JP4676519B2 - 半導体発光装置および半導体発光デバイスの製造方法 - Google Patents
半導体発光装置および半導体発光デバイスの製造方法 Download PDFInfo
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- JP4676519B2 JP4676519B2 JP2008206464A JP2008206464A JP4676519B2 JP 4676519 B2 JP4676519 B2 JP 4676519B2 JP 2008206464 A JP2008206464 A JP 2008206464A JP 2008206464 A JP2008206464 A JP 2008206464A JP 4676519 B2 JP4676519 B2 JP 4676519B2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77342—Silicates
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7735—Germanates
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- C—CHEMISTRY; METALLURGY
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S6/00—Lighting devices intended to be free-standing
- F21S6/002—Table lamps, e.g. for ambient lighting
- F21S6/003—Table lamps, e.g. for ambient lighting for task lighting, e.g. for reading or desk work, e.g. angle poise lamps
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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- H01L33/502—Wavelength conversion materials
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S6/00—Lighting devices intended to be free-standing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
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- F21Y2115/10—Light-emitting diodes [LED]
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- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
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- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
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Description
(Sr1−a1−b1−x Baa1Cab1Eux )2 SiO4
(0≦a1≦0.3、0≦b1≦0.8、0<x<1)
で表される少なくとも1種類の化合物を主体にして構成される珪酸塩蛍光体である。
(Sr1−a3−b3−x Baa3Cab3Eux )2 SiO4
(0≦a3≦1、0≦b3≦1、0<x<1)
で表される化合物を主体にして構成される珪酸塩蛍光体であることが好ましい。このようにすると、上記緑色系蛍光体の組成や結晶構造が、黄色系発光を放つ上記珪酸塩蛍光体と似通ったものになるため、緑色系蛍光体を含む半導体発光デバイスにおける色むらが比較的少ないものとなるだけでなく、半導体発光デバイスの製造工程などにおいても、新たな技術を取り入れる必要がなく、簡略な工程で製造できるものとなる。
(Sr1−a1−b1−x Baa1Cab1Eux )2 SiO4
(0≦a1≦0.3、0≦b1≦0.8、0<x<1)
で表される少なくとも1種類の化合物を主体にして構成される珪酸塩蛍光体である。
(Sr1−a1−b1−x Baa1Cab1Eux )2 SiO4
(0≦a1≦0.3、0≦b1≦0.8、0<x<1)
で表される少なくとも1種類の化合物を主体にして構成される珪酸塩蛍光体を用いることができる。
(Sr1−a1−b1−x Baa1Cab1Eux )2 SiO4
(0≦a1≦0.3、0≦b1≦0.8、0<x<1)
で表される少なくとも1種類の化合物を主体にして構成される珪酸塩蛍光体を用いる方法である。
(Sr1−a1−b1−x Baa1Cab1Eux )2 SiO4
(0≦a1≦0.3、0≦b1≦0.8、0<x<1)
で表される少なくとも1種類の化合物を主体にして構成される珪酸塩蛍光体を用いる方法である。
(Sr1−a1−b1−x Baa1Cab1Eux )2 SiO4
(0≦a1≦0.3、0≦b1≦0.8、0<x<1)
で表される少なくとも1種類の化合物を主体にして構成される珪酸塩蛍光体を用いる方法である。
以下、本発明の半導体発光デバイスおよび半導体発光デバイスの色むら抑制方法に関する第1の実施形態について、図面を参照しながら説明する。
(Sr1−a1−b1−x Baa1Cab1Eux )2 SiO4 (1)
で表される化合物を主体にしてなる珪酸塩蛍光体である。ただし、化学式(1)において、a1、b1、xは、各々、0≦a1≦0.3、0≦b1≦0.8、0<x<1の範囲にある数値である。
(Sr1−a1−b2−x Baa1Cab2Eux )2 SiO4 (2)
で表される化合物を主体にしてなる珪酸塩蛍光体に限定される。ただし、化学式(2)において、a1,b2,xは、それぞれ、0≦a1≦0.3,0≦b2≦0.6,0<x<1を満足する数値である。a1,b2,xは、それぞれ、0<a1≦0.2,0<b2≦0.4,0.005<x<0.1を満足する数値であることが好ましい。a1,b2,xは、それぞれ、0<a1≦0.15,0<b2≦0.3,0.01<x<0.05を満足する数値であることがさらに好ましい。a1,b2,xは、それぞれ、0.01≦a1≦0.1,0.001≦b2≦0.05,0.01<x≦0.02を満足する数値であることがもっとも好ましい。
(Sr1−a1−b1−x Baa1Cab1Eux )2 Si1−z Gez O4 (3)
で表される化合物を主体にしてなる珪酸塩蛍光体である半導体発光デバイスであってもよい。ただし、a1,b1,x,zは、それぞれ、0≦a1≦0.3,0≦b1≦0.8,0<x<1,0≦z<1(好ましくは0≦z≦0.2)を満足する数値である。Siの一部をGeで置換すると、発光強度が大きく下がる傾向が認められるものの、少なくとも、Ge置換量が20原子%以上では、主発光ピークが短波長側にシフトし、緑味がかった発光を得ることができるようになる。但し、発光強度保持の観点から、Ge置換量zは少ないほどよく、zの数値は0.2を越えない範囲に留めることが好ましい。
(Sr1−a3−b3−x Baa3Cab3Eux )2 SiO4 (4)
で表される化合物を主体にしてなる珪酸塩蛍光体がある。
本発明の半導体発光デバイスの具体的な製造方法の例については、後に詳しく説明するが、まず、蛍光体粒子が分散した構造を有する蛍光体層3の製造方法の概略や、好ましい実施形態について説明する。
u={2×r2 ×(ρ2 −ρ1 )×g}/(9×η) (5)
で表される。但し、式(5)において、gは重力加速度(単位:m・s−2)である。
1.真比重の小さな、軽い蛍光体粒子を用いる。
2.真比重の大きな樹脂を用いる。
3.中心粒径の小さな蛍光体粒子を用いる。
4.粘度の高い樹脂を用いる。
但し、上記の方法1.〜4には、それぞれ、製造工程からみた制約、コストからみた制約、蛍光体層の発光性能からみた制約など、種々の制約がある。
次に、本発明の発光装置の実施形態について、図面を参照しながら説明する。 なお、本明細書では、半導体発光デバイスを用いた各種表示装置(例えばLED情報表示端末、LED交通信号灯、自動車のLEDストップランプやLED方向指示灯など)や各種照明装置(LED屋内外照明灯、車内LED灯、LED非常灯、LED面発光源など)を広く発光装置と定義している。
珪酸塩蛍光体の製造方法
本発明の半導体発光デバイスに用いる珪酸塩蛍光体の製造方法は、以下に説明する製造方法に限定されるものではないが、珪酸塩蛍光体は、例えば以下の方法によって製造することができる。
第1の処理:蛍光体原料の秤量・調合
第2の処理:蛍光体原料の混合
第3の処理:混合蛍光体原料の焼成
第4の処理:焼成物の後処理(解砕、分級、洗浄、乾燥など)
の各処理を経て得ることができる。以下、各処理の内容についてさらに詳しく説明する。
まず、蛍光体原料を秤量・調合する。蛍光体原料としては、各種の、アルカリ土類金属化合物、珪素化合物、ユーロピウム化合物などの各種粉末を用いることができる。なお、上記アルカリ土類金属化合物の一例は、アルカリ土類金属の、炭酸塩(炭酸ストロンチウム、炭酸バリウム、炭酸カルシウム)、硝酸塩(硝酸ストロンチウム、硝酸バリウム、硝酸カルシウム)、水酸化物(水酸化ストロンチウム、水酸化バリウム、水酸化カルシウム)、酸化物(酸化ストロンチウム、酸化バリウム、酸化カルシウム)、硫酸塩(硫酸ストロンチウム、硫酸バリウム、硫酸カルシウム)、蓚酸塩(蓚酸ストロンチウム、蓚酸バリウム、蓚酸カルシウム)などである。また、ハロゲン化物(塩化ストロンチウム、塩化バリウム、塩化カルシウム、弗化ストロンチウム、弗化バリウム、弗化カルシウム、臭化ストロンチウム、臭化バリウム、臭化カルシウムなど)も使用可能である。また、上記珪素化合物の一例は、二酸化珪素や一酸化珪素などの酸化物であるが、窒化珪素などの非酸化物も条件によっては使用し得る。なお、蛍光体原料同士の反応性を高める目的には、“アエロジル”の商品名で知られるデグサ社(独)製の、超微粉末シリカ等の超微粉末の二酸化珪素を用いることが好ましい。また、上記ユーロピウム化合物の一例は、酸化ユーロピウム、弗化ユーロピウム、塩化ユーロピウムなどである。なお、先に触れたゲルマニウムを含む蛍光体に関するゲルマニウム原料としては酸化ゲルマニウムなどのゲルマニウム化合物を用いることができる。
次に、上記第1の処理において秤量・調合した、所定のモル割合または重量割合の蛍光体原料を混合し、混合蛍光体原料を得る。蛍光体原料の混合には様々な手法を用いることができる。一例を上げると、乳鉢による混合、ボールミルによる混合、V字型混合機による混合、クロスロータリーミキサーによる混合、ジェットミルによる混合、攪拌機による混合などがあり、これらの混合方法は周知の技術である。また、混合方式としては、溶媒を全く用いず蛍光体原料だけを混合する乾式混合、あるいは、水や有機溶媒などの溶媒中に蛍光体原料を投入し、上記溶媒中でこれを分散させて混合する湿式混合などを用いることができる。上記有機溶媒としては、エタノール、メタノールなどを使用することができる。なお、上記湿式混合を実施した場合、一般には、蛍光体原料と溶媒からなる懸濁液から、例えばブフナー濾過器などを用いて混合蛍光体原料を濾過し、その後、乾燥機などを用いて、濾過後の混合蛍光体原料を、60〜200℃程度の温度で数時間〜数十時間乾燥して混合蛍光体原料を得る。
次に、以下の手順により、混合蛍光体原料を焼成する。焼成には電気炉やガス炉などの加熱装置を用いる。加熱装置の種類は特に限定されるものではなく、混合蛍光体原料を所望温度の所望雰囲気中で所望時間、焼成し得るものであれば使用し得る。加熱装置として電気炉を用いる場合の一例を上げると、管状雰囲気炉、雰囲気制御箱形炉、ベルトコンベア炉、ローラーハース炉、トレイプッシャ連続炉などを用いることができる。また、一般には、混合蛍光体原料を、るつぼやボートなどの焼成容器に入れ、場合によっては焼成容器に蓋をし、焼成容器と共に加熱するが、焼成容器を用いずに混合蛍光体原料だけを焼成してもよい。なお、焼成容器としては、材質が、白金、石英、アルミナ、ジルコニア、マグネシア、シリコンカーバイト、窒化珪素、磁器、カーボンなどからなるものが使用可能であり、場合によってはこれらを複合して用いる。
最後に、上記焼成によって得られた焼成物(蛍光体)に後処理を施して珪酸塩蛍光体を得る。後処理は、主に、解砕工程(ほぐして粉末状にする工程をいう)、分級工程、洗浄工程、乾燥工程を含んでいる。
以下、珪酸塩蛍光体の製造方法の具体例を、フラックスの効果を交え、実験データを用いて説明する。
次に、本発明の半導体発光デバイスの製造方法の具体例について図面を参照しながら説明する。第1の具体例として、トランスファー工法による白色発光の半導体発光デバイスの製造方法及び製造装置について説明する。図12(a)〜(d)は、第1の具体例における半導体発光デバイスの製造工程を示す断面図である。
第2の具体例として、砲弾型の白色発光の半導体発光デバイスの製造方法及び製造装置について説明する。図14(a)〜(c)は、第2の具体例における半導体発光デバイスの製造工程のうち前半部分を示す断面図である。図15(a),(b)は、第2の具体例における半導体発光デバイスの製造工程のうち後半部分を示す断面図である。
設ける工程(又は手段)とを有する製造方法(又は製造装置)である。更に詳細には、上記青色発光ダイオードを設置部に設ける工程(又は手段)と、上記青色発光ダイオードから発する光が通過するように蛍光体を有する第1の樹脂を設ける工程(又は手段)と、上記青色発光ダイオードから発する光が通過するように蛍光体を有さない第2の樹脂を設ける工程(又は手段)とを有する製造方法(又は製造装置)である。ここで、第1の樹脂には熱により硬化しない樹脂を、第2の樹脂には熱により硬化する樹脂を選択することが望ましい。
第3の具体例として、サイドビュー型の白色発光の半導体発光デバイスの製造方法及び製造装置について説明する。図16(a)〜(c)は、第3の具体例における半導体発光デバイスの製造工程のうち前半部分を示す断面図である。
第1の具体例では、樹脂の硬化中に振動を加える方法及び装置について説明する。図17(a),(b)は、半導体発光デバイスの製造工程で超音波振動を加える2つの方法をそれぞれ示す平面図である。すなわち、図17(a)に示すように、超音波振動層130(KAIJODENNKI社製)中に型107を設置して、樹脂106を硬化させている間、型107全体に振動を加えることにより樹脂106中に蛍光体粒子108を均一に分散させることができる。また、図17(b)に示すように、振動付加手段131(超音波ホーンなど)により型107に直接振動を加えてもよい。例えば樹脂106と蛍光体粒子108との比重差が大きいために、図21(b)に示すごとく、蛍光体層109中で樹脂106の底部に蛍光体粒子108が沈降していたとしても、図17(a),(b)に示すように、型107を振動させることにより、蛍光体粒子108及び樹脂106が振動して図21(d)に示すように、樹脂106中に蛍光体粒子108が均一に分散するようになる。
第2の具体例では、樹脂の硬化中に型を上下反転させる方法及び装置について説明する。図19(a),(b)は、半導体発光デバイスの製造工程中において型を上下反転させる方法を示す平面図であって、型を上下反転させる際の状態を示している。すなわち、図19(a)に示すように、回転軸141と回転軸141を回転させる駆動モータ(図示せず)とを有する反転手段を用い、型107に回転軸141を取り付けて、樹脂106を硬化させている間、型107全体を図19(a)に示す正常位置と図19(b)に示す反転位置との間で繰り返し上下反転させることにより、樹脂106中に蛍光体粒子108を均一に分散させることができる。例えば樹脂106と蛍光体粒子108との比重差が大きいために、図21(b)に示すごとく、蛍光体層109中で樹脂106の底部に蛍光体粒子108が沈降していたとしても、図19(a),(b)に示すように、型107を上下反転させることにより、蛍光体粒子106及び樹脂106が移動して図21(d)に示すように、樹脂106中に蛍光体粒子108が均一に分散するようになる。
図20(a),(b)は、半導体発光デバイスの第2の具体例に係る製造工程中の図15(a)に示す工程で、型を上下反転させる際の状態を示している。すなわち、図20(a)に示すように、回転軸141と回転軸141を回転させる駆動モータ(図示せず)とを有する反転手段を用い、型117に回転軸141を取り付けて、樹脂115を硬化させている間、型117全体を図20(a)に示す正常位置と図20(b)に示す反転位置との間で繰り返し上下反転させることにより、樹脂115中に蛍光体粒子116を均一に分散させることができる。例えば樹脂115と蛍光体粒子116との比重差が大きいために、図21(a)に示すごとく、蛍光体層119中で樹脂115の底部に蛍光体粒子116が沈降していたとしても、図18(a),(b)に示すように、型117を上下反転させることにより、蛍光体粒子116及び樹脂115が移動して図21(c)に示すように、樹脂115中に蛍光体粒子116が均一に分散するようになる。
同様に、半導体発光デバイスの製造方法の第3の具体例(サイドビュー型半導体発光デバイスの製造方法)の図16(c)に示す工程で、反転手段を使用することができる。その場合にも、例えば樹脂125と蛍光体粒子126との比重差が大きいために、蛍光体層129中で樹脂125の底部に蛍光体粒子126が沈降していたとしても、蛍光体粒子126及び樹脂125を上下反転させることにより、樹脂125中に蛍光体粒子126が均一に分散するようになる。
第3の具体例では、樹脂を凹部や型に充填した後硬化させる処理を複数回に分けて行なう方法について説明する。
第4の具体例では、蛍光体層を形成する際に高粘度の樹脂を使用する方法について説明する。
第5の具体例では、蛍光体層を形成する際に硬化のために加熱を必要としない樹脂を使用する方法について説明する。
図22は、半導体発光デバイスのキャビティ内に珪酸塩蛍光体を含む蛍光体ペーストを流し込む際に用いられる蛍光体ペースト吐出装置の好ましい具体例を示す断面図である。図22において、200は原料タンク、201はヘッド、CAは半導体発光デバイスのキャビティ、204はポンプ、205は分散ノズル、206は蛍光体ペースト、207は蛍光体ペースト206中に含まれる蛍光体粒子、208は蛍光体ペースト206中の樹脂である。ヘッド201は、例えば、原料タンク200から移動してきた蛍光体ペースト206を貯えるタンク室202と、蛍光体ペースト206をキャビティCAに噴出するノズル203と、タンク室202内に配置された金属球Sとを備えている。原料タンク200に貯えられた蛍光体ペーストは、循環ポンプ204の加圧によってタンク室202に供給されて、ノズル203からキャビティCAに連続的に噴出される。
YAG系蛍光体が沈積する原因として、蛍光体と母材の比重差が大きいことに起因して生じるものとしてきたが、その他の原因としてYAG系蛍光体が正に帯電していることが考えられる。つまり、母材である樹脂が同じ正に帯電していると、一般に両者は互いに反発し合うのでYAG系蛍光体が沈積する。
以下、本発明の半導体発光デバイスにかかる実施例を記述する。
まず、黄色系光を放つ組成の珪酸塩蛍光体粒子を作製した。蛍光体原料として、炭酸バリウム(BaCO3 )、炭酸ストロンチウム(SrCO3 )、酸化ユーロピウム(Eu2 O3 )、二酸化珪素(SiO2 )の各粉末を用い、フラックスとして塩化カルシウム(CaCl2 )を用いた。蛍光体原料の純度は全て99.9%以上で、蛍光体原料の中心粒径は10nm以上で5μm以下の範囲内のものを用いた。なお、各原料については、吸着ガスによる秤量の誤差をなくすために、あらかじめ約900℃の大気中での加熱前後における重量変化を調べ、これを把握した。
以下、上記手順によって製造した珪酸塩蛍光体の特性を詳細に説明する。図53は、参考のために珪酸塩蛍光体の代表的な組成と特性とを表にして示す図である。図53中に示す組成は、基本的にはICP発光分光分析法によって定量評価した組成、または、上述の定量分析の結果から推定し得る組成である。
550nm未満の緑色領域にあるのに対して、斜方晶系の結晶構造を有する、少なくともEu濃度(x)が0.001≦x≦0.3の範囲内の(Sr0.95−xBa0.05Eux )2 SiO4 蛍光体と、x=0.3の(Sr1−x Eux )2 SiO4 蛍光体との主発光ピーク波長は、550nm以上で600nm以下の黄色領域にある。
黄色の波長は550nm以上で600nm以下の範囲であるので、図32よりこの化合物から黄色の波長を得るための条件は、Ba置換量が組成比0.0〜0.3の範囲であることがわかる。なお、Ba置換量が組成比で0.3の化合物の実験結果は、図32に示されていないが、組成比bが0.24の化合物の実験結果と、組成比bが0.43の化合物の実験結果から、組成比bが0.3の化合物においても黄色の波長が得られることは容易に推測できる。
図33から、この化合物から黄色の波長を得るための最適条件は、Ca置換量が組成比で0.0〜0.6であることがわかる。なお、Caの組成比が0.7の化合物の実験結果は示されてないが、Ca置換量が組成比で0.57の化合物の実験結果と、置換量が組成比で0.76の化合物の実験結果から、Ca置換量が組成比で0.7の化合物においても黄色の波長が得られるものと推測できる。また、実験結果では、Ca置換量が組成比で0.8の化合物の発光ピーク波長は黄色の波長から外れていると推測されるが、実験誤差も含まれることを考慮すると、Ca置換量が組成比で0.0〜0.6の範囲の化合物に加えて、組成比0.7,0.8も含めた組成比0.0〜0.8が黄色の波長を得るための化合物のCa組成比の条件と考えることが出来る。
図34,図38から、Srを全く含まない化合物は、黄色を発光しないことが解る。
図42から、結晶構造が単斜晶のものはEu置換量に関わらず黄色を得られず、結晶構造が斜方晶のものはEu置換量に関わらず黄色の波長が得られることが解る。
図43から、結晶構造が斜方晶のものは、Eu置換量に関わらず黄色の波長が得られるが、発光ピーク高さを考慮するとEu置換量は10%以下が望ましいことがわかる。
まず、YAG系蛍光体を用いた半導体発光デバイスと、珪酸塩蛍光体を用いた半導体発光素子との輝度特性の違いについて説明する。
次に、半導体発光デバイスの珪酸塩蛍光体に超微粉末シリカ等の超微粉末の二酸化珪素(商品名“アエロジル”デグサ社(独)製)をチキソトロピー付与剤(ここでは、チキソトロピー指数を高くする機能を有するもの)として挿入した場合の効果について説明する。
本実施形態においては、薄い蛍光体層を形成するため方法について説明する。本実施形態は、化学式(Sr1−a1−b1−x Baa1Cab1Eux )2 SiO4 (a1,b1,xは、各々、0≦a1≦0.3、0≦b1≦0.8(より理想的には0≦b1≦0.6)、0<x<1の範囲にある数値)で表され、550nm以上で600nm以下の波長領域に発光ピークを有する光を放つ黄色系蛍光体を図1,図2,図3に示す半導体発光デバイスのように、発光ダイオード近傍に密集させることにより、蛍光体層を薄くし、光が透過する厚みを少なくすることで光の減衰を低減するものである。例えば、蛍光体層の青色発光素子の光取り出し面上に位置する部分の実質厚みが50μm以上で1000μm以下の範囲にある半導体発光デバイスを形成するための方法である。
図50(a)〜(c)は、本実施形態の製造方法の第1の例における製造工程を示す断面図である。
図51(a)〜(c)は、本実施形態の製造方法の第2の例における製造工程を示す断面図である。
図52(a)〜(d)は、本実施形態の製造方法の第3の例における製造工程を示す断面図である。
YAG系蛍光体が沈積する理由として、蛍光体と母材の比重差に起因して生じるものとしてきたが、その他の理由としてYAG系蛍光体が正に帯電していることが考えられる。つまり、母材である樹脂が同じ正に帯電していると、一般に両者は互いに反発し合うのでYAG系蛍光体が沈積する。
上記各実施形態においては、半導体発光デバイスにおいて、青色発光素子である青色LEDが単数の場合について説明したが、本発明の半導体発光デバイスは、かかる実施形態に限定されるものではない。
Claims (8)
- 蛍光体層と発光素子とを組み合わせた半導体発光装置において、
前記蛍光体層は、エポキシ樹脂、アクリル樹脂、ポリイミド樹脂、ユリア樹脂又はシリコーン樹脂である透光性樹脂と、蛍光体粒子と、超微粒子とからなり、
前記蛍光体粒子が前記蛍光体層中に分散され、前記超微粒子の一次粒子の平均径が3nm以上50nm以下の範囲内にあり、
前記蛍光体粒子は前記発光素子が放つ光を吸収して蛍光を放ち、前記発光素子が放つ光が前記蛍光体層を通過することによって前記発光素子が放つ光と前記蛍光とが加色された光が発光面から放たれるように前記蛍光体層が前記発光素子の少なくとも主光取り出し面から出光される光が通過する位置に設けられており、
前記発光素子を複数備え、
前記蛍光体層は、単一で各前記発光素子の主光取り出し面を覆い、
前記蛍光体層の上面は平担であり、
前記発光面は、前記発光素子の主光取り出し面に対して平行であり、
前記発光素子の主光取り出し面上に位置する前記蛍光体層の実質厚みは50μm以上1000μm以下であり、
前記蛍光体粒子は、真比重が前記透光性樹脂よりも大きい材料からなり、且つ中心粒径が0.5μm以上30μm以下の範囲にある
ことを特徴とする半導体発光装置。 - 複数の前記発光素子は、主面上にアノードとカソードとを有する複数の発光ダイオードであって、前記主光取り出し面は、前記主面を下にして上方に向いている請求項1に記載の半導体発光装置。
- 前記複数の発光ダイオードが、一つの基板上にフリップチップ接続法によって固定されている請求項2に記載の半導体発光装置。
- 発光素子と、該発光素子が放つ光を吸収して蛍光を放つ蛍光体粒子を含む蛍光体層とを備えた半導体発光デバイスの製造方法であって、
エポキシ樹脂、アクリル樹脂、ポリイミド樹脂、ユリア樹脂又はシリコーン樹脂である透光性を有する樹脂と前記蛍光体粒子とを有する蛍光体ペースト中に、さらに一次粒子の平均径が3nm以上50nm以下の範囲内にある前記超微粒子を含める工程と、
前記発光素子の少なくとも主光取り出し面から出光される光が通過する位置に前記蛍光体層が設けられるように前記蛍光体ペーストを前記発光素子に塗布し、硬化させる工程とを備え、
前記蛍光体層は、前記蛍光体粒子が分散した構造を有しており、
前記発光素子を複数備え、
前記蛍光体層は、単一で各前記発光素子の主光取り出し面を覆い、
前記蛍光体層の上面は平担であり、
前記発光面は、前記発光素子の主光取り出し面に対して平行であり、
前記発光素子の主光取り出し面上に位置する前記蛍光体層の実質厚みは50μm以上1000μm以下であり、
前記蛍光体粒子は、真比重が前記透光性樹脂よりも大きい材料からなり、且つ中心粒径が0.5μm以上30μm以下の範囲にある
ことを特徴とする半導体発光デバイスの製造方法。 - 前記蛍光体ペーストを前記発光素子の実装面を除く周囲に塗布する方法として、フォトリソグラフィー法、スクリーン印刷法、転写法のいずれかが用いられていることを特徴とする請求項4記載の半導体発光デバイスの製造方法。
- 前記蛍光体ペーストを前記発光素子に塗布する方法として、前記蛍光体ペーストを型へ流し込むことが用いられていることを特徴とする請求項4記載の半導体発光デバイスの製造方法。
- 前記蛍光体ペーストを前記発光素子の実装面を除く周囲に塗布する方法として、スクリーン印刷法が用いられており、さらに、前記発光素子を基板上にフリップチップ状態で搭載する工程を備えることを特徴とする請求項5記載の半導体発光デバイスの製造方法。
- 請求項4から7のいずれか1項に記載の半導体発光デバイスの製造方法において、
透光性を有する樹脂がシリコーン樹脂であることを特徴とする半導体発光デバイスの製造方法。
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Also Published As
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US20040104391A1 (en) | 2004-06-03 |
WO2003021691A1 (en) | 2003-03-13 |
US7629620B2 (en) | 2009-12-08 |
JP5308318B2 (ja) | 2013-10-09 |
CN101335322A (zh) | 2008-12-31 |
JP2009021613A (ja) | 2009-01-29 |
TW595012B (en) | 2004-06-21 |
US7023019B2 (en) | 2006-04-04 |
US7772769B2 (en) | 2010-08-10 |
US20080135862A1 (en) | 2008-06-12 |
JP2010050490A (ja) | 2010-03-04 |
JP3749243B2 (ja) | 2006-02-22 |
EP1367655A1 (en) | 2003-12-03 |
EP2017901A1 (en) | 2009-01-21 |
US20060124942A1 (en) | 2006-06-15 |
CN1633718A (zh) | 2005-06-29 |
CN100423296C (zh) | 2008-10-01 |
US7592639B2 (en) | 2009-09-22 |
US7422504B2 (en) | 2008-09-09 |
JP2012099863A (ja) | 2012-05-24 |
KR20040029313A (ko) | 2004-04-06 |
US20070046169A1 (en) | 2007-03-01 |
CN101335322B (zh) | 2010-12-08 |
EP1367655A4 (en) | 2009-05-06 |
US20050227569A1 (en) | 2005-10-13 |
USRE47453E1 (en) | 2019-06-25 |
JPWO2003021691A1 (ja) | 2004-12-24 |
KR100923804B1 (ko) | 2009-10-27 |
KR20080087049A (ko) | 2008-09-29 |
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