JP5509997B2 - Method for producing ceramic composite for light conversion - Google Patents
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Description
本発明は、ディスプレイ、照明、バックライト光源等に利用される発光ダイオードなどに用いられる光変換用セラミック複合体の製造方法に関する。 The present invention relates to a method for producing a ceramic composite for light conversion used for a light emitting diode used for a display, illumination, a backlight light source and the like.
近年、青色発光素子を発光源とする白色発光装置の研究開発が盛んに行われている。特に青色発光素子を用いた白色発光装置は、寿命が長く、白熱灯や蛍光灯に比べて消費電力が小さいだけでなく、水銀のような有害物質を使用しないことから、現在、白色発光装置を用いた照明機器が実用化されつつある。 In recent years, research and development of white light-emitting devices using a blue light-emitting element as a light source have been actively conducted. In particular, white light-emitting devices using blue light-emitting elements have a long life span and not only consume less power than incandescent and fluorescent lamps, but also do not use harmful substances such as mercury. The used lighting equipment is being put into practical use.
青色発光素子の青色光を光源として白色光を得る方法として最も一般的に行なわれている方法は、青色と補色関係にある黄色を混色することにより擬似的に白色を得るものである。 The most common method for obtaining white light using blue light of a blue light emitting element as a light source is to obtain a pseudo white color by mixing yellow having a complementary color relationship with blue.
例えば、典型的な白色発光装置では、青色発光素子から放出された青色光によって黄色を発する蛍光体（例えば、ＹＡＧ（Ｙ３Ａｌ５Ｏ１２）蛍光体）を含有する透明な樹脂によって封止されている。この青色発光素子から青色光（波長４５０〜４６０ｎｍ）が放出され、青色光の一部によってＹＡＧ蛍光体が励起されて、この蛍光体から黄色光が放出される。 For example, in a typical white light emitting device, sealing is performed by a transparent resin containing a phosphor that emits yellow light by blue light emitted from a blue light emitting element (for example, YAG (Y 3 Al 5 O 12 ) phosphor). ing. Blue light (wavelength 450 to 460 nm) is emitted from the blue light emitting element, the YAG phosphor is excited by a part of the blue light, and yellow light is emitted from the phosphor.
また、特許文献１、２に示されているように、発光素子の光取出側で封止部材の光出射面を覆う蛍光体板を備える発光装置が提案されている。 Further, as disclosed in Patent Documents 1 and 2, a light-emitting device including a phosphor plate that covers a light-emitting surface of a sealing member on the light extraction side of a light-emitting element has been proposed.
さらに、特許文献３では、蛍光体含有の板部材内に入射した発光素子からの光をその光出射面から出射し易くし、光取出効率を高めることができる蛍光体板およびこれを備えた発光装置が提案されている。 Furthermore, in Patent Document 3, a phosphor plate capable of easily emitting light from a light emitting element that has entered the phosphor-containing plate member from its light exit surface and improving light extraction efficiency, and light emission provided with the phosphor plate. A device has been proposed.
しかしながら、こうした蛍光体を含有する波長変換用の板部材を用いた白色発光装置において、特許文献１乃至３に記載されているような蛍光体を含有する板部材では、蛍光体粉末を樹脂やガラス等に混合したものであるため、その板材表面に凹凸形状を形成して蛍光体の蛍光強度を向上させようとした場合、蛍光だけでなく、光源から変換されることない透過光の出射光も影響を受けるため、白色発光装置の色むら・バラツキが生じやすいという問題が生じる。 However, in a white light emitting device using a wavelength conversion plate member containing such a phosphor, in the plate member containing the phosphor as described in Patent Documents 1 to 3, the phosphor powder is made of resin or glass. In order to improve the fluorescence intensity of the phosphor by forming an uneven shape on the surface of the plate material, not only the fluorescence but also the emitted light of the transmitted light that is not converted from the light source Due to the influence, there arises a problem that color unevenness and variation of the white light emitting device are likely to occur.
本発明者らは、蛍光体を発するＣｅを含有するＹＡＧ（ＹＡＧ：Ｃｅ）蛍光体相とＡｌ２Ｏ３相を含む複数の酸化物相が連続的にかつ三次元的に相互に絡み合って形成されている凝固体からなる光変換用セラミック複合体及び青色発光素子を用いて構成される白色発光装置を提案している。光変換用セラミック複合体は、蛍光体相が均一に分布するため均質な黄色蛍光を安定して得ることができ、またセラミックであるため耐熱性に優れる。このため光変換用セラミック複合体を用いた白色発光装置は、色むら・バラツキが小さく、耐久性に優れる。特に、高輝度発光装置に極めて好適である。 The present inventors formed a YAG (YAG: Ce) phosphor phase containing Ce emitting phosphor and a plurality of oxide phases including an Al 2 O 3 phase continuously and intertwined with each other three-dimensionally. A white light emitting device composed of a solidified ceramic composite for light conversion and a blue light emitting element has been proposed. The ceramic composite for light conversion can stably obtain uniform yellow fluorescence because the phosphor phase is uniformly distributed, and is excellent in heat resistance because it is a ceramic. For this reason, the white light emitting device using the ceramic composite for light conversion has small color unevenness and variation, and is excellent in durability. In particular, it is extremely suitable for a high brightness light emitting device.
これまでにも、本発明者らは、特許文献４に記載されているように、光変換用セラミック複合体の表面粗さを制御することにより、色調を調整する方法を提案している。この特許文献４に記載されたものは、光変換用セラミック複合体の表面の蛍光体相を凸状にすることによって、凹凸面を形成するものであり、その製造方法として挙げられているのは、１４００℃の高温ガス雰囲気下における熱処理である。 In the past, the present inventors have proposed a method for adjusting the color tone by controlling the surface roughness of the ceramic composite for light conversion, as described in Patent Document 4. What is described in this Patent Document 4 is to form a concavo-convex surface by making the phosphor phase on the surface of the ceramic composite for light conversion convex. This is a heat treatment in a high-temperature gas atmosphere at 1400 ° C.
しかしながら、特許文献４における処理温度は、光変換用セラミック複合体を構成するＹＡＧ：Ｃｅ蛍光体相とＡｌ２Ｏ３相の融点に近くなるため、各相および相界面に対する熱的な歪が大きくなり、その後の加工工程において破損等の不具合が生じるという問題がある。 However, since the processing temperature in Patent Document 4 is close to the melting point of the YAG: Ce phosphor phase and the Al 2 O 3 phase constituting the ceramic composite for light conversion, thermal distortion to each phase and phase interface is large. Therefore, there is a problem that defects such as breakage occur in subsequent processing steps.
このため、表面の蛍光体相を凸状に形成する従来の光変換用セラミック複合体の製造方法では、光変換用セラミック複合体の蛍光体相および非蛍光体相の融点近くまで高温にして処理することにより、熱的な歪が生じて、歩留まり等において生産性が低下してしまうことが問題となり、実用上、表面の蛍光体相が凸状に形成された光変換用セラミック複合体の製造方法として用いることはできない。また、今後さらに求められる白色発光装置の高出力化・高効率化に際して、発光効率を高く保ったまま、かつ組み合わせる青色発光素子の発光波長に対し最適な波長に調整された蛍光を発することができる光変換用材料が求められている。 For this reason, in the conventional method for producing a ceramic composite for light conversion in which the phosphor phase on the surface is formed in a convex shape, the surface is processed at a high temperature close to the melting point of the phosphor phase and non-phosphor phase of the ceramic composite for light conversion. As a result, there is a problem that thermal distortion occurs and productivity decreases in yield and the like, and practically, the production of a ceramic composite for light conversion in which the surface phosphor phase is formed in a convex shape It cannot be used as a method. In addition, it is possible to emit fluorescence adjusted to an optimum wavelength with respect to the emission wavelength of the blue light emitting element to be combined while keeping the luminous efficiency high when the white light emitting device to be further demanded in the future increases in efficiency and efficiency. There is a need for light conversion materials.
そこで、本発明は、蛍光を効率良く、かつ蛍光のピーク波長を５５０〜５６０ｎｍに調整して発することができ、また得られる蛍光が均質かつ安定しており、耐熱性・耐久性に優れた、青色発光素子と組み合わせて高出力・高効率な白色発光装置を構成するに好適な光変換用セラミック複合体の蛍光体相の表面形状を容易に凸状に形成することができる光変換用セラミック複合体の製造方法を提供することを目的とする。 Therefore, the present invention is capable of emitting the fluorescence efficiently and adjusting the peak wavelength of the fluorescence to 550 to 560 nm, and the obtained fluorescence is homogeneous and stable, and has excellent heat resistance and durability. A ceramic composite for light conversion that can easily form a surface shape of a phosphor phase of a ceramic composite for light conversion suitable for constituting a high-output and high-efficiency white light-emitting device in combination with a blue light-emitting element. It aims at providing the manufacturing method of a body.
以上の目的を達成するために、本発明者らは、鋭意検討した結果、少なくともＡｌ２Ｏ３相及び蛍光を発する酸化物結晶相からなる複数の酸化物相が連続的にかつ三次元的に相互に絡み合った組織を有する凝固体をアルカリ水溶液中で加熱処理することにより、Ａｌ２Ｏ３相を凹ませて光変換用セラミック複合体の蛍光体相の表面形状を容易に凸状に形成することができることを見出した。すなわち、本発明は、少なくともＡｌ２Ｏ３相及び蛍光を発する酸化物結晶相からなる複数の酸化物相が連続的にかつ三次元的に相互に絡み合った組織を有する凝固体をアルカリ水溶液中で加熱処理することにより、前記蛍光を発する酸化物結晶相よりＡｌ２Ｏ３相を凹状に形成する工程を備えたことを特徴とする光変換用セラミックス複合体の製造方法である。 In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, a plurality of oxide phases composed of at least an Al 2 O 3 phase and a fluorescent oxide crystal phase are continuously and three-dimensionally formed. By heat-treating a solidified body having an intertwined structure in an alkaline aqueous solution, the Al 2 O 3 phase is recessed to easily form the surface shape of the phosphor phase of the ceramic composite for light conversion into a convex shape. I found that I can do it. That is, the present invention provides a solidified body having a structure in which a plurality of oxide phases composed of at least an Al 2 O 3 phase and a fluorescent oxide crystal phase are continuously and three-dimensionally entangled in an alkaline aqueous solution. A method for producing a ceramic composite for light conversion, comprising a step of forming an Al 2 O 3 phase in a concave shape from the fluorescent oxide crystal phase by heat treatment.
以上のように、本発明によれば、蛍光を効率良く、かつ蛍光のピーク波長を５５０〜５６０ｎｍに調整して発することができ、また得られる蛍光が均質かつ安定しており、耐熱性・耐久性に優れた、青色発光素子と組み合わせて高出力・高効率な白色発光装置を構成するに好適な光変換用セラミック複合体の蛍光体相の表面形状を容易に凸状に形成することができる光変換用セラミック複合体の製造方法を提供することができる。 As described above, according to the present invention, fluorescence can be emitted efficiently and the peak wavelength of fluorescence can be adjusted to 550 to 560 nm, and the obtained fluorescence is homogeneous and stable, and is heat resistant and durable. The surface shape of the phosphor phase of the ceramic composite for light conversion suitable for constructing a white light emitting device with high power and high efficiency combined with a blue light emitting element can be easily formed into a convex shape. A method for producing a ceramic composite for light conversion can be provided.
本発明に係る光変換用セラミック複合体の製造方法において、アルカリ水溶液は、０．１〜１０ｍｏｌ／Ｌの濃度のＮａＯＨ水夜液であることが好ましく、その濃度が１〜５ｍｏｌ／Ｌであることがさらに好ましい。また、アルカリ水溶液中での加熱の温度は、４０〜２００℃であることが好ましく、１５０〜２００℃であることがさらに好ましい。さらに、その加熱時間は、０．５〜８時間であることが好ましく、１〜３時間であることがさらに好ましい。 In the method for producing a ceramic composite for light conversion according to the present invention, the alkaline aqueous solution is preferably a NaOH aqueous solution having a concentration of 0.1 to 10 mol / L, and the concentration is 1 to 5 mol / L. Is more preferable. Moreover, it is preferable that the temperature of the heating in aqueous alkali solution is 40-200 degreeC, and it is more preferable that it is 150-200 degreeC. Furthermore, the heating time is preferably 0.5 to 8 hours, and more preferably 1 to 3 hours.
本発明に係る光変換用セラミック複合体の製造方法は、蛍光を発する酸化物結晶相とＡｌ２Ｏ３相の段差が０．００１〜５μｍの範囲となるように調整されることが好ましい。このような段差の調整は、上述のアルカリ水溶液の濃度や、加熱温度及び加熱時間などを適宜変更することによって行なうことができる。 The method for producing a ceramic composite for light conversion according to the present invention is preferably adjusted so that the level difference between the oxide crystal phase emitting fluorescence and the Al 2 O 3 phase is in the range of 0.001 to 5 μm. Such a level difference can be adjusted by appropriately changing the concentration of the aqueous alkali solution, the heating temperature, the heating time, and the like.
本発明に係る光変換用セラミック複合体の製造方法は、原料酸化物を融解後、凝固した凝固体を所定の厚さに加工し、その表面を鏡面研磨などの研磨加工した後に、アルカリ水溶液中での加熱処理を行なうことが好ましい。この鏡面研磨加工は、機械的研磨（Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ：ＭＰ）やＣＭＰ（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ）などにより行なわれる。 In the method for producing a ceramic composite for light conversion according to the present invention, after melting the raw material oxide, the solidified solidified body is processed to a predetermined thickness, and the surface is subjected to polishing processing such as mirror polishing, and then in an alkaline aqueous solution. It is preferable to perform the heat treatment at. This mirror polishing is performed by mechanical polishing (MP) or CMP (Chemical Mechanical Polishing).
本発明に係る光変換用セラミック複合体に用いられる凝固体は、原料酸化物を融解後、凝固させることによって作製される。例えば、所定温度に保持したルツボに仕込んだ溶融物を、冷却温度を制御しながら冷却凝結させる簡単な方法で凝固体を得ることができるが、最も好ましいのは一方向凝固法により作製されたものである。一方向凝固を行なうことにより含まれる結晶相が単結晶状態で連続的に成長し、部材内での光の減衰が減少するためである。 The solidified body used in the ceramic composite for light conversion according to the present invention is produced by melting and solidifying the raw material oxide. For example, it is possible to obtain a solidified body by a simple method of cooling and condensing a melt charged in a crucible held at a predetermined temperature while controlling the cooling temperature, but the most preferable one is produced by a unidirectional solidification method. It is. This is because the crystal phase contained by the unidirectional solidification is continuously grown in a single crystal state, and the attenuation of light in the member is reduced.
このような凝固体としては、蛍光を発する酸化物相が含まれていることを除き、本出願人が先に出願した特開平７−１４９５９７号公報、特開平７−１８７８９３号公報、特開平８−８１２５７号公報、特開平８−２５３３８９号公報、特開平８−２５３３９０号公報および特開平９−６７１９４号公報並びにこれらに対応する米国出願（米国特許第５，５６９，５４７号、同第５，４８４，７５２号、同第５，９０２，９６３号）等に開示されたセラミック複合材料と同様のものを用いることができ、これらの出願（特許）に開示された製造方法によって製造できるものを用いることができる。 As such a solidified body, except that an oxide phase that emits fluorescence is contained, JP-A-7-149597, JP-A-7-187893, JP-A-8-8, filed earlier by the present applicant. -81257, JP-A-8-253389, JP-A-8-253390, and JP-A-9-67194, and the corresponding US applications (US Pat. Nos. 5,569,547, 5). 484,752 and 5,902,963) can be used, and those that can be manufactured by the manufacturing method disclosed in these applications (patents) can be used. be able to.
本発明に係る光変換用セラミック複合体の製造方法に用いられる凝固体の蛍光を発する酸化物結晶相として、例えば、（Ｙ、Ｃｅ）３Ａｌ５Ｏ１２相は、４００〜５００ｎｍの紫〜青色励起光で、ピーク波長５３０〜５６０ｎｍの蛍光を発することから、白色発光装置用光変換部材として好適である。このことから、組成成分として少なくともＹ元素、Ａｌ元素とＣｅ元素を含むこと、例えばＣｅを含有するＹＡＧ相が好ましい。加えてＧｄ元素を含むと蛍光を発する結晶相として（Ｙ、Ｇｄ、Ｃｅ）３Ａｌ５Ｏ１２相が生成し、より長波長側のピーク波長５４０〜５８０ｎｍの蛍光を発することができるので、ＣｅやＧｄを含有するＹＡＧ相が好ましい。 As the oxide crystal phase that emits fluorescence of the solidified body used in the method for producing a ceramic composite for light conversion according to the present invention, for example, (Y, Ce) 3 Al 5 O 12 phase is 400 to 500 nm of purple to blue. Since excitation light emits fluorescence with a peak wavelength of 530 to 560 nm, it is suitable as a light conversion member for a white light emitting device. Therefore, it is preferable that the composition component contains at least a Y element, an Al element, and a Ce element, for example, a YAG phase containing Ce. In addition, when a Gd element is included, a (Y, Gd, Ce) 3 Al 5 O 12 phase is generated as a crystal phase that emits fluorescence, and can emit fluorescence having a peak wavelength of 540 to 580 nm on the longer wavelength side. And a YAG phase containing Gd is preferred.
本発明に係る光変換用セラミック複合体の製造方法に用いられる凝固体には、Ａｌ２Ｏ３相及び蛍光を発する酸化物結晶相以外の相が含まれても良く、例えば、ＣｅＡｌ１１Ｏ１８相や、Ｙ２Ｏ３相、ＣｅＯ２相等が含まれても良い。Ａｌ２Ｏ３相及び蛍光を発する酸化物結晶相の含有率は、９０体積％以上であることが好ましい。 The solidified body used in the method for producing a ceramic composite for light conversion according to the present invention may contain a phase other than the Al 2 O 3 phase and the oxide crystal phase that emits fluorescence. For example, CeAl 11 O 18 Phase, Y 2 O 3 phase, CeO 2 phase and the like may be included. The content of the Al 2 O 3 phase and the oxide crystal phase that emits fluorescence is preferably 90% by volume or more.
本発明に係る光変換用セラミック複合体の製造方法によって製造された光変換用セラミック複合体の各相の境界は、アモルファス等の境界層が存在せず、酸化物相同士が直接接している。このため光変換用セラミック複合体内での光の損失が少なく、光透過率も高い。また、蛍光を発する酸化物相（蛍光相）が連続的にかつ三次元的に相互に絡み合った構造をとり、全体として各酸化物相が光変換用セラミック複合体内に均一に分布するため、部分的な偏りのない均質な蛍光を得ることができる。さらに、光変換用セラミック複合体に励起光を入射することにより、蛍光体相からの蛍光および透過光相からの透過光を同時に得ることができる。光出射面を蛍光体相が凸形状となるように表面凹凸形状に形成した場合、蛍光体相の表面積について出射面に占める割合が増加することにより、光出射面に表面凹凸形状が無い場合に比べて強度の強い白色光を得ることができる。 The boundary of each phase of the ceramic composite for light conversion manufactured by the method for manufacturing a ceramic composite for light conversion according to the present invention does not have a boundary layer such as amorphous, and the oxide phases are in direct contact with each other. For this reason, there is little loss of light in the ceramic composite for light conversion, and the light transmittance is also high. In addition, the oxide phase (fluorescent phase) that emits fluorescence has a structure that is continuously and three-dimensionally entangled with each other, and as a whole, each oxide phase is uniformly distributed in the ceramic composite for light conversion. And uniform fluorescence with no bias. Furthermore, by making excitation light incident on the ceramic composite for light conversion, fluorescence from the phosphor phase and transmitted light from the transmitted light phase can be obtained simultaneously. When the light exit surface is formed in a concave-convex shape so that the phosphor phase has a convex shape, the proportion of the phosphor phase surface area in the exit surface increases, so that there is no surface concave-convex shape on the light exit surface. Compared with this, white light having a higher intensity can be obtained.
また、本発明に係る光変換用セラミック複合体の製造方法により製造された光変換用セラミック複合体は、全て無機酸化物セラミックで構成されているため耐熱性・耐久性に優れると共に、光による劣化等もない。このため青色発光素子と組み合わせて高効率の白色発光装置を構成するに好適な光変換用セラミック複合体を提供することができる。 In addition, since the ceramic composite for light conversion produced by the method for producing a ceramic composite for light conversion according to the present invention is composed of an inorganic oxide ceramic, it is excellent in heat resistance and durability and deteriorated by light. Not even. For this reason, the ceramic composite for light conversion suitable for comprising a highly efficient white light-emitting device in combination with a blue light-emitting element can be provided.
本発明に係る光変換用セラミック複合体の製造方法により製造された光変換用セラミック複合体を用いた発光装置の一実施形態の模式的断面図を図１に示す。この光発光装置は、波長４００ｎｍ〜５００ｎｍにピークを有する光を発する発光素子２と、波長５５０〜５６０ｎｍにピークを有する黄色蛍光を発する酸化物結晶相が凸形状である光変換用セラミック複合体１とからなり、発光素子２から発する光を光変換用セラミック複合体１に照射し、光変換用セラミック複合体１を透過した光及び発光素子２から発する光を光変換用セラミック複合体１に含まれる蛍光体相により波長変換された蛍光を利用することを特徴とする。図中、符合３は、フリップチップ電極端子であり、符合４は、アノード電極であり、符合５は、カノード電極である。 FIG. 1 shows a schematic cross-sectional view of an embodiment of a light emitting device using a ceramic composite for light conversion produced by the method for producing a ceramic composite for light conversion according to the present invention. This light-emitting device includes a light-emitting element 2 that emits light having a peak at a wavelength of 400 nm to 500 nm, and a ceramic composite for light conversion 1 in which an oxide crystal phase that emits yellow fluorescence having a peak at a wavelength of 550 to 560 nm has a convex shape. The light conversion ceramic composite 1 is irradiated with the light emitted from the light emitting element 2, and the light transmitted through the light conversion ceramic composite 1 and the light emitted from the light emitting element 2 are included in the light conversion ceramic composite 1. It is characterized by using fluorescence converted in wavelength by a phosphor phase. In the figure, reference numeral 3 is a flip chip electrode terminal, reference numeral 4 is an anode electrode, and reference numeral 5 is a canode electrode.
波長４００ｎｍ〜５００ｎｍにピークを有する光を発する発光素子は、紫色〜青色の光を発光する素子であり、例えば、発光ダイオード素子やレーザー光を発生する素子から発する紫色〜青色光を、その波長に合わせて白色が得られるように色度の調整をおこなった光変換用セラミック複合体に入射する。それによって励起された蛍光体相からの黄色の蛍光と非蛍光体相からの紫色〜青色の透過光が、酸化物相が連続的にかつ三次元的に相互に絡み合い均一に分布する構造により、均質に混合されることで、色むらが小さい白色光を得ることができる。発光素子として発光ダイオード素子を用いた場合の白色発光装置を白色発光ダイオードという。 A light emitting element that emits light having a peak at a wavelength of 400 nm to 500 nm is an element that emits purple to blue light. For example, purple to blue light emitted from a light emitting diode element or an element that generates laser light is used for the wavelength. In addition, the light enters the ceramic composite for light conversion whose chromaticity is adjusted so that white color is obtained. Due to the structure in which the yellow fluorescence from the phosphor phase excited thereby and the violet to blue transmitted light from the non-phosphor phase are uniformly entangled with each other in three dimensions in a continuous manner, By uniformly mixing, white light with small color unevenness can be obtained. A white light emitting device in which a light emitting diode element is used as the light emitting element is referred to as a white light emitting diode.
次に、本発明に係る光変換用セラミック複合体の製造方法の実施例について説明するが、本発明は、これら実施例に限定されるものではない。 Next, examples of the method for producing a ceramic composite for light conversion according to the present invention will be described, but the present invention is not limited to these examples.
参考例
先ず、実施例に用いられる凝固体を製造する。α−Ａｌ２Ｏ３粉末（純度９９．９９％）をＡｌＯ３／２換算で０．８２モル、Ｙ２Ｏ３粉末（純度９９．９％）をＹＯ３／２換算で０．１７５モル、ＣｅＯ２粉末（純度９９．９％）を０．００５モルとなるよう秤量した。これらの粉末をエタノール中、ボールミルによって１６時間湿式混合した後、エバポレーターを用いてエタノールを脱媒して原料粉末を得た。原料粉末は、真空炉中で予備溶解し一方向凝固の原料とした。次に、この原料をそのままモリブデンルツボに仕込み、一方向凝固装置にセットし、１．３３×１０−３Ｐａ（１０−５Ｔｏｒｒ）の圧力下で原料を融解した。次に同一の雰囲気においてルツボを５ｍｍ／時間の速度で下降させ、Ａｌ２Ｏ３（サファイア）相、（Ｙ、Ｃｅ）３Ａｌ５Ｏ１２相、ＣｅＡｌ１１Ｏ１８相の３つの酸化物相からなる凝固体を得た。
Reference Example First, a solidified body used in Examples is manufactured. α-Al 2 O 3 powder (purity 99.99%) is 0.82 mol in terms of AlO 3/2 , Y 2 O 3 powder (purity 99.9%) is 0.175 mol in terms of YO 3/2 , CeO 2 powder (purity 99.9%) was weighed to 0.005 mol. These powders were wet mixed in ethanol by a ball mill for 16 hours, and then ethanol was removed using an evaporator to obtain a raw material powder. The raw material powder was pre-melted in a vacuum furnace and used as a raw material for unidirectional solidification. Next, this raw material was directly charged into a molybdenum crucible and set in a unidirectional solidification apparatus, and the raw material was melted under a pressure of 1.33 × 10 −3 Pa (10 −5 Torr). Next, the crucible is lowered at a speed of 5 mm / hour in the same atmosphere, and from three oxide phases of Al 2 O 3 (sapphire) phase, (Y, Ce) 3 Al 5 O 12 phase, and CeAl 11 O 18 phase. A solidified body was obtained.
実施例１
次に、参考例において製造された凝固体から３ｍｍ×３ｍｍ×０．５ｍｍの板状試料を切り出し、アルカリ水溶液中で加熱して形成することによって、蛍光体相の表面形状が凸状である実施例１に係る光変換用セラミック複合体を得た。板状試料は、あらかじめ鏡面研磨加工により鏡面状態とし、蛍光体相と非蛍光体相の段差が０．０１μｍ以下である。これをアルカリ濃度１０．０ｍｏｌ／ＬのＮａＯＨ水溶液に試料を浸漬し、２００℃／３時間の加熱処理を行ったところ、蛍光体相の表面が凸状に形成されており、蛍光体相と非蛍光体相の段差が５μｍである表面凹凸形状を得ることができた。実施例１に係る光変換用セラミック複合体の組織構造の一例を示す電子顕微鏡写真を図２に示す。
Example 1
Next, a 3 mm × 3 mm × 0.5 mm plate sample is cut out from the solidified body produced in the reference example and heated in an alkaline aqueous solution to form the phosphor phase having a convex surface shape. A ceramic composite for light conversion according to Example 1 was obtained. The plate-like sample is made into a mirror surface state by mirror polishing in advance, and the level difference between the phosphor phase and the non-phosphor phase is 0.01 μm or less. When the sample was immersed in an aqueous NaOH solution with an alkali concentration of 10.0 mol / L and subjected to heat treatment at 200 ° C. for 3 hours, the surface of the phosphor phase was formed in a convex shape, and the phosphor phase was not in contact with the phosphor phase. An uneven surface shape with a phosphor phase step of 5 μm could be obtained. The electron micrograph which shows an example of the structure of the ceramic composite for light conversion which concerns on Example 1 is shown in FIG.
実施例２乃至５
上記鏡面研磨加工によると凝固体表面は、材料物性の違いから非蛍光体相の表面形状が凸状となる。この鏡面研磨加工された表面形状を有する凝固体をアルカリ水溶液中で加熱処理することにより、蛍光体相の表面形状を凸状にすることができる。このときの蛍光体相と非蛍光体相の段差は、アルカリ濃度と加熱時間、加熱温度により決定することができる。そこで、アルカリ濃度が、０．１、０．５、１．０、５．０ｍｏｌ／ＬのＮａＯＨ水溶液に実施例１と同様の板状資料を浸漬し、２００℃／１．５時間の加熱処理を行ったところ、凹凸形状の段差が異なる表面形状を得ることができた（それぞれ順に実施例２乃至５とする。）。このときの処理条件を表１に示し、表面形状を図３乃至６に示す。この酸化物相の表面凹凸形状及び段差は、ＡＦＭ（原子間力顕微鏡）を用いて形状測定を行った。アルカリ濃度が高いほど蛍光体相と非蛍光体相の段差が大きくなっている。
Examples 2 to 5
According to the mirror polishing process, the surface of the solidified body has a convex surface shape due to the difference in material properties. The surface shape of the phosphor phase can be made convex by heat-treating the solidified body having a mirror-polished surface shape in an alkaline aqueous solution. The level difference between the phosphor phase and the non-phosphor phase at this time can be determined by the alkali concentration, the heating time, and the heating temperature. Therefore, a plate-like material similar to that in Example 1 is immersed in an aqueous NaOH solution having an alkali concentration of 0.1, 0.5, 1.0, 5.0 mol / L, and heat treatment at 200 ° C./1.5 hours. As a result, it was possible to obtain surface shapes with different uneven steps (referred to as Examples 2 to 5, respectively). The processing conditions at this time are shown in Table 1, and the surface shapes are shown in FIGS. The surface unevenness shape and level difference of the oxide phase were measured using an AFM (Atomic Force Microscope). The higher the alkali concentration, the greater the level difference between the phosphor phase and the non-phosphor phase.
アルカリ濃度５．０（ｍｏｌ／Ｌ）で作製した実施例５に係る光変換用セラミック複合体と青色(４５０ｎｍ)を発する発光ダイオード素子とを組み合わせ、白色発光装置を構成し、発光スペクトルの測定を行った。この白色発光装置から得られた発光スペクトルを図７に示す。青色（４５０ｎｍ）、光変換用セラミック複合体からの黄色（５５８ｎｍ）をそれぞれピークとする光成分が混合されていることが認められる。ＣＩＥ色座標はｘ=０．３３、ｙ=０．３２で白色に調整されていることがわかる。 Combining the ceramic composite for light conversion according to Example 5 produced at an alkali concentration of 5.0 (mol / L) and a light emitting diode element emitting blue (450 nm) to constitute a white light emitting device, and measuring the emission spectrum went. An emission spectrum obtained from this white light emitting device is shown in FIG. It can be seen that light components having blue (450 nm) and yellow (558 nm) peaks from the ceramic composite for light conversion are mixed. It can be seen that the CIE color coordinates are adjusted to white at x = 0.33 and y = 0.32.
次に、実施例２乃至５に係る光変換用セラミック複合体と青色（４５０ｎｍ）を発する発光ダイオード素子とを組み合わせ、白色発光装置を構成し、それぞれの発光スペクトルの測定をおこなった。その結果を図８に示す。図８に示すように、高濃度で処理した試料、つまり蛍光体相凸形状で段差の大きい試料ほど発光強度の指標となる全光束の値が大きくなった。 Next, the ceramic composite for light conversion according to Examples 2 to 5 and the light emitting diode element emitting blue (450 nm) were combined to constitute a white light emitting device, and the respective emission spectra were measured. The result is shown in FIG. As shown in FIG. 8, the value of the total luminous flux, which is an indicator of the light emission intensity, increased as the sample processed at a high concentration, that is, a sample having a phosphor phase convex shape and a large step.
以上のことから、本発明の製造方法により光変換用セラミック複合体の厚みを保ったまま、表面凹凸形状を制御することで、発光効率の高い、蛍光体相が凸形状である光変換用セラミック複合体を白色発光装置に適用できることがわかる。 From the above, by controlling the surface irregularity shape while maintaining the thickness of the ceramic composite for light conversion by the production method of the present invention, the ceramic for light conversion having a high phosphor efficiency and a phosphor phase having a convex shape It can be seen that the composite can be applied to a white light emitting device.
１ 光変換用セラミック複合体
２ 発光素子（発光ダイオード素子）
３ フリップチップ電極端子
４ アノード電極
５ カソード電極
1 Ceramic composite for light conversion 2 Light emitting element (light emitting diode element)
3 Flip chip electrode terminal 4 Anode electrode 5 Cathode electrode
Claims (4)
前記アルカリ水溶液中での加熱の温度が４０〜２００℃であり、加熱時間が０．５〜８時間であることを特徴とする光変換用セラミックス複合体の製造方法。 By heat-treating a solidified body having a structure in which a plurality of oxide phases composed of at least an Al 2 O 3 phase and a fluorescent oxide crystal phase continuously and three-dimensionally intertwined with each other in an alkaline aqueous solution, A method for producing a ceramic composite for light conversion comprising a step of forming an Al 2 O 3 phase in a concave shape from an oxide crystal phase that emits fluorescence ,
The method for producing a ceramic composite for light conversion, wherein the heating temperature in the alkaline aqueous solution is 40 to 200 ° C and the heating time is 0.5 to 8 hours .
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