KR100726973B1 - Blue light-emitting phosphor and a preparation method thereof - Google Patents

Blue light-emitting phosphor and a preparation method thereof Download PDF

Info

Publication number
KR100726973B1
KR100726973B1 KR1020060018686A KR20060018686A KR100726973B1 KR 100726973 B1 KR100726973 B1 KR 100726973B1 KR 1020060018686 A KR1020060018686 A KR 1020060018686A KR 20060018686 A KR20060018686 A KR 20060018686A KR 100726973 B1 KR100726973 B1 KR 100726973B1
Authority
KR
South Korea
Prior art keywords
calcium
aqueous solution
europium
phosphate
distilled water
Prior art date
Application number
KR1020060018686A
Other languages
Korean (ko)
Inventor
박인용
Original Assignee
한밭대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한밭대학교 산학협력단 filed Critical 한밭대학교 산학협력단
Priority to KR1020060018686A priority Critical patent/KR100726973B1/en
Application granted granted Critical
Publication of KR100726973B1 publication Critical patent/KR100726973B1/en

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K13/00—Seats or covers for all kinds of closets
    • A47K13/24—Parts or details not covered in, or of interest apart from, groups A47K13/02 - A47K13/22, e.g. devices imparting a swinging or vibrating motion to the seats
    • A47K13/30—Seats having provisions for heating, deodorising or the like, e.g. ventilating, noise-damping or cleaning devices
    • A47K13/307—Seats with ventilating devices
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D9/00—Sanitary or other accessories for lavatories ; Devices for cleaning or disinfecting the toilet room or the toilet bowl; Devices for eliminating smells
    • E03D9/04—Special arrangement or operation of ventilating devices
    • E03D9/05—Special arrangement or operation of ventilating devices ventilating the bowl
    • E03D9/052—Special arrangement or operation of ventilating devices ventilating the bowl using incorporated fans

Abstract

A calcium halo phosphate-based blue light-emitting phosphor for long-wavelength ultraviolet rays is provided to exhibit a high absorption peak in the ultraviolet region from 300 to 410nm and have excellent luminous brightness. The calcium halo phosphate-based blue light-emitting phosphor for long-wavelength ultraviolet rays is prepared by the steps of: dissolving a calcium compound and a europium compound in distilled water to make a calcium/europium aqueous solution; dissolving a phosphorous compound selected from ammonium phosphate, diammonium hydrogen phosphate, or ammonium dihydrogen phosphate in distilled water to make a phosphorous aqueous solution; reacting the calcium/europium aqueous solution with the phosphorous aqueous solution in a molar ratio of the sum of calcium-europium and phosphorous of 1.8-2.6 to obtain precipitates, followed by obtaining powder by heating the precipitate-containing aqueous solution to evaporate water or freeze-drying the precipitate-containing aqueous solution; heat-treating the powder under a reducing atmosphere at 800-1000°C for 1-5 hours; and washing the heat-treated powder with distilled water to obtain a calcium halo phosphate-based blue light-emitting phosphor represented by a formula 1 which is Ca2-xPO4Cl:Eux^2+, wherein x is more than 0, and less than or equal to 0.20.

Description

청색 발광 형광체 및 그 제조방법{Blue light-emitting phosphor and a preparation method thereof}Blue light-emitting phosphor and a preparation method

도 1은 본 발명의 비교실시예 1에 따른 청색 형광체 Ca2-xPO4Cl:Eux 2+에 대한 X선 회절 그래프이고,1 is an X-ray diffraction graph of the blue phosphor Ca 2-x PO 4 Cl: Eu x 2+ according to Comparative Example 1 of the present invention;

도 2는 본 발명의 실시예에 따른 청색 형광체 Ca2-xPO4Cl:Eux 2+와 시판용 청색 형광체 (Ca,Ba,Sr,Eu)10(PO4)6Cl2에 대한 380nm의 여기파장을 사용한 광 발광 스펙트럼이고,2 is an excitation of 380 nm for the blue phosphor Ca 2-x PO 4 Cl: Eu x 2+ and the commercially available blue phosphor (Ca, Ba, Sr, Eu) 10 (PO 4 ) 6 Cl 2 according to an embodiment of the present invention. It is a light emission spectrum using a wavelength,

도 3은 본 발명의 실시예에 따른 청색 형광체 Ca2-xPO4Cl:Eux 2+ 분말의 주사전자현미경(SEM) 사진이고,3 is a scanning electron microscope (SEM) photograph of a blue phosphor Ca 2-x PO 4 Cl: Eu x 2+ powder according to an embodiment of the present invention,

도 4는 도 3은 본 발명의 실시예에 따른 청색 형광체 Ca2-xPO4Cl:Eux 2+와 시판용 청색 형광체 (Ca,Ba,Sr,Eu)10(PO4)6Cl2에 대한 광 흡수 스펙트럼이다.4 is a blue phosphor Ca 2-x PO 4 Cl: Eu x 2+ and commercially available blue phosphor (Ca, Ba, Sr, Eu) 10 (PO 4 ) 6 Cl 2 according to an embodiment of the present invention Light absorption spectrum.

본 발명은 장파장 자외선용 청색 형광체 및 그의 제조방법에 관한 것으로 보다 구체적으로는 칼슘 유로피움 할로인산염을 결정상으로 하는 형광체로 장파장 자외선용 청색 형광체 및 그의 제조방법에 관한 것이다.The present invention relates to a blue phosphor for long wavelength ultraviolet light and a method for producing the same, and more particularly, to a blue phosphor for long wavelength ultraviolet light and a method for producing the same as a phosphor having calcium europium halophosphate as a crystal phase.

청색, 녹색 또는 적색의 발광 다이오드(light emitting diode; LED)를 제조하기 위해서는 InGaN, GaN, GaAs 등의 기판을 각각 제조하여 서로 다른 반도체 박막을 활용하여야 하기 때문에, LED 제조 공정에 투자비가 많이 들고 제조 단가가 비싸지는 문제점이 있다. 따라서 한 종류의 반도체 박막을 이용하여 청색, 녹색 및 적색 발광을 하는 LED를 제조할 수 있다면 공정이 간단해지고 제조비용 및 투자비용을 획기적으로 줄일 수 있다. LCD(liquid crystal display)용 후면광원(backlight)으로 각광받고 있는 백색 LED는 청색 또는 자외선과 같은 단파장 영역의 LED에 야그(yttrium aluminum garnet, YAG)계, Sr3-xSiO5:Eu2+ 형광체가 개시되어 있으나, 청색 LED를 활용한 백색 LED는 여기원으로 450nm의 파장을 가지며, 이에 적합한 형광물질이 한정되므로, 예를 들면, YAG:Ge, Sr3-xSiO5:Eu2+ 등을 이용한 백색 LED만을 구현할 수 있다. 이러한 문제점을 해결하기 위해 UV LED를 활용하여 청색, 녹색, 적색 및 백색 LED를 개발하려는 노력이 활발하며, 이러한 UV LED의 응용에 있어서, 즉 360 내지 420nm 범위의 여기원에서 발광효율이 우수한 청색, 녹색 및 적색 형광물질의 개발이 시급하다.In order to manufacture blue, green or red light emitting diodes (LEDs), substrates such as InGaN, GaN, GaAs, etc. must be manufactured to utilize different semiconductor thin films. There is a problem that the unit price is expensive. Therefore, if the LED which emits blue, green and red light using one kind of semiconductor thin film can be manufactured, the process can be simplified and the manufacturing cost and investment cost can be drastically reduced. The white LED, which has been spotlighted as a backlight for liquid crystal displays (LCDs), is a short-wavelength LED such as blue or ultraviolet light, and has a yttrium aluminum garnet (YAG) -based, Sr 3-x SiO 5 : Eu 2+ phosphor. Although disclosed, a white LED utilizing a blue LED has a wavelength of 450 nm as an excitation source, and suitable fluorescent materials are limited. For example, YAG: Ge, Sr 3-x SiO 5 : Eu 2+ , and the like. Only used white LED can be realized. In order to solve this problem, efforts are being made to develop blue, green, red and white LEDs using UV LEDs, and in the application of such UV LEDs, that is, blue light having excellent luminous efficiency in an excitation source in the range of 360 to 420 nm, Development of green and red phosphors is urgent.

또한 청색 형광물질은 청색 및 백색 LED 뿐만 아니라 능동 발광형 액정 디스 플레이에서는 액정의 보호를 위해 장파장 UV를 후면광원으로 사용하여야 하므로 장파장 UV에서 효율이 우수한 형광물질은 능동 발광형 액정 디스플레이 개발에 있어서도 매우 중요하다. 현재 254nm 및 365nm의 중·장파장 UV용으로 개발된 청색 형광물질로서 Sr10(PO4)6Cl2:EU2+이 개발되었고, 대한민국공개특허공보 제94-20463호에는 고연색 3파장형 형광램프용 청색발광 형광체로서 (SraBabCac)10(PO4)6Cl2:Eu+2 d (0.5 ≤a ≤0.9, 0.1≤b ≤0.3, 0.1 ≤c ≤0.4, 0.01 ≤d ≤0.1)의 형광물질을 제시하고 있으나, 상기 청색 형광물질들은 장파장용 UV에서 발광 강도가 저하되는 문제점이 있다.In addition, blue fluorescent materials, as well as blue and white LEDs, have to use long wavelength UV as a back light source for the protection of liquid crystals in active light emitting liquid crystal displays. Therefore, fluorescent materials having high efficiency in long wavelength UV are very effective in developing active light emitting liquid crystal displays. It is important. Currently, Sr 10 (PO 4 ) 6 Cl 2 : EU 2+ has been developed as a blue fluorescent material developed for medium and long wavelength UV of 254 nm and 365 nm. Blue emitting phosphor for lamps (Sr a Ba b Ca c ) 10 (PO 4 ) 6 Cl 2 : Eu +2 d (0.5 ≤ a ≤ 0.9, 0.1 ≤ b ≤ 0.3, 0.1 ≤ c ≤ 0.4, 0.01 ≤ d ≤ 0.1), but the blue phosphors have a problem in that the emission intensity is lowered in long wavelength UV.

본 발명의 목적은 칼슘 할로인산염에 활성제로 유로피움을 첨가하여 장파장 UV LED, 능동 발광형 액정 디스플레이용 및 램프용 등으로 적합한 고효율 청색 형광체를 제공하는 것이다.An object of the present invention is to add europium as an activator to calcium halophosphate to provide a high efficiency blue phosphor suitable for long wavelength UV LEDs, active light emitting liquid crystal displays and lamps.

본 발명에서는 화학식 Ca2-xPO4Cl:Eux 2+(0＜X＜0.2)로 표시되는 장파장 자외선용 칼슘 할로인산염계 청색 형광체 및 이의 제조방법 및 상기의 형광체를 포함하는 자외선 발광소자(LED)를 제공한다.In the present invention, a long-wavelength calcium halophosphate blue phosphor represented by the formula Ca 2-x PO 4 Cl: Eu x 2+ (0 <X <0.2), a method for preparing the same, and an ultraviolet light emitting device including the phosphor LED).

이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 화학식 Ca2-xPO4Cl:Eux 2+(0＜X＜0.2)로 표시되는 장파장 자외선용 칼슘 할로인산염계 청색 형광체는 형광체 원료로서 칼슘, 유로피움 화합물을 용매인 증류수에 용해시키고, 다른 용기에는 인 화합물을 증류수에 용해시킨 후, 이 두 용액을 반응시켜 침전물을 얻는다. 이 침전물을 증발 내지는 동결건조시켜 얻어진 분말을 800℃ 내지 1000℃ 범위에서 1시간 내지 4시간 동안 환원분위기 하에서 소성한 후 증류수로 수회 세척하여 마이크로미터 크기의 청색 분말 형광체를 제조할 수 있다. The calcium halophosphate blue phosphor for long wavelength ultraviolet rays represented by the formula Ca 2-x PO 4 Cl: Eu x 2+ (0 <X <0.2) according to the present invention is used as a phosphor raw material in distilled water as a solvent. In the other vessel, the phosphorus compound is dissolved in distilled water, and then the two solutions are reacted to obtain a precipitate. The powder obtained by evaporating or lyophilizing the precipitate may be calcined in a reducing atmosphere for 1 hour to 4 hours in a range of 800 ° C. to 1000 ° C., and then washed several times with distilled water to prepare a blue powder phosphor having a micrometer size.

상기 제조방법에 있어서, 원료물질인 칼슘 및 유로피움 화합물로서는 이들의 염화물, 질산염, 초산염, 탄산염, 수산화물, 또는 황산염이 바람직하고, 인 화합물로서는 인산암모늄(ammonium phosphate), 인산수소암모늄(ammonium hydrogen phosphate), 인산이수소암모늄(ammonium dihydrogen phosphate)또는 인산이 바람직하며, 클로린(Cl)은 상기 금속 화합물, 즉 칼슘 및 유로피움 화합물의 일부를 그의 염화물로 사용하여 공급할 수 있다.In the above production method, calcium and europium compounds as raw materials are preferably chlorides, nitrates, acetates, carbonates, hydroxides, or sulfates, and as phosphorus compounds, ammonium phosphate and ammonium hydrogen phosphate. Ammonium dihydrogen phosphate or phosphoric acid is preferred, and chlorine (Cl) can be supplied using some of the metal compounds, ie calcium and europium compounds, as its chlorides.

상기 형광체 원료물질을 이용한 형광체 분말 제조에 있어서, 암모늄 포스페이트를 이용하는 일반적인 고상법이나 액상법 등이 모두 적용될 수 있으나, 바람직하게는 액상법이 좋다. 고상법에 비해 액상법은 원자크기 상태에서 각 성분이 균질하게 혼합되어 결정상 및 결정입자의 조절이 용이하여 보다 규칙적인 형상의 형광체 입자를 얻을 수 있어, 이를 소자에 적용할 경우, 도포 및 발광 특성에서 우수하다.In the production of the phosphor powder using the phosphor raw material, all of a general solid phase method or a liquid phase method using ammonium phosphate may be applied, but a liquid phase method is preferable. Compared to the solid phase method, the liquid phase method uniformly mixes each component in the atomic size state, so that the crystal phase and the crystal grains can be easily controlled to obtain a more regular shape of the phosphor particles. great.

상기와 같이 수득된 형광체 분말의 소성 공정은 1 내지 20％수소와 80 내지 99％ 아르곤 혹은 질소의 혼합 가스를 유량 10 내지 100 ml/min의 존재하에 수행되며, 이때 유로피움이 3가에서 2가로 환원된다.The firing process of the phosphor powder thus obtained is carried out in the presence of a flow rate of 10 to 100 ml / min of a mixed gas of 1 to 20% hydrogen and 80 to 99% argon or nitrogen, where the europium is from trivalent to divalent Reduced.

본 발명의 방법에 따라 제조된, 상기 화학식 1로 표시되는 칼슘 할로인산염 청색 형광체는 형광체 모체인 칼슘 할로인산염에 활성제로 유로피움을 첨가함으로써 종래의 칼슘 바륨스트론튬 할로인산염 청색 형광체에 비해 300 내지 410nm 범위의 장파장 자외선 영역에서 고발광 고효율을 나타낸다.Calcium halophosphate blue phosphor represented by the formula (1) prepared according to the method of the present invention is 300 to 410nm range compared to conventional calcium barium strontium halophosphate blue phosphor by adding europium as an activator to calcium halophosphate as a phosphor matrix It shows high emission efficiency in the long wavelength UV region.

본 발명은 또한 상기 장파장 자외선용 칼슘 할로인산염계 청색 형광물질을 포함하는 장파장 자외선 발광소자(LED)를 제공한다. 칼슘 할로인산염을 기본으로 하고 유로피움 성분이 도핑된 본 발명의 청색 형광체는 UV LED 및 능동 발광형 액정 디스플레이에 적용되었을 때 높은 발광효율을 가진다.The present invention also provides a long wavelength ultraviolet light emitting device (LED) comprising the calcium halophosphate blue fluorescent material for the long wavelength ultraviolet light. The blue phosphor of the present invention based on calcium halophosphate and doped with europium components has a high luminous efficiency when applied to UV LEDs and active light emitting liquid crystal displays.

본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

실시예Example

실시예 1: Ca2-xPO4Cl:Eux 2+ 형광체의 제조Example 1: Preparation of Ca 2-x PO 4 Cl: Eu x 2+ Phosphors

원료물질로서, CaCl2·2H2O, EuCl3·6H2O 및 H3PO4 염들을 증류수에 혼합시켜 농도가 1M이 되도록 용액을 제조하였고, 암모니아수를 물로 희석하여 1M이 되게 제조하였다. 다음으로 이들 염 용액을 자력교반기로 교반하면서 암모니아수 용액을 첨가하거나 암모니아수 용액을 교반하면서 염 용액을 첨가하는 방법 등 두 가지 중 한 가지를 이용함으로써 백색 침전물이 생성된다. 생성된 침전물을 포함하는 용액을 가열장치가 부착된 자력교반기에 의하여 가열됨으로서 수분이 증발되어 백색 분말내지는 덩어리 상태의 물질이 얻어진다. 생성된 분말들을 알루미나 보트에 넣고 환원분위기가 가능한 전기로에 장입하고 4％수소/아르곤 혼합 가스를 30 ml/min로 흘려주면서 유로피움(Eu)이 3가에서 2가로 환원되도록 분위기를 조성하면서 800 ℃내지 1000℃에서 1시간 내지 5시간 동안 열처리를 실시하였다. 이때, (Ca+Eu)와 P의 몰비를 1.8에서 2.6까지 변화시키고, 활성물질인 유로피움의 첨가량(x)을 0.02에서 0.20까지 변화시키면서 형광체 입자를 제조하였다.As a raw material, a solution was prepared by mixing CaCl 2 · 2H 2 O, EuCl 3 · 6H 2 O, and H 3 PO 4 salts in distilled water to have a concentration of 1M, and diluted with water to prepare 1M. Next, a white precipitate is produced by using one of two methods, such as adding an ammonia water solution while stirring these salt solutions with a magnetic stirrer, or adding a salt solution while stirring the ammonia water solution. The solution containing the resulting precipitate is heated by a magnetic stirrer with a heating device to evaporate moisture to obtain a white powder or mass material. The resulting powders were placed in an alumina boat, charged into an electric furnace capable of reducing atmosphere, and the atmosphere was formed to reduce the europium (Eu) from trivalent to divalent while flowing 4% hydrogen / argon mixed gas at 30 ml / min. Heat treatment was performed for 1 to 5 hours at -1000 ° C. In this case, the phosphor particles were prepared by changing the molar ratio of (Ca + Eu) and P from 1.8 to 2.6, and changing the amount of the active substance europium (x) from 0.02 to 0.20.

상기와 같이 제조된 형광물질 중 일부에 대하여 상대적인 발광 세기를 380nm의 자외선 파장을 사용하여 측정하였다.The relative luminescence intensity of some of the fluorescent materials prepared as described above was measured using an ultraviolet wavelength of 380 nm.

실시예 2: Ca2-xPO4Cl:Eux 2+ 형광체의 제조Example 2: Preparation of Ca 2-x PO 4 Cl: Eu x 2+ Phosphors

원료물질로서, NH4H2PO4을 사용한 것을 제외하고는, 비교실시예 1과 동일한 방법에 의해 백색 분말의 침전물을 얻는 과정은 동일하며, 이들 침전물이 포함된 용액을 증발시키는 방법은 비교실시예 1과 동일한 증발방법 내지는 동결건조 방법을 이용하여 형광체 입자를 제조하기 위한 전구체(precursor)를 얻는다.Except that NH 4 H 2 PO 4 was used as a raw material, the procedure of obtaining a precipitate of white powder was the same as in Comparative Example 1, and the method of evaporating the solution containing these precipitates was compared. A precursor for preparing phosphor particles is obtained by using the same evaporation method or lyophilization method as in Example 1.

상기 비교실시예 1과 마찬가지로, 칼슘 및 유로피움과 인의 몰비의 변화에 따른 형광물질의 상대적인 발광 세기를 각각에 대해 측정하였으며, 그 결과를 도2에 나타내었다. 도 3에 (Ca+Eu)와 P의 몰비가 2.2이고 유로피움의 첨가량(x)이 0.06인 형광물질(Ca2-xPO4Cl:Eux 2+)분말의 주사전자현미경(SEM)사진을 나타내었다.As in Comparative Example 1, the relative light emission intensity of the fluorescent material according to the change in the molar ratio of calcium, europium and phosphorus was measured for each, and the results are shown in FIG. 2. 3 is a scanning electron microscope (SEM) photograph of a fluorescent material (Ca 2-x PO 4 Cl: Eu x 2+ ) powder having a molar ratio of (Ca + Eu) and P of 2.2 and an amount of europium added (x) of 0.06. Indicated.

실시예 3: 형광물질의 발광 특성Example 3: Luminescent Properties of Fluorescent Materials

실시예 1 및 실시예 2에서 제조한 형광물질들의 200 내지 425nm 사이에서의 흡수 스펙트럼을 도 4에 나타내었다.Absorption spectra between 200 and 425 nm of the fluorescent materials prepared in Examples 1 and 2 are shown in FIG. 4.

도 4의 흡수 스펙트럼에서, 비교실시예 1 및 2의 형광물질은 300nm 내지 410nm의 중·장파장 UV에서 높은 흡수 피크를 보이며, 370nm에서 흡수 피크가 최대를 나타내고 있다. 그러나, 종래 기술의 고연색 3파장형 형광램프용 청색발광 형광체 (Sr,Ba,Ca)10(PO4)6Cl2:Eu+2의 흡수피크의 형태는 비교실시예 1및 2의 형광물질과 비슷하나 강도가 낮게 나타났다. 따라서 Ca2-xPO4Cl:Eux 2+ 는 300nm에서 410nm 사이에서 다량의 자외선을 방출하는 여기 에너지원을 사용하는 응용 분야에 있어서 중요한 청색 형광물질로 사용될 수 있다.In the absorption spectrum of FIG. 4, the fluorescent materials of Comparative Examples 1 and 2 show high absorption peaks at medium and long wavelength UV of 300 nm to 410 nm, and the maximum absorption peaks at 370 nm. However, the shape of the absorption peak of the blue light emitting phosphor (Sr, Ba, Ca) 10 (PO 4 ) 6 Cl 2 : Eu +2 for the high color three-wavelength fluorescent lamp of the prior art is the fluorescent material of Comparative Examples 1 and 2. Similar to, but with low intensity. Thus, Ca 2-x PO 4 Cl: Eu x 2+ can be used as an important blue phosphor in applications that use excitation energy sources that emit large amounts of ultraviolet light between 300 nm and 410 nm.

이상에서 상술한 바와 같이, 본 발명의 청색 전기발광소자 및 그 제조방법은 다음과 같은 효과가 있다.As described above, the blue electroluminescent device of the present invention and its manufacturing method have the following effects.

Ca2-xPO4Cl:Eux 2+ 형광체는 300 내지 410nm의 중·장파장 자외선 영역, 특히 370nm 근처에서 월등히 높은 흡수 피크를 가지며, 종래의 청색 발광 형광체인 (Sr,Ba,Ca)10(PO4)6Cl2:Eu+2에 비해 휘도가 최대 1.5배 이상 높기 때문에 자외선 발광소자의 고효율 청색 형광물질로 적용될 수 있으며, 이를 활용한 능동 발광형 액정디스플레이에 적합하다.The Ca 2-x PO 4 Cl: Eu x 2+ phosphor has an extremely high absorption peak in the medium and long wavelength ultraviolet region of 300 to 410 nm, particularly around 370 nm, and is a conventional blue light emitting phosphor (Sr, Ba, Ca) 10 ( Since the brightness is up to 1.5 times higher than that of PO 4 ) 6 Cl 2 : Eu +2 , it can be applied as a high-efficiency blue fluorescent material of an ultraviolet light emitting device, and is suitable for an active light emitting liquid crystal display using the same.

Claims (4)

삭제delete 칼슘 화합물 및 유로피움 화합물을 증류수에 용해시켜 칼슘/유로피움 수용액을 만드는 단계;Dissolving the calcium compound and the europium compound in distilled water to form a calcium / uropium aqueous solution; 인산암모늄, 인산수소암모늄 또는 인산이수소암모늄로부터 선택되는 인 화합물을 증류수에 용해시켜 인 수용액을 만드는 단계;Dissolving a phosphorus compound selected from ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate in distilled water to form an aqueous solution of phosphorus; 상기 칼슘/유로피움 수용액과 상기 인 수용액을 칼슘 및 유로피움의 합과 인의 몰비를 1.8 내지 2.6으로 반응시켜 침전물을 얻은 후, 상기 침전물을 포함한 수용액을 가열하여 수분을 증발시키거나 또는 동결건조하여 분말을 얻는 단계;The calcium / europium aqueous solution and the phosphorus aqueous solution were reacted with a molar ratio of calcium and europium and the molar ratio of phosphorus at 1.8 to 2.6 to obtain a precipitate, and then the aqueous solution including the precipitate was heated to evaporate water or freeze-dried to powder Obtaining; 상기 분말을 환원 분위기에서 800℃ 내지 1000℃에서 1시간 내지 5시간 열처리하는 단계;Heat-treating the powder for 1 hour to 5 hours at 800 ° C. to 1000 ° C. in a reducing atmosphere; 상기 열처리가 끝난 분말을 증류수로 세척하여 칼슘 할로인산염계 청색 형광체를 얻는 단계를 포함하여 제조되며 The thermally treated powder is prepared by washing with distilled water to obtain a calcium halophosphate-based blue phosphor. 상기 칼슘 할로인산염계 청색 형광체가 하기의 화학식 1인 것을 특징으로 하는 장파장 자외선용 칼슘 할로인산염계 청색 형광체의 제조방법.The calcium halophosphate-based blue phosphor is a method of producing a calcium halophosphate-based blue phosphor for ultraviolet wavelengths, characterized in that the formula (1) below. 화학식 1Formula 1 Ca2-xPO4Cl:Eux 2+ Ca 2-x PO 4 Cl: Eu x 2+ 상기 식에서, 0＜x≤0.20이다.In the above formula, 0 <x≤0.20. 제2항에 있어서, The method of claim 2, 상기 칼슘 및 유로피움 화합물이 염화물인 것을 특징으로 하는 장파장 자외선용 칼슘 할로인산염계 청색 형광체의 제조방법.Method for producing a calcium halophosphate-based blue phosphor for long wavelength ultraviolet light, characterized in that the calcium and europium compounds are chlorides. 삭제delete
KR1020060018686A 2006-02-27 2006-02-27 Blue light-emitting phosphor and a preparation method thereof KR100726973B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020060018686A KR100726973B1 (en) 2006-02-27 2006-02-27 Blue light-emitting phosphor and a preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020060018686A KR100726973B1 (en) 2006-02-27 2006-02-27 Blue light-emitting phosphor and a preparation method thereof

Publications (1)

Publication Number Publication Date
KR100726973B1 true KR100726973B1 (en) 2007-06-14

Family

ID=38358982

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020060018686A KR100726973B1 (en) 2006-02-27 2006-02-27 Blue light-emitting phosphor and a preparation method thereof

Country Status (1)

Country Link
KR (1) KR100726973B1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000034331A (en) * 1998-06-02 2000-02-02 Bayer Ag High solid content polyurethane-urea dispersion having improved storage stability
JP2005060468A (en) * 2003-08-08 2005-03-10 Mitsubishi Chemicals Corp Light emission device, manifestation device, and image display device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000034331A (en) * 1998-06-02 2000-02-02 Bayer Ag High solid content polyurethane-urea dispersion having improved storage stability
JP2005060468A (en) * 2003-08-08 2005-03-10 Mitsubishi Chemicals Corp Light emission device, manifestation device, and image display device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
대한민국공개특허공보 제2000-34331호
일본공개특허공보 2005-60468호

Similar Documents

Publication Publication Date Title
Pereira et al. Red, green and blue (RGB) emission doped Y3Al5O12 (YAG) phosphors prepared by non-hydrolytic sol–gel route
Yu et al. Synthesis and luminescence properties of a novel red-emitting phosphor Ba3La (PO4) 3: Eu3+ for solid-state lighting
JP4799549B2 (en) White light emitting diode
Bandi et al. Citric based sol–gel synthesis and luminescence characteristics of CaLa2ZnO5: Eu3+ phosphors for blue LED excited white LEDs
Annadurai et al. Synthesis and photoluminescence properties of Ba2CaZn2Si6O17: Tb3+ green phosphor
JP5355613B2 (en) Yellow phosphor having oxyapatite structure, production method and white light emitting diode device thereof
Liu et al. Characterization and properties of green emitting Ca3SiO4Cl2: Eu2+ powder phosphor for white light-emitting diodes
Dhoble et al. Synthesis of Sr5SiO4Cl6: Eu3+, NaAlSiO4: Tb3+ and Sr2P2O7: Dy3+ phosphors for solid state lighting applications
Lai et al. Thermally stable luminescence properties and energy transfer of green-emitting LiBaPO4: Tb3+, Ce3+ Phosphor
Woo et al. Soluble silica assisted synthesis and luminescent characteristics of yellow emitting CaSrSiO4: Eu2+ phosphors for warm white light production
Xu et al. Photoluminescence properties and energy transfer of color tunable MgZn 2 (PO 4) 2: Ce 3+, Tb 3+ phosphors
Guo et al. Crystal structure, thermally stability and photoluminescence properties of novel Sr10 (PO4) 6O: Eu2+ phosphors
Zhong et al. A novel green phosphor Sr8ZnY (PO4) 7: Eu2+, Ln3+ (Ln= Pr, Tm, Yb) with broad emission band for high color rendering white-lighting-emitting diodes
Balaji et al. Sol–gel synthesis and luminescent properties of Eu3+: CsGd (WO4) 2 red emitting phosphors
Sun et al. Tunable luminescence of Ce3+/Mn2+-coactivated Sr3Gd (PO4) 3 with efficient energy transfer for white-light-emitting diode
Guantong et al. Luminescence properties of Eu2+-doped Ba3Si6O12N2 green phosphor: concentration quenching and thermal stability
Yue et al. Tunable emission, energy transfer and thermal stability of a single-phased Sr (1-xy) MgP2O7: xCe3+, yDy3+ phosphor for ultraviolet converted white LEDs
Meng et al. Synthesis and luminescent properties of Tb3Al5O12: Ce3+ phosphors for warm white light emitting diodes
Yang et al. Microstructure, luminescence and thermal stability properties of NaSrPO4: Tb3+ phosphors with various doping concentrations prepared using conventional solid-state sintering
KR100726973B1 (en) Blue light-emitting phosphor and a preparation method thereof
Xie et al. Eu3+/Eu2+/Tb3+ co-activated single-phase Gd2O2S: A high-performance white light emitting phosphor for light emitting diode
KR100979468B1 (en) Red Phospher and White Light Emitting Device Comprising It
KR100902413B1 (en) Synthesis and luminescence properties of a novel red-emitting phosphor under longer UV wavelength excitation
Wei et al. Single-component white light emission from Eu3+ doped BaIn6Y2O13 nanophosphors
KR100907091B1 (en) A red-emitting chlorapatite phosphor using for longer wavelength ultraviolet Light Emitting Diode

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20120427

Year of fee payment: 6

FPAY Annual fee payment

Payment date: 20130430

Year of fee payment: 7

LAPS Lapse due to unpaid annual fee