`
`U800i531960B2
`
`(12) United States Patent
`Shimizu et al.
`
`(10) Patent N0.:
`(45) Date of Patent:
`
`US 7,531,960 32
`May 12, 2009
`
`(54}
`
`1,[(;][']' EMff'rlxu DEVICE WITH BLUE
`LlGl-IT LEDANI) PHOSPHOR COMPONENTS
`
`3 135-198- 5.12:
`(58} Field of Classification Search .........
`428116902 257’ 103
`See application tile liar complete search history.
`
`(75)
`
`Inventors: Yoshinori Shimizu. Tokushima (JP):
`Kensho Sakanu. Anon (.11’):Yasuoobu
`.Voguchi. 'lokushimzt (.11’); 'l‘oshio
`Morigm'hi- Allan (JP)
`
`(55)
`
`References (fined
`11.8. l’.’\'l‘|-'.N'1'])(}('l.lM|EN‘I'S
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`3.5 ItL'r‘ftE A
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`5-19-10 mum
`
`(73} Assignee: Niehia Corporation. Anon-511i (JP)
`
`(
`
`’9' ) Notice:
`
`Subject to any disclaimer. the term ol‘tltis
`patent
`is extended or adjusted under 35
`[1.5.0. 15401) by 233 days.
`
`(letillllt‘dl
`l-‘(JRl-LKEN l’.’\'l‘l-'.N‘l' DOCUMIEN'I'S
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`3804393 AI
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`(21)
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`22
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`M . S, 2007
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`Prior Publication Data
`US 2(X)?!015‘)060A1
`Jul. 12. 2007
`
`_
`.
`‘
`Related U-S- Applleatlon Data
`
`(62) Division ol‘atpplicotioii No. “0609.402. tiled on .1111. 1.
`2003. now Pat. No. "1.362.048. which is a division ol‘
`application No. 091453.024. 1‘1ch on Dec. 10. 1999.
`now Pat. No. 0.014.l 71)“ which is El lelSlUtt ol‘appli-
`cationNo.091300.315.iiledon.-'\pr. 28. 1999.11ow1’at.
`No. 6.069.440. which is It division ol‘opplicotion No.
`081’901725. tiled 011111129. 1997. now l’ot. No. 5.998.
`925.
`
`(30)
`Jul. 2‘). 1996
`Sep. 17. 1996
`Sep. 18. 1996
`Dec. 27' 1996
`Mair. 3 |
`_ 1997
`
`1
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`.
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`.
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`11 Drug" Applicant)" Priority Data
`(.ll’)
`1’ [JR-1985.85
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`(51)
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`{52)
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`int. (j1_
`”053 33/00
`[F.S. (Tl.
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`(2006.01)
`3131512: 257:”103'. 428K190
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`_
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`((.'ont1nued)
`()‘I'I lliR pun] .lC‘A'lilONS
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`.11.. Development and applications of highbright while
`limnko cl
`1.111) l:LItips.No\-’. 2‘). 1996. The 264th i’roeeetlingsol‘lhe Institute 01‘
`Phosphor Society. pp. 4-16 oi‘the English translation.
`
`(Continued)
`_
`Prime Examiner'- -JOSEPh L Williams
`(7-4) .‘itmrttqt'. Agent. or Firm Birch. Stewart. Kolosch &
`Birch. LU,
`
`(57)
`
`"“5 ' RM- '
`
`A linht etnittin 1 device includes 2: 1i tht etnittin 1 com onent:
`and: phospltorkcapable oi‘absorbing: part ol‘ligkht emiited by
`the light emitting component and emitting. light ol‘ :1 wove-
`length different from that oi‘the absorbed light.A straight line
`connecting a point ol‘chromotieitycorresponding too peokol‘
`the spectrum generated by the light emitting component and
`at point ol‘eiironioticity corresponding to 11 peak ol‘ the spec-
`trum generated by the phosphor is disposed along with the
`black body radiation locus in the chromatieity diagram.
`
`23 (.‘lailns, 19 Drawing Sheets
`
`£09
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`203
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`202
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`201
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`TCL 1036, Page 1
`LOWES 1036, Page 1
`
`LOWES 1036, Page 1
`
`
`
`US 7,531,960 B2
`
`Page 2
`
`US. PATENT DOCUMENTS
`.
`3519?}! Pinnow 21.11.
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`11-1981 Bongers et a].
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`2:198? do Hair :31 a1.
`4.644.223 A
`12.5198?
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`4.? 16.33? A
`2:"1988 van Kemenade et a].
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`2.51900 (‘hinone et a1.
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`431991 Maisuoka Cl a1.
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`332003 Duggal el :11.
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`‘
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`
`TCL 1036, Page 3
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`Sheet 1 0119
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`US 7,531,960 32
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`Sheet 2 of 19
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`US 7,531,960 32
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`naay 12,2009
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`TCL 1036, Page 8
`LOWES 1036, Page 8
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`May 12, 2009
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`TCL 1036, Page 9
`LOWES 1036, Page 9
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`LOWES 1036, Page 9
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`
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`U.S. Patent
`
`May 12, 2009
`
`Sheet 7 of 19
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`US 7,531,960 32
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`Fig. 10
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`TCL 1036, Page 10
`LOWES 1036, Page 10
`
`Image data memory
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`LOWES 1036, Page 10
`
`
`
`US. Patent
`
`May 12, 2009
`
`Sheet 8 of l9
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`US 7,531,960 32
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`TCL 1036, Page 11
`LOWES 1036, Page 11
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`LOWES 1036, Page 11
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`US. Patent
`
`May 12, 2009
`
`Sheet 9 of 19
`
`US 7,531,960 32
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`TCL 1036, Page 12
`LOWES 1036, Page 12
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`LOWES 1036, Page 12
`
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`
`US. Patent
`
`May 12, 2009
`
`Sheet 10 of 19
`
`Us 7,531,960 32
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`TCL 1036, Page 13
`LOWES 1036, Page 13
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`LOWES 1036, Page 13
`
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`
`US. Patent
`
`May 12, 2009
`
`Sheet 11 of 19
`
`US 7,531,960 32
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`TCL 1036, Page 14
`LOWES 1036, Page 14
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`LOWES 1036, Page 14
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`US. Patent
`
`May 12, 2009
`
`Sheet ]2 of 19
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`US 7,531,960 132
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`LOWES 1036, Page 15
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`LOWES 1036, Page 16
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`US. Patent
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`May 12, 2009
`
`Sheet 14 of 19
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`US 7,531,960 32
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`
`TCL 1036, Page 17
`LOWES 1036, Page 17
`
`LOWES 1036, Page 17
`
`
`
`US. Patent
`
`May 12,2009
`
`Sheet 15 of 19
`
`Us 7,531,960 32
`
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`380
`
`430
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`480
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`
`TCL 1036, Page 18
`LOWES 1036, Page 18
`
`LOWES 1036, Page 18
`
`
`
`US. Patent
`
`May 12, 2009
`
`Sheet 16 of 19
`
`US 7,531,960 32
`
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`
`TCL 1036, Page 19
`LOWES 1036, Page 19
`
`LOWES 1036, Page 19
`
`
`
`U.S. Patent
`
`May 12‘ 2009
`
`Sheet 17 of 19
`
`US 7,531,960 32
`
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`Wavelength (nm)
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`480
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`530
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`Fig 210
`
`Wavelength (nm)
`
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`Wavelength (nm)
`
`TCL 1036, Page 20
`LOWES 1036, Page 20
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`LOWES 1036, Page 20
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`
`
`U.S. Patent
`
`May 12, 2009
`
`Sheet 18 of 19
`
`US 7,531,960 132
`
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`430
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`Wavelength (nm)
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`480
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`630
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`
`TCL 1036, Page 21
`LOWES 1036, Page 21
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`LOWES 1036, Page 21
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`
`
`U.S. Patent
`
`May 12. 2009
`
`Sheet 19 of 19
`
`US 7,531,960 32
`
`
`
`Wavelength(nm)
`
`550600650700750
`
`450500
`
`400
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`350
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`
`TCL 1036, Page 22
`LOWES 1036, Page 22
`
`Fig.23
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`LOWES 1036, Page 22
`
`
`
`US 7,531,960 B2
`
`1
`LIGHT EMITTING DEVICE WITH BLUE
`LIGII’I‘ LEDANI) PIIOSPIIOR (IOMPUNIL ”IS
`
`'lhis application is a 37 (Kl-IR. § l.53(b) divisional ol‘US.
`application No. l()i’6()9.402. tiled .1111. I. 2003. now tJ.S. Pat.
`No. ?.362.048 which is a divisional ofU.S. application Ser.
`No. GEN-458.024. filed Dec. 10. 1999. now US. Pat. No. 6.614.
`179 which is a divisional ol‘U.S. application Ser. No. 09800.
`315. filed on Apr. 28. [999. now US. Pat. No. 6.069.440.
`which is a divisional ol'U .8. application Ser. No. ORNDZJZS.
`tiled on lid. 29. 199?. now US. Pat. No. 5.998.925. the entire
`contents of which are hereby incorporated by reference.
`
`:3
`
`1t|
`
`BACKGROUND OF T HE INVENTION
`
`1. Field of the Invention
`
`The present invention relates to a light emitting diode ttsed
`in LED display. back light source. traflic signal. Hallway
`signal. illuminating switch. indicator. etc. More particularly.
`it relates to a light emitting device (I .l ED) comprising a phos-
`phor. which converts the wavelength of light entitled by a
`light etnitting component and emits light. and a display
`device using the light emitting device.
`2. Description of Related Art
`A light emitting diode is compact and etnits light ol'clear -
`color with high eflicicncy. It is also free from such a trouble as
`bum-out and has good initial drive characteristic. high vibra-
`tion resistance and durability to endure repetitive ONIOFF
`operations. because it is a semiconductor element. Thus it has
`been tlsed widely in such applications as various indicators
`and various light sources. Recently light emitting diodes for
`R013 (red. green and blue) colors having ultra-high lumi-
`nance and high elliciency have been developed. and large
`screen [.lil) displays using these light elnitting diodes have
`a) 'Jl
`been put into use. The LED display can be operated with less _
`power and has such good characteristics as light weight and
`long life. and is therefore expected to be more widely used in
`the future.
`
`.ttt
`
`4o
`
`Recently. various attempts have been made to make white
`light sources by using light etnitting diodes. Because the light
`emitting diode has a favorable emission spectrum to generate
`tnonochromatic light. making a light source for white light
`requires it to arrange three light emitting components of R. G
`and 13 closely to each other while dillusing and mixing the
`light emitted by them. When generating white light with such
`an arrangement. there has been such a problem that white
`light ofthe desired lone cannot be generated due to variations
`in the tone. luminance and other factors of the light emitting
`component. Also when the light emitting components are
`tnade ol'ditl'crent materials. electric power required for driv—
`ing differs frotn one light emitting diode to another. making it
`necessary to apply different voltages different light emitting
`components. which leads to complex drive circuit. Moreover.
`because the light emitting components are semiconductor
`light emitting components. color tone is subject to variation .
`dtte to the difl'erence in temperature characteristics. chrono—
`logical changes and operating environment. or unevenness in
`color may be caused dtte to failure in uniformly mixing the
`light emitted by the light emitting components. 'l'ltus light
`emitting diodes are clTective as light emitting devices for
`generating individual colors. although a satislactory light
`source capable ofemitting white light by using light emitting
`components has not been obtained so far.
`In order to solve these problems. the present applicant
`previously developed light emitting diodes which convert the
`color oflight. which is emitted by light emitting components.
`by means of a fluorescent material disclosed in Japanese
`
`50
`
`an
`
`2
`Patent Kokai Nos. 5—152609. ?—99345. 7— 1 76?94 and 8—7614.
`The light emitting diodes disclosed in these publications are
`such that. by using light emitting components ol'one kind. are
`capable ol‘generating light et'white and other colors. and are
`constituted as follows.
`
`The light emitting diode disclosed in the above gazettes are
`made by mounting a light emitting component. having a large
`energy band gap of light etnitting layer. in a cup provided at
`the tip ol'a lead frame. and having a fluorescent material that
`absorbs light emitted by the light emitting component and
`emits light ol‘a wavelength difl‘erent from that ol‘the absorbed
`light (wavelength conversion). contained in a resin mold
`which covers the light emitting component.
`The light emitting diode disclosed as described above
`capable ol'emitting white light by mixing the light ol'a pitt—
`rality of sources can be tnade by using a light emitting com-
`ponent capable of emitting blue light and molding the light
`emitting component with a resin including a lluorescent
`material that absorbs the light emitted by the blue light emit-
`ting diode and emits yellowish light.
`llowcver. conventional
`light emitting diodes have such
`problems as deterioration of the fluorescent material leading
`to color tone deviation and darkening ol‘the fluorescent mate
`rial resulting in lowered elliciency of extracting light. Dark-
`ening here re l’ers to. in the case of using an inorganic fluores-
`cent material such as (C‘d. ZEUS fluorescent material. [or
`example. part of metal elements constituting the fluorescent
`material precipitate or change their properties leading to col-
`oration. or. in the case of using an organic fluorescent mate—
`rial. coloration due to breakage of double bond in the mol—
`ecule. Especially when a light emitting component made ol‘a
`semiConductor having a high energy band gap is used to
`improve the conversion eiliciency ofthe fluorescent material
`(that is. energy of light emitted by the semiconductor is
`increased and number of photons having energies above a
`threshold which can be absorbed by the fluorescent material
`increases. resulting in tuore light being absorbed). or the
`quantity of fluorescent material consumption is decreased
`(that is. the fluorescent material is irradiated with relatively
`higher energy).
`light energy absorbed by the fluorescent
`material
`inevitably increases resulting in more significant
`degradation o f the fluorescent material. Use ofthe light emit-
`ting component with higher intensity of light emission for an
`extended period oi‘time causes further tnore significant deg—
`radat ion of the fluorescent tnaterial.
`
`A] so the fluorescent material provided in the vicinity ol‘the
`light emitting component may be exposed to a high tempera-
`ture such as rising temperature ol‘the light emitting compo
`nent and heat transmitted from the external environment (for
`example. sunlight in case the device is used outdoors).
`l-‘urther. sotne fluorescent materials are subject to acceler-
`ated deterioration clue to combination of moisture entered
`
`from the outside or introduced during the production process.
`the light and heat transmitted from the light emitting compo-
`nent.
`
`When it comes to an organic dye of ionic property. direct
`current electric liCld in the vicinity of the chip may cause
`electrophoresis. resulting in a change in the color tone.
`
`SUMMARY OF THE INVI'EN'I‘ION
`
`Thus. an object of the present invention is to solve the
`problems described above and provide a light emitting device
`which experiences only extremely low degrees of deteriora—
`tion in emission light intensity. light emission efliciency and
`color shift over a long time of tlsc with high luminance.
`
`TCL 1036, Page 23
`LOWES 1036, Page 23
`
`LOWES 1036, Page 23
`
`
`
`US 7,531,960 B2
`
`3
`
`invention
`The present applicant completed the present
`through researches based on the assumption that a light emit-
`ting device having a light entitling component and a fluores-
`cent material must meet
`the following requirements to
`achieve the above-mentioned object.
`The light entitling component must be capable ofemitting
`light of high luminance with light emitting characteristic
`which is stable over a long time of use.
`The fluorescent material being provided in the vicinity of
`the high-luminance light emitting component. must show
`excellent resistance against light and heat so that the proper-
`ties thereof do not change even when used over an extended
`period oftitne while being exposed to light of high intensity
`emitted by the light emitting component (particularly the
`fluorescent material provided in the vicinity ofthe light etnit—
`ting component is exposed to light ofa radiation intensity as
`high as about 30 to 40 times that of sunlight according to our
`estimate. and is required to have more durability against light
`as light emitting component of higher luminance is used ).
`With regard to the relationship with the light emitting corn-
`ponent. the fluorescent material must be capable ofabsorbing
`with high eiticiency the light of high monochromaticity emit—
`ted by the light emitting cotnponent and emitting light ol'a
`wavelength dilferent from that ofthe light emitted by the light
`emitting component.
`'lhus the present invent ion prov ides a light emitting device.
`comprising a light emitting component and a phosphor
`capable of absorbing a part of light emitted by the light
`emitting component and entitling light of wavelength differ-
`ent from that of the absorbed light:
`wherein said light emitting component comprises a nitride
`compound semiconductor represented by the formula: lnifiaJ
`AIAN where 0E1, Uéj. tlék and i+j+k l ) and said phosphor
`contains a garnet fluorescent material comprising at least one
`element selected from the group consisting o fY. [.11. Se. [.a.
`(id and Sm. and at least one element selected from the group
`consisting o fAl. Ga and In. and being activated with cerium.
`The nitride compound semiconductor (generally repre-
`sented by chemical formula ln,('ia,-Al;(N where 0%]. Oéj.
`Uék and i+j+k I) mentioned above contains various mate-
`rials including lnGaN and GaN doped with various impuri—
`ties.
`
`The phosphor mentioned above contains various materials
`defined as described above.
`including Y3Ai50l31'e and
`C.id_.[1150m:Ce.
`Because the light emitting device of the present invention
`uses the light emitting component made of a nitride com-
`pound semiconductor capable of emitting light with high
`luminance. the light emitting device is capable of emitting
`light with high luminance. Also the phosphor tlsed in the light
`emitting device has excellent resistance against light so that
`the fluorescent properties thereofexperience less change even
`when used over an extended period of time while being
`exposed to light of high intensity. This makes it possible to
`redttce the degradation of characteristics during long period
`of use and reduce deterioration due to light of high intensity
`emitted by the light emitting component as well as extraneous
`light (sunlight including ultraviolet light. etc.) during outdoor
`use. thereby to provide a light emitting device which experi-
`ences extremely less color shift and less luminance decrease.
`The light emitting device of the present invention can also be
`used in such applications that require response speeds as high
`as 120 nsec.. for example, because the phosphor used therein
`allows after glow only for a short period of time.
`The phosphor used in the light emitting diode ofthe present
`invention preferably contains ant yttrium-alumintun-garnet
`
`1tt
`
`Rut
`
`Lu 'JI
`
`4o
`
`50
`
`55
`
`on
`
`4
`fluorescent material that contains Y and A]. which enables it
`to increase the luminance of the light emitting device.
`In the light emitting device of the present invention. the
`phosphor may be a fluorescent material represented by a
`general
`formula
`(Re1__Sm’.)_.(Al|‘_‘_('ia_‘_)5()lliCe. where
`Oér-cl and Dis; 1 and Re is at least one selected from Y and
`Gd. in which case good characteristics can be obtained simi—
`larly to the case where the yttrium—alumimun—garnet fluores—
`cent material is used.
`
`Also in the light emitting device ofthe present invention. it
`is preferable. for the purpose of reducing the temperature
`dependence of light emission characteristics (wavelength of
`emitted light. intensity of light emission. etc.). to us ‘ a fluo-
`rescent material represented by a general formula (Ylgflr,
`Cide‘equ,.)_.(AlJ__¥.Ga5)5()l2
`as
`the
`phosphor. where
`Uépéflfi. (LUO3§L1§0.2. 0.0003§r§0.08 and [J-Zzsé 1.
`Also in the light emitting device of the present invention.
`the phosphor may contain two or more yttriumvaluminum-
`garnet fluorescent materials. activated with ceriutu. oi‘differ-
`ent compositions including ‘t’ and A]. With this configuration.
`light ofdesired color can be emitted by controlling the emis—
`sion spectrum of the phosphor according to the property
`(wavelength of emitted light) of the light emitting compo-
`nent.
`
`Further in the light emitting device ol‘the present invention.
`in order to have light o fa specified wavelength emitted by the
`light emitting device. it is preferable that the phosphor con-
`tains two or tnore fluorescent materials of different composi—
`tions represented by general formula (Re J _,.Sm,.)_.(Al ,__,.Cia_‘}5
`()nzf'c. where Uérél and ()ésél and Re is at least one
`selected from Y and (id.
`
`Also in the light emitting device ofthe present invention. in
`order to control the wavelength ofetn i tted light. the phosphor
`may contain a first fluorescent material represented by gen-
`eral formula Y_.(All_sGas)5012:Ce and a second fluorescent
`material
`represented by general
`fonnula Re3Al5012:Ce.
`where Oésél and Re is at least one selected from Y. (id and
`La.
`
`Also in the light emitting device ofthe present invention. in
`order to control the wavelength ofem i tted light. the phosphor
`may be an yttrium-aluminum-garnet
`fluorescent material
`containing a first fluorescent material and a second fluores—
`cent material. with diflerent parts ofeach yttrium being sub—
`stituted with gadolinium.
`l-'tti1her in the light emitting device ofthe present invention.
`it is preferable that main emission peak of the light emitting
`component is set within the range from 400 nm to 530 mu and
`main emission wavelength ol‘the phosphor is