KR100501741B1 - Red phosphor comprising samarium for ultraviolet LED and manufacturing method thereof and applicable device thereof - Google Patents
Red phosphor comprising samarium for ultraviolet LED and manufacturing method thereof and applicable device thereof Download PDFInfo
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- KR100501741B1 KR100501741B1 KR10-2003-0015145A KR20030015145A KR100501741B1 KR 100501741 B1 KR100501741 B1 KR 100501741B1 KR 20030015145 A KR20030015145 A KR 20030015145A KR 100501741 B1 KR100501741 B1 KR 100501741B1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229910052772 Samarium Inorganic materials 0.000 title description 13
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 title description 13
- PSNPEOOEWZZFPJ-UHFFFAOYSA-N alumane;yttrium Chemical compound [AlH3].[Y] PSNPEOOEWZZFPJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 19
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001940 europium oxide Inorganic materials 0.000 claims abstract description 9
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000013543 active substance Substances 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 5
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 5
- 229940075630 samarium oxide Drugs 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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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
- C09K11/08—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
- C09K11/7766—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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- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
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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
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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
- C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
- C09K11/7764—Aluminates; Silicates
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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
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
발광다이오드(Light Emitting Diode) 및 능동 발광형 액정표시소자에 사용되고, 자외선 장파장영역 하에서 여기되어 발광하는 UV LED용 알루미늄산이트륨계 적색형광체 및 그 제조방법과 이를 이용한 소자에 대해 개시한다. 본 발명은, 형광체 모체인 알루미늄산이트륨(Y3Al5O12)에 공부활제로 산화유로피움(Eu2 O3)과 산화사마륨(Sm2O3)을 첨가함으로써 350 ∼ 410nm의 여기되는 부분에서 발광 휘도가 우수하고 UV LED 및 능동 발광형 액정표시소자용 적색형광체로 적합하도록 고휘도를 갖는 다음 「화학식 1」로 표시되는 UV LED용 알루미늄산이트륨계 적색형광체 및 그 제조방법과 이를 이용한 소자에 관한 것이다.Disclosed are a yttrium-aluminum-based red phosphor for a UV LED, which is used in a light emitting diode (LED) and an active light emitting liquid crystal display device and is excited and emitted under an ultraviolet long wavelength region, and a manufacturing method thereof and a device using the same. The present invention provides excitation of 350 to 410 nm by adding europium oxide (Eu 2 O 3 ) and samarium oxide (Sm 2 O 3 ) to the yttrium aluminate (Y 3 Al 5 O 12 ), which is a phosphor matrix, as an active agent. Yttrium-aluminum-based red phosphor for UV LED, which has excellent luminance and has high brightness to be suitable as a red phosphor for UV LEDs and active light emitting liquid crystal display devices, and is represented by the following Chemical Formula 1; It is about.
(Y1-aEua)3Al5O12:Smb ㆍㆍㆍㆍㆍㆍ「화학식 1」(Y 1-a Eu a ) 3 Al 5 O 12 : Sm b [ Formula 1]
상기 「화학식 1」에서 0.05≤a≤0.3이고, 0＜b≤0.3이다. In said "formula 1", it is 0.05 <= a <= 0.3 and 0 <b <= 0.3.
Description
본 발명은 UV LED 및 능동발광형 액정표시소자용 적색형광체에 관한 것으로, 더욱 상세하게는 형광체 모체인 알루미늄산이트륨(Y3Al5O12)에 공부활제로 산화유로피움과 산화사마륨을 첨가함으로써 사마륨을 첨가하지 않은 알루미늄산이트륨 형광체보다 발광휘도가 우수한 UV LED용 알루미늄산이트륨계 적색형광체 및 그 제조방법과 이를 이용한 소자에 관한 것이다.The present invention relates to a red phosphor for UV LEDs and active light-emitting liquid crystal display device, and more particularly, by adding europium oxide and samarium oxide to yttrium aluminum alumina (Y 3 Al 5 O 12 ), which is a phosphor matrix, as an active agent. The present invention relates to a yttrium-aluminum-based red phosphor for UV LEDs having a higher luminous intensity than a yttrium alumina phosphor without samarium, and a method of manufacturing the same and a device using the same.
현재 적색, 녹색 및 청색 등의 LED를 제조하기 위해서는 GaAs, AlGaInP, InGaN, GaN등의 서로 다른 기판을 제조하여 서로 다른 반도체 박막을 활용해야 하기 때문에 LED 제조공정에 투자비가 많이 들고 제조단가가 비싸지는 문제점을 가지고 있다. 따라서 동일한 반도체 박막을 활용하여 적색, 녹색 및 청색 발광을 하는 LED제조가 가능하다면 공정이 간단해지므로 제조비용 및 투자비용을 획기적으로 줄일 수 있다. In order to manufacture LEDs such as red, green, and blue, it is necessary to manufacture different substrates such as GaAs, AlGaInP, InGaN, and GaN to utilize different semiconductor thin films, which causes high investment cost and high manufacturing cost in the LED manufacturing process. Have Therefore, if it is possible to manufacture LEDs emitting red, green, and blue light using the same semiconductor thin film, the process can be simplified, and manufacturing and investment costs can be drastically reduced.
또한 조명, 노트북, 핸드폰 등의 LCD용 배면광원으로 각광받고있는 백색 LED는 현재 청색 LED에 YAG:Ce형광체를 결합하여 제조되어지고 있다. 청색 LED를 이용한 백색 LED는 450 ∼ 470nm 파장의 청색광원에 의해 상부층에 위치한 황색형광체를 여기 시킴으로써 청색과 황색의 혼합에 의해 백색 LED를 제조하기 때문에 여기에 적합한 형광물질에 많은 문제점을 가지고 있다. 즉, 450 ∼ 470nm 파장의 청색 LED를 가지고서는 YAG:Ce을 이용한 백색 LED밖에 구현이 어렵다. In addition, the white LED, which is in the spotlight as a back light source for LCDs such as lighting, notebooks, and mobile phones, is currently manufactured by combining a YAG: Ce phosphor with a blue LED. White LEDs using blue LEDs have many problems with fluorescent materials suitable for the manufacture of white LEDs by mixing blue and yellow by exciting a yellow phosphor located in an upper layer by a blue light source having a wavelength of 450 to 470 nm. That is, with a blue LED having a wavelength of 450 ~ 470nm, it is difficult to implement only a white LED using YAG: Ce.
이러한 문제점들을 해결하기 위해 UV LED를 활용한 적색, 녹색, 청색 및 백색 LED를 개발하려는 노력이 활발하다. 즉, 350 ∼ 410nm 사이의 여기에너지원에서 발광효율이 우수한 적색, 녹색, 및 청색형광물질 개발이 시급하다. To solve these problems, efforts are being made to develop red, green, blue and white LEDs utilizing UV LEDs. That is, it is urgent to develop red, green, and blue fluorescent materials having excellent luminous efficiency from an excitation energy source between 350 and 410 nm.
한편, 장파장 UV에 효율이 우수한 형광물질은 능동발광형 액정표시소자용 형광물질 개발에 있어서도 매우 중요하다. 능동발광형 액정표시소자는 배면광원에서 조사되는 광원이 배향성을 이용하여 빛을 통과시키거나 통과되지 않도록 하는 액정층을 통과하게 되며 액정층을 통과한 배면광은 형광체를 여기 시킴으로써 원하는 화상을 구현할 수 있도록 구성되어있다. 이러한 구성의 능동발광형 액정표시소자는 배면광원이 액정표시소자의 전면에 도포된 형광체를 직접 여기 시켜 발광하는 구조이므로 형광체의 효율이 우수한 것이어야 할 필요가 있다. On the other hand, a fluorescent material having excellent efficiency for long wavelength UV is also very important in the development of a fluorescent material for an active light emitting liquid crystal display device. In the active light emitting liquid crystal display, a light source irradiated from a back light source passes through a liquid crystal layer that prevents light from passing through the light by using an alignment property, and the back light passing through the liquid crystal layer excites a phosphor to realize a desired image. Is configured to. The active light emitting liquid crystal display device having such a structure needs to have excellent efficiency of the phosphor since the rear light source directly excites the phosphor coated on the front surface of the liquid crystal display device to emit light.
능동발광형 액정표시소자에서는 액정의 보호를 위하여 380 ∼ 420nm 파장의 장파장 UV를 배면광원으로 사용되어야 하며, 장파장 UV에서 효율이 우수한 적색형광물질의 개발은 적색 및 백색 LED개발에서와 마찬가지로 능동발광형 액정표시소자 개발에 있어서도 매우 중요하다. In active light emitting liquid crystal display device, long wavelength UV of 380 ~ 420nm wavelength should be used as a back light source for the protection of liquid crystal. The development of red fluorescent material with high efficiency in long wavelength UV is the same as the development of red and white LED. It is also very important in the development of liquid crystal display devices.
현재 장파장 UV용으로 개발되어진 무기계 형광물질로는 K5Eu(WO4)6.25등이 있지만, 410nm 이상의 여기에너지원에서 발광효율이 매우 낮은 문제점을 가지고 있다.Inorganic fluorescent materials currently developed for long wavelength UV include K 5 Eu (WO 4 ) 6.25 , but have a very low luminous efficiency at excitation energy sources of 410 nm or more.
따라서, 본 발명의 목적은 산화이트륨(Y2O3) 및 산화알루미늄(Al2O3 )을 형광체 원료로 사용한 알루미늄산이트륨(Y3Al5O12)을 모체로 사용하고 여기에 공부활제로 산화유로피움(Eu2O3)과 산화사마륨(Sm2O3)을 첨가함으로써 350 ∼ 410nm의 여기광원에 의해 발광강도가 우수하고 UV LED 및 능동발광형 액정표시소자용으로 적합한 UV LED용 알루미늄산이트륨계 적색형광체 및 그 제조방법과 이를 이용한 소자를 제공하는데 있다.Accordingly, an object of the present invention is to use yttrium aluminum (Y 3 Al 5 O 12 ) using yttrium oxide (Y 2 O 3 ) and aluminum oxide (Al 2 O 3 ) as the raw material of the phosphor as a parent and to study here By adding europium oxide (Eu 2 O 3 ) and samarium oxide (Sm 2 O 3 ), it is excellent in luminous intensity by excitation light source of 350 ~ 410nm and suitable for UV LED and active light emitting liquid crystal display device. An object of the present invention is to provide a yttrium-based red phosphor and a method of manufacturing the same.
상기한 본 발명의 목적을 달성하기 위한 본 발명의 UV LED용 알루미늄산이트륨계 적색형광체는, 하기 「화학식 1」로 표시되는 알루미늄산이트륨계 적색형광체인 것을 특징으로 한다. The yttrium-aluminum-based red phosphor for UV LED of the present invention for achieving the above object of the present invention is characterized in that the yttrium-aluminum-based red phosphor represented by the following formula (1).
(Y1-aEua)3Al5O12:Smb ㆍㆍㆍㆍㆍㆍ「화학식 1」(Y 1-a Eu a ) 3 Al 5 O 12 : Sm b [ Formula 1]
상기 「화학식 1」에서 0.05≤a≤0.3이고, 0＜b≤0.3이다. In said "formula 1", it is 0.05 <= a <= 0.3 and 0 <b <= 0.3.
또한, 본 발명의 UV LED용 알루미늄산이트륨계 적색형광체의 제조방법은, 알루미늄산이트륨을 모체로 하고, 여기에 산화 유로피움(Eu2O3)과 산화사마륨(Sm2 O3)을 첨가하고, 혼합하는 단계; 상기 혼합단계에서 수득된 혼합물을 건조시키고, 1,200℃ ∼ 1,700℃ 사이의 온도에서 열처리하는 단계; 및 분쇄 등의 후처리단계를 포함하여 이루어진 것을 특징을 한다.In the method for producing a yttrium-aluminum red phosphor for UV LED of the present invention, yttrium aluminum is used as a matrix, and europium oxide (Eu 2 O 3 ) and samarium oxide (Sm 2 O 3 ) are added thereto. Mixing; Drying the mixture obtained in the mixing step and heat-treating at a temperature between 1,200 ° C and 1,700 ° C; And a post-treatment step such as grinding.
한편, 상기한 UV LED용 알루미늄산이트륨계 적색형광체의 제조방법을 이용하여 제조된 표시소자는 적색형광물질을 발광층에 포함하는 UV LED, Pink LED, 능동 발광액정표시소자 및 이 파장대의 UV를 에너지원으로 하는 표시소자 등을 포함한다. On the other hand, the display device manufactured by using the manufacturing method of the above yttrium-aluminum-based red phosphor for the UV LED is a UV LED, a pink LED, an active light emitting liquid crystal display device and a UV in this wavelength band containing a red phosphor in the light emitting layer And a display element that is a circle.
이하, 본 발명의 바람직한 실시예에 대해 상세하게 설명한다. Hereinafter, the preferred embodiment of the present invention will be described in detail.
본 발명에 따른 알루미늄산이트륨계 적색형광체는 350 ∼ 410nm UV LED로부터 발생되는 광원에 의해 충분히 여기되어 적색 발광이 이루어지며 특히, 발광강도가 우수하여 UV LED 및 능동발광형 액정표시소자용으로 적합한 효과를 가진다. The yttrium aluminum-based red phosphor according to the present invention is sufficiently excited by a light source generated from 350 to 410 nm UV LEDs to produce red light. In particular, it is excellent in light emission intensity and is suitable for UV LEDs and active light emitting liquid crystal display devices. Has
특히, 본 발명에서는 알루미늄산이트륨(Y3Al5O12)에 공부활제로 산화유로피움(Eu2O3)과 산화사마륨(Sm2O3)을 첨가함으로써 적색 발광휘도가 우수한 결과를 얻을 수 있는 특징이 있다.In particular, in the present invention, by adding europium oxide (Eu 2 O 3 ) and samarium oxide (Sm 2 O 3 ) as a study aid to yttrium aluminum (Y 3 Al 5 O 12 ) it is possible to obtain an excellent red light emission luminance There is a characteristic.
이와 같은 본 발명의 알루미늄산이트륨(Y3Al5O12)계 적색형광체를 그 제조방법에 의거하여 더욱 상세하게 설명하면 다음과 같다.Such a yttrium aluminum (Y 3 Al 5 O 12 ) -based red phosphor of the present invention will be described in more detail based on the manufacturing method as follows.
먼저, 산화이트륨(Y2O3) 및 산화알루미늄(Al2O3)에 공부활제로서 산화유로피움(Eu2O3)과 산화사마륨(Sm2O3)을 첨가하여 혼합한다. 이때 공부활제로서 사용되는 산화유로피움은 알려져 있는 0.1 mol을 첨가하고 산화사마륨에 대하여는 0.01 내지 0.3 mol, 바람직하게는 0.01 내지 0.05 mol로 첨가하는데, 만일 그 사용량이 0.01 mol 미만이면 공부활제로서의 기능을 하기에 충분한 양이 되지 못하며, 0.05 mol을 초과하면 농도퀀칭(quenching) 효과에 따른 휘도 저하가 일어나는 문제점이 있을 수 있다.First, europium oxide (Eu 2 O 3 ) and samarium oxide (Sm 2 O 3 ) are added and mixed as yttrium oxide (Y 2 O 3 ) and aluminum oxide (Al 2 O 3 ) as a activator. At this time, the europium oxide used as the study agent is added 0.1 mol known and samarium oxide is added in 0.01 to 0.3 mol, preferably 0.01 to 0.05 mol, if the amount is less than 0.01 mol to function as a study aid. It may not be sufficient amount, and if it exceeds 0.05 mol, there may be a problem that the luminance decrease due to the concentration quenching effect.
상기와 같은 형광체 원료물질과 공부활제를 원하는 조성에 따른 각각의 소정비가 되도록 평량하고 보다 효과적인 혼합을 위해 아세톤 용매 하에서 볼밀링(ball milling) 또는 마노유발과 같은 혼합기를 이용하여 균일한 조성이 되도록 충분히 혼합한다. 그 후, 이 혼합물을 오븐에 넣고 100 내지 150℃에서 1 ∼ 2시간 동안 건조한다. 건조한 혼합물을 고순도 알루미나 보트에 넣고 전기로를 사용하여 1,200℃ ∼ 1,700℃ 사이의 온도에서 3 ∼ 6시간동안 열처리한 후, 충분히 분쇄한다. In order to mix the phosphor raw material and the study active agent with a predetermined ratio according to the desired composition, it is sufficient to have a uniform composition by using a mixer such as ball milling or agate induction under acetone solvent for more efficient mixing. Mix. Thereafter, the mixture is placed in an oven and dried at 100 to 150 ° C. for 1 to 2 hours. The dry mixture is placed in a high purity alumina boat and heat treated at an temperature between 1,200 ° C. and 1,700 ° C. for 3-6 hours using an electric furnace, followed by pulverization.
이들 분말에 대하여 빛 발광강도(Photoluminescence, PL)를 측정한 결과, 390 nm 여기 하에서 590 ∼ 700nm의 영역에서 강한 발광스펙트럼을 나타내고, 발광 휘도가 매우 우수한 상기 「화학식 1」로 표시되는 적색형광체가 수득된다. As a result of measuring the light emission intensity (Photoluminescence, PL) with respect to these powders, a red phosphor represented by the above-mentioned "Formula 1" exhibiting a strong emission spectrum in the region of 590 to 700 nm under 390 nm excitation and having excellent emission luminance was obtained. do.
이와 같이 본 발명에서 제조한 알루미늄산이트륨계 적색형광체는 자외선 장파장 영역 하에서 발광 휘도가 우수한 적색 발광을 하므로, UV LED 및 능동발광형 액정표시소자에 적용시 매우 높은 발광효율을 가진다. As described above, the yttrium-aluminum-based red phosphor manufactured in the present invention emits red light having excellent light emission luminance under the ultraviolet long wavelength region, and thus has very high luminous efficiency when applied to UV LEDs and active light emitting liquid crystal display devices.
이와 같은 본 발명을 이하의 실시예에 의거하여 상세하게 설명하겠는 바, 이 실시예는 예시적인 것으로서 이해되어야 하며, 본 발명이 본 실시예에 한정되는 것은 아니다. The present invention will be described in detail based on the following examples, which should be understood as illustrative, and the present invention is not limited to this embodiment.
비교예 1: (Y0.9Eu0.1)3Al5O12 형광체의 제조Comparative Example 1: Preparation of (Y 0.9 Eu 0.1 ) 3 Al 5 O 12 phosphor
산화이트륨 0.9 mol, 산화알루미늄 1 mol, 산화유로피움 0.1 mol의 비율로 평량하고, 이것을 마노유발을 사용하여 아세톤 중에서 충분히 고르게 혼합한다. 혼합한 시료를 오븐을 사용하여 130℃에서 1시간 동안 건조한다. 얻어진 혼합물을 고순도 알루미나 보트에 넣고 전기로를 사용하여 대기 중에서 1,200℃ ∼ 1,700℃ 사이의 온도에서 3 ∼ 6시간 동안 열처리한 후, 충분히 분쇄 처리하여 (Y0.9Eu0.1)3Al5O12 으로 표시되는 적색형광체를 수득한다.It is weighed at a ratio of 0.9 mol of yttrium oxide, 1 mol of aluminum oxide, and 0.1 mol of europium oxide, which is mixed evenly in acetone using agate induction. The mixed sample is dried at 130 ° C. for 1 hour using an oven. The obtained mixture was placed in a high purity alumina boat and heat-treated in an atmosphere using an electric furnace at a temperature between 1,200 ° C. and 1,700 ° C. for 3 to 6 hours, and then sufficiently pulverized to be represented as (Y 0.9 Eu 0.1 ) 3 Al 5 O 12 . Obtain a red phosphor.
실시예 1: (Y0.9Eu0.1)3Al5O12:Smx형광체의 제조Example 1: Preparation of (Y 0.9 Eu 0.1 ) 3 Al 5 O 12 : Sm x Phosphor
제조 조건은 비교예 1과 유사하고 단지 산화사마륨(Sm2O3)을 0.005 에서 0.3까지 변화시키고 있다. 제조되어진 형광물질을 350nm에서 500nm사이에서의 흡수스펙트럼을 관찰하였으며, 390nm UV를 여기에너지원으로 하였을 때의 발광특성을 관찰하였다.The production conditions were similar to those of Comparative Example 1 and only the samarium oxide (Sm 2 O 3 ) was changed from 0.005 to 0.3. The absorption spectrum of the prepared fluorescent material was observed between 350 nm and 500 nm, and the luminescence properties when 390 nm UV was used as the excitation energy source were observed.
도 1은 제조되어진 형광물질의 흡수스펙트럼을 나타낸 것이다. 흡수스펙트럼은 361, 380, 392 및 458nm에서 높은 흡수 피크를 보여주고 있어, UV LED, 능동발광형 액정표시소자, Pink LED구현 및 이 파장대의 UV를 에너지원으로 하는 응용분야에 있어서 이 적색형광물질이 적합함을 알 수 있다. Figure 1 shows the absorption spectrum of the prepared fluorescent material. Absorption spectra show high absorption peaks at 361, 380, 392, and 458 nm, which are red phosphors for UV LEDs, active light-emitting liquid crystal display devices, pink LED implementations, and UV-based applications. It can be seen that this is suitable.
도 2는 사마륨을 첨가하였을 때와 첨가하지 않았을 때의 적색발광스펙트럼을 나타낸 것이다. 사마륨을 0.02 mol 첨가한 형광물질이 비교예 1의 사마륨을 첨가하지 않은 형광물질보다 발광강도가 우수함을 알 수 있다. Figure 2 shows the red light emission spectrum with and without the addition of samarium. It can be seen that the fluorescent material to which 0.02 mol of samarium is added is superior in luminescence intensity to the fluorescent material to which samarium is not added in Comparative Example 1.
도 3은 사마륨의 첨가량에 따른 상기 형광물질의 상대적인 발광세기를 나타낸 것으로 사마륨 첨가량이 0.02 mol 보다 많은 경우 농도퀀칭(quenching) 효과가 일어나 발광 휘도를 감소시킴을 확인할 수 있었다. 따라서, 특히 우수한 발광 휘도를 나타낼 수 있는 사마륨의 농도는 0.02 mol임을 확인할 수 있다. 3 shows the relative luminescence intensity of the fluorescent material according to the amount of samarium added, and when the amount of samarium added is more than 0.02 mol, it was confirmed that concentration quenching effect occurred to decrease the luminescence brightness. Therefore, it can be seen that the concentration of samarium, which can exhibit particularly excellent luminescence brightness, is 0.02 mol.
상술한 바와 같이, 본 발명에 따른 UV LED용 알루미늄산이트륨계 적색형광체 및 그 제조방법과 이를 이용한 소자는, 알루미늄산이트륨계 형광체에 공부활제로서 유로피움과 사마륨을 첨가함으로써, 장파장 UV 영역인 380 ∼ 410nm 여기 하에서 고휘도를 갖는 매우 우수한 적색발광을 나타내므로 UV LED, 능동발광형 액정표시소자 및 장파장 UV를 에너지원으로 하는 응용분야에 적용할 수 있다. 본 발명은 상술한 실시예에 한정되지 않으며, 본 발명의 기술적 사상 내에서 당분야의 통상의 지식을 가진 자에 의하여 많은 변형이 가능함은 명백할 것이다. As described above, the yttrium-aluminum-based red phosphor for UV LEDs according to the present invention and a manufacturing method thereof and the device using the same include a long wavelength UV region of 380 by adding europium and samarium to the yttrium-based phosphor. It exhibits very good red light emission with high brightness under ~ 410 nm excitation, so that it can be applied to applications such as UV LEDs, active light emitting liquid crystal display devices and long wavelength UV as energy sources. The present invention is not limited to the above-described embodiment, and it will be apparent that many modifications are possible by those skilled in the art within the technical spirit of the present invention.
도 1은 본 발명의 사마륨을 첨가한 적색형광물질의 흡수스펙트럼을 나타낸 그래프, 1 is a graph showing the absorption spectrum of the red phosphor added with samarium of the present invention,
도 2는 사마륨을 첨가하지 않은 적색형광물질과 본 발명의 사마륨을 첨가한 적색형광물질의 상대 빛 발광스펙트럼을 나타낸 그래프, 2 is a graph showing a relative light emission spectrum of a red fluorescent substance without samarium and a red fluorescent substance with samarium of the present invention;
도 3은 사마륨을 첨가량에 따른 상대 발광 강도를 나타낸 그래프이다. 3 is a graph showing relative emission intensity according to the amount of samarium added.
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