KR100484097B1 - Blue light emitting phosphor for plasma display panel - Google Patents
Blue light emitting phosphor for plasma display panel Download PDFInfo
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Abstract
본 발명은 일반식: BaMgaAlbO1+a+1.5b:Eu,M (여기서, a는 0.7∼2.5이고, b는 4.0∼10이며, M은 테르븀(Tb), 세륨(Ce), 프라세오디뮴(Pr), 디스프로슘(Dr) 및 에르븀(Er)으로 이루어진 군으로부터 선택된 적어도 하나의 희토류 원소이다)으로 표시되는 PDP용 청색발광형광체에 관한 것으로서, 본 발명에 따른 PDP용 청색발광형광체는 휘도는 물론 색순도가 우수하다.The present invention is a general formula: BaMg a Al b O 1 + a + 1.5b : Eu, M (where a is 0.7 to 2.5, b is 4.0 to 10, M is terbium (Tb), cerium (Ce), A blue light emitting phosphor for PDP represented by at least one rare earth element selected from the group consisting of praseodymium (Pr), dysprosium (Dr) and erbium (Er), wherein the blue light emitting phosphor for PDP according to the present invention has a luminance Of course, the color purity is excellent.
Description
본 발명은 플라즈마 디스플레이 패널 (이하, PDP라 함)에 적용될 수 있는 청색발광형광체에 관한 것으로서, 보다 상세하게는 색순도 및 휘도가 우수한 PDP용 청색발광형광체에 관한 것이다. The present invention relates to a blue light emitting phosphor that can be applied to a plasma display panel (hereinafter referred to as PDP), and more particularly, to a blue light emitting phosphor for PDP having excellent color purity and luminance.
형광체라 함은 에너지 자극에 의해 온도방사 이외의 원인으로 발광하는 성질을 지니는 물질을 의미하며, 오늘날 실용화되고 있는 대부분의 형광체는 천연산의 광물보다는 공업적 기술에 의해 인위적으로 합성된 것이 일반적이다.Phosphor refers to a material having a property of emitting light due to energy stimulation other than temperature radiation, and most of the phosphors that are practically used today are artificially synthesized by industrial technology rather than minerals of natural acid.
형광체는 일반적으로 형광램프, 형광수은램프, 복사용 램프 등과 같은 광원용; 음극선관, 전계발광소자, 전자현미경 등과 같은 표시용; 및 X선 증감지, 신틸레이터(scintillater) 등과 같은 검지용 기기등에 사용되고 있으며 새로운 멀티미디어 기기의 개발과 더불어 향후에도 다양한 용도에 이용될 전망이다. Phosphors are generally used for light sources such as fluorescent lamps, fluorescent mercury lamps, radiation lamps and the like; For displays such as cathode ray tubes, electroluminescent devices, electron microscopes and the like; And it is used for detection devices such as X-ray sensitizer and scintillater, and is expected to be used for various purposes in the future with the development of new multimedia devices.
상기와 같은 형광체는 적용되는 기기가 노출되는 광원의 파장대에서 여기하는 특성을 갖는 것으로 선택되어야 하며, 각 적용 기기에 알맞는 전류포화특성, 열화특성, 휘도, 색순도, 잔광특성, 고전류밀도하에서의 저항력 및 기타 물성이 바람직하게 갖추어져야 한다. Such phosphors should be selected to have the characteristics of excitation in the wavelength range of the light source to which the applied device is exposed, the current saturation characteristics, deterioration characteristics, luminance, color purity, afterglow characteristics, resistance under high current density and Other physical properties should be provided preferably.
이러한 조건을 고려할 때, PDP용 청색발광형광체로는 여기광이 147nm 또는 172nm인 광원에 의해 발광하는 알루미네이트계의 청색발광형광체가 주로 사용되고 있다. In consideration of such conditions, an aluminate-based blue light-emitting phosphor which emits light by a light source having an excitation light of 147 nm or 172 nm is mainly used as a blue light-emitting phosphor for PDP.
이러한 알루미네이트계 청색발광형광체의 대표적인 예로서 BaMgAl10O17:Eu, BaMg2Al16O27:Eu, BaMgAl14O23:Eu 등을 들 수 있으며, 이중 수명특성면에서 볼 때 가장 바람직한 것은 BaMgAl10O17:Eu이다.BaMgAl 10 O 17 : Eu, BaMg 2 Al 16 O 27 : Eu, BaMgAl 14 O 23 : Eu and the like are representative examples of such an aluminate-based blue light-emitting phosphor, and BaMgAl is most preferable in view of double life characteristics. 10 O 17 : Eu.
이러한 통상의 PDP용 청색발광형광체는 x=0.150±0.005, y=0.076±0.01 수준 (측정기기: DARSA, PSI 제품)의 색좌표를 나타낸다. 그러나, PDP의 구동 특성 등을 고려해볼 때 색좌표 특성, 특히 색좌표의 y값이 0.065±0.005 수준으로 낮아져야 더 우수한 색순도를 얻을 수 있다. This conventional blue light emitting phosphor for PDP has a color coordinate of x = 0.150 ± 0.005, y = 0.076 ± 0.01 level (measurement device: DARSA, PSI). However, in consideration of the driving characteristics of the PDP, better color purity can be obtained when the color coordinate characteristic, in particular, the y value of the color coordinate is lowered to 0.065 ± 0.005.
색좌표의 값은 형광체의 총량에 대하여 통상 3중량% 정도인 부활제(Eu)의 첨가량을 제어함으로써 조절되며, 특히 색좌표의 y값을 상기와 같은 바람직한 수준으로 낮추기 위해서는 부활제의 첨가량을 감소시키는 것이 일반적이다. 그러나, 부활제의 첨가량이 감소하면 발광원으로부터 공급되는 에너지에 충분히 여기할 수 없다. 즉, 충분량의 부활제를 포함하지 않은 형광체 형성용 조성물은 베이킹시 열안정성이 떨어지기 때문에 그로부터 형성되는 형광체의 휘도가 저하되는 것을 막을 수 없게 된다. The value of the color coordinate is controlled by controlling the addition amount of the activator (Eu), which is usually about 3% by weight, based on the total amount of the phosphor. It is common. However, when the addition amount of the activator is reduced, it cannot be sufficiently excited by the energy supplied from the light emitting source. That is, the composition for forming a phosphor that does not contain a sufficient amount of the activator is inferior in thermal stability during baking, so that the luminance of the phosphor formed therefrom cannot be prevented from being lowered.
본 발명이 이루고자 하는 기술적 과제는 휘도 저하를 일으키지 않으면서도 바람직한 색좌표 특성을 가질 수 있는 PDP용 청색발광형광체를 제공하는 것이다. The technical problem to be achieved by the present invention is to provide a blue light emitting phosphor for PDP that can have desirable color coordinate characteristics without causing a decrease in luminance.
본 발명의 기술적 과제는 하기 일반식으로 표시되는 PDP용 청색발광형광체에 의하여 이루어질 수 있다: Technical problem of the present invention can be achieved by a blue light emitting phosphor for PDP represented by the following general formula:
BaMgaAlbO1+a+1.5b:Eu,MBaMg a Al b O 1 + a + 1.5b : Eu, M
(여기서, a는 0.7∼2.5이고, b는 4.0∼10이며, M은 테르븀(Tb), 세륨(Ce), 프라세오디뮴(Pr), 디스프로슘(Dr) 및 에르븀(Er)으로 이루어진 군으로부터 선택된 적어도 하나의 희토류 원소이다). Wherein a is 0.7 to 2.5, b is 4.0 to 10, and M is at least one selected from the group consisting of terbium (Tb), cerium (Ce), praseodymium (Pr), dysprosium (Dr), and erbium (Er) Rare earth elements).
본 발명에 따른 PDP용 청색발광형광체에 있어서, 부활제인 Eu의 첨가량은 형광체의 총량을 기준으로 하여 1∼5중량%이고, 공부활제인 M의 첨가량은 3ppm∼50,000ppm, 더 바람직하게는 100ppm∼1,000ppm이다. In the blue light emitting phosphor for PDP according to the present invention, the addition amount of Eu as the activator is 1 to 5% by weight based on the total amount of the phosphor, and the addition amount of M as the study activator is 3 ppm to 50,000 ppm, more preferably 100 ppm to 1,000 ppm.
상기 공부활제 M의 첨가량이 3ppm 미만이면 첨가량이 너무 적어 그 효과가 미미한 반면, 1,000ppm을 초과할 경우에는 휘도의 저하를 일으킬 수 있으므로 바람직하지 않다. If the addition amount of the study agent M is less than 3ppm, the addition amount is too small and the effect is insignificant, but if it exceeds 1,000ppm, it is not preferable because it may cause a decrease in luminance.
또한, 본 발명에 따른 PDP용 청색발광형광체의 색좌표는 부활제의 첨가량을 3중량% 수준으로 제어하였을 때 각각 x=0.015±0.005, y=0.065±0.005이다. Further, the color coordinates of the blue light emitting phosphor for PDP according to the present invention are x = 0.015 ± 0.005 and y = 0.065 ± 0.005, respectively, when the amount of the activator is controlled at the level of 3 wt%.
본 발명에 따른 PDP용 청색발광형광체는 부활제인 Eu의 첨가량을 줄이지 않는 대신 테르븀(Tb), 세륨(Ce), 프라세오디뮴(Pr), 디스프로슘(Dr) 및 에르븀(Er)으로 이루어진 군으로부터 선택된 적어도 하나의 희토류 원소를 공부활제로서 미량 첨가함으로써 휘도의 감소 없이도 색좌표 특성을 개선할 수 있다. At least one selected from the group consisting of terbium (Tb), cerium (Ce), praseodymium (Pr), dysprosium (Dr) and erbium (Er) instead of reducing the addition amount of Eu, an activator, according to the present invention By adding a small amount of the rare earth element as a activator, the color coordinate characteristics can be improved without reducing the luminance.
즉, 적절한 희토류 원소를 극소량 첨가하면 형광체의 에너지 밴드 갭이 넓어지는데, 이로 인해 고에너지의 빛이 발생하게 되어 색좌표 특성이 양호해지는 것으로 판단된다. In other words, when a small amount of the appropriate rare earth element is added, the energy band gap of the phosphor is widened, and thus, high energy light is generated and color coordinate characteristics are considered to be good.
본 발명에 따른 PDP용 청색발광형광체는 통상의 제조방법에 따라 실시될 수 있는데, 보다 구체적으로 설명해보면 다음과 같다.The blue light emitting phosphor for PDP according to the present invention can be carried out according to a conventional manufacturing method, which will be described in more detail as follows.
먼저, Ba, Mg, Al, Eu, 및 테르븀(Tb), 세륨(Ce), 프라세오디뮴(Pr), 디스프로슘(Dr) 및 에르븀(Er)으로 이루어진 군으로부터 선택된 적어도 하나의 희토류 원소 각각의 산화물을 융제와 함께 혼합한 다음, 2단계에 걸쳐 소성함으로써 제조될 수 있다. 이때, 제1 단계의 소성 공정은 약 1,200∼1,800℃ 범위의 온도에서 실시되는 일종의 산화소성 공정으로서 입자의 결정이 성장하는 단계이다. 이에 반하여 제2 단계 소성은 1,200∼1,500℃의 온도에서 약환원성 분위기 하에 실시됨으로써 Eu의 원자가를 +3에서 +2로 바꾸어준다. First, an oxide of each of at least one rare earth element selected from the group consisting of Ba, Mg, Al, Eu, and terbium (Tb), cerium (Ce), praseodymium (Pr), dysprosium (Dr) and erbium (Er) Can be prepared by mixing together and then firing in two steps. At this time, the firing process of the first step is a kind of oxidizing process performed at a temperature in the range of about 1,200 to 1,800 ° C., in which crystals of the particles are grown. In contrast, the second stage firing is carried out in a weakly reducing atmosphere at a temperature of 1,200 to 1,500 ° C. to change the valence of Eu from +3 to +2.
전술한 바와 같은 제조방법에 따라 만들어진 PDP용 청색발광형광체는 휘도가 우수할 뿐 아니라 좌표값이 소정범위로 낮아져서 색순도가 우수해진다. The blue light emitting phosphor for PDP made according to the manufacturing method as described above not only has excellent brightness, but also has a low coordinate value, thereby improving color purity.
이하, 실시예 및 비교예를 들어 본 발명을 보다 상세하게 설명하고자 한다. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
실시예 1Example 1
16.77g의 BaCO3, 4.03g의 MgO, 50.98g의 Al2O3 및 2.64g의 Eu2O3를 0.2g의 AlF3, 0.001g의 Tb4O7와 혼합한 다음, 1,400℃로 소성한 다음, 냉각시켰다. 이어서, H2 5%/N2 95%의 혼합 가스 주입하에 상기 결과물을 1,300℃로 다시 소성하여 구조식이 BaMgAl10O17:Eu,Tb인 형광체를 수득하였다.16.77 g BaCO 3 , 4.03 g MgO, 50.98 g Al 2 O 3 and 2.64 g Eu 2 O 3 were mixed with 0.2 g AlF 3 and 0.001 g Tb 4 O 7 and then calcined at 1,400 ° C. Then cooled. Subsequently, the resultant was calcined again at 1,300 ° C. under a mixed gas injection of H 2 5% / N 2 95% to obtain a phosphor having the structural formula BaMgAl 10 O 17 : Eu, Tb.
상기 수득된 형광체의 색좌표(측정기기: DARSA, PSI 제품) 및 휘도를 측정하여 그 결과를 하기 표 1에 나타내었다. Color coordinates (measurement device: DARSA, PSI product) and luminance of the obtained phosphor were measured and the results are shown in Table 1 below.
실시예 2Example 2
Tb4O7의 첨가량을 0.01g으로 하는 것을 제외하고는 실시예 1에서와 동일한 방법으로 형광체를 제조하고, 그의 색좌표, 휘도 및 주발광 피이크를 측정하여 그 결과를 하기 표 1에 나타내었다.A phosphor was prepared in the same manner as in Example 1 except that the amount of Tb 4 O 7 was 0.01 g, and the color coordinates, luminance, and main emission peak thereof were measured, and the results are shown in Table 1 below.
실시예 3Example 3
Tb4O7의 첨가량을 0.1g으로 하는 것을 제외하고는 실시예 1에서와 동일한 방법으로 형광체를 제조하고, 그의 색좌표, 휘도 및 주발광 피이크를 측정하여 그 결과를 하기 표 1에 나타내었다.A phosphor was prepared in the same manner as in Example 1 except that the amount of Tb 4 O 7 added was 0.1 g, and the color coordinates, luminance, and main emission peak thereof were measured, and the results are shown in Table 1 below.
실시예 4Example 4
Tb4O7의 첨가량을 1g으로 하는 것을 제외하고는 실시예 1에서와 동일한 방법으로 형광체를 제조하고, 그의 색좌표, 휘도 및 주발광 피이크를 측정하여 그 결과를 하기 표 1에 나타내었다.A phosphor was prepared in the same manner as in Example 1 except that the amount of Tb 4 O 7 added was 1 g, and the color coordinates, luminance, and main emission peak thereof were measured, and the results are shown in Table 1 below.
실시예 5Example 5
Tb4O7의 첨가량을 5g으로 하는 것을 제외하고는 실시예 1에서와 동일한 방법으로 형광체를 제조하고, 그의 색좌표, 휘도 및 주발광 피이크를 측정하여 그 결과를 하기 표 1에 나타내었다.A phosphor was prepared in the same manner as in Example 1 except that the amount of Tb 4 O 7 added was 5 g, and the color coordinates, luminance, and main emission peak thereof were measured, and the results are shown in Table 1 below.
실시예 6Example 6
Tb4O7 대신에 0.1g의 CeO2를 첨가하는 것을 제외하고는 실시예 1에서와 동일한 방법을 실시하여 구조식이 BaMgAl10O17:Eu,Ce인 형광체를 수득하였다. 그의 색좌표, 휘도 및 주발광 피이크를 측정하여 그 결과를 하기 표 1에 나타내었다.A phosphor having the structural formula BaMgAl 10 O 17 : Eu, Ce was obtained in the same manner as in Example 1 except that 0.1 g of CeO 2 was added instead of Tb 4 O 7 . Its color coordinates, luminance and main emission peaks were measured and the results are shown in Table 1 below.
실시예 7Example 7
Tb4O7 대신에 0.1g의 Pr6O11를 첨가하는 것을 제외하고는 실시예 1에서와 동일한 방법을 실시하여 구조식이 BaMgAl10O17:Eu,Pr인 형광체를 수득하였다. 그의 색좌표, 휘도 및 주발광 피이크를 측정하여 그 결과를 하기 표 1에 나타내었다.A phosphor having the structural formula BaMgAl 10 O 17 : Eu, Pr was obtained in the same manner as in Example 1 except that 0.1 g of Pr 6 O 11 was added instead of Tb 4 O 7 . Its color coordinates, luminance and main emission peaks were measured and the results are shown in Table 1 below.
실시예 8Example 8
Tb4O7 대신에 0.1g의 Dy2O3를 첨가하는 것을 제외하고는 실시예 1에서와 동일한 방법을 실시하여 구조식이 BaMgAl10O17:Eu,Dy인 형광체를 수득하였다. 그의 색좌표, 휘도 및 주발광 피이크를 측정하여 그 결과를 하기 표 1에 나타내었다.A phosphor having the structural formula BaMgAl 10 O 17 : Eu, Dy was obtained in the same manner as in Example 1 except that 0.1 g of Dy 2 O 3 was added instead of Tb 4 O 7 . Its color coordinates, luminance and main emission peaks were measured and the results are shown in Table 1 below.
비교예 1Comparative Example 1
Tb4O7을 첨가하지 않는 것을 제외하고는 실시예 1에서와 동일한 방법을 실시하여 구조식이 BaMgAl10O17:Eu인 형광체를 수득하였다. 그의 색좌표, 휘도 및 주발광 피이크를 측정하여 그 결과를 하기 표 1에 나타내었다.Except not adding Tb 4 O 7 The same procedure as in Example 1 was carried out to obtain a phosphor having the structural formula BaMgAl 10 O 17 : Eu. Its color coordinates, luminance and main emission peaks were measured and the results are shown in Table 1 below.
비교예 2Comparative Example 2
Eu2O3의 첨가량은 0.1g으로 하는 것을 제외하고는 실시예 1에서와 동일한 방법으로 형광체를 수득하고 그의 색좌표 및 휘도를 측정하여 그 결과를 하기 표 1에 나타내었다.A phosphor was obtained in the same manner as in Example 1 except that the amount of Eu 2 O 3 added was 0.1 g, and the color coordinates and luminance thereof were measured, and the results are shown in Table 1 below.
상기 표 1의 결과로부터 알 수 있듯이, 본 발명에 따른 PDP용 청색발광형광체(실시예 1 내지 8)는 색좌표값이 x=0.148±0.005, y=0.07∼0.055범위에 있어 색순도가 개선된 것을 알 수 있다. As can be seen from the results of Table 1, the blue light emitting phosphors (Examples 1 to 8) for the PDP according to the present invention show that the color purity is improved when the color coordinate value is in the range of x = 0.148 ± 0.005 and y = 0.07 to 0.055. Can be.
이에 반하여, 비교예 1의 경우에는 색순도의 y 좌표값이 0.075로서 바람직한 색순도를 나타내기에는 적합하지 않았으며, 비교예 2의 경우에는 색좌표 특성은 우수하나, 부활제인 Eu의 첨가량 감소에 따라 휘도가 저하된 것으로 나타났다. On the contrary, in the case of Comparative Example 1, the y-coordinate value of the color purity was 0.075, which was not suitable for showing a desirable color purity. It was found to be degraded.
본 발명에 따르면, 적절한 희토류 원소를 공부활제로서 소량 첨가함으로써 색좌표의 y값을 0.07∼0.055 수준으로 낮추었으며, 이에 따라 휘도의 저하 없이 색순도가 개선된 PDP용 청색발광형광체를 얻을 수 있다. According to the present invention, by adding a small amount of a suitable rare earth element as a study active agent, the y value of the color coordinate is lowered to 0.07 to 0.055 level, and thus a blue light emitting phosphor for PDP having improved color purity can be obtained without lowering luminance.
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JPH0711250A (en) * | 1993-04-28 | 1995-01-13 | Nemoto Tokushu Kagaku Kk | Light-storing fluorescent material |
JPH08127772A (en) * | 1994-11-01 | 1996-05-21 | Nemoto Tokushu Kagaku Kk | Photostimulable phosphor |
JPH0913028A (en) * | 1995-06-30 | 1997-01-14 | Nemoto Tokushu Kagaku Kk | White phosphorescent phosphor |
JPH0932367A (en) * | 1995-07-24 | 1997-02-04 | Terax:Kk | Grip |
KR19990079766A (en) * | 1998-04-09 | 1999-11-05 | 손욱 | Blue phosphor for active light emitting liquid crystal display device |
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JPH0711250A (en) * | 1993-04-28 | 1995-01-13 | Nemoto Tokushu Kagaku Kk | Light-storing fluorescent material |
JPH08127772A (en) * | 1994-11-01 | 1996-05-21 | Nemoto Tokushu Kagaku Kk | Photostimulable phosphor |
JPH0913028A (en) * | 1995-06-30 | 1997-01-14 | Nemoto Tokushu Kagaku Kk | White phosphorescent phosphor |
JPH0932367A (en) * | 1995-07-24 | 1997-02-04 | Terax:Kk | Grip |
KR19990079766A (en) * | 1998-04-09 | 1999-11-05 | 손욱 | Blue phosphor for active light emitting liquid crystal display device |
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