KR950011229B1 - Green emitting luminescent material - Google Patents
Green emitting luminescent material Download PDFInfo
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- KR950011229B1 KR950011229B1 KR1019920014355A KR920014355A KR950011229B1 KR 950011229 B1 KR950011229 B1 KR 950011229B1 KR 1019920014355 A KR1019920014355 A KR 1019920014355A KR 920014355 A KR920014355 A KR 920014355A KR 950011229 B1 KR950011229 B1 KR 950011229B1
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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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/77742—Silicates
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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
- C09K11/77492—Silicates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
- H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
- H01J29/18—Luminescent screens
- H01J29/20—Luminescent screens characterised by the luminescent material
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Abstract
Description
제 1 도는 본 발명(a) 및 종래(b)의 녹색 발광형광체의 파장에 따른 발광강도를 나타낸 그래프이고,1 is a graph showing the emission intensity according to the wavelength of the green light emitting phosphor of the present invention (a) and conventional (b),
제 2 도는 본 발명(a) 및 종래(b)의 녹색 발광형광체의 온도에 따른 상대휘도를 나타낸 그래프이다.2 is a graph showing the relative luminance according to the temperature of the green light-emitting phosphor of the present invention (a) and conventional (b).
본 발명은 녹색 발광형광체에 관한 것으로서, 상세하게는 Y2SiO5: Tb형광체 모체에 희토류 원소 Pr을 첨가함으로써 발광효율 및 온도에 대한 안정성을 향상시킨 신규한 녹색 발광형광체에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a green light emitting phosphor, and more particularly, to a novel green light emitting phosphor which improves luminous efficiency and temperature stability by adding a rare earth element Pr to a Y 2 SiO 5 : Tb phosphor matrix.
칼라 음극선관용의 녹색 발광형광체로는 동부활, 금, 알루미늄 공부활 황화아연 형광체(ZnS : Cu, Au, Al) 및 동부활 알루미늄 공부활 황화아연 형광체(ZnS : Cu, Al) 등의 ZnS계 형광체가 통상적으로 사용되고 있으며 Y2SiO5: Tb형광체도 사용된다.Green luminescent phosphors for color cathode ray tubes include ZnS-based phosphors such as eastern bow, gold, and aluminum lead-activated zinc sulfide phosphors (ZnS: Cu, Au, Al) and copper-linked aluminum lead-active zinc sulfide phosphors (ZnS: Cu, Al). Is commonly used and a Y 2 SiO 5 : Tb phosphor is also used.
최근 투사형 TV, 고선명 TV(HD-TV)등의 발달과 함께 화면이 대형화 됨에 따라 고휘도의 형광막이 요구되고 있는데, 형광막의 휘도를 높이기 위해서는 고속 전압, 고전류밀도에 의한 자극이 필요하다. 즉, 고휘도가 요구되는 HD-TV나 투사관용으로 사용하기 위해서는 일반 칼라 음극선관용과는 달리 27kV이상의 아주 높은 전압이 요구되기 때문에, 고속전압, 고전류밀도에 견딜수 있고 고온에도 안정성이 높은 형광체가 필요하다.As the screen is enlarged with the development of projection TV and high-definition TV (HD-TV), a high brightness fluorescent film is required. In order to increase the brightness of the fluorescent film, stimulation by high voltage and high current density is required. In other words, in order to use HD-TV or projection tube which requires high brightness, very high voltage of 27kV or more is required unlike general color cathode ray tube. Therefore, phosphor which can withstand high voltage and high current density and high stability at high temperature is required. .
종래에 사용하던 ZnS계 형광체나 Y2SiO5: Tb형광체 등의 녹색 발광형광체는 고전류밀도 하에서 휘도포화 현상이 나타나므로 고전류에 의한 형광체의 발광휘도가 낮고, 열에 대한 안정성도 낮다는 문제가 있다.Green light emitting phosphors such as ZnS-based phosphors and Y 2 SiO 5 : Tb phosphors used in the related art have a luminance saturation phenomenon under a high current density, and thus have a problem of low luminance and low thermal stability due to high current.
고속전압, 고전류밀도의 자극에 의한 고휘도화가 요구되는 투사관이나 HD-TV에 사용할 수 있는 형광체는 다음과 같은 특성을 가지고 있어야 한다.Phosphors that can be used in projection tubes or HD-TVs that require high brightness due to high voltage and high current density stimulation should have the following characteristics.
1) 휘도포화 특성이 양호하여야 한다.1) Good brightness saturation characteristics.
고속전압, 고전류밀도하에서도 휘도가 저하되지 않아야 한다.Luminance shall not decrease even under high voltage and high current density.
2) 온도에 대한 안정성이 있어야 한다.2) It must have stability against temperature.
고온에서도 발광 효율이 저하되지 않고 안정하여야 한다.It should be stable without deterioration of luminous efficiency even at high temperature.
3) 수명이 길어야 한다.3) Long lifespan.
형광체의 수명은 TV의 수명과 같은 의미가 있기 때문에 장시간 사용하여도 색상이 변하지 않고 휘도가 저하되지 않아야 한다.Since the lifetime of the phosphor has the same meaning as the lifetime of the TV, the color should not change and the brightness should not decrease even after long use.
그러나 상기의 조건을 갖춘 고선명 TV(HD-TV)용, 또는 투사관용 녹색 발광형광체로서 만족스러운 것은 현재까지 없다고 할 수 있다.However, it can be said that there is no satisfactory thing as a green light-emitting phosphor for high-definition TV (HD-TV) or a projection tube with the above conditions.
따라서 본 발명의 목적은 고속전압, 고전류밀도하에서 발광휘도가 높으면서도 온도에 대한 안정성이 양호하여, 고선명 TV(HD-TV) 또는 투사관용으로 적합한 녹색 발광형광체를 제공하는 것이다.Accordingly, an object of the present invention is to provide a green light-emitting phosphor suitable for high-definition television (HD-TV) or projection tubes because of its high luminance and high stability under high voltage and high current density.
상기의 목적을 달성하기 위하여 본 발명에서는 일반식 Y2-x-yPrxTbySiO5(단 1×10-5≤x≤5×10-3, 0.1≤y≤0.14)로 표시되는 것을 특징으로 하는 녹색 발광형광체를 제공한다.In order to achieve the above object, the present invention is represented by the general formula Y 2-xy Pr x Tb y SiO 5 (wherein 1 × 10 -5 ≤ x ≤ 5 × 10 -3 , 0.1 ≤ y ≤ 0.14) It provides a green light emitting phosphor.
본 발명의 녹색 발광형광체는 산화이트륨과 이산화규소를 모체원료로 하고 테르븀을 부활제로 하여 제조하는 Y2SiO5: Tb형광체에 희토류 원소인 프라세오디뮴(Pr)을 첨가한 것으로서, 발광효율을 향상시키고 온도에 대한 안정성을 개선할 수 있었다.The green luminescent phosphor of the present invention is made by adding a rare earth element praseodymium (Pr) to Y 2 SiO 5 : Tb phosphor prepared by using yttrium oxide and silicon dioxide as a parent material and terbium as an activator. Stability for was improved.
여기에서 첨가되는 Pr의 양은 모체인 산화이트륨의 양을 기준으로 하여 1×10-5내지 5×10-3몰의 양으로 첨가된다. Pr의 첨가량이 1×10-5보다 적으면 첨가에 따른 효과가 미미하여 나타나지 않고, 이 양이 5×10-3보다 많으면 Pr의 발광강도가 낮아지므로 상기의 양으로 첨가한다.The amount of Pr added here is added in an amount of 1 × 10 -5 to 5 × 10 -3 moles based on the amount of yttrium parent. If the amount of Pr added is less than 1 × 10 −5 , the effect of addition is insignificant and does not appear. If the amount is more than 5 × 10 −3 , the emission intensity of Pr is lowered, so it is added in the above amount.
또한, 부활제인 Tb는 모체인 산화이트륨의 양을 기준으로 하여 0.1 내지 0.14몰의 양으로 첨가한다. Tb의 첨가량이 0.1보다 적으면 색좌표에서 x좌표가 매우 낮아 불리하고, 이 양이 0.14보다 많으면 x좌표가 높아 원하는 색순도가 변하므로 상기의 양으로 첨가한다.In addition, the activator Tb is added in an amount of 0.1 to 0.14 moles based on the amount of yttrium parent. If the amount of Tb added is less than 0.1, the x-coordinate is very low in the color coordinates. If the amount is more than 0.14, the x-coordinate is high and the desired color purity is changed, so it is added in the above-mentioned amount.
본 발명의 Y2-x-yPrxTbySiO5녹색 발광형광체는 다음과 같은 방법에 의하여 제조된다.Y 2-xy Pr x Tb y SiO 5 green light-emitting phosphor of the present invention is prepared by the following method.
모체원료인 산화이트륨(Y2O3)과 이산화규소(SiO2), 부활제인 산화테르븀(Tb4O7)을 각각 일정량씩 취하고 여기에 순수를 가한다. 이를 교반하면서 본 발명의 첨가 성분의 산화물인 산화프라세오디뮴(Pr6O11)을 일정량 첨가하여 균일하게 혼합한다. 이것을 건조시킨 분말에 용제를 넣고 잘 혼합하여 알루미나 도가니에 넣어서 1,200 내지 1,400도에서 2 내지 4시간 소성한다. 소성이 끝난 후 냉각시켜 분쇄, 세정 및 건조하여 본 발명의 녹색 발광형광체를 얻는다.A certain amount of yttrium oxide (Y 2 O 3 ), silicon dioxide (SiO 2 ), and terbium oxide (Tb 4 O 7 ), which is a parent material, is added thereto and pure water is added thereto. While stirring this, a predetermined amount of praseodymium oxide (Pr 6 O 11 ), which is an oxide of the additive component of the present invention, is added and mixed uniformly. The solvent is added to the dried powder, mixed well, put into an alumina crucible, and calcined at 1,200 to 1,400 degrees for 2 to 4 hours. After the firing is completed, the mixture is cooled, pulverized, washed and dried to obtain the green light-emitting phosphor of the present invention.
이하 실시예를 통하여 본 발명을 보다 상세히 설명한다. 단, 하기의 실시예는 본 발명의 예시일 뿐, 본 발명이 이에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only examples of the present invention, and the present invention is not limited thereto.
[실시예 1]Example 1
모체원료로서 Y2O3100g(이트륨으로 0.886몰) 및 SiO232g, 부활제로서 Tb4O712g(테르븀으로 0.064몰)을 취하여 용량 1리터 비이커에 넣고 여기에 순수 500ml를 가한다. 이를 교반하면서 Pr6O110.02g(프라세오디뮴으로 0.12×10-3몰)을 첨가하여 균일하게 혼합한다. 충분히 혼합한 후 건조기에 넣고 약 120℃에서 약 36시간 건조하여 분말로 만든다. 건조된 혼합 분말에 융제로서 불화칼륨(KF) 7g을 넣고 다시 잘 혼합하여 알루미나 도가니에 넣어서 약 1,300℃에서 약 2시간 30분 동안 소성한다. 소성이 끝난후 냉각시켜 분쇄, 세정 및 건조하여 본 발명의 녹색 발광형광체를 얻는다.100 g of Y 2 O 3 (0.886 mol in yttrium) and 32 g of SiO 2 and 12 g of Tb 4 O 7 (0.064 mol in terbium) as an activator were added to a 1-liter beaker and 500 ml of pure water was added thereto. While stirring this, 0.02 g of Pr 6 O 11 (0.12 × 10 −3 mol of praseodymium) is added and mixed uniformly. After mixing sufficiently, put into a dryer and dry at about 120 ℃ for about 36 hours to make a powder. 7 g of potassium fluoride (KF) was added to the dried mixed powder, mixed well, and placed in an alumina crucible and calcined at about 1,300 ° C. for about 2 hours 30 minutes. After firing, the mixture is cooled, pulverized, washed and dried to obtain the green light-emitting phosphor of the present invention.
[실시예 2]Example 2
상시 실시예 1과 동일하게 실시하되 Pr6O10.03g(프라세오디뮴으로 0.18×10-3몰) 첨가하여 본 발명의 녹색 발광형광체를 얻는다.In the same manner as in Example 1, Pr 6 O 1 0.03 g (0.18 × 10 −3 moles of praseodymium) was added to obtain a green light-emitting phosphor of the present invention.
[실시예 3]Example 3
상시 실시예 1과 동일하게 실시하되 Pr6O11을 0.04g(프라세오디뮴으로 0.24×10-3몰) 첨가하여 본 발명의 녹색 발광형광체를 얻는다.In the same manner as in Example 1, Pr 6 O 11 was added 0.04 g (0.24 × 10 −3 mol of praseodymium) to obtain a green light-emitting phosphor of the present invention.
[실시예 4]Example 4
상시 실시예 1과 동일하게 실시하되 Pr6O11을 0.05g(프라세오디뮴으로 0.30×10-3) 첨가하여 본 발명의 녹색 발광형광체를 얻는다.But the same manner as in Example 1, all times to obtain a green light-emitting fluorescent substance of the present invention by addition of a Pr 6 O 11 0.05g (0.30 × 10 -3 to praseodymium).
상기와 같이 제조한 본 발명의 녹색 발광형광체와 프라세오디뮴을 첨가하지 않는 종래의 녹색 발광형광체에 대하여 아노드전압 27kV, 포커스전압 8kV, 캐소오드전류 500uA의 조건에서 PTE(Phosphor Test Equipment) 시스템으로 발광휘도를 측정하여, 종래의 녹색 발광형광체를 100%로 한 상태휘도를 하기의 표 1에 나타내었다.The green light emitting phosphor of the present invention prepared as described above and the conventional green light emitting phosphor which does not add praseodymium have a light emission luminance with a PTE (Phosphor Test Equipment) system under an anode voltage of 27 kV, a focus voltage of 8 kV, and a cathode current of 500 uA. Was measured, and the state luminance of 100% of the conventional green light-emitting phosphor is shown in Table 1 below.
[표 1]TABLE 1
상기의 표 1에서 보듯이 Pr을 첨가한 본 발명의 녹색 발광형광체는 종래의 것에 비하여, 색좌표는 거의 변화가 없으면서 발광휘도는 약 6 내지 11% 상승한 것을 알 수 있다.As shown in Table 1 above, the green light-emitting phosphor of the present invention to which Pr is added can be seen that the emission luminance is increased by about 6 to 11% with little change in color coordinates.
제 1 도는 본 발명의 실시예 1에 따라 제조한 녹색 발광형광체(a) 및 Pr을 포함하지 않는 종래의 Y2SiO5: Tb녹색 발광형광체(b)의 파장에 따른 발광강도를 나타낸 그래프이다. 이로부터 550nm이하의 녹색 영역에서 주피크의 강도가 본 발명의 형광체에서 보다 크게 나타남을 알 수 있다.1 is a graph showing the emission intensity according to the wavelength of the conventional Y 2 SiO 5 : Tb green light emitting phosphor (b) containing no green light emitting phosphor (a) and Pr prepared according to Example 1 of the present invention. From this, it can be seen that the intensity of the main peak in the green region of 550 nm or less is greater in the phosphor of the present invention.
제 2 도는 온도변화에 따른 본 발명(a) 및 종래(b)의 녹색 발광형광체의 휘도변화를, 50℃에서의 휘도를 기준으로 한 상대휘도로서 나타낸 것이다. 이로부터 본 발명의 녹색 발광형광체는 종래의 것에 비해 온도에 대한 안정성이 우수하여 고온에서도 발광휘도의 저하가 작은 것을 알 수 있다.2 shows the luminance change of the green light-emitting phosphors of the present invention (a) and the conventional (b) according to the temperature change as relative luminance based on the luminance at 50 ° C. From this, it can be seen that the green light-emitting phosphor of the present invention is excellent in stability to temperature compared to the conventional one, and the emission luminance is low even at high temperatures.
즉, 본 발명의 녹색 발광형광체는 종래의 Y2SiO5: Tb형광체에 비하여 발광휘도가 높고 고온에서의 안정성이 뛰어나서, 고선명 텔레비젼(HD-TV)이나 투사관 용으로 사용할 수 있는 개선된 녹색 발광형광체이다.That is, the green luminescent phosphor of the present invention has a higher luminescence brightness and excellent stability at high temperature than the conventional Y 2 SiO 5 : Tb phosphor, and thus can be used for high-definition television (HD-TV) or projection tube. Phosphor.
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| KR (1) | KR950011229B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100496517B1 (en) * | 1998-09-17 | 2005-09-02 | 주식회사 휴비스 | Manufacturing method of elastic yarn with improved seaability |
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1992
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| Publication number | Publication date |
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| KR940004694A (en) | 1994-03-15 |
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