0 wt% and 70 wt% in total. manufactured.
- Composite ceramics were produced in the same manner as in Example 11 except that the contents of (LaY) 3 Si 6 N 11 , (CaAl)SiN 3 and Al 2 O 3 were 20 wt %, 10 wt % and 70 wt %, respectively.
- Composite ceramics were produced in the same manner as in Example 11 except that the contents of (LaY) 3 Si 6 N 11 , (CaAl)SiN 3 and Al 2 O 3 were 25 wt %, 5 wt % and 70 wt %, respectively.
- Example 6 A composite ceramic was produced in the same manner as in Example 11 except that the contents of (LaY) 3 Si 6 N 11 , (CaAl)SiN 3 and Al 2 O 3 were 30 wt %, 0 wt % and 70 wt %, respectively.
- Composite ceramics were produced in the same manner as in Example 1 except that the contents of (LaY) 3 Si 6 N 11 , MgO and Al 2 O 3 were 30 wt %, 70 wt % and 0 wt %, respectively.
- Composite ceramics were produced in the same manner as in Example 1 except that the contents of (LaY) 3 Si 6 N 11 , MgO and Al 2 O 3 were 30 wt %, 60 wt % and 10 wt %, respectively.
- Composite ceramics were produced in the same manner as in Example 1 except that the contents of (LaY) 3 Si 6 N 11 , MgO and Al 2 O 3 were 10 wt %, 50 wt % and 40 wt %, respectively.
- the object color (L * value, a * value, b * value and saturation) in the L * a * b * color system was measured using a colorimeter.
- the object color before annealing was also measured.
- the fluorescence power was measured before and after annealing, and the ratio of the maximum fluorescence power after annealing to the maximum fluorescence power before annealing was determined.
- the ratio is the ratio of the maximum fluorescence power after annealing to the saturated fluorescence power before annealing, as shown in FIG.
- the ratio of the saturated fluorescence power after annealing to the saturated fluorescence power before annealing is the results.
- the fluorescence power is increased by the annealing treatment in the ammonia atmosphere. Moreover, as shown in FIGS. 28 and 29, the fluorescence power after annealing tends to reach saturation at the excitation light power compared to before annealing. Therefore, it can be seen that the pumping light power resistance is also enhanced by the annealing treatment.
- Reference Example 17 The composite ceramic of Reference Example 8 was annealed by heating at 1150° C. for 3 hours in a nitrogen atmosphere to obtain a composite ceramic of Reference Example 17. The composite ceramic of Reference Example 17 turned white, and fluorescence was not observed.
- the saturation decreased due to nitrogen leakage or the deactivation of the activator, and the internal quantum efficiency decreased. This is believed to be due to nitrogen loss in the composition or deactivation of the activator.
- annealing the sintered phosphors in an ammonia atmosphere further enhances the fluorescence intensity. did.
- both thermal conductivity and Vickers hardness tend to increase as the amount of matrix increases.
- Binary systems tend to exhibit sufficiently high numerical values for both thermal conductivity and Vickers hardness.
- both thermal conductivity and Vickers hardness tend to decrease depending on the degree of sintering.
- Phosphor element A is configured by forming a mirror body on one main surface of the composite ceramics of Example 21 having a thickness of 100 ⁇ m, and bonding the composite ceramics to a copper alloy base material with an inorganic adhesive on the mirror side surface. It is Phosphor element B is manufactured in the same manner as phosphor element A except that the thickness of the composite ceramics of Example 18 is 50 ⁇ m.
- FIG. 30 shows the relationship between the excitation light power when laser light is applied to the composite ceramics and the fluorescence power at that time.
- the fluorescence power increases as the excitation light power increases.
- the phosphor element B further increases the fluorescence power with an increase in the excitation light power.
- the excitation light power is more appropriately converted into fluorescence power than in the phosphor element A. Therefore, it can be seen that the composite ceramics of Example 21 efficiently emits fluorescence even though it is thin.
- a phosphor element of the present invention was prepared, and fluorescence power was measured when laser light was continuously irradiated. The results are shown in FIG.
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Abstract
Description
図1は、本実施形態に係るコンポジットセラミックス1の組織の一例を示す断面図である。
本開示において、ガーネット系蛍光体成分2とは、結晶構造がガーネット構造を有する蛍光体を示す。ガーネット系蛍光体成分2は、屈折率が大きく、蛍光特性に優れた蛍光体であり、例えば、青色励起光によって、黄色~緑色の黄色系の蛍光を発光する。また、励起光のうち励起に寄与しなかった光は、散乱させて透過する。このため、ガーネット系蛍光体成分2は、青色散乱光と、黄色系の蛍光とを出力する。
本開示において、窒化物系蛍光体成分3とは、窒素を含む蛍光体を示す。窒化物系蛍光体成分3としては、具体的には、窒化物蛍光体および酸窒化物蛍光体からなる群より選ばれる少なくとも一種の蛍光体が挙げられる。
マトリックス成分4は、MgO(酸化マグネシウム)およびAl2O3(酸化アルミニウム)からなる群より選ばれる少なくとも一種である。マトリックス成分4は、MgOであってもよく、Al2O3であってもよく、MgOとAl2O3とが混在していてもよい。
コンポジットセラミックス1におけるマトリックス成分4の含有率は、コンポジットセラミックス1における全成分の31wt%以上、95wt%以下の範囲内である。
コンポジットセラミックス1に含まれる、ガーネット系蛍光体成分2および窒化物系蛍光体成分3の粒径は、これらガーネット系蛍光体成分2および窒化物系蛍光体成分3の種類に応じて、所望の発光スペクトルを得ることができるように適宜設定すればよい。このため、これらガーネット系蛍光体成分2および窒化物系蛍光体成分3の粒径は、特に限定されるものではない。
また、コンポジットセラミックス1は、焼結助剤をさらに含んでいてもよい。前記ガーネット系蛍光体成分2の原料として用いられる原料粉、窒化物系蛍光体成分3の原料として用いられる原料粉、マトリックス成分4の原料として用いられる原料粉を含む原料粉(第1原料粉)が焼結助剤を含む場合、コンポジットセラミックス1も焼結助剤を含む。
コンポジットセラミックス1の厚みは、特に限定されるものではないが、レーザー照明装置の蛍光体素子に用いる場合、例えば、10μm以上、10mm以下の範囲内であることが好ましい。
コンポジットセラミックス1は、光散乱性が大きいことが望ましい。コンポジットセラミックス中で発生した蛍光または励起光が、蛍光体素子の横方向に伝搬すると、蛍光体素子から出射されるビームがボケてしまう。
コンポジットセラミックス1の物体色は、L*a*b*表色系で表示され得る。上記のL*は明度であり、上記のa*は赤-緑間の色度であり、上記のb*は黄-青間の色度である。また、彩度は、a*およびb*のそれぞれの二乗の和の平方根で表される。コンポジットセラミックス1の物体色は、L*a*b*表色系における適当な範囲内で表されることがコンポジットセラミックスの蛍光パワーを高める観点から好ましい。
次に、コンポジットセラミックス1の製造方法について説明する。
図3は、本実施形態に係るコンポジットセラミックス11の組織の一例を示す断面図である。
図4は、本実施形態に係るコンポジットセラミックス21の組織の一例を示す断面図である。
図5は、本実施形態に係るコンポジットセラミックス31の組織の一例を示す断面図である。
図6は、本実施形態に係る、一方の主面にAR(反射防止)コート膜41が設けられたコンポジットセラミックス1を示す図である。
前記したように、コンポジットセラミックスは、レーザー照明用の蛍光体素子(言い換えれば、レーザー照明装置の蛍光体素子)に好適に用いることができる。
本発明の実施形態におけるコンポジットセラミックスは、本発明の効果が得られる範囲において、ガーネット系蛍光体成分に代えて前述のLa3Si6N11系蛍光体成分(窒化物蛍光体(C))を有していてもよい。この場合、「窒化物系蛍光体成分」は、La3Si6N11系蛍光体成分以外の窒化物系蛍光体成分から選ばれ得る。
本発明の実施形態におけるコンポジットセラミックスは、本発明の効果が得られる範囲において、蛍光体成分として実質的にLa3Si6N11系蛍光体成分(窒化物蛍光体(C))のみを有していてもよい。すなわち、実施形態8のコンポジットセラミックスは、La3Si6N11系蛍光体成分およびマトリックス成分のみを実質的に含む焼結体からなるコンポジットセラミックスであって、上記マトリックス成分は、Al2O3、Al2O3とMgOの混合物、および、MgAlO2、からなる群より選ばれる少なくとも一種の成分であり、上記マトリックス成分の含有率が、全成分の31wt%以上、95wt%以下の範囲内であり、上記マトリックス成分は、上記La3Si6N11系蛍光体成分系蛍光体を取り囲んで焼結されていてもよい。
本発明の第一の態様は、ガーネット系蛍光体成分と、窒化物系蛍光体成分と、マトリックス成分とを含む焼結体からなるコンポジットセラミックスであって、上記マトリックス成分は、MgOおよびAl2O3からなる群より選ばれる少なくとも一種であり、上記マトリックス成分の含有率が、全成分の31wt%以上、95wt%以下の範囲内であり、上記マトリックス成分は、上記ガーネット系蛍光体成分と上記窒化物系蛍光体成分とを取り囲んで焼結されていることを特徴とする。
上記窒化物系蛍光体成分の含有率が59wt%であり、上記マトリックス成分の含有率が31wt%であり、上記ガーネット系蛍光体成分の含有率が10wt%である点Aと、
上記窒化物系蛍光体成分の含有率が8wt%であり、上記マトリックス成分の含有率が90wt%であり、上記ガーネット系蛍光体成分の含有率が2wt%である点Bと、
上記窒化物系蛍光体成分の含有率が2wt%であり、上記マトリックス成分の含有率が90wt%であり、上記ガーネット系蛍光体成分の含有率が8wt%である点Cと、
上記窒化物系蛍光体成分の含有率が10wt%であり、上記マトリックス成分の含有率が31wt%であり、上記ガーネット系蛍光体成分の含有率が59wt%である点Dとを結ぶ直線で囲まれた範囲内にあることを特徴とする。
上記マトリックス成分がAl2O3である場合、Si3N4、SiO2、CaO、MgO、ZnOおよびY2O3からなる群より選ばれる少なくとも一種であり、
上記マトリックス成分が、MgOおよびAl2O3のうち少なくともMgOを含む場合、Si3N4、SiO2、CaO、ZnOおよびY2O3からなる群より選ばれる少なくとも一種であることを特徴とする。
以下、実施例および比較例により、本開示に係るコンポジットセラミックスについて具体的に説明するが、本開示に係るコンポジットセラミックスは、これら実施例に限定されるものではない。なお、以下の実施例および比較例において、原料粉としてのYAGには、2mol%のCeで賦活された、数平均粒径が15μmのYAGを使用した。また、原料粉としてのSr2Si5N8には、2mol%のEuで賦活された、数平均粒径が13μm(一部凝集した粉を含む)のSr2Si5N8を使用した。原料粉としてのAl2O3には、数平均粒径が0.1μmのAl2O3を使用した。原料粉としてのMgOには、数平均粒径が0.05μmのMgOを使用した。原料粉としてのAlNには、数平均粒径が1μmのAlNを使用した。
図10に示すように、実施例1では、ガーネット系蛍光体成分であるYAGと、窒化物系蛍光体成分であるSr2Si5N8と、マトリックス成分であるAl2O3との含有量が、それぞれ25wt%、25wt%、50wt%となるように各原料粉を混合した。
図10に示すように、実施例2では、YAGと、Sr2Si5N8と、Al2O3との含有量が、それぞれ15wt%、15wt%、70wt%となるように各原料粉を混合した。この点を除けば、実施例2では、実施例1と同じ操作を行ってコンポジットセラミックスを製造した。
図10に示すように、実施例3では、YAGと、Sr2Si5N8と、Al2O3との含有量が、それぞれ5wt%、5wt%、90wt%となるように各原料粉を混合し、1300℃で焼結した。この点を除けば、実施例3では、実施例1と同じ操作を行ってコンポジットセラミックスを製造した。
図10に示すように、YAG、Sr2Si5N8およびAl2O3の含有量をそれぞれ34.5wt%、34.5wt%および31wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。また、実施例1と同様にして、得られたコンポジットセラミックスの蛍光パワーのレーザーパワー依存性を測定した。蛍光の飽和点の励起光パワーは3Wであり、励起光パワー耐性は、/(3.1415×0.05×0.05)=0.38kW/cm2となる。また、実施例1と同様にして、上記コンポジットセラミックスからレンズを透過させて出力したビームの蛍光スペクトルを測定した。ピーク波長は600nmであった。
図10に示すように、YAG、Sr2Si5N8およびAl2O3の含有量をそれぞれ20wt%、10wt%および70wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。また、実施例1と同様にして、得られたコンポジットセラミックスの蛍光パワーのレーザーパワー依存性を測定した。蛍光の飽和点の励起光パワーは10Wであり、励起光パワー耐性は、10/(3.1415×0.05×0.05)=1.3kW/cm2となる。また、実施例1と同様にして、上記コンポジットセラミックスからレンズを透過させて出力したビームの蛍光スペクトルを測定した。ピーク波長は590nmであった。
図10に示すように、比較例1ではSr2Si5N8のみを成形型に充填し、1800℃で焼結した。この点を除けば、比較例1では、実施例1と同じ操作を行って、比較用のコンポジットセラミックスを製造した。
図10に示すように、Sr2Si5N8赤色蛍光体とAl2O3の2元系のコンポジットセラミックスである。
図10に示すように、YAG、とAl2O3の2元系のコンポジットセラミックスである。
図10に示すように、YAG、Sr2Si5N8およびAl2O3の含有量をそれぞれ15wt%、65wt%および20wt%とする以外は実施例1と同様にしてコンポジットセラミックスの製造を試みたが、焼結体が割れ又は破損してコンポジットが得られず、特性評価にいたらなかった。この原因としては、粒径のおおきなYAG蛍光体粒子や、Sr2Si5N8蛍光体粒子を多く含むため、焼結がうまくできていないと考えられる。
実施例5のYAG、Sr2Si5N8およびAl2O3の含有量以外は同様に検討をおこなった。割れ、破損の状況は比較例4と同様であった。
図22に示すように、実施例6では、Al2O3に代えてMgOを使用し、YAGと、Sr2Si5N8と、MgOとの含有量が、それぞれ15wt%、15wt%、70wt%となるように各原料粉を混合し、1300℃で焼結した。この点を除けば、実施例6では、実施例1と同じ操作を行ってコンポジットセラミックスを製造した。
図22に示すように、実施例7では、MgOの約10%を光散乱成分としてのAlNに変更し、YAGと、Sr2Si5N8と、MgOと、AlNの含有量が、それぞれ15wt%、15wt%、63wt%、7wt%となるように各原料粉を混合した。この点を除けば、実施例7では、実施例1と同じ操作を行ってコンポジットセラミックスを製造した。
図22に示すように、比較例6はSr2Si5N8とMgOの2元系からなるコンポジットセラミックスである。
図22に示すように、YAG、MgOからなる2元系のコンポジットセラミックスである。
図22に示すように、YAG、Sr2Si5N8、MgOの含有量をそれぞれ65wt%、15wt%、および20wt%とする以外は実施例6と同様にしてコンポジットセラミックスの製造を試みたが、焼結体が崩れるか又は割れてしまい、コンポジットセラミックスが得られなかった。
図22に示すように、YAG、Sr2Si5N8、MgOの含有量をそれぞれ15wt%、65wt%、および20wt%とする以外は実施例6と同様にしてコンポジットセラミックスの製造を試みたが、焼結体が崩れるか又は割れてしまい、コンポジットセラミックスが得られなかった。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ15wt%、15wt%および70wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。また、実施例1と同様にして、得られたコンポジットセラミックスの蛍光パワーのレーザーパワー依存性を測定した。蛍光の飽和点の励起光パワーは6Wであり、励起光パワー耐性は、6/(3.1415×0.05×0.05)=0.76kW/cm2となる。また、実施例1と同様にして、上記コンポジットセラミックスからレンズを透過させて出力したビームの蛍光スペクトルを測定した。ピーク波長は605nmであった。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ20wt%、10wt%および70wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。また、実施例1と同様にして、得られたコンポジットセラミックスの蛍光パワーのレーザーパワー依存性を測定した。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ25wt%、5wt%および70wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。また、実施例1と同様にして、得られたコンポジットセラミックスの蛍光パワーのレーザーパワー依存性を測定した。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ8wt%、2wt%および90wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。また、実施例1と同様にして、得られたコンポジットセラミックスの蛍光パワーのレーザーパワー依存性を測定した。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ35wt%、33wt%および32wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ85wt%、15wt%および0wt%とする以外は実施例8と同様にしてコンポジットセラミックスの製造を試みたが、焼結体が崩れるか又は割れてしまい、コンポジットセラミックスが得られなかった。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ40wt%、40wt%および20wt%とする以外は実施例8と同様にしてコンポジットセラミックスの製造を試みたが、焼結体が崩れるか又は割れてしまい、コンポジットセラミックスが得られなかった。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ0wt%、30wt%および70wt%とする以外は実施例8と同様にしてコンポジットセラミックスを製造した。
図26に示すように、YAG、(BaSr)2Si5N8、およびAl2O3の含有量をそれぞれ30wt%、0wt%および70wt%とする以外は実施例8と同様にしてコンポジットセラミックスを製造した。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ15wt%、15wt%および70wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ20wt%、10wt%および70wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ25wt%、5wt%および70wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ25wt%、25wt%および50wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ35wt%、33wt%および32wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ10wt%、5wt%および85wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ30wt%、0wt%および70wt%とする以外は実施例13と同様にしてコンポジットセラミックスを製造した。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ85wt%、15wt%および0wt%とする以外は実施例13と同様にしてコンポジットセラミックスの製造を試みたが、焼結体が崩れて成形体が得られず、コンポジットセラミックスが得られなかった。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ40wt%、40wt%および20wt%とする以外は実施例13と同様にしてコンポジットセラミックスの製造を試みたが、焼結体が崩れて成形体が得られず、コンポジットセラミックスが得られなかった。
図27に示すように、YAG、(CaAl)SiN3、およびAl2O3の含有量をそれぞれ0wt%、30wt%および70wt%とする以外は実施例13と同様にしてコンポジットセラミックスを製造した。
YAG、(CaAl)SiN3および(LaY)3Si6N11、ならびにAl2O3の含有量をそれぞれ20wt%、総じて10wt%ならびに70wt%とする以外は実施例11と同様にしてコンポジットセラミックスを製造した。
YAG、(CaAl)SiN3および(LaY)3Si6N11、ならびにAl2O3の含有量をそれぞれ25wt%、総じて5wt%ならびに70wt%とする以外は実施例11と同様にしてコンポジットセラミックスを製造した。
YAG、(CaAl)SiN3および(LaY)3Si6N11、ならびにAl2O3の含有量をそれぞれ30wt%、総じて0wt%ならびに70wt%とする以外は実施例11と同様にしてコンポジットセラミックスを製造した。
(LaY)3Si6N11、(CaAl)SiN3およびAl2O3の含有量をそれぞれ20wt%、10wt%および70wt%とする以外は実施例11と同様にしてコンポジットセラミックスを製造した。
(LaY)3Si6N11、(CaAl)SiN3およびAl2O3の含有量をそれぞれ25wt%、5wt%および70wt%とする以外は実施例11と同様にしてコンポジットセラミックスを製造した。
(LaY)3Si6N11、(CaAl)SiN3およびAl2O3の含有量をそれぞれ30wt%、0wt%および70wt%とする以外は実施例11と同様にしてコンポジットセラミックスを製造した。
(LaY)3Si6N11、ならびにMgOおよびAl2O3の含有量をそれぞれ30wt%、0wt%および70wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
(LaY)3Si6N11、ならびにMgOおよびAl2O3の含有量をそれぞれ30wt%、35wt%および35wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
(LaY)3Si6N11、ならびにMgOおよびAl2O3の含有量をそれぞれ30wt%、70wt%および0wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
(LaY)3Si6N11、ならびにMgOおよびAl2O3の含有量をそれぞれ30wt%、60wt%および10wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
(LaY)3Si6N11、ならびにMgOおよびAl2O3の含有量をそれぞれ10wt%、50wt%および40wt%とする以外は実施例1と同様にしてコンポジットセラミックスを製造した。
実施例11のコンポジットセラミックスをアンモニア雰囲気で1000℃、3時間加熱するアニール処理を施して参考例12のコンポジットセラミックスを得た。また、実施例18のコンポジットセラミックスをアンモニア雰囲気で1250℃、2時間加熱するアニール処理を施して参考例13のコンポジットセラミックスを得た。また、参考例4のコンポジットセラミックスをアンモニア雰囲気で1000℃、3時間加熱するアニール処理を施して参考例14のコンポジットセラミックスを得た。また、参考例9のコンポジットセラミックスをアンモニア雰囲気で1250℃、2時間加熱するアニール処理を施して参考例15のコンポジットセラミックスを得た。また、参考例8のコンポジットセラミックスをアンモニア雰囲気で1000℃、3時間加熱するアニール処理を施して参考例16のコンポジットセラミックスを得た。
参考例8のコンポジットセラミックスを窒素雰囲気下で1150℃、3時間加熱するアニール処理を施して参考例17のコンポジットセラミックスを得た。参考例17のコンポジットセラミックスは白色化し、また蛍光が観察されなかった。
実施例16~18ならびに参考例7、8および11のコンポジットセラミックスのそれぞれについて、熱伝導率を測定した。また、実施例16~18ならびに参考例7、8および11のコンポジットセラミックスのそれぞれについて、ビッカース硬度を測定した。結果を以下の表4に示す。
実施例18のコンポジットセラミックスを用いて蛍光体素子Aおよび蛍光体素子Bを作製した。蛍光体素子Aは、厚さ100μmの実施例21のコンポジットセラミックスの一主面に鏡体を形成し、当該鏡体側の面でコンポジットセラミックスを無機接着剤によって銅合金の基材に接着して構成されている。蛍光体素子Bは、実施例18のコンポジットセラミックスの厚さが50μmである以外は蛍光体素子Aと同様に作製されている。
本発明の蛍光体素子を用意し、レーザー光を連続して照射したときの蛍光パワーを測定した。結果を図31に示す。
2 ガーネット系蛍光体成分
3 窒化物系蛍光体成分
4 マトリックス成分
12 光散乱成分
22 第1セラミックス層
23 第2セラミックス層
31a 凹凸
50 蛍光体素子
51 基材
60 レーザー照明装置
61 レーザー光源
62、63 レンズ
Claims (22)
- ガーネット系蛍光体成分と、窒化物系蛍光体成分と、マトリックス成分とを含む焼結体からなるコンポジットセラミックスであって、
上記マトリックス成分は、MgOおよびAl2O3からなる群より選ばれる少なくとも一種であり、
上記マトリックス成分の含有率が、全成分の31wt%以上、95wt%以下の範囲内であり、
上記マトリックス成分は、上記ガーネット系蛍光体成分と上記窒化物系蛍光体成分とを取り囲んで焼結されていることを特徴とするコンポジットセラミックス。 - 当該コンポジットセラミックスの単位体積当たりに含まれる上記マトリックス成分の数平均粒径が、0.01μm以上、10μm以下の範囲内であることを特徴とする請求項1に記載のコンポジットセラミックス。
- 上記ガーネット系蛍光体成分が、(Ce,Y)3Al5O12、(Ce,Lu)3Al5O12、(Ce,Lu,Y)3Al5O12、(Ce,Lu,Y)3(Al,Ga)5O12からなる群より選ばれる少なくとも一種を含むことを特徴とする請求項2に記載のコンポジットセラミックス。
- 上記窒化物系蛍光体成分が、それぞれEuおよびCeのうち少なくとも一方の元素で賦活された、Sr2Si5N8、(Sr,Ba)2Si5N8、(Ca,Sr,Ba)2Si5N8からなる群より選ばれる少なくとも一種を含むことを特徴とする請求項1に記載のコンポジットセラミックス。
- 上記Siの一部および上記Nの一部のうち少なくとも一方が置換されており、
上記Siの一部が置換されている場合、上記SiはAlに置換されており、
上記Nの一部が置換されている場合、上記NはOに置換されていることを特徴とする請求項4に記載のコンポジットセラミックス。 - 上記窒化物系蛍光体成分が、それぞれEuおよびCeのうち少なくとも一方の元素で賦活された、CaAlSiN3および(Ca,Sr)AlSiN3からなる群より選ばれる少なくとも一種を含むことを特徴とする請求項1に記載のコンポジットセラミックス。
- 上記窒化物系蛍光体成分、上記マトリックス成分、および上記ガーネット系蛍光体成分の合計の含有率を100wt%とする三角図において、上記窒化物系蛍光体成分、上記マトリックス成分、および上記ガーネット系蛍光体成分のそれぞれの含有率が、
上記窒化物系蛍光体成分の含有率が59wt%であり、上記マトリックス成分の含有率が31wt%であり、上記ガーネット系蛍光体成分の含有率が10wt%である点Aと、
上記窒化物系蛍光体成分の含有率が8wt%であり、上記マトリックス成分の含有率が90wt%であり、上記ガーネット系蛍光体成分の含有率が2wt%である点Bと、
上記窒化物系蛍光体成分の含有率が2wt%であり、上記マトリックス成分の含有率が90wt%であり、上記ガーネット系蛍光体成分の含有率が8wt%である点Cと、
上記窒化物系蛍光体成分の含有率が10wt%であり、上記マトリックス成分の含有率が31wt%であり、上記ガーネット系蛍光体成分の含有率が59wt%である点Dとを結ぶ直線で囲まれた範囲内にあることを特徴とする請求項1に記載のコンポジットセラミックス。 - 屈折率が上記マトリックス成分よりも0.21以上高い光散乱成分をさらに含み、
上記マトリックス成分と上記光散乱成分との合計の含有率が、全成分の31wt%以上、95wt%以下であることを特徴とする請求項1に記載のコンポジットセラミックス。 - 上記光散乱成分が、AlN、cBN、SiC、AlN-SiC固溶体、およびダイアモンドからなる群より選ばれる少なくとも一種であることを特徴とする請求項8に記載のコンポジットセラミックス。
- 当該コンポジットセラミックスの単位体積当たりに含まれる上記光散乱成分の数平均粒径が、0.25μm以上、40μm以下であることを特徴とする請求項8に記載のコンポジットセラミックス。
- 厚み100μmでの波長450nmの光の直線透過率が、0.01%以上、20%以下であることを特徴とする請求項1に記載のコンポジットセラミックス。
- 焼結助剤をさらに含み、
上記焼結助剤は、
上記マトリックス成分がAl2O3である場合、Si3N4、SiO2、CaO、MgO、ZnOおよびY2O3からなる群より選ばれる少なくとも一種であり、
上記マトリックス成分が、MgOおよびAl2O3のうち少なくともMgOを含む場合、Si3N4、SiO2、CaO、ZnOおよびY2O3からなる群より選ばれる少なくとも一種であることを特徴とする請求項1に記載のコンポジットセラミックス。 - 一方の主面に、MgOおよびAl2O3からなる群より選ばれる少なくとも一種からなる層が接合された積層構造を有していることを特徴とする請求項1に記載のコンポジットセラミックス。
- 励起光パワー耐性が0.5kW/cm2以上であることを特徴とする請求項1に記載のコンポジットセラミックス。
- 一方の主面に凹凸が形成されていることを特徴とする請求項1に記載のコンポジットセラミックス。
- 請求項1~15の何れか1項に記載のコンポジットセラミックスと、
上記コンポジットセラミックスを固定する基材とを備えていることを特徴とする蛍光体素子。 - 請求項16に記載の蛍光体素子と、
上記蛍光体素子における上記コンポジットセラミックスに励起光を照射するレーザー光源と、
上記蛍光体素子における上記コンポジットセラミックスから出力された光を集光する集光部材とを備えていることを特徴とするレーザー照明装置。 - ガーネット系蛍光体成分と、窒化物系蛍光体成分と、マトリックス成分とを含む第1原料粉を混合する混合工程と、
混合した上記第1原料粉を成形型に収容する第1原料粉収容工程と、
上記成形型に収容した上記第1原料粉を、放電プラズマ焼結法またはホットプレス法で焼結する焼結工程と、
上記焼結工程で得られた焼結体を上記成形型から取り出す離型工程とを含むことを特徴とするコンポジットセラミックスの製造方法。 - MgOおよびAl2O3からなる群より選ばれる少なくとも一種からなる、上記第1原料粉よりも少ない第2原料粉を上記成形型に収容する第2原料粉収容工程をさらに含み、
上記焼結工程で、上記成形型に収容した、上記第1原料粉および上記第2原料粉を焼結することで、上記第1原料粉の焼結体と、上記第1原料粉よりも薄い、上記第2原料粉の焼結体とが接合された焼結体を形成することを特徴とする請求項18に記載のコンポジットセラミックスの製造方法。 - 上記焼結体に対し、切断および研磨のうち少なくとも一方を施す切断/研磨工程をさらに含むことを特徴とする請求項18に記載のコンポジットセラミックスの製造方法。
- 上記焼結体の一方の主面に凹凸を形成する凹凸形成工程をさらに含むことを特徴とする請求項18に記載のコンポジットセラミックスの製造方法。
- 上記凹凸形成工程では、ダイサー、レーザー加工、または研磨により上記凹凸を形成することを特徴とする請求項21に記載のコンポジットセラミックスの製造方法。
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