KR100187484B1 - Element phosphorescent - Google Patents
Element phosphorescent Download PDFInfo
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- KR100187484B1 KR100187484B1 KR1019980006357A KR19980006357A KR100187484B1 KR 100187484 B1 KR100187484 B1 KR 100187484B1 KR 1019980006357 A KR1019980006357 A KR 1019980006357A KR 19980006357 A KR19980006357 A KR 19980006357A KR 100187484 B1 KR100187484 B1 KR 100187484B1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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Abstract
(목적) La2O2S를 모체로 하는 형광체에 방습처리를 하여 내습성을 향상시키고, 전자선 여기 형광체로서 사용하도록 한다.(Purpose) improve the moisture resistance by a moisture-proof treatment on a phosphor La 2 O 2 S as a matrix and, to be used as an electron beam excited phosphor.
(구성) La2O2S로 표시되는 형광체 모체의 입자표면에 금속산화물로부터 형성된 투명보호막을 형성한다. 상기 금속산화물로는 Al2O3, SiO3, TiO2, GeO2로부터 선택된 1 내지 2이상의 물질이 바람직하고, 상기한 형광체 모체에 대해 상기 금속산화물을 50∼2000ppm 첨가하여 상기 투명보호막을 형성시키면, 양호한 결과가 얻어질 수 있다. 각 형광체에서, 보호막의 피복량이 40ppm 이상이 되면 휘도가 신속하게 상승되기 시작하고, 3000ppm 부근을 넘으면 종래예 보다도 저하하게 된다. 상대휘도가 110 보다 높은 것을 양호한 범위라고 고려하면, 형광체에 대한 보호막의 양은 50∼2000ppm이 바람직하다.(Configuration) A transparent protective film formed of a metal oxide is formed on the particle surface of the phosphor matrix represented by La 2 O 2 S. The metal oxide is preferably at least one or two or more materials selected from Al 2 O 3 , SiO 3 , TiO 2 and Fe 2 , and the transparent protective film is formed by adding 50 to 2000 ppm of the metal oxide to the phosphor matrix. , Good results can be obtained. In each phosphor, when the coating amount of the protective film is 40 ppm or more, the luminance starts to rise rapidly, and when it exceeds 3000 ppm, it is lower than the conventional example. Considering that the relative luminance is higher than 110 as a good range, the amount of the protective film for the phosphor is preferably 50 to 2000 ppm.
Description
(산업상의 이용분야)(Industrial use)
본 발명은 형광표시관이나 고휘도용 광원등의 발광·표시부에 사용되는, 전자 조사충돌을 받아 발광하는 형광체에 관한 것으로, 특히 100V∼2RV 정도의 비교적 낮은 양극전압에서 가속된 전자에 의해 여기 발광된 전자선 여기 형광체에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a phosphor that emits light upon collision of electron irradiation, which is used in a light emitting / display portion such as a fluorescent display tube or a light source for high luminance. It relates to an electron beam excited phosphor.
(종래기술)(Prior Art)
희토류 형광체로는 Y2O2S: Eu, Gd2O2S: Eu,La2O2S: Eu등이 알려져 있다. 이것들은 CRT용의 형광체로서 적용하는 것을 목표로하여 개발된 것으로, 통상 30kV 정도의 고전압으로 가속한 고속전자의 조사충돌을 받아서 발광한다.As the rare earth phosphor, X 2 O 2 S: Eu, Vd 2 O 2 S: Eu, La 2 O 2 S: Eu and the like are known. These products were developed with the aim of being applied as a phosphor for CrT, and emit light under the irradiation collision of high-speed electrons accelerated to a high voltage of about 30 kV.
CRT에 있어서, 표시면에 형광체를 도포하는 방법으로서는 슬러리법이 사용되고 있다. 우선, 수용성의 폴리비닐알코올과 광반응성의 중크롬산암모늄의 혼합수용액에 형광체를 분산시킨다. 이 분산액을 슬러리라 부른다. 슬러리를 CRT의 표시면에 도포한 후, 수은등으로 노출하여 수불용성으로 하고, 다시 온수로 현상한다.In the CRT, a slurry method is used as a method of applying a phosphor to a display surface. First, the phosphor is dispersed in a mixed aqueous solution of water-soluble polyvinyl alcohol and photoreactive ammonium dichromate. This dispersion is called a slurry. After apply | coating a slurry to the display surface of CrT, it exposes with a mercury lamp, makes it insoluble in water, and develops again with hot water.
상기한 바와같이 슬러리법에서는 물을 사용하므로 내수성이나 내습성이 나쁜 형광체를 사용할 수는 없다. 그런데, 상기한 CRT용으로 되어 있는 각종 형광체중, La2O2S를 모체로 하는 형광체는 Y2O2S나 Gd2O2S를 모체로 하는 형광체에 비교하여 내습성이 나쁘고, 실제로는 슬러리법으로 도포하면 슬러리중에서 형광체가 가수분해된다고 하는 문제가 있었다.As mentioned above, since the slurry method uses water, it is impossible to use a phosphor having poor water resistance or moisture resistance. By the way, among the above-mentioned various phosphors used for Crt, the phosphors having LA 2 O 2 S as a mother have poor moisture resistance compared to the phosphors having X 2 O 2 S or CD 2 O 2 S as a mother, and in reality, When applied by the slurry method, there is a problem that the phosphor is hydrolyzed in the slurry.
이와같이 La2O2S를 모체로 하는 형광체의 내습성이 나쁜것은 La2O3가 대단히 흡착성이 높은 산화물이며, 이것에 S를 붙여서 La2O2S로서도 흡습성이 유지된다고 생각되기 때문이다. 형광체 형성후의 방치시간에 따라 각 형광체를 형광표시관의 표시부에 적용하여 그 상대휘도를 비교하면, 도 3에 도시한 것처럼 된다. 즉, Y2O2S: Eu 형광체의 경우에는 방치시간에 불구하고 휘도가 일정하게 되어 있으나, 상기 La2O2S: Eu 형광체에서는 24시간 후에 상대휘도가 50%로 저하하고, 48시간후에는 75%로 저하, 다시 72시간 후에는 거의 빛이나지 않게 된다.The reason why the moisture resistance of the phosphor having LA 2 O 2 S as a mother is poor is that LA 2 O 3 is an oxide having very high adsorption, and it is thought that hygroscopicity is maintained even as LA 2 O 2 S by attaching S to this. When the phosphors are applied to the display unit of the fluorescent display tube according to the leaving time after the formation of the phosphors, their relative luminances are compared, as shown in FIG. That is, in the case of the X 2 O 2 S: Eu phosphor, the luminance is constant despite the standing time, but in the LA 2 O 2 S: Eu phosphor, the relative luminance decreases to 50% after 24 hours, and after 48 hours. Decreases to 75% and becomes almost luminous after 72 hours.
이상의 설명과 같이 전기한 La2O2S: Eu 형광체는 CRT용 고속전자 여기 형광체로서 개발된 것으로, 흡습성이 높아서 안정한 발광성능이 얻어질 수 없는 문제가 있었다.As described above, the LA 2 O 2 S: Eu phosphor developed as a high-speed electron-excited phosphor for CRTs has a problem of high hygroscopicity and no stable light emission performance.
이에 대하여, 본 발명자는 다음의 사항에 착안하였다. 즉 La2O2S을 모체로 하는 형광체는 에너지 차이 Eg가 4.4V이고, Y2O2S의 4.6eV나 Gd2O2S의 4.5eV 보다도 작아서, 모체저항이 작다. 따라서 본 발명자는 모체저항이 그 정도로 작은 형광체라면 통상 1RV 이하의 저전압으로 구동시키는 전자선 여기 형광체로서 사용할 수 있고, 높은 초기휘도 외에 양호한 수명 특성으로 사용할 수 있지 않을까 착안했다.In contrast, the present inventors have focused on the following matters. In other words the phosphor La 2 O 2 S as a matrix is an energy difference Eg is 4.4V, less than 4.5eV of Y 2 O 2 S 4.6eV or Gd 2 O 2 S of, the matrix resistance is small. Therefore, the inventors of the present invention focused on whether or not the phosphor having a low mother resistance can be used as an electron beam excitation phosphor to be driven at a low voltage of 1 RV or less, and can be used for good life characteristics in addition to high initial luminance.
이로서, 본 발명자는 La2O2S을 모체로 하는 형광체에 방습처리를 실시하여 내습성을 향상시키고, 전자선 여기 형광체로서 사용에 제공한다는 과제를 얻게 되었다.As a result, the inventors of the present invention have achieved the problem of improving moisture resistance by subjecting the phosphor having LA 2 O 2 S as a mother to improve moisture resistance and to use it as an electron beam excited phosphor.
도 1는 본발명의 각 실시예에 있어서, 각 형광체의 입자를 피복하는 보호막의 부착량(ppm)과 각각의 초기 휘도(輝度)와의 관계를 예시하는 그래프,BRIEF DESCRIPTION OF THE DRAWINGS In each Example of this invention, the graph which illustrates the relationship between the adhesion amount (ppm) of the protective film which coat | covers the particle | grains of each fluorescent substance, and each initial luminance,
도 2는 본발명의 각 실시예와 비교예인 종래의 각 형광체를 사용한 형광표시관을 각각 1000시간 연속점등한 후의 휘도를 측정하고, 초기 휘도를 100%로 했을 때의 잔존휘도를 예시하는 그래프,FIG. 2 is a graph illustrating luminance after measuring the luminance after continuously lighting the fluorescent display tubes using the conventional phosphors according to the Examples and Comparative Examples of the present invention for 1000 hours, and setting the initial luminance to 100%.
제 3도는 La2O2S를 모체로 하는 종래의 형광체와 Y2O2S를 모체로 하는 형광체를 각각 형광표시관에 적용한 경우에 있어서, 각 형광체 제조후에 형광표시관에 편입하기 까지의 방치시간과 각 형광표시관의 상대휘도의 관계를 비교하여 도시하는 그래프.FIG. 3 shows that the conventional fluorescent substance having LA 2 O 2 S and the fluorescent substance having X 2 O 2 S as the mother are applied to the fluorescent display tubes, respectively, until the incorporation into the fluorescent display tube after production of each phosphor. Graph showing the relationship between time and relative luminance of each fluorescent display tube.
(과제를 해결하기 위한 수단)(Means to solve the task)
본발명의 전자선 여기 형광체는 일반식 La2O2S: R로 표시되는 형광체 모체의 입자표면에 열적으로 안정시킨, 금속산화물로 형성되는 투명보호막을 형성하여 이루어지는 것을 특징으로 한다.The electron beam-excited phosphor of the present invention is characterized by forming a transparent protective film formed of a metal oxide thermally stabilized on the particle surface of the phosphor matrix represented by the general formula La 2 O 2 S: R.
상기 금속산화물은 Al2O3, SiO3, TiO2, GeO2에서 선택된 1 내지 2 이상의 물질일 수 있다.The metal oxide may be one or two or more materials selected from Al 2 O 3 , SiO 3 , TiO 2 and Fe 2 .
상기 투명 보호막은 상기 형광체에 대하여 상기 금속산화물을 50∼2000ppm 첨가하여 형성할 수 있다.The transparent protective film may be formed by adding 50 to 2000 ppm of the metal oxide to the phosphor.
(작용)(Action)
또, La2O2S로 표시되는 형광체 모체의 입자표면은 금속산화물로 이루어지는 투명보호막으로 보호되어 있으므로, 이것을 모체로 하는 형광체는 내습성이 우수하다. 따라서, 슬러리법등에 의해 표시부에 설치하여도, 전자선 여기 형광체로서 우수한 발광성능을 나타낸다.In addition, since the particle surface of the fluorescent substance matrix represented by La 2 O 2 S is protected by a transparent protective film made of a metal oxide, a phosphor for this as the matrix is excellent in moisture resistance. Therefore, even if it is provided in a display part by the slurry method etc., the light emission performance excellent as an electron beam excited fluorescent substance is exhibited.
(실시예)(Example)
(1) 제 1실시예(1) First embodiment
본 실시예의 전자선 여기 형광체는 La2O2S를 모체로 하는 형광체인 La2O2S: Eu의 입자표면에 금속산화물인 Al2O3의 보호막을 형성한 것이다. 형광체입자의 평균입경은 3∼6μm 이다. 이하에 그 제조방법을 설명한다.In this embodiment the electron beam excitation fluorescent material is a phosphor La 2 O 2 S 2 O 2 S in which the La Matrix: to form a protective film of a metal oxide on the surface of the particles of Al 2 O 3 Eu. The average particle diameter of fluorescent substance particles is 3-6 micrometers. The manufacturing method is explained below.
Al2O3의 원료인 질산알루미늄을 IPA (이소프로필알코올)에 용해시킨다. 용해시키는 질산알루미늄의 양은 형광체의 중량에 대하여 외부형광체에 피복되는 Al2O3의 비율이 10∼10000ppm으로 되도록 정한다. 즉, 형광체 1kg에 대하여 Al2O3가 10∼10000ppm 피복되도록 Al(NO2)3를 43∼43000mg 용해시킨다.Aluminum nitrate, which is a raw material of Al 2 O 3 , is dissolved in IPA (isopropyl alcohol). The amount of aluminum nitrate to be dissolved is determined so that the ratio of Al 2 O 3 coated on the external phosphor to the weight of the phosphor is 10 to 10000 ppm. That is, 43-43000 mg of A (N0 2 ) 3 is dissolved so as to coat 10-10000 ppm of Al 2 O 3 with respect to 1 kg of the phosphor.
상기 알코올용액에 La2O2S: Eu 형광체를 침지시킨후, 알코올을 증발시킨다. 이것을 대기중에 있어서 300∼500℃의 온도로 소성하고, Al2O3의 박막을 상기 형광체입자의 표면에 형성한다.After dipping the LA 2 O 2 S: Eu phosphor into the alcohol solution, the alcohol is evaporated. This is baked at a temperature of 300 to 500 ° C. in the air, and a thin film of Al 2 O 3 is formed on the surface of the phosphor particles.
상기한 바와같이 처리한 상기 형광체의 입자표면을 오제(Auger) 분석법이나 ESCA로 분석하면, 표면의 모든 위치로 부터 Al이 관찰되었다. 이들 표면의 각 분석법은 입자의 표면으로 부터 수십옹스트롬의 층을 분석하는 것이다. 또, 이 형광체의 Al2O3는 SEM으로 관찰할 수 없고, SEM에 의한 관찰 한계의 100 옹스트롬 보다 얇은 것을 알수 있었다. 따라서, 본 실시예의 형광체에 있어서의 Al2O3의 박막은 수십옹스트롬의 두께인 것으로 추정된다.When the particle surface of the phosphor treated as described above was analyzed by Auger analysis or EscA, Al was observed from all positions on the surface. Each analysis of these surfaces involves analyzing layers of tens of angstroms from the surface of the particles. It was also found that the Al 2 O 3 of this phosphor could not be observed by the SEM but was thinner than 100 angstroms of the observation limit by the SEM. Therefore, it is assumed that the thin film of Al 2 O 3 in the phosphor of the present embodiment has a thickness of several tens of angstroms.
(2) 제 2실시예(2) Second Embodiment
본 실시예의 전자선 여기 형광체는 La2O2S를 모체로 하는 형광체인 La2O2S: Tb의 입자표면에 금속산화물인 SiO2의 보호막을 형성한 것이다. 형광체입자의 평균입경은 3∼6μm 이다. 보호막의 재료로서는 테트라부톡시실란 Si(O-n-C4H9)4를 사용한다. 이것을 알코올에 용해한 후의 처리는 제 1실시예와 동일하다. 또, 형광체의 입자표면에 형성된 SiO2보호막의 두께는 상기 제 1실시예와 동일하다.In this embodiment the electron beam excitation fluorescent material is a phosphor La 2 O 2 S 2 O 2 S in which the La Matrix: to form a protective film of a metal oxide on the surface of the particles of SiO 2 Tb. The average particle diameter of fluorescent substance particles is 3-6 micrometers. As the material of the protective film, tetrabutoxysilane Si (O-n-C 4 H 9 ) 4 is used. The treatment after dissolving this in alcohol is the same as in the first embodiment. The thickness of the SiO 2 protective film formed on the particle surface of the phosphor is the same as that of the first embodiment.
(3) 제 3실시예(3) Third embodiment
본 실시예의 전자선 여기 형광체는 La2O2S를 모체로 하는 형광체인 La2O2S: Sm의 입자표면에 금속산화물인 TiO2의 보호막을 형성한 것이다. 형광체입자의 평균입경은 3∼6μm 이다. 보호막의 재료로서는 테트라부톡시티탄 Ti(O-n-C4H9)4를 사용한다. 이것을 알코올에 용해한 후의 처리는 제 1실시예와 동일하다. 또 형광체의 입자표면에 형성된 TiO2보호막의 두께는 상기 제 1실시예와 동일하다.In this embodiment the electron beam excitation fluorescent material is a phosphor La 2 O 2 S 2 O 2 S in which the La Matrix: to form a protective film of a metal oxide on the surface of the particles of the TiO 2 Sm. The average particle diameter of fluorescent substance particles is 3-6 micrometers. As the material of the protective film, tetrabutoxytitanium Ti (O-n-C 4 H 9 ) 4 is used. The treatment after dissolving this in alcohol is the same as in the first embodiment. The thickness of the TiO 2 protective film formed on the particle surface of the phosphor is the same as in the first embodiment.
(4) 제 4실시예(4) Fourth Embodiment
본 실시예의 전자선 여기 형광체는 La2O2S를 모체로 하는 형광체인 La2O2S: Eu의 입자표면에 금속산화물인 GeO2의 보호막을 형성한 것이다. 형광체입자의 평균입경은 3∼6μm이다. 보호막의 재료로서는 테트라부톡시게르마늄 Ge(O-n-C4H9)4를 사용한다. 이것을 알코올에 용해한 후의 처리는 제 1실시예와 동일하다. 또 형광체의 입자표면에 형성된 GeO2보호막의 두께는 상기 제 1실시예와 동일하다.In this embodiment the electron beam excitation fluorescent material is a phosphor La 2 O 2 S 2 O 2 S in which the La Matrix: to form a protective film of a metal oxide on the particle surfaces of the Eu GeO 2. The average particle diameter of fluorescent substance particles is 3-6 micrometers. As the material of the protective film, tetrabutoxygermanium Fe (O-n-C 4 H 9 ) 4 is used. The treatment after dissolving this in alcohol is the same as in the first embodiment. The thickness of the hetero 2 protective film formed on the surface of the phosphor is the same as that of the first embodiment.
이상 설명한 각 실시예 마다, 보호막의 피복량을 조금씩 바꾼 복수종류의 형광체를 만들고, 이들 각 형광체를 사용하여 형광표시관을 제조한다. 즉, ITO로 형성되는 양극도체가 형성된 유리의 양극기판을 준비하고, 형광체를 양극도체상에 20μm 이하의 막두께로 피착시킨다. 이와같은 양극기판을 사용하여 형광표시관을 구성하고, 형광체의 발광휘도를 측정하여 평가에 제공하였다. 또한, 형광체의 피착두께를 20μm 으로한 것은 형광체입자의 입경이 3∼6μm 이므로, 형광체의 막두께가 이것보다 두꺼우면 입자간의 접촉저항이 너무 커져, 양극 전압이 2kV 이하의 전자선에서는 발광하기 어렵게되기 때문이다.In each of the embodiments described above, a plurality of kinds of phosphors having little change in the coating amount of the protective film are made, and each of these phosphors is used to manufacture a fluorescent display tube. That is, a positive electrode substrate made of glass having a positive electrode formed of ITO is prepared, and the phosphor is deposited on the positive electrode conductor with a film thickness of 20 μm or less. Using such a positive electrode substrate, a fluorescent display tube was constructed, and the emission luminance of the phosphor was measured and used for evaluation. In addition, since the particle size of the phosphor particles is 3 to 6 μm, the deposition thickness of the phosphor is 20 μm. If the film thickness of the phosphor is thicker than this, the contact resistance between the particles becomes too large, and the anode voltage becomes difficult to emit light in an electron beam of 2 kV or less. Because.
도 1는 각 실시예에 있어서, 각 형광체의 입자를 피복하는 보호막의 부착량(ppm)과 초기휘도와의 관계를 도시하고 있다. 여기서 보호막이 없는 종래의 형광체를 비교예로 하고, 그 초기휘도를 100%로 하였다. 도 2는 각 실시예와 상기 비교예의 각 형광체를 사용한 형광표시관을 각각 1000시간 연속점등한 후의 휘도를 측정하고, 초기휘도를 100%로 했을 때의 잔존휘도를 표시하고 있다.FIG. 1 shows the relationship between the adhesion amount (ppm) of the protective film covering the particles of each phosphor and the initial luminance in each example. Here, the conventional fluorescent substance without a protective film was made into the comparative example, and the initial luminance was set to 100%. Fig. 2 shows the luminance after the fluorescent lamps using the phosphors of the examples and the comparative examples were continuously lighted for 1000 hours, respectively, and shows the residual luminance when the initial luminance was 100%.
또한, 도 1 및 도 2의 결과를 얻은 실험에 있어서, 각 형광표시관은 양극전압 400V로 구동하였다.1 and 2, each fluorescent display tube was driven at an anode voltage of 400V.
도 1에 도시한 바와같이, 각 형광체 공히, 보호막의 피복량이 40ppm 이상으로 되면 휘도가 급속히 상승하기 시작하며, 3000ppm 부근을 초과하면 종래예 보다도 저하되고 만다. 그래서 상대휘도가 110 보다도 위를 양호한 범위로 생각하면 형광체에 대한 보호막의 양은 50∼2000ppm 이 바람직하다.As shown in Fig. 1, when each phosphor has a coating amount of 40 ppm or more, the luminance starts to rise rapidly, and when it exceeds 3000 ppm, it is lower than the conventional example. Therefore, considering the relative luminance above 110 in the good range, the amount of the protective film for the phosphor is preferably 50 to 2000 ppm.
도 2에 있어서, 휘도잔존율 80% 이상을 양호한 범위로 생각하면, 형광체에 대한 보호막의 양은 50∼10000ppm이 바람직하다. 단, 상기한 초기휘도를 합쳐서 고려하면, 형광체에 대한 보호막의 양의 바람직한 범위는 50∼2000ppm으로 된다.In Fig. 2, when the luminance residual ratio of 80% or more is considered to be in a good range, the amount of the protective film for the phosphor is preferably 50 to 10,000 ppm. In view of the above-mentioned initial luminance, however, the preferable range of the amount of the protective film for the phosphor is 50 to 2000 ppm.
본발명에 관한 전자선 여기 형광체에 의하면, 형광체입자의 표면이 금속산화물로 형성되는 투명한 보호막으로 피복되어 있으므로, 내수성 또는 내습성에 우수하며 형광체로서 안정되어 있다. 따라서 저속전자의 조사충돌에 의해 극히 안정적으로 여기발광할 수 있으며, 초기휘도가 높고, 소정기간 점등 후의 휘도잔존율도 높다.According to the electron beam excited phosphor according to the present invention, since the surface of the phosphor particles is covered with a transparent protective film formed of a metal oxide, it is excellent in water resistance or moisture resistance and stable as a phosphor. Therefore, excitation light can be extremely stably emitted by the irradiation collision of low-speed electrons, the initial luminance is high, and the luminance residual ratio after a predetermined period of light is also high.
Claims (3)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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JP93-192499 | 1993-08-03 | ||
JP5192499A JPH0748570A (en) | 1993-08-03 | 1993-08-03 | Electron beam excited phosphor |
JP93-216237 | 1993-08-31 | ||
JP5216237A JPH0762340A (en) | 1993-08-31 | 1993-08-31 | Fluorescencer |
KR1019940017765A KR0164442B1 (en) | 1993-08-03 | 1994-07-22 | Element phosphorescent |
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KR1019940017765A Division KR0164442B1 (en) | 1993-08-03 | 1994-07-22 | Element phosphorescent |
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