TWI479011B - 螢光材料與紫外光發光裝置 - Google Patents
螢光材料與紫外光發光裝置 Download PDFInfo
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- TWI479011B TWI479011B TW100132977A TW100132977A TWI479011B TW I479011 B TWI479011 B TW I479011B TW 100132977 A TW100132977 A TW 100132977A TW 100132977 A TW100132977 A TW 100132977A TW I479011 B TWI479011 B TW I479011B
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- fluorescent material
- excitation
- kca
- light emitting
- combination
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- 239000000463 material Substances 0.000 claims description 41
- 230000005284 excitation Effects 0.000 claims description 25
- 230000005855 radiation Effects 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 241001669680 Dormitator maculatus Species 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 description 35
- 239000011575 calcium Substances 0.000 description 18
- 239000012190 activator Substances 0.000 description 15
- 238000000295 emission spectrum Methods 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000695 excitation spectrum Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 229910052693 Europium Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- -1 oxides (Oxides) Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7795—Phosphates
- C09K11/7796—Phosphates with alkaline earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J65/00—Lamps without any electrode inside the vessel; Lamps with at least one main electrode outside the vessel
- H01J65/04—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels
- H01J65/042—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels by an external electromagnetic field
- H01J65/046—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels by an external electromagnetic field the field being produced by using capacitive means around the vessel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Description
本發明係關於一種螢光材料，更特別關於此種材料於發光裝置之應用。
無機螢光材料(Phosphors)，其激發與發光等項特性多由「主體材料(Host materials)」、「活化劑/發光中心(Activators)」及其他「摻雜物(Dopants)」等組成因素決定，亦即不同的主體材料或摻雜物所組成的螢光材料，可能具有相異的發光特性，而「組成」自然地也成為調控螢光材料光電特性的最重要因素。其中，無機螢光材料的主體材料多數由硫化物(Sulfides)、氧化物(Oxides)、硫氧化物(Oxysulfides)與其他複合氧化物(Complex oxides；Silicates、Aluminates、Phosphates etc)所組成，近年來則有逐漸朝往氮化物(Nitrides)與氮氧化物(Oxynitrides)發展的趨勢。至於活化劑/發光中心則主要為過渡元素(Transition metal elements)或稀土族元素(Rare-earth elements)的離子為主。
未來光源應用具有低汞/無汞的環保訴求，是故高效率的氙準分子燈(Xe2
* excimer lamp)與發光二極體(Light emitting diode；LED)，皆可能成為未來的主要光源。然而實際應用時，為符合放射波長的特性需求，不管氙準分子燈或發光二極體，需搭配螢光材料進行光轉換的作用，始能達成應用的目的。氙準分子燈主要的放射波長為172nm的真空紫外光(Vacuum ultra violet、VUV)，透過適當螢光材料的光轉換作用，可放射UV-C(波長介於200nm至280nm)，以應用於殺菌(Disinfection)或淨化(Purification；TOC reduction)等領域。發光二極體具有窄波段的放射特性，倘若搭配適當螢光材料的光轉換作用，則可製作白光LED而應用於照明與顯示等用途。不論如何，氙準分子燈與發光二極體對於螢光粉的需求均相當殷切。然而，目前能應用於氙準分子燈的紫外光放射螢光粉相當少見，而能應用LED的螢光粉又受到現有的專利束縛，是故新型螢光粉的開發屬極重要的研究任務。
本發明一實施例提供一種螢光材料，具有化學式如下：M(M’1-y-z
Euy
Mnz
)(M”1-x
Prx
)(PO4
)2
；其中M為一價金屬元素，且M係Li、Na、K、或上述之組合；M’、Eu、及Mn為二價金屬元素，且M’係Ca、Sr、Ba、Mg、Zn、或上述之組合；M”及Pr為三價金屬元素，且M”係Sc、Y、La、Lu、Al、Ga、In、或上述之組合；0x0.2；0y0.1；0z0.2；以及x+y+z≠0。
本發明一實施例提供一種紫外光發光裝置，包括激發光源；以及上述之螢光材料，其中激發光源係放射波長介於140nm至240nm。
本發明一實施例提供一種可見光發光裝置，包括激發光源；以及上述之螢光材料，其中激發光源之放射波長介於250nm至450nm。
一般而言，磷酸鹽類主體材料多數具有寬能隙特性，可以搭配不同活化劑而展現出各種相異的激發與放射特徵，可謂是多功能性的主體材料系統。本發明之實施例選擇較罕見的MM’M”(PO4
)2
為主體材料系統，並搭配Pr3+
、Eu2+
及Mn2+
為活化劑。M為一價金屬元素如Li、Na、K、或上述之組合。M’為二價金屬元素如Ca、Sr、Ba、Mg、Zn、或上述之組合。M”為Sc、Y、La、Lu、Al、Ga、In、或上述之組合。其中Pr3+
離子因具有放射UV-C的適當能階，結合MM’M”(PO4
)2
磷酸鹽類主體材料可以作為紫外光放射螢光材料，可結合Xe2
*準分子燈而製作無汞的UV-C紫外光光源。另一方面，Eu2+
與Mn2+
為敏化配對，共掺雜時具有能量傳輸效應。改變Eu2+
與Mn2+
於MM’M”(PO4
)2
之相對掺雜濃度可變化放射的可見光光色，可作為光色可調控之螢光材料以製作白光LED，以應用於照明及顯示用途。
本發明之實施例所提出之磷酸鹽類螢光粉材料，其化學式如下：
M(M’1-y-z
Euy
Mnz
)(M”1-x
Prx
)(PO4
)2
(式1)
在式1中，M為一價金屬元素如Li、Na、K、或上述之組合。M’、Eu、及Mn為二價金屬元素，且M係Ca、Sr、Ba、Mg、Zn、或上述之組合。M”及Pr為三價金屬元素，且M”係Sc、Y、La、Lu、Al、Ga、In、或上述之組合。0≦x≦0.2，0≦y≦0.1，0≦z≦0.2，且x+y+z≠0。
若式1中的螢光材料化學式中的y=z=0，上述之螢光材料的化學式為MM’(M”1-x
Prx
)(PO4
)2
，且x≠0。經140nm至240nm之波長的光激發後，上述螢光材料放射紫外光，且紫外光之主放射波峰介於240nm至320nm之間。上述螢光材料MM’(M”1-x
Prx
)(PO4
)2
可應用於紫外光發光裝置。在本發明一實施例中，紫外光發光裝置10具有燈管12、激發光源16、電極18、及塗佈於燈管12內壁上的螢光材料14(MM’(M”1-x
Prx
)(PO4
)2
)，如第1圖所示。激發光源16可為氙準分子燈(Xenon excimer lamp)或其他放射類似波長(140nm至240nm)的光源。
若式1中的螢光材料x=0，上述螢光材料的化學式為M(M’1-y-z
Euy
Mnz
)M”(PO4
)2
，且y+z≠0。經250nm至450nm之波長的光激發後，上述螢光材料放射可見光，且可見光之主放射波峰介於450nm至750nm之間。上述螢光材料M(M’1-y-z
Euy
Mnz
)M”(PO4
)2
可應用於可見光發光裝置。在本發明一實施例中，可見光發光裝置100具有激發光源102，其正極與負極分別連接至相反電位的導線架104。將螢光材料106(M(M’1-y-z
Euy
Mnz
)M”(PO4
)2
)混入透明樹脂108後，包覆激發光源102。最後再以封裝材料110封住上述結構，即形成第2圖所示之可見光發光裝置。激發光源102可為發光二極體、雷射二極體、或其他放射類似波長(250nm至450nm)的光源。
此外，本發明亦提供上述磷酸鹽螢光材料之製造方法，包含以下步驟：首先，混合以下成份得到混合物：(1)具有M之含氧化合物；(2)具有M’之含氧化合物；(3)磷酸氫二銨((NH4
)2
HPO4
)或磷酸二氫銨((NH4
)H2
PO4
)；以及(4)具有Pr(或Eu及Mn)之含氧化合物。接著對混合物進行燒結，且燒結溫度介於950℃-1250℃之間。當混合物升溫至燒結溫度後，維持在燒結溫度下8至32小時，以燒結混合物。根據本發明之實施例，該(1)具有M之含氧化合物可為具有Li、Na、或K之金屬氧化物、金屬碳酸化合物、或金屬硝酸化合物。另外，除磷酸氫二銨((NH4
)2
HPO4
)或磷酸二氫銨((NH4
)H2
PO4
)外，Pr或Eu及Mn之含氧化合物可為金屬氧化物或金屬硝酸化合物。
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖式，作詳細說明如下：
【實施例】
實施例1
依化學劑量比例取碳酸鉀、碳酸鈣、氧化釔、氧化鐠、及磷酸氫二銨，均勻混合後研磨10分鐘，並放入坩鍋，置入高溫爐，於空氣下950℃~1250℃燒結，以製備不同Y/Pr比例的KCa(Y1-x
Prx
)(PO4
)2
。其中x係分別為0.01、0.02、0.05、0.1、及0.15。
第3圖為KCa(Y0.9
Pr0.1
)(PO4
)2
之X光繞射圖譜(XRD)，顯示其結晶特性良好，少量的Pr3+
掺雜並未影響其晶體結構。
第4圖為KCa(Y0.9
Pr0.1
)(PO4
)2
之激發光譜及放射光譜(PLE/PL)。由第4圖可知其激發波段介於140到240nm，放射波段從240nm到320nm。
第5圖為KCa(Y1-x
Prx
)(PO4
)2
在不同Pr3+
活化劑掺雜比例(x分別為0.01、0.02、0.05、0.1及0.15)下的放射光譜圖。
第6圖為KCa(Y1-x
Prx
)(PO4
)2
在不同Pr3+
活化劑掺雜比例及波長為172nm之激發光源下，於253nm之放射強度分佈圖。第6圖顯示Pr3+
活化劑的最佳掺雜比例約為10%(x≒0.1)左右。
為確認KCa(Y1-x
Prx
)(PO4
)2
為良好的紫外光放射螢光材料，同時進行廣波段的放射光譜分析。第7圖為KCa(Y0.9
Pr0.1
)(PO4
)2
在波長為172nm之激發光源下廣波段的放射光譜，顯示其除了在550nm波長附近具有微量可見光的放射之外，其餘放射皆為介於240nm至320nm之間的紫外光，顯示其為特性良好的紫外光放射螢光材料。
同樣地，MM’(M”1-x
Prx
)(PO4
)2
之合成亦可以改變原料種類，各依化學劑量比例及相同合成方式，研製其他具有不同陽離子的紫外光放射螢光粉。第8圖為KCa(M”0.9
Pr0.1
)(PO4
)2
(M”=Y、La、或Lu)與CYP(Ca9
(Y1-x
Prx
)(PO4
)7
，見中華民國專利申請號98134483之實施例23)的放射光譜比較圖。第9圖為KSr(M”0.9
Pr0.1
)(PO4
)2
(M”=Y、La、或Lu)的放射光譜比較圖。第10圖為NaCa(M”0.9
Pr0.1
)(PO4
)2
(M”=Y、La、或Lu)的放射光譜比較圖。由第8-10圖可知，KCa(Lu0.9
Pr0.1
)(PO4
)2
及KSr(Y0.9
Pr0.1
)(PO4
)2
，亦是與KCa(Y0.9
Pr0.1
)(PO4
)2
效能相當的紫外光放射螢光粉。
實施例2
依化學劑量比例取碳酸鉀、碳酸鈣、氧化釔、氧化銪、氧化錳、及磷酸氫二銨，均勻混合後研磨10分鐘後放入坩鍋，置入高溫爐於空氣下950℃~1250℃燒結，以製備不同掺雜比例的K(Ca0.99-z
Eu0.01
Mnz
)Y(PO4
)2
，其中z係分別為0、0.01、0.02、0.04、0.05、0.07及0.10。
第11圖為K(Ca0.98
Eu0.01
Mn0.01
)Y(PO4
)2
之X光繞射圖譜(XRD)，顯示其結晶特性良好，少量的Eu2+
、Mn2+
掺雜並未影響其晶體結構。
第12圖為K(Ca0.99
Eu0.01
)Y(PO4
)2
之激發光譜及放射光譜(PLE/PL)，由第12圖可知其激發波段介於250nm到450nm，放射波段從425nm到700nm，放射波峰則為480nm左右。
第13圖為K(Ca1-y-z
Euy
Mnz
)Y(PO4
)2
之Eu2+
放射光譜與Mn2+
激發光譜圖，其中y+z≠0。由第13圖可知，Eu2+
放射光譜與Mn2+
激發光譜具有重疊現象，即存在能量傳遞(Energy transfer)。換言之，Eu2+
可作為Mn2+
的敏化劑。
第14圖為K(Ca0.99-z
Eu0.01
Mnz
)Y(PO4
)2
在不同Mn2+
活化劑掺雜比例下之放射光譜比較圖，顯示於1%Eu2+
之狀況下，調控Mn2+
活化劑不同掺雜比例的放射光譜變化。
第15圖為K(Ca0.99-z
Eu0.01
Mnz
)Y(PO4
)2
在不同Mn2+
活化劑掺雜比例下之色度座標圖，顯示於1%Eu2+
之狀況下，增加Mn2+
活化劑不同掺雜比例，其色度座標會由藍綠色往紅紫色方向位移，至於詳細的色度座標變化，則如第1表所示：
第16圖則為K(Ca0.94
Eu0.01
Mn0.05
)Y(PO4
)2
結合放射380nm之near-UV LED晶片所製作的白光LED及其放射光譜的說明圖，顯示利用具有雙放射波峰的單一K(Ca0.94
Eu0.01
Mn0.05
)Y(PO4
)2
螢光材料結合近紫外光LED晶片，即可製作具有7325K色溫及色度座標為(0.314,0.277)的白光LED。
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
1、2、3、4、5、6、7．．．螢光粉編號
10、100．．．發光裝置
12．．．燈管
14、106．．．螢光材料
16、102．．．激發光源
18．．．電極
104．．．導線架
108．．．透明樹脂
110．．．封裝材料
第1圖係本發明一實施例中，紫外光發光裝置的示意圖；
第2圖係本發明一實施例中，可見光發光裝置的示意圖；
第3圖係本發明一實施例中，KCa(Y0.9
Pr0.1
)(PO4
)2
之X光繞射圖譜(XRD)；
第4圖係本發明一實施例中，KCa(Y0.9
Pr0.1
)(PO4
)2
之激發光譜及放射光譜(PLE/PL)；
第5圖係本發明一實施例中，KCa(Y1-x
Prx
)(PO4
)2
在不同Pr3+
活化劑掺雜比例(x分別為0.01、0.02、0.05、0.1及0.15)下的放射光譜圖；
第6圖係本發明一實施例中，KCa(Y1-x
Prx
)(PO4
)2
在不同Pr3+
活化劑掺雜比例及波長為172nm之激發光源下，於253nm之放射強度分佈圖；
第7圖係本發明一實施例中，KCa(Y0.9
Pr0.1
)(PO4
)2
在波長為172nm之激發光源下廣波段的放射光譜；
第8圖係本發明一實施例中，KCa(M”0.9
Pr0.1
)(PO4
)2
(M”=Y、La、或Lu)與CYP的放射光譜比較圖；
第9圖係本發明一實施例中，KSr(M”0.9
Pr0.1
)(PO4
)2
(M”=Y、La、或Lu)的放射光譜比較圖；
第10圖係本發明一實施例中，NaCa(M”0.9
Pr0.1
)(PO4
)2
(M”=Y、La、或Lu)的放射光譜比較圖；
第11圖係本發明一實施例中，K(Ca0.98
Eu0.01
Mn0.01
)Y(PO4
)2
之X光繞射圖譜(XRD)；
第12圖係本發明一實施例中，K(Ca0.99
Eu0.01
)Y(PO4
)2
之激發光譜及放射光譜(PLE/PL)；
第13圖係本發明一實施例中，K(Ca1-y-z
Euy
Mnz
)Y(PO4
)2
之Eu2+
放射光譜與Mn2+
激發光譜圖；
第14圖係本發明一實施例中，K(Ca0.99-z
Eu0.01
Mnz
)Y(PO4
)2
在不同Mn2+
活化劑掺雜比例下之放射光譜比較圖；
第15圖係本發明一實施例中，K(Ca0.99-z
Eu0.01
Mnz
)Y(PO4
)2
在不同Mn2+
活化劑掺雜比例下之色度座標圖；以及
第16圖係本發明一實施例中，K(Ca0.94
Eu0.01
Mn0.05
)Y(PO4
)2
結合放射380nm之near-UV LED晶片所製作的白光LED之放射光譜圖。
10．．．發光裝置
12．．．燈管
14．．．螢光材料
16．．．激發光源
18．．．電極
Claims (5)
- 一種螢光材料，具有化學式如下：MM’(M”1-x Prx )(PO4 )2 ；其中M為一價金屬元素，且M係Li、Na、K、或上述之組合；M’為二價金屬元素，且M’係Ca、Sr、Ba、Mg、Zn、或上述之組合；M”及Pr為三價金屬元素，且M”係Sc、Y、La、Lu、Al、Ga、In、或上述之組合；0<x0.2。
- 如申請專利範圍第1項所述之螢光材料，其中該螢光材料且經140nm至240nm之波長的光激發後放射一紫外光，且該紫外光的主放射波峰介於240nm至320nm之間。
- 如申請專利範圍第1項所述之螢光材料，其化學式如下：KCa(Y1-x Prx )(PO4 )2 、KCa(La1-x Prx )(PO4 )2 、KCa(Lu1-x Prx )(PO4 )2 、KSr(Y1-x Prx )(PO4 )2 、KSr(La1-x Prx )(PO4 )2 、KSr(Lu1-x Prx )(PO4 )2 、或NaCa(Y1-x Prx )(PO4 )2 。
- 一種紫外光發光裝置，包括：一激發光源；以及申請專利範圍第1項所述之螢光材料，其中該激發光源係放射波長介於140nm至240nm。
- 如申請專利範圍第4項所述之紫外光發光裝置，其中該激發光源包括氙準分子燈。
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| CN201110356915.2A CN102994087B (zh) | 2011-09-14 | 2011-11-11 | 荧光材料、可见光发光装置与紫外光发光装置 |
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| JP6195117B2 (ja) * | 2013-12-03 | 2017-09-13 | パナソニックＩｐマネジメント株式会社 | 酸塩化物蛍光体、発光装置、照明装置、及び車両 |
| CA2993825C (en) * | 2015-07-30 | 2020-08-25 | Vital Vio, Inc. | Single diode disinfection |
| CN106085429A (zh) * | 2016-07-11 | 2016-11-09 | 河北大学 | 一系列颜色可调的宽谱led荧光粉及其制备方法 |
| US10884268B2 (en) | 2016-12-29 | 2021-01-05 | King Abdullah University Of Science And Technology | Color-tunable transmission mode active phosphor based on III-nitride nanowire grown on transparent substrate |
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| EP3623446A1 (en) | 2018-09-13 | 2020-03-18 | Xylem Europe GmbH | A phosphor for a uv emitting device and a uv generating device utilizing such a phosphor |
| EP3703104A1 (en) | 2019-02-27 | 2020-09-02 | Xylem Europe GmbH | A phosphor combination for a uv emitting device and a uv generating device utilizing such a phosphor combination |
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Non-Patent Citations (1)
| Title |
|---|
| Shaolong Tie et al., "Investigation on the Luminescence of Ln3+(Ln=Eu, Gd, and Dy) in Hexagonal KCaR(PO4)2 phosphates (R= Gd, Y)", Phys. Stat, Sol. 1995, Vol. 147, pages 267-276 * |
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| CN102994087A (zh) | 2013-03-27 |
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