KR100348967B1 - Blue Luminescence comprising thulium for low voltage cathodoluminescence and manufacturing method thereof - Google Patents
Blue Luminescence comprising thulium for low voltage cathodoluminescence and manufacturing method thereof Download PDFInfo
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Abstract
본 발명은 형광 표시관의 발광부에 사용되고, 전자선으로 여기되어 발광하는 갈륨산아연계 청색 형광체 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 형광체 모체인 갈륨산아연(ZnGa2O4)에 공부활제로 산화툴리움과 탄산리튬을 첨가함으로써 저속 전자선에서 발광휘도와 색순도가 우수하고, 고진공에서도 안정한 물성을 가지며, 저전압 전자선 여기에 의해 구동하는 전계방출디스플레이(Field Emission Display ; FED)에 적합하도록 고휘도를 갖는 하기 화학식 1로 표시되는 갈륨산아연계 청색 형광체 및 그 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc galliumate-based blue phosphor used in the light emitting portion of a fluorescent display tube and excited by an electron beam, and to a method of manufacturing the same. More specifically, the present invention relates to zinc gallium sulfate (ZnGa 2 O 4 ), which is a phosphor matrix. By adding thorium oxide and lithium carbonate, it has excellent luminescence brightness and color purity in low-speed electron beam, stable properties even in high vacuum, and high brightness to be suitable for field emission display (FED) driven by low-voltage electron beam excitation. It relates to a zinc galliumate-based blue phosphor represented by the following formula (1) and a method for producing the same.
화학식 1Formula 1
(Zn1-aLia)(Ga1-bTmb)2O4 (Zn 1-a Li a ) (Ga 1-b Tm b ) 2 O 4
상기 화학식 1에서 0.05≤a≤0.25이고, 0≤b≤0.1이다.In Formula 1, 0.05 ≦ a ≦ 0.25 and 0 ≦ b ≦ 0.1.
Description
본 발명은 갈륨산아연계 청색 형광체 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 형광체 모체인 갈륨산아연(ZnGa2O4)에 공부활제로 산화툴리움과 탄산리튬을 첨가함으로써 저속 전자선에서 발광휘도와 색순도가 우수하고, 고진공에서도 안정한 물성을 가지며, 저전압 전자선 여기에 의해 구동하는 전계방출디스플레이(Field Emission Display ; FED)에 적합하도록 고휘도를 갖는 하기 화학식 1로 표시되는 갈륨산아연계 청색 형광체 및 그 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc galliumate blue phosphor and a method for manufacturing the same, and more particularly, to light emitting luminance in a low-speed electron beam by adding tulium oxide and lithium carbonate as a studying agent to zinc gallium sulfate (ZnGa 2 O 4 ), which is a phosphor matrix. Zinc galliumate-based blue phosphor represented by the following Chemical Formula 1 having excellent color purity, stable physical properties even at high vacuum, and high luminance to be suitable for a field emission display (FED) driven by low-voltage electron beam excitation and its manufacture It is about a method.
상기 화학식 1에서 0.05≤a≤0.25이고, 0≤b≤0.1이다.In Formula 1, 0.05 ≦ a ≦ 0.25 and 0 ≦ b ≦ 0.1.
전계방출디스플레이(FED)는 정보표시용 디스플레이로 가장 많이 사용되어 온 음극선관(CRT ; Cathode Ray Tube)의 단점을 보완, 대체할 수 있는 차세대 평판 디스플레이의 하나로서, 진공 평판 음극선 튜브를 사용하는 새로운 형태의 디스플레이이며, 이는 1kV이하의 저전압 음극선 여기를 기본으로 한다.Field emission display (FED) is one of the next generation flat panel displays that can supplement and replace the shortcomings of Cathode Ray Tube (CRT), which is the most used for information display. Display, which is based on low voltage cathode excitation below 1 kV.
그런데, 약 1kV이하의 양극 구동전압을 갖는 전계방출디스플레이를 구동시키기 위해서는 전계방출디스플레이용 형광체로서 저속 전자선용 형광체가 요구된다. 음극선관에서 상용화되고 있는 청색 형광체인 ZnS:Ag, Cl 등과 같은 황화물 형광체를 전계방출디스플레이에 사용할 경우 황화물이 함유되어 있어서, 음극으로부터 방출된 전자가 가속되어 황화물 형광체층과 충돌할 때 형광체를 발광시키는 작용 외에 형광체층 표면을 분해하는 작용 및 형광체 자체의 분해로 인한 디바이스의 여기원에 악영향을 주는 것으로 알려져 있다. 한편, 저전압 형광체로 현재 널리 알려져 있는 ZnO:Zn 형광체는 발광영역이 매우 넓어서 천연색 디스플레이의 형광체로 적용하기에는 여러가지 문제가 있다.By the way, in order to drive a field emission display having an anode drive voltage of about 1 kV or less, a phosphor for a low speed electron beam is required as a phosphor for field emission display. When sulfide phosphors such as ZnS: Ag, Cl, etc., which are commercially available in cathode ray tubes, are used in field emission displays, sulfides are contained. In addition to the action, it is known to adversely affect the excitation source of the device due to the decomposition of the surface of the phosphor layer and the decomposition of the phosphor itself. On the other hand, the ZnO: Zn phosphor, which is widely known as a low voltage phosphor, has a wide light emitting area and thus has various problems to be applied as a phosphor of a color display.
이에 본 발명자들은 산화아연(ZnO) 및 산화갈륨(Ga2O3)을 형광체 원료로 사용한 갈륨산아연(ZnGa2O4)을 모체로 사용하고 여기에 공부활제로 산화툴리움(Tm2O3)과 탄산리튬(Li2O3)을 첨가함으로써 전계방출디스플레이용으로 적합한 청색 형광체를 제조할 수 있음을 밝혀내고 본 발명을 완성하였다.Therefore, the present inventors use zinc gallium oxide (ZnGa 2 O 4 ) using zinc oxide (ZnO) and gallium oxide (Ga 2 O 3 ) as the raw material for phosphors as a parent, and as a study active agent, thulium (Tm 2 O 3) ) And lithium carbonate (Li 2 O 3 ) were found to be capable of producing a blue phosphor suitable for field emission display and completed the present invention.
따라서, 본 발명은 저속 전자관에서 발광휘도와 색순도가 우수하고, 고진공에서도 안정한 물성을 가지며, 전계방출디스플레이에 적합한 갈륨산아연계 청색 형광체 및 그 제조방법을 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide a zinc galliumate-based blue phosphor having excellent luminescence brightness and color purity in a low-speed electron tube, stable properties even at high vacuum, and suitable for field emission displays and a method of manufacturing the same.
도 1은 본 발명에 따라 수득된 청색 형광체에 대하여 주사전자현미경을 사용하여 관찰한 표면 형상을 도 1에 나타내었다.FIG. 1 shows the surface shape observed using a scanning electron microscope for the blue phosphor obtained according to the present invention.
도 2는 본 발명에 따라 수득된 청색 형광체의 툴리움 도핑량에 따른 상대 휘도의 변화를 나타내는 그래프이다.2 is a graph showing a change in relative luminance according to the amount of tulium doping of the blue phosphor obtained according to the present invention.
도 3은 본 발명에 따라 수득된 청색 형광체의 툴리움 도핑량에 따른 상대 빛 발광강도의 변화를 나타내는 그래프이다.3 is a graph showing the change in relative light emission intensity according to the amount of tulium doping of the blue phosphor obtained according to the present invention.
도 4는 본 발명에 따라 수득된 청색 형광체의 툴리움 도핑량에 따른 상대 음극선 발광강도의 변화를 나타내는 그래프이다.4 is a graph showing the change in the relative cathode emission intensity according to the amount of tulium doping of the blue phosphor obtained according to the present invention.
본 발명은 하기 화학식 1로 표시되는 갈륨산아연계 청색 형광체를 그 특징으로 한다.The present invention is characterized by a zinc galliumate-based blue phosphor represented by the following formula (1).
화학식 1Formula 1
(Zn1-aLia)(Ga1-bTmb)2O4 (Zn 1-a Li a ) (Ga 1-b Tm b ) 2 O 4
상기 화학식 1에서 0.05≤a≤0.25이고, 0≤b≤0.1이다.In Formula 1, 0.05 ≦ a ≦ 0.25 and 0 ≦ b ≦ 0.1.
또한, 본 발명에 따른 청색 형광체의 제조방법은 갈륨산아연을 모체로 하고, 여기에 산화툴리움과 탄산리튬을 첨가하고, 혼합하는 단계; 상기 혼합단계에서 수득된 혼합물을 건조시키고, 대기중에서 1,200℃에서 소성시키는 단계; 상기 소성단계에서 수득된 소성물을 냉각하고, 1,000℃ 이하의 약환원성 분위기에서 열처리하는 단계; 및 분쇄 등의 후처리단계; 들을 포함하여 이루어짐을 특징으로 한다.In addition, the method for producing a blue phosphor according to the present invention comprises the steps of zinc galliumate as a matrix, to which to add and add a tulium oxide and lithium carbonate to it; Drying the mixture obtained in the mixing step and calcining at 1,200 ° C. in air; Cooling the calcined product obtained in the calcining step and heat-treating in a weakly reducing atmosphere of 1,000 ° C. or less; And post-treatment steps such as grinding. Characterized by including them.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명에 따른 갈륨산아연계 청색 형광체는 화학적으로 대단히 안정한 장수명의 물질로, 특히 고진공 상태에서 전자충돌 후에도 안정성을 유지하고, 유해가스를 방출하지 않으며, 다른 산화물 형광체에 비해 전기적 전도성이 우수하여 저전압용 전계방출디스플레이에 적합한 효과를 가진다.Zinc gallium-based blue phosphor according to the present invention is a chemically very stable long-life material, especially in a high vacuum state to maintain stability even after electron collision, does not emit harmful gases, excellent electrical conductivity than other oxide phosphors for low voltage It has an effect suitable for field emission display.
특히, 본 발명에서는 갈륨산아연(ZnGa2O4)에 공부활제로 산화툴리움(Tm2O3)과 탄산리튬(Li2O3)을 첨가함으로써 청색 발광휘도 및 색순도가 우수한 효과를 얻을 수 있는 특징이 있다.Particularly, in the present invention, the addition of thulium (Tm 2 O 3 ) and lithium carbonate (Li 2 O 3 ) as a activator to zinc galliumate (ZnGa 2 O 4 ) can provide excellent blue light emission luminance and color purity. There is a characteristic.
이와 같은 본 발명의 갈륨산아연(ZnGa2O4)계 청색 형광체를 그 제조방법에 의거하여 더욱 상세하게 설명하면 다음과 같다.The zinc galliumate (ZnGa 2 O 4 ) -based blue phosphor of the present invention will be described in more detail based on the preparation method as follows.
먼저, 산화아연(ZnO) 및 산화갈륨(Ga2O3)에 공부활제로서 산화툴리움(Tm2O3)과 탄산리튬(Li2O3)을 첨가하여 혼합한다. 이때 공부활제로서 사용되는 산화툴리움은 형광체 원료물질 중 산화갈륨에 대하여 0.005 내지 0.1mol, 바람직하게는 0.01 내지 0.02mol로 첨가하는데, 만일 그 사용량이 0.005mol 미만이면 공부활제로서의 기능을 하기에 충분한 양이 되지 못하며, 0.02mol을 초과하면 농도 효과(concentration quenchong effect)에 따른 휘도 저하가 일어나는 문제점이 있을 수 있다. 본 발명에서는 공부활제인 산화툴리움과 탄산리튬을 함께 사용하는데, 최적의 사용량은 Li : Tm의 몰비가 0.1 : 0.01이 되도록 사용하는 것이다.First, thulium oxide (Tm 2 O 3 ) and lithium carbonate (Li 2 O 3 ) are added to and mixed with zinc oxide (ZnO) and gallium oxide (Ga 2 O 3 ). At this time, thulium used as a study agent is added in an amount of 0.005 to 0.1 mol, preferably 0.01 to 0.02 mol, based on gallium oxide in the phosphor raw material. If the amount is less than 0.005 mol, it is sufficient to function as a study agent. If the amount is not more than 0.02 mol, there may be a problem in that the luminance decreases due to the concentration quenchong effect. In the present invention, the study active material is used together with thulium oxide and lithium carbonate, the optimal amount is to use so that the molar ratio of Li: Tm is 0.1: 0.01.
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 24시간 동안 건조한다. 건조한 혼합물을 고순도 알루미나 보트에 넣고 전기로를 사용하여 1,200℃에서 3시간 동안 소성한다. 전기로의 분위기는 대기 중에서 행한다. 이때, 소성온도는 매우 중요한 바, 만일 소성온도가 1,000℃ 미만이면 갈륨산아연의 결정이 완전하게 생성되지 못하여 발광이 잘 일어나지 못하고, 1,200℃를 초과하면 산화아연의 높은 휘발성 때문에 결정성이 떨어지는 문제점이 있을 수 있다. 그리고, 소성한 후 시간당 300℃의 온도로 낮추어 냉각하고, 이를 1,000℃ 이하의 약환원성 분위기에서 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. The mixture is then placed in an oven and dried at 100-150 ° C. for 24 hours. The dry mixture is placed in a high purity alumina boat and calcined at 1,200 ° C. for 3 hours using an electric furnace. The atmosphere of an electric furnace is performed in air | atmosphere. At this time, the calcination temperature is very important. If the calcination temperature is less than 1,000 ° C., the crystals of zinc galliumate are not completely produced and light emission does not occur well. If the calcination temperature exceeds 1,200 ° C., the crystallinity is poor due to the high volatility of zinc oxide. This can be. And after baking, it cools by lowering to the temperature of 300 degreeC per hour, heat-processing it in the weak reducing atmosphere of 1,000 degreeC or less, and fully grinding.
이들 분말에 대하여 분말X선회절분석기를 사용하여 생성상을 조사하고, 1kV 이하의 저전압 전자선 여기에 의해 음극선 발광(CL ; cathodoluminescence)을 측정한 결과, 460nm에서 최대발광피크를 가지며, 420 내지 475nm의 영역에서 강한 발광스펙트럼을 나타내고, 발광휘도 및 색순도가 매우 우수한 상기 화학식 1로 표시되는 청색 형광체가 수득된다.These powders were irradiated with a product using a powder X-ray diffractometer, and cathodoluminescence (CL) was measured by low voltage electron beam excitation of 1 kV or less. As a result, they had a maximum emission peak at 460 nm and a peak emission peak of 420 to 475 nm. A blue phosphor represented by the formula (1) exhibiting a strong emission spectrum in the region and excellent in emission luminance and color purity is obtained.
이와 같이 본 발명에서 제조한 갈륨산아연계 청색 형광체는 저속전자선에서 발광휘도와 색순도가 우수하고, 고진공에서도 안정한 물성을 가지며, 저전압 전자선 여기에 의하여 구동되는 전계방출디스플레이에 적합한 고휘도를 갖는다.As described above, the zinc galliumite-based blue phosphor prepared in the present invention has excellent luminance and color purity in low-speed electron beams, has stable physical properties even in high vacuum, and has high luminance suitable for field emission displays driven by low-voltage electron beam excitation.
이와 같은 본 발명을 이하의 실시예에 의거하여 상세하게 설명하겠는 바, 이 실시예는 예시적인 것으로서 이해되어야 하며, 본 발명이 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 the examples.
실시예 : (Zn0.9Li0.1)(Ga0.99Tm0.01)2O4형광체의 제조Example: Preparation of (Zn 0.9 Li 0.1 ) (Ga 0.99 Tm 0.01 ) 2 O 4 phosphor
산화아연 0.9mol, 산화갈륨 0.99mol, 산화툴리움 0.01mol, 탄산리튬 0.1mol의 비율로 평량하고, 이것을 마노유발을 사용하여 아세톤 중에서 충분히 고르게 혼합하였다. 혼합한 시료를 오븐을 사용하여 130℃에서 24시간 동안 건조하였다. 얻어진 혼합물을 고순도 알루미나 보트에 넣고 전기로를 사용하여 대기 중에서 1,200℃에서 3시간 동안 소성하였다. 소성후에 얻어진 소성물을 1,000℃ 이하의 약환원성 분위기에서 열처리한 후, 충분히 분쇄처리하여 (Zn0.9Li0.1)(Ga0.99Tm0.01)2O4로 표시되는 청색형광체를 수득하였다.It was basis weight in the ratio of 0.9 mol of zinc oxide, 0.99 mol of gallium oxide, 0.01 mol of tulium oxide, and 0.1 mol of lithium carbonate, and this was mixed evenly in acetone using agate induction. The mixed samples were dried at 130 ° C. for 24 hours using an oven. The resulting mixture was placed in a high purity alumina boat and calcined for 3 hours at 1,200 ° C. in air using an electric furnace. The calcined product obtained after firing was heat-treated in a weak reducing atmosphere of 1,000 ° C. or lower, and then sufficiently pulverized to obtain a blue phosphor represented by (Zn 0.9 Li 0.1 ) (Ga 0.99 Tm 0.01 ) 2 O 4 .
실험예 1 : 리튬, 툴리움이 첨가된 갈륨산아연계 청색 형광체의 표면 형상Experimental Example 1 Surface Shape of Zinc Gallium-Based Blue Phosphor Added Lithium and Tulium
상기 실시예와 동일한 방법으로 하되, 산화툴리움의 함량을 0.01mol과 탄산리튬 0.1mol을 각각 첨가하여 (Zn0.9Li0.1)(Ga0.99Tm0.01)2O4로 표시되는 청색 형광체를 수득하였다. 그런 다음, 수득된 청색 형광체에 대하여 주사전자현미경을 사용하여 관찰한 표면 형상을 도 1에 나타내었다.In the same manner as in the above Example, the content of thulium was added to 0.01 mol and 0.1 mol of lithium carbonate, respectively, to obtain a blue phosphor represented by (Zn 0.9 Li 0.1 ) (Ga 0.99 Tm 0.01 ) 2 O 4 . Then, the surface shape observed using the scanning electron microscope for the obtained blue phosphor is shown in FIG.
도 1에 나타난 바와 같이, 본 발명의 갈륨산아연계 청색 형광체는 분말이 봉형이고, 비교적 입도가 균일한 입자임을 확인할 수 있었다.As shown in FIG. 1, the zinc galliumate-based blue phosphor of the present invention was confirmed that the powder is rod-shaped and relatively uniform particle size.
실험예 2 : 툴리움 함량에 따른 갈륨산아연계 청색 형광체의 상대 빛 발광강도Experimental Example 2 Relative Light Emission Intensity of Zinc Gallium-Based Blue Phosphor According to Tulium Content
상기 실시예에서 수득된 (Zn0.9Li0.1)(Ga0.99Tm0.01)2O4로 표시되는 청색 형광체에 있어서 툴리움 도핑량을 변화시킨 시료들에 대하여 상대 빛 발광강도를 측정하고, 그 결과를 도 2에 나타내었다.The relative light emission intensity of the blue phosphors represented by (Zn 0.9 Li 0.1 ) (Ga 0.99 Tm 0.01 ) 2 O 4 obtained in the above example was measured by measuring the relative light emission intensity. 2 is shown.
도 2에 나타낸 바와 같이, 본 발명의 청색 형광체에 툴리움을 첨가함에 따라 발광휘도가 증가하나, 툴리움의 도핑량이 0.01mol 보다 많은 경우에는 농도 효과(concentration quenchong effect)가 일어나 발광휘도를 감소시킴을 확인할 수 있었다. 따라서, 특히 우수한 발광휘도를 나타낼 수 있는 툴림의 첨가범위는 0.01 내지 0.02mol임을 확인할 수 있었다.As shown in FIG. 2, the luminance of luminescence increases with the addition of tulium to the blue phosphor of the present invention, but the concentration quenchong effect occurs when the dolium is more than 0.01 mol, thereby reducing the luminance. Could confirm. Therefore, it was confirmed that the addition range of tulim, which can exhibit particularly excellent luminance, was 0.01 to 0.02 mol.
실험예 3 : 갈륨산아연 및 이에 리튬, 툴리움을 첨가한 형광체의 발광스펙트럼의 비교Experimental Example 3: Comparison of emission spectra of zinc galliumate and phosphors added with lithium and tulium
상기 실시예에서 수득된 (Zn0.9Li0.1)(Ga0.99Tm0.01)2O4로 표시되는 청색 형광체와 갈륨산아연 형광체에 대하여 빛 발광스펙트럼을 측정하고, 그 결과를 도 3에 나타내었다.The light emission spectrum of the blue phosphor represented by (Zn 0.9 Li 0.1 ) (Ga 0.99 Tm 0.01 ) 2 O 4 obtained in the above example and the zinc galliumate phosphor was measured, and the results are shown in FIG. 3.
도 3에 나타낸 바와 같이, 본 발명의 청색 형광체는 리튬 및 툴리움이 각각 0.1mol, 0.01mol 첨가됨에 따라 피크파장이 460nm를 갖는 청색 발광을 나타내며, 갈륨산아연 형광체의 발광스펙트럼과 비교하여 볼 때, 발광휘도 및 색순도가 우수한 청색 형광체 임을 확인할 수 있었다. 이는 갈륨산아연 형광체에 비해 리튬이온(Li+)이 아연(Zn2+) 자리에 치환된 형태로 위치하여 결정성을 우수하게 하고, 툴리움 이온(Tm3+)으로의 에너지전달(energy transfer) 역할을 함으로써 결국 툴리움 이온이 갈륨산아연 형광체의 청색발광에 크게 기여함을 확인할 수 있었다.As shown in FIG. 3, the blue phosphor of the present invention exhibits blue light emission having a peak wavelength of 460 nm as 0.1 mol and 0.01 mol of lithium and thrium are added, respectively, as compared with the emission spectrum of the zinc gallium phosphate phosphor. It was confirmed that the blue phosphor was excellent in the light emission luminance and color purity. Compared to the zinc gallium phosphate phosphor, lithium ions (Li + ) are substituted in the form of zinc (Zn 2+ ) to improve crystallinity, and energy transfer to tulium ions (Tm 3+ ) is performed. As a result, it was confirmed that tulium ions contributed greatly to the blue light emission of the zinc gallium phosphate phosphor.
실험예 4 : 갈륨산아연 및 이에 리튬, 툴리움을 첨가한 청색 형광체의 음극선 발광스펙트럼의 비교Experimental Example 4 Comparison of Cathode Radiation Spectrum of Zinc Gallate and Lithium and Thulium-Added Blue Phosphors
상기 실시예에서 수득한 본 발명의 (Zn0.9Li0.1)(Ga0.99Tm0.01)2O4로 표시되는 청색 형광체와 갈륨산아연 형광체에 대하여 800V의 가속전압으로 여기시킨 음극선 발광스펙트럼을 측정하고, 그 결과를 도 4에 나타내었다.Cathode light emission spectra of the blue phosphor represented by (Zn 0.9 Li 0.1 ) (Ga 0.99 Tm 0.01 ) 2 O 4 of the present invention obtained in the above example and zinc gallium phosphate excited at an acceleration voltage of 800 V were measured. The results are shown in FIG.
도 4에 나타난 바와 같이, 본 발명의 청색 형광체에서 툴리움의 첨가량을 0.005mol, 0.01mol 및 0.02mol로 변화시킨 발광스펙트럼은 피크파장이 460nm를 갖는 청색 발광을 나타내며, 또한 툴리움의 양이 변화하여도 스펙트럼의 형상은 변화하지 않는 것으로부터 툴리움의 첨가량에 따라 청색발광이 변화하지 않음을 확인할 수 있었었으며, 본 발명에 따른 청색 형광체와 갈륨산아연 형광체의 발광 강도를 비교하여 볼 때, 본 발명의 청색 형광체의 발광휘도 및 색순도가 우수함을 확인할수 있었다.As shown in FIG. 4, the emission spectrum of the addition of thriumium to 0.005 mol, 0.01 mol and 0.02 mol in the blue phosphor of the present invention shows blue light emission having a peak wavelength of 460 nm, and also the amount of tulium Even though the shape of the spectrum did not change, it was confirmed that the blue light emission did not change with the amount of the addition of tulium, and when comparing the emission intensity of the blue phosphor and the zinc gallium phosphate phosphor according to the present invention, It was confirmed that the light emission luminance and color purity of the blue phosphor of the invention were excellent.
이상에서 기술한 바와 같이, 본 발명에 따라 갈륨산아연계 형광체에 공부활제로서 툴리움과 리튬을 첨가함으로써, 1kV 이하의 저전압 전자산 여기하에서도 고휘도를 가지며, 색순도가 매우 우수한 청색 발광을 나타내는 효과가 있으며, 이는 황(S), 카드뮴(Cd) 등을 포함하지 않는 산화물 형광체이므로 종래의 황화물계 형광체에서 발생하는 황화물에 의한 음극의 오염 및 공해에 대한 문제점을 해결하는 효과가 있으며, 전계방출디스플레이에 효과적으로 적용할 수 있는 청색 형광체를 제공하는 효과가 있다.As described above, according to the present invention, by adding tulium and lithium as a study accelerator to the zinc gallium-based phosphor, the effect of showing high luminance even under low-voltage electron acid excitation of 1 kV or less and excellent color purity is exhibited. It is an oxide phosphor that does not contain sulfur (S), cadmium (Cd), etc., and thus has the effect of solving the problems of pollution and pollution of the cathode by sulfides generated in conventional sulfide-based phosphors. There is an effect of providing a blue phosphor which can be effectively applied.
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