KR20020080550A - Phosphors - Google Patents
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- KR20020080550A KR20020080550A KR1020010020172A KR20010020172A KR20020080550A KR 20020080550 A KR20020080550 A KR 20020080550A KR 1020010020172 A KR1020010020172 A KR 1020010020172A KR 20010020172 A KR20010020172 A KR 20010020172A KR 20020080550 A KR20020080550 A KR 20020080550A
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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
- C09K11/7701—Chalogenides
- C09K11/7703—Chalogenides with alkaline earth metals
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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
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7716—Chalcogenides
- C09K11/7718—Chalcogenides with alkaline earth metals
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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
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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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
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/7744—Chalcogenides
- C09K11/7746—Chalcogenides with alkaline earth metals
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Abstract
Description
본 발명은 형광표시관(Vaccum Florescent Display, 이하 VFD라 칭함)과 전계방출소자(Field Emission Display, 이하 FED라 칭함) 등과 같은 표시장치에 사용할 수 있는 형광체에 관한 것이다.The present invention relates to a phosphor that can be used in a display device such as a fluorescent display tube (hereinafter referred to as VFD) and a field emission device (hereinafter referred to as FED).
VFD는 CRT와 마찬가지로 형광체를 이용한 자기발광표시소자로서 가전기기의 숫자표시, 자동차계기판 등에 널리 사용되고 있다. 숫자, 문자, 기호 등 표시용량이 적은 소형제품에 주로 사용되어 왔으나 지금은 고밀도 그래픽 표시까지 가능하여 머지 않아 총천연색, 대표시용량의 형광표시관도 상용화될 시점에 이르고 있다.VFD, like CRT, is a self-luminous display device using a phosphor and is widely used for numeric display of a home appliance and an automotive substrate. It has been mainly used for small products with small display capacity such as numbers, letters, and symbols, but now it is possible to display high density graphic, and soon it is time to commercialize fluorescent display tubes with full color and representative capacity.
FED는 LCD 등의 평판디스플레이 및 CRT의 장점을 모두 갖춘 표시장치로 주목을 받으며 현재 많은 연구개발이 활발히 진행되고 있는 차세대 표시장치이다. 미세팁으로부터 전자들이 전계장방출되는 원리를 이용한 것으로, 크기에 따라 부피, 무게가 엄청나게 불어나는 CRT의 단점을 해결하면서 가격 및 대형화, 시야각의 단점이 있는 LCD의 문제를 해결할 수 있는 성능을 가지는 것으로 알려져 있다. FED는 또한 박형, 저전력 소비, 저공정 비용, 뛰어난 온도 특성, 고속동작 등의 고른 장점을 갖추고 있어 소형 컬러텔레비젼에서부터 산업용 제품과 컴퓨터 등에 이르기까지 광범위하게 활용되고 있으며, 가장 큰 수요처는 TFT LCD와 마찬가지로 노트북 PC와 모니터, 그리고 텔레비젼을 들 수 있다.FED is attracting attention as a display device having both the advantages of flat panel display such as LCD and CRT, and is a next generation display device that is currently being actively researched and developed. It is based on the principle that electrons are emitted from the fine tip, and it has the performance to solve the problem of LCD, which has the disadvantages of price, large size, and viewing angle, while solving the disadvantage of CRT, which greatly increases the volume and weight according to the size. Known. FED also has the advantages of thinness, low power consumption, low process cost, excellent temperature characteristics, high speed operation, and is widely used in small color televisions, industrial products and computers. Laptops, monitors, and televisions.
이와 같은 VFD나 FED용의 형광체로서, 1kV 이하인 양극 구동 전압에서 발광시키기 위해서는 저속 전자선용 형광체가 필요하다. 종래의 저속 전자선용 형광체는 모체저항으로 분류하면 크게 2종류로 분류할 수 있으며, 구체적으로는 (1) 저저항의 형광체 모체를 사용하는 형광체, (2) 고저항의 형광체에 도전물질을 혼합하여 형광체층을 형성하여 형광체층의 저항을 적게 하여 사용하는 형광체로 분류할 수 있다.As such a phosphor for VFD or FED, a phosphor for a low speed electron beam is required in order to emit light at an anode drive voltage of 1 kV or less. Conventional low-speed electron beam phosphors can be broadly classified into two types, which can be classified into (1) phosphors using a low-resistance phosphor matrix, and (2) phosphors of high resistance. The phosphor layer can be formed and classified into phosphors to be used with less resistance of the phosphor layer.
상기 형광체의 모체에는 S가 포함되어 있으므로 이러한 형광체를 황화물 형광체라고 칭하고 있으며, 이와 같은 황화물 형광체는 전자의 충돌로 분해되기 쉽고, 분해된 황화물계의 물질이 형광표시관 내부를 비산한다는 것은 알려져 있다. 이 황화물계 물질이 형광표시관 내부의 음극에 피착하면 음극을 오염시키고, 그에 따라 방출능이 저하된다는 문제점을 가지고 있다. 또한 다른 산화물 형광체에 황화물이 피착하여 양극이 오염된다고 하는 문제점도 있다. 더욱이 ZnCdS계 모체에는 공해물질인 Cd를 사용하고 있으므로 환경측면에서도 바람직하지 않다.Since the mother of the phosphor contains S, such a phosphor is called a sulfide phosphor, and such a sulfide phosphor is easily decomposed by collision of electrons, and it is known that the decomposed sulfide-based material scatters inside the fluorescent display tube. When the sulfide-based material is deposited on the negative electrode inside the fluorescent display tube, it has a problem of contaminating the negative electrode and thereby lowering the emission ability. In addition, there is a problem that sulfide is deposited on other oxide phosphors to contaminate the anode. Furthermore, since ZdCdS-based matrix uses Cd, which is a pollutant, it is not preferable in terms of environment.
이를 위해 일본 특허공보 특개평8-85788호에는 알칼리 토류금속과 Ti이 산화물로 된 모체에 희토류 원소 및 삼족원소를 첨가시킨 형광체가 개시되어 있다. 이 형광체는 모체중에 S를 포함하고 있지 않는 비황화물인 동시에 Cd를 포함하지 않고 저속 전자선으로 여기 발광하지만, 수명특성에 문제가 있어 아직까지 실용화에는 이르지 못하고 있는 실정이다.For this purpose, Japanese Patent Laid-Open No. Hei 8-85788 discloses a phosphor in which a rare earth element and a tri group element are added to a matrix of an alkaline earth metal and an oxide of Ti. This phosphor is a non-sulfide that does not contain S in the mother and emits light with a low-speed electron beam without containing Cd. However, this phosphor has a problem in lifespan characteristics and has not yet been put into practical use.
이에 본 발명이 이루고자 하는 기술적 과제는 모체중에 S를 포함하고 있지 않는 비황화물인 동시에 Cd를 포함하지 않으면서도 수명특성이 양호한 형광체를 제공하는 것이다.The technical problem to be achieved by the present invention is to provide a phosphor having a long lifespan, which is a non-sulfide that does not contain S in the mother and does not contain Cd.
본 발명은, 상기 기술적 과제를 달성하기 위하여 알칼리토류 금속과 Ti의 산화물로 된 모체와The present invention, in order to achieve the above technical problem and a matrix of an oxide of alkaline earth metal and Ti and
(1) 희토류 원소;(1) rare earth elements;
(2) 주기율표의 IIIA족 원소; 및(2) group IIIA elements of the periodic table; And
(3) Hf 화합물을 포함하는 형광체를 제공한다.(3) A phosphor containing an Hf compound is provided.
본 발명의 일 실시예에 의하면 상기 알칼리 토류 금속이 Mg, Sr, Ca 또는 Ba로 이루어지는 군으로부터 선택되는 원소가 바람직하다.According to one embodiment of the present invention, an element selected from the group consisting of Mg, Sr, Ca or Ba is preferable.
본 발명의 일 실시예에 의하면 상기 희토류원소는 Ce, Pr, Eu, Tb 또는 Tm으로 이루어지는 군으로부터 선택되는 원소가 바람직하다.According to one embodiment of the present invention, the rare earth element is preferably an element selected from the group consisting of Ce, Pr, Eu, Tb or Tm.
본 발명의 일 실시예에 의하면 상기 희토류 원소의 첨가량은 0.05 내지 5 몰%인 것이 바람직하다.According to one embodiment of the present invention, the amount of the rare earth element added is preferably 0.05 to 5 mol%.
본 발명의 일 실시예에 의하면 상기 IIIA족 원소는 Al, Ga, In 또는 Tl로 이루어지는 군으로부터 선택되는 원소가 바람직하다.According to an embodiment of the present invention, the group IIIA element is preferably an element selected from the group consisting of Al, Ga, In or Tl.
본 발명의 일 실시예에 의하면 상기 IIIA족 원소의 첨가량이 0.05 내지 80 몰%인 것이 바람직하다.According to one embodiment of the present invention, it is preferable that the addition amount of the group IIIA element is 0.05 to 80 mol%.
본 발명의 일 실시예에 의하면 상기 Hf 화합물의 첨가량은 0.0001 내지 5 몰%인 것이 바람직하다.According to one embodiment of the present invention, the amount of Hf compound added is preferably 0.0001 to 5 mol%.
본 발명의 일 실시예에 의하면 상기 형광체는 SrTiO3:Pr,Hf인 것이 바람직하다.According to an embodiment of the present invention, the phosphor is preferably SrTiO 3 : Pr, Hf.
본 발명은 알칼리 토류금속과 Ti이 산화물로 된 모체에 희토류 원소 및 삼족원소를 포함하는 종래의 형광체에 Hf 화합물을 첨가하여 형광체의 결정성을 강화시킴으로써 형광체의 수명 특성을 향상시킨 것으로, 상기 첨가물의 첨가량은 0.0001 내지 5 몰%인 것이 바람직하며, 첨가량이 0.0001 몰% 미만인 경우와 첨가량이 5 몰%를 초과하는 경우에는 수명개선의 효과가 크지 않다는 문제가 있다.The present invention improves the lifespan characteristics of phosphors by adding Hf compounds to conventional phosphors containing rare earth elements and trigroup elements in a matrix of alkaline earth metals and Ti oxides, thereby enhancing the crystallinity of the phosphors. The addition amount is preferably 0.0001 to 5 mol%, and there is a problem that the effect of life improvement is not large when the addition amount is less than 0.0001 mol% and when the addition amount is more than 5 mol%.
본 발명에 따르는 형광체는 통상의 형광체 제조방법을 사용하여 얻을 수 있다.The phosphor according to the present invention can be obtained using a conventional phosphor production method.
본 발명에 따라 얻어진 형광체는 모체중에 S를 포함하고 있지 않는 비황화물이면서도 휘도 및 수명 특성이 양호하고, 환경 유해물질인 Cd를 포함하지 않으므로 환경친화적인 반면에 수명특성이 양호한 것을 주요 특징으로 한다.The phosphor obtained according to the present invention is a non-sulfide that does not contain S in the mother, and has good brightness and life characteristics, and does not contain Cd, which is an environmentally harmful substance.
이하에서 구체적인 실시예를 들어 본 발명을 상세히 설명하지만, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention is not limited thereto.
실시예 1Example 1
SrCO31 몰, TiO21몰, Al(OH)323몰%, PrCl30.5몰% 및 HfO20.01몰%를 알루미나 유발에 넣고 갈아서 1200℃에서 3시간 소성하여 형광체를 제조하였다.1 mole of SrCO 3, 1 mole of TiO 2 , 23 mole% of Al (OH) 3 , 0.5 mole% of PrCl 3 and 0.01 mole% of HfO 2 were put into an alumina trigger, and ground and calcined at 1200 ° C. for 3 hours to prepare a phosphor.
얻어진 형광체에 대하여 휘도를 측정하여 표 2에 기재하였다.The luminance was measured for the obtained phosphor and shown in Table 2.
실시예 2 내지 3Examples 2 to 3
하기 표 1에 기재된 조건을 사용하여 실시예 1과 동일한 방법으로 형광체를 제조하였다.A phosphor was prepared in the same manner as in Example 1 using the conditions described in Table 1 below.
얻어진 형광체에 대하여 휘도를 측정하여 표 2에 기재하였다.The luminance was measured for the obtained phosphor and shown in Table 2.
비교예Comparative example
SrCO31 몰, TiO21몰, Al(OH)323몰% 및 PrCl30.5몰%를 알루미나 유발에 넣고 갈아서 1200℃에서 3시간 소성하여 형광체를 제조하였다.1 mole of SrCO 3, 1 mole of TiO 2 , 23 mole% of Al (OH) 3 and 0.5 mole% of PrCl 3 were put in an alumina induction and ground and calcined at 1200 ° C. for 3 hours to prepare a phosphor.
얻어진 형광체에 대하여 휘도를 측정하여 표 2에 기재하였다.The luminance was measured for the obtained phosphor and shown in Table 2.
상기 표 2의 결과로부터 알 수 있는 바와 같이, 본 발명에 따르는 Hf가 포함되는 형광체는 Hf을 포함하지 않은 형광체와 비교하여 1000시간 경과 후 휘도잔존율이 보다 우수함을 알 수 있다.As can be seen from the results of Table 2, it can be seen that the phosphor containing Hf according to the present invention has a better luminance residual ratio after 1000 hours compared to the phosphor containing no Hf.
상기에서 살펴 본 바와 같이, 본 발명의 형광체는 환경유해물질인 Cd를 사용하지 않으면서도 종래 형광체와 비교하여 수명특성이 우수한 형광체를 제공하며, VFD 또는 FED를 비롯한 다양한 표시소자에 유용하게 사용될 수 있다.As described above, the phosphor of the present invention provides a phosphor having excellent lifespan characteristics compared to a conventional phosphor without using Cd, which is an environmentally harmful substance, and can be usefully used for various display devices including VFD or FED. .
Claims (8)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422287C (en) * | 2004-07-14 | 2008-10-01 | 湖南师范大学 | Red long persistence luminescent materials and their synthesis process and use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100422287C (en) * | 2004-07-14 | 2008-10-01 | 湖南师范大学 | Red long persistence luminescent materials and their synthesis process and use |
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