KR20000059660A - A red fluorescent body based SrTiO3and process for preparing them - Google Patents

A red fluorescent body based SrTiO3and process for preparing them Download PDF

Info

Publication number
KR20000059660A
KR20000059660A KR1019990007436A KR19990007436A KR20000059660A KR 20000059660 A KR20000059660 A KR 20000059660A KR 1019990007436 A KR1019990007436 A KR 1019990007436A KR 19990007436 A KR19990007436 A KR 19990007436A KR 20000059660 A KR20000059660 A KR 20000059660A
Authority
KR
South Korea
Prior art keywords
red phosphor
strontium titanate
phosphor
mol
srtio
Prior art date
Application number
KR1019990007436A
Other languages
Korean (ko)
Inventor
박희동
류호진
박정규
Original Assignee
김충섭
한국화학연구소
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 김충섭, 한국화학연구소 filed Critical 김충섭
Priority to KR1019990007436A priority Critical patent/KR20000059660A/en
Publication of KR20000059660A publication Critical patent/KR20000059660A/en

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

PURPOSE: A SrTiO3-based red fluorescent substance and its preparation method are provided, which has the excellent light-emitting brightness and color purity and the stable physical properties in high vacuum, and is suitable for field emission display (FED). CONSTITUTION: The SrTiO3-based red fluorescent substance is represented by the formula 1, wherein a is 0.0005 or more and 0.01 or less; and b is above 0 and 1.0 or less than. The method comprises the steps of adding PrCl3 and Al(OH)3 to SrTiO3 for the ratio of Pr to Al to be 0.001/0.02 to 0.005/0.50 by mol; drying the mixture; calcining it at 1,000-1,400°C at atmosphere; and pulverizing the calcined one. Preferably the ratio of PrCl3 to SrTiO3 is 0.0005-0.01 : 1 by mol; and the ratio of Al(OH)3 to SrTiO3 is less than one by mol.

Description

티탄산스트론튬계 적색 형광체와 이의 제조방법{A red fluorescent body based SrTiO3and process for preparing them}Strontium titanate-based red phosphor and a method for preparing the same {A red fluorescent body based SrTiO3and process for preparing them}

본 발명은 티탄산스트론튬계 적색 형광체와 이의 제조방법에 관한 것으로서, 더욱 상세하게는 형광체 모체인 티탄산스트론튬(SrTiO3)에 공부활제로 수산화알루미늄과 염화프라세오디움을 소정의 함량비에 함께 첨가함으로써 저속전자선에서의 발광휘도와 색순도가 우수할 뿐만 아니라 고진공에서도 안정한 물성을 가지며, 저전압 전자선 여기에 의해 구동하는 전계 방출 디스플레이(Field Emission Display, FED)에 적합하도록 고휘도를 갖는 다음 화학식 1로 표시되는 티탄산스트론튬계 적색 형광체와 이의 제조방법에 관한 것이다.The present invention relates to a strontium titanate-based red phosphor and a method of manufacturing the same, and more particularly, to a strontium titanate (SrTiO 3 ), which is a phosphor matrix, by adding aluminum hydroxide and prasedium chloride together at a predetermined content ratio as a activator. Strontium titanate represented by the following Chemical Formula 1 having excellent luminance and color purity as well as stable physical properties even at high vacuum, and having high luminance to be suitable for a field emission display (FED) driven by low voltage electron beam excitation. The present invention relates to a red phosphor and a method of manufacturing the same.

화학식 1Formula 1

상기 화학식 1에서 : 0.0005≤a≤0.01 이고, 0＜b≤1.0 이다.In Chemical Formula 1, 0.0005 ≦ a ≦ 0.01, and 0 <b ≦ 1.0.

정보표시용 디스플레이로서 음극선관(CRT)이 가장 많이 사용되고 있으며, 이러한 음극선관(CRT)의 단점을 보완 및 대체할 수 있는 차세대 평판 디스플레이의 하나로 전계 방출 디스플레이(FED)가 각광받고 있다.Cathode ray tubes (CRTs) are most frequently used as information display displays, and field emission displays (FEDs) are in the spotlight as one of the next-generation flat panel displays that can supplement and replace the disadvantages of the cathode ray tubes (CRTs).

전계 방출 디스플레이(Field Emission Display, FED)는 진공 평판 음극선 튜브를 사용한 새로운 형태의 디스플레이로서, 이는 1 ㎸ 이하의 저전압 음극선 여기를 기본으로 한다. 그러나, 약 1 kV 이하의 양극 구동전압을 갖는 FED를 구동시키기 위해서는 FED용 형광체로서 저속 전자선용 형광체가 필요하다.Field Emission Display (FED) is a new type of display using a vacuum flat cathode tube, which is based on low voltage cathode excitation below 1 kW. However, in order to drive an FED having an anode driving voltage of about 1 kV or less, a phosphor for a low speed electron beam is required as the phosphor for the FED.

현재 사용되고 있는 대표적인 FED용 형광체로서 ZnO:Zn 형광체가 있는 바, 이는 발광영역이 매우 넓어서 천연색 디스플레이로서 적용하기에는 부적합한 문제가 있다.There is a ZnO: Zn phosphor as a representative FED phosphor currently in use, which has a wide light emitting area, which is not suitable for use as a color display.

또한, 적색 형광체로서 (Zn, Cd)S:Ag, Cl 등과 같은 유화물 형광체가 공지되어 있지만, 음극으로부터 방출된 전자가 가속되어 황화물 형광체층에 충돌할 때 형광체층을 발광시키는 작용 이외에 형광체층 표면을 분해하는 작용 및 형광체 자체의 분해로 인한 디바이스의 여기원에 악영향을 주는 것으로 알려져 있다. 그 밖에도, 적색 형광체로서 Y2O3:Eu계 형광체가 널리 알려져 있으나, 이는 절연성을 높이기 위하여 도전물질로 In2O3를 다량 혼합하여 사용함으로써 In2O3를 통하여 흐르는 무효전류가 많아져 저전압 구동영역에서의 발광 효율이 낮아지며, 신뢰성도 저하되는 문제점을 가지고 있다. 또 다른 적색 형광체로서, SnO2:Eu계 형광체는 휘도포화 및 색순도에 문제가 있어서 실용적으로 사용하기에는 부적당하다.In addition, emulsion phosphors such as (Zn, Cd) S: Ag, Cl and the like are known as red phosphors, but in addition to the action of emitting the phosphor layer when the electrons emitted from the cathode are accelerated and collide with the sulfide phosphor layer, the surface of the phosphor layer is changed. It is known to adversely affect the excitation source of the device due to the degrading action and decomposition of the phosphor itself. In addition, Y 2 O 3 : Eu-based phosphors are widely known as red phosphors. However, in order to increase insulation, a large amount of In 2 O 3 is used as a conductive material to increase the reactive current flowing through In 2 O 3 . The luminous efficiency in the driving region is lowered and the reliability is also lowered. As another red phosphor, SnO 2 : Eu-based phosphors have problems in luminance saturation and color purity and are not suitable for practical use.

이에 본 발명자들은 티탄산스트론튬(SrTiO3)을 모체로 하는 적색 형광체에 있어 공부활제로 염화프라세오디움(PrCl3)과 수산화알루미늄(Al(OH)3)을 함께 첨가하면 보다 효율적인 발광과 높은 발광강도를 얻을 수 있음을 알게됨으로써 본 발명을 완성하였다.The present inventors have found that strontium titanate (SrTiO 3) the in the red phosphor to a matrix study lubricant chloride plastic Seo Stadium (PrCl 3) and aluminum hydroxide (Al (OH) 3) the addition with a more efficient light emission with high luminous intensity The present invention was completed by knowing that can be obtained.

따라서, 본 발명은 저속전자관에서 발광휘도와 색순도가 우수하고, 고진공에서도 안정한 물성을 가지며, 전계 방출 디스플레이(FED)에 적합한 티탄산스트론튬계 적색 형광체와 이의 제조방법을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a strontium titanate-based red phosphor suitable for a field emission display (FED), and a method of manufacturing the same, having excellent luminance and color purity in a low-speed electron tube, having stable physical properties even at high vacuum.

도 1은 본 발명의 티탄산스트론튬계 적색 형광체에 있어, Al의 첨가량에 따른 회절강도 및 회절각의 변화를 나타낸 그래프이고,1 is a graph showing a change in diffraction intensity and diffraction angle according to the amount of Al added in the strontium titanate-based red phosphor of the present invention,

도 2는 본 발명의 티탄산스트론튬계 적색 형광체에 있어, Al의 첨가량에 따른 상대휘도 변화를 나타낸 그래프이고,2 is a graph showing a change in relative luminance according to the amount of Al added in the strontium titanate-based red phosphor of the present invention,

도 3은 본 발명의 티탄산스트론튬계 적색 형광체에 있어, Pr의 첨가량에 따른 음극선 발광 스펙트럼 변화를 나타낸 그래프이고,3 is a graph showing the change in cathode ray emission spectrum according to the amount of Pr added in the strontium titanate-based red phosphor of the present invention,

도 4는 종래의 Y2O3:Eu 적색 형광체와 본 발명 티탄산스트론튬계 적색 형광체에 대한 음극선 발광 스펙트럼을 나타낸 그래프이고,4 is a graph showing the cathode emission spectrum of the conventional Y 2 O 3 : Eu red phosphor and the present invention strontium titanate-based red phosphor,

도 5는 종래의 Y2O3:Eu 적색 형광체와 본 발명 티탄산스트론튬계 적색 형광체에 대한 색좌표를 나타내는 CIE색도 그래프이다.5 is a CIE chromaticity graph showing color coordinates of a conventional Y 2 O 3 : Eu red phosphor and a strontium titanate-based red phosphor of the present invention.

본 발명은 다음 화학식 1로 표시되는 티탄산스트론튬계 적색 형광체를 그 특징으로 한다.The present invention is characterized by a strontium titanate-based red phosphor represented by the following formula (1).

화학식 1Formula 1

상기 화학식 1에서 : 0.0005≤a≤0.01 이고, 0＜b≤1.0 이다.In Chemical Formula 1, 0.0005 ≦ a ≦ 0.01, and 0 <b ≦ 1.0.

또한, 본 발명은 티탄산스트론튬(SrTiO3)을 모체로 하고 여기에 염화프라세오디움(PrCl3)과 수산화알루미늄(Al(OH)3)을 첨가하고 혼합한 다음, 이를 건조하고 대기 중에서 1,000 ∼ 1,400℃에서 소성, 분쇄하여 상기 화학식 1로 표시되는 티탄산스트론튬계 적색 형광체를 제조하는 방법을 포함한다.In addition, the present invention is based on strontium titanate (SrTiO 3 ) as a matrix, and added and mixed with prasedium chloride (PrCl 3 ) and aluminum hydroxide (Al (OH) 3 ), and then dried and 1,000 to 1,400 in the air It includes a method for producing a strontium titanate-based red phosphor represented by the formula (1) by firing and grinding at ℃.

이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명은 적색 형광체의 모체로 SrTiO3를 사용함으로써 종래의 Y2O3:Eu계 형광체에서 가질 수 없었던 저전압 구동영역에서의 발광 효율을 높이고, 또한 SnO2:Eu계 형광체에서 가질 수 없었던 저속전자관에서 발광휘도와 색순도가 우수해지며, 산화물계 형광체이기 때문에 고진공에서도 안정한 물성을 가지므로 전계 방출 디스플레이(FED)에 적합한 효과를 가지는 티탄산스트론튬(SrTiO3)계 적색 형광체에 관한 것이다. 특히, 본 발명에 따른 티탄산스트론튬(SrTiO3)계 적색 형광체에는 SrTiO3모체에 공부활제로 프라세오디움(Pr)과 알루미늄(Al)을 함께 첨가함으로써 적색 발광휘도 및 색순도 까지도 우수해지는 효과를 얻는다.According to the present invention, the use of SrTiO 3 as a matrix of the red phosphor improves the luminous efficiency in the low voltage driving region, which was not possible in the conventional Y 2 O 3 : Eu-based phosphor, and also has a low-speed electron tube which the SnO 2 : Eu-based phosphor could not have. The present invention relates to a strontium titanate (SrTiO 3 ) -based red phosphor having excellent luminescence brightness and color purity and having stable properties even at high vacuum because it is an oxide-based phosphor, and thus has an effect suitable for field emission display (FED). In particular, the strontium titanate (SrTiO 3 ) -based red phosphor according to the present invention obtains an effect of excellent red luminescence brightness and color purity by adding together prasedium (Pr) and aluminum (Al) as a activator to the SrTiO 3 matrix.

상기와 같은 본 발명의 티탄산스트론튬(SrTiO3)계 적색 형광체를 그 제조방법에 의거하여 더욱 상세히 설명하면 다음과 같다.The strontium titanate (SrTiO 3 ) -based red phosphor of the present invention as described above will be described in more detail based on the preparation method as follows.

먼저, 탄산스트론튬(SrCO3) 및 이산화티탄(TiO2)를 형광체 원료로 사용하여 제조한 SrTiO3모체에 공부활제로서 염화프라세오디움(PrCl3)과 수산화알루미늄(Al(OH)3)를 첨가하여 혼합한다. 이때, 모체를 구성하는 탄산스트론튬(SrCO3) 및 이산화티탄(TiO2)의 함량은 형광체의 Sr/Ti 몰비가 화학양론적으로 1 : 1이 되도록 하는 것이 바람직하다.First, the addition of strontium carbonate (SrCO 3) and titanium dioxide chloride plastic Seo Stadium (PrCl 3) and aluminum hydroxide (TiO 2) the as a SrTiO 3 study lubricant to the matrix manufactured by using a phosphor raw material (Al (OH) 3) To mix. In this case, the content of strontium carbonate (SrCO 3 ) and titanium dioxide (TiO 2 ) constituting the parent is preferably such that the Sr / Ti molar ratio of the phosphor is 1: 1 in stoichiometric terms.

특히, 본 발명은 공부활제로서 염화프라세오디움과 수산화알루미늄을 함께 사용하는데 그 특징이 있는데, 공부활제로서 염화프라세오디움을 단독으로 사용하기 보다는 수산화알루미늄을 함께 사용하므로써 알루미늄에 의한 프라세오디움의 전하보상효과를 얻을 수 있고, 또한 수산화알루미늄이 입사된 에너지의 전달체 역할을 하여 발광 중심인 프라세오디움의 효율적인 발광을 돕고 발광강도를 높이도록 한다. 공부활제로서 염화프라세오디움은 티탄산스트론튬(SrTiO3)에 대하여 0.0005 ∼ 0.01 몰비, 바람직하기로는 0.001 ∼ 0.003 몰비로 첨가하는데, 만일 염화프라세오디움의 사용량이 0.0005 몰비 미만이면 공부활제로서의 기능을 하기에 충분한 양이 되지 못하며, 0.01 몰비를 초과하면 농도퀀칭효과에 따른 휘도저하가 일어난다. 또한, 공부활제로서 함께 사용되는 염화프라세오디움과 수산화알루미늄의 바람직한 사용량은 Pr/Al의 몰비가 0.001/0.02 ∼ 0.005/0.50 되도록 하는 것이다.In particular, the present invention is characterized in that the use of prasedium chloride and aluminum hydroxide together as a study lubricant, the use of aluminum hydroxide rather than the use of prasedium chloride alone as a study agent The charge compensation effect can be obtained, and aluminum hydroxide acts as a carrier of incident energy to help efficient emission of Prasedium, which is a light emission center, and to increase emission intensity. Prasedium chloride is added as 0.0005 to 0.01 molar ratio, preferably 0.001 to 0.003 molar ratio, with respect to strontium titanate (SrTiO 3 ) as an active agent. If the amount is not sufficient, and the amount exceeds 0.01 molar ratio, the luminance decreases due to the concentration quenching effect. In addition, the preferred amount of prasedium chloride and aluminum hydroxide used together as a study active agent is such that the molar ratio of Pr / Al is 0.001 / 0.02 to 0.005 / 0.50.

상기와 같은 함량비 범위내에서 형광체 원료물질과 공부활제를 원하는 조성에 따른 각각의 소정비가 되도록 평량하고, 또한 보다 효과적인 혼합을 위하여 아세톤 용매 하에서 볼밀링(ball milling) 또는 마노 유발과 같은 혼합기를 이용하여 균일한 조성이 되도록 충분히 혼합한다. 그리고, 혼합물을 오븐에 넣고 100 ∼ 150℃ 온도에서 24 시간동안 건조한다. 건조한 혼합물을 고순도 알루미나 보트에 넣고 전기로를 사용하여 1,000 ∼ 1,400℃ 온도에서 1 ∼ 24 시간 동안 소성한다. 전기로의 분위기는 대기 중에서 행한다. 이때, 소성 온도가 매우 중요한 바, 만일 소성 온도가 1,000℃ 미만이면 티탄산스트론튬의 결정이 완전하게 생성되지 못하여 발광이 잘 일어나지 못하고, 1,400℃를 초과하면 불규칙적이며 판상의 입자모양을 가지므로 휘도가 저하하는 문제가 있다. 소성이 완료되면 시간당 200℃ 정도로 냉각시킨다. 그런 다음, 1 ∼ 5 ㎛ 정도로 충분히 분쇄한다.Within the content ratio range as described above, the phosphor raw material and the study active agent are weighed to each predetermined ratio according to the desired composition, and a mixer such as ball milling or agate induction in acetone solvent is used for more effective mixing. And mix sufficiently to make a uniform composition. The mixture is then placed in an oven and dried at a temperature of 100-150 ° C. for 24 hours. The dry mixture is placed in a high purity alumina boat and calcined for 1 to 24 hours at a temperature of 1,000 to 1,400 ° C. 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., crystals of strontium titanate are not completely produced and light emission does not occur well. There is a problem. When firing is completed, it is cooled to about 200 ° C per hour. Then, it grind | pulverizes enough about 1-5 micrometers.

이상에서 설명한 바와 같은 제조방법으로 제조된 본 발명의 적색 형광체 분말에 대해서는 분말 X선 회절기를 사용하여 생성상을 조사하였고, 1 kV 이하의 저전압 전자선 여기에 의해 음극선 발광(Cathodoluminescence, CL)을 측정한 결과, 600 ∼ 650 ㎚ 영역에서 강한 발광 스펙트럼을 나타내었고, 고휘도 및 색순도가 매우 우수함을 확인할 수 있었다.The red phosphor powder of the present invention prepared by the manufacturing method as described above was irradiated with a production phase 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, it showed a strong emission spectrum in the 600 ~ 650 nm region, it was confirmed that the high brightness and color purity is very excellent.

이와 같은 본 발명을 실시예에 의거하여 상세하게 설명하겠는 바, 본 발명이 실시예에 한정되는 것은 아니다.Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

실시예 : SrTiO3:0.002Pr,0.17Al 형광체의 제조Example: Preparation of SrTiO 3 : 0.002 Pr, 0.17 Al phosphor

탄산스트론튬(SrCO3) 1 ㏖, 이산화티탄(TiO2) 1 ㏖, 염화프라세오디움(PrCl3) 0.002 ㏖ 및 수산화알루미늄(Al(OH)3) 0.17 ㏖의 비율로 평량하고 이것을 마노 유발을 사용하여 아세톤중에서 충분히 고르게 혼합하였다. 혼합한 시료를 오븐을 사용하여 130℃ 온도에서 24 시간동안 건조하였다. 얻어진 혼합물을 고순도 알루미나 보트에 넣고 전기로를 사용하여 대기 중에서 1,300℃ 온도에서 6 시간동안 소성하였다. 소성 후에 얻어진 소성물을 충분히 분쇄처리하여 SrTiO3:0.002Pr,0.17Al로 표시되는 적색 형광체를 얻었다.1 mol of strontium carbonate (SrCO 3 ), 1 mol of titanium dioxide (TiO 2 ), 0.002 mol of prasedium chloride (PrCl 3 ) and 0.17 mol of aluminum hydroxide (Al (OH) 3 ) And mixed evenly in acetone. 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 6 hours at 1,300 ° C. in air using an electric furnace. The fired product obtained after firing was sufficiently milled to obtain a red phosphor represented by SrTiO 3 : 0.002 Pr and 0.17 Al.

실험예 1 : Al 함량에 따른 적색 형광체의 회절강도 측정Experimental Example 1 Measurement of Diffraction Intensity of Red Phosphor According to Al Content

상기 실시예와 동일한 방법으로 하되, 수산화알루미늄(Al(OH)3)의 함량을 0 ㏖, 0.1 ㏖, 0.2 ㏖ 및 0.5 ㏖로 각각 달리 첨가하여 SrTiO3:0.002Pr,bAl로 표시되는 적색 형광체를 얻었다. 그런 다음 얻어진 적색 형광체의 회절각에 따른 회절강도를 측정하고, 그 결과를 도 1에 나타내었다.Red phosphor represented by SrTiO 3 : 0.002 Pr, b Al by the same method as in the above embodiment, except that aluminum hydroxide (Al (OH) 3 ) is added in an amount of 0 mol, 0.1 mol, 0.2 mol, and 0.5 mol, respectively. Got. Then, the diffraction intensity according to the diffraction angle of the red phosphor obtained was measured, and the results are shown in FIG.

도 1에 나타낸 바와 같이, 본 발명의 티탄산스트론튬계 적색 형광체는 공부활제로 사용되는 Al의 함량이 증가함에 따라 회절강도가 약간씩 작아지고, 또한 α-Al2O3상과 같은 알루미늄과 관련된 부산물의 양이 점점 증가함을 알 수 있다.As shown in FIG. 1, the strontium titanate-based red phosphor of the present invention has a slightly smaller diffraction intensity as the content of Al used as a activator increases, and is also a by-product associated with aluminum such as α-Al 2 O 3 phase. It can be seen that the amount of increases gradually.

실험예 2 : Al 함량에 따른 적색 형광체의 상대휘도 측정Experimental Example 2 Measurement of Relative Brightness of Red Phosphor According to Al Content

상기 실시예에서 얻은 SrTiO3:0.002Pr,0.17Al 적색 형광체의 상대휘도를 측정하고, 그 결과를 도 2에 나타내었다.The relative luminance of SrTiO 3 : 0.002 Pr, 0.17 Al red phosphor obtained in the above Example was measured, and the results are shown in FIG. 2.

도 2는 본 발명의 적색 형광체에 함유되는 알루미늄의 함량을 달리하여 첨가하였을 때의 상대휘도를 나타내는 것으로, 알루미늄에 의한 프라세오디움의 전하보상효과와 발광중심인 프라세오디움으로 원활한 에너지를 전달하여 효율적인 발광을 얻기 위해서이며, 특히 매우 우수한 휘도를 나타낼 수 있는 알루미늄의 첨가범위는 0.05 ∼ 0.4 ㏖임을 알 수 있다.Figure 2 shows the relative luminance when added to varying the amount of aluminum contained in the red phosphor of the present invention, by delivering a smooth energy to the charge compensation effect of the Prasedium and the light emitting center of the Prasedium In order to obtain efficient light emission, it can be seen that the addition range of aluminum, which can exhibit particularly excellent luminance, is 0.05 to 0.4 mol.

실험예 3 : Pr의 함량에 따른 적색 형광체의 음극선 발광 스펙트럼 측정Experimental Example 3 Measurement of Cathode Radiation Spectrum of Red Phosphor According to Pr Content

상기 실시예와 동일한 방법으로 수행하되, 공부활제인 염화프라세오디움의 함량을 각각 0 mol, 0.0005 mol, 0.001 ㏖, 0.002 ㏖, 0.003 mol, 0.005 mol 및 0.01 ㏖로 변화하여 SrTiO3:aPr,0.17Al로 표시되는 적색 형광체를 얻었다. 그런다음 얻어진 적색 형광체의 음극선 발광 스펙트럼을 측정하고, 그 결과를 도 3에 나타내었다.In the same manner as in the above, except that the content of the Prasedium chloride as an active agent is changed to 0 mol, 0.0005 mol, 0.001 mol, 0.002 mol, 0.003 mol, 0.005 mol and 0.01 mol, respectively, SrTiO 3 : a Pr, A red phosphor represented by 0.17 Al was obtained. Then, the cathode emission spectrum of the obtained red phosphor was measured, and the result is shown in FIG.

도 3에 나타낸 바와 같이, 본 발명의 적색 형광체는 공부활제인 프라세오디움의 첨가량이 0.002 mol이 될 때까지 발광휘도가 증가하며, 그 이상의 첨가후에는 발광휘도가 오히려 감소함을 알 수 있다.As shown in Figure 3, the red phosphor of the present invention increases the emission luminance until the addition amount of the Prasedium, which is a study agent is 0.002 mol, it can be seen that the emission luminance is rather reduced after further addition.

실험예 4 : SrTiO3계 적색 형광체와 Y2O3:Eu 형광체의 발광 스펙트럼 비교Experimental Example 4 Comparison of emission spectra of SrTiO 3 -based red phosphors and Y 2 O 3 : Eu phosphors

상기 실시예에서 얻은 본 발명의 SrTiO3:0.002Pr,0.17Al 적색 형광체와 종래의 Y2O3:Eu 형광체에 대하여 음극선 발광 스펙트럼을 측정하고, 그 결과를 도 4에 나타내었다.Cathode emission spectra of the SrTiO 3 : 0.002 Pr, 0.17 Al red phosphor and the conventional Y 2 O 3 : Eu phosphor of the present invention obtained in the above Example were measured, and the results are shown in FIG. 4.

도 4에 나타낸 바와 같이 음극선 발광 측정 조건이 800V, 600V 및 400V로 낮아지면서 점점 발광강도는 감소하고 있다. 그러나, 본 발명의 적색 형광체는 상용화되어 있는 Y2O3:Eu 형광체보다 저전압에서 우수한 발광강도를 보이고 있다.As shown in FIG. 4, the emission intensity decreases gradually as the cathode ray emission measurement conditions are lowered to 800V, 600V, and 400V. However, the red phosphor of the present invention shows superior luminous intensity at low voltage than commercially available Y 2 O 3 : Eu phosphors.

실험예 5 : SrTiO3계 적색 형광체와 Y2O3:Eu 형광체의 색도 비교Experimental Example 5: Comparison of chromaticity between SrTiO 3 -based red phosphor and Y 2 O 3 : Eu phosphor

상기 실시예에서 제조한 SrTiO3:0.002Pr,0.17Al계 적색 형광체와 종래의 Y2O3:Eu계 적색 형광체의 색도를 CIE 색좌표에 의하여 측정하고, 그 결과를 도 5에 나타내었다.The chromaticity of the SrTiO 3 : 0.002 Pr, 0.17 Al-based red phosphor prepared in Example and the conventional Y 2 O 3 : Eu-based red phosphor were measured by CIE color coordinates, and the results are shown in FIG. 5.

도 5에 나타낸 바와 같이, 본 발명의 형광체의 색좌표 x=0.657, y=0.338 이었고, 종래의 적색 형광체인 Y2O3:Eu 형광체의 색좌표(x=0.621, y=0.363)와 비교하여 볼 때 색좌표가 보다 적색쪽에 위치하고 있어 적색 형광체로서 색순도도 우수함을 알 수 있다.As shown in FIG. 5, the color coordinates of the phosphor of the present invention were x = 0.657 and y = 0.338, and compared with the color coordinates of the conventional Y 2 O 3 : Eu phosphor (x = 0.621, y = 0.363). Since the color coordinate is located on the red side more, it can be seen that the color phosphor is also excellent as the red phosphor.

상술한 바와 같이, 본 발명의 티탄산스트론튬(SrTiO3)계 적색 형광체는 공부활제로서 알루미늄과 프라세오디움을 함께 첨가함으로써, 1 kV 이하의 저전압 전자선 여기 하에서 고휘도를 갖으며 색순도가 매우 우수한 적색발광을 나타내는데, 이는 황(S), 카드늄(Cd)을 포함하지 않는 산화물 형광체이므로 종래의 칼라 형광체에서 발생하는 유화물에 의한 음극의 오염 및 공해에 대한 문제점이 해결될 수 있는 효과가 있으므로 전계 방출 디스플레이(FED)에 적용할 수 있는 가능성이 매우 크다.As described above, the strontium titanate (SrTiO 3 ) -based red phosphor of the present invention has a high luminance and excellent color purity under low voltage electron beam excitation of 1 kV or less by adding aluminum and prasedium together as an active agent. Since it is an oxide phosphor that does not contain sulfur (S) and cadmium (Cd), the field emission display (FED) is effective because it can solve the problem of pollution and pollution of the cathode by the emulsion generated from the conventional color phosphor. It is very likely to be applicable to).

Claims (4)

다음 화학식 1로 표시되는 것임을 특징으로 하는 티탄산스트론튬계 적색 형광체.Strontium titanate-based red phosphor, characterized in that represented by the formula (1). 화학식 1Formula 1 상기 화학식 1에서 : 0.0005≤a≤0.01 이고, 0＜b≤1.0 이다.In Chemical Formula 1, 0.0005 ≦ a ≦ 0.01, and 0 <b ≦ 1.0. 티탄산스트론튬(SrTiO3)을 모체로 하고, 여기에 공부활제로서 염화프라세오디움(PrCl3)과 수산화알루미늄(Al(OH)3)을 첨가하되 Pr/Al의 몰비가 0.001/0.02 ∼ 0.005/0.50 되도록 첨가 혼합한 다음, 건조하고 대기 중에서 1,000 ∼ 1,400℃에서 소성, 분쇄하여 제조하는 것을 특징으로 하는 다음 화학식 1로 표시되는 티탄산스트론튬계 적색 형광체의 제조방법.Strontium titanate (SrTiO 3 ) is used as a mother, and prasedium chloride (PrCl 3 ) and aluminum hydroxide (Al (OH) 3 ) are added as a catalyst for the study, and the molar ratio of Pr / Al is 0.001 / 0.02 to 0.005 / 0.50. Method of producing a strontium titanate-based red phosphor represented by the following formula (1), characterized in that the mixture is mixed so as to be mixed, then dried and calcined at 1,000 to 1,400 ℃ in the air. 화학식 1Formula 1 상기 화학식 1에서 : 0.0005≤a≤0.01 이고, 0＜b≤1.0 이다.In Chemical Formula 1, 0.0005 ≦ a ≦ 0.01, and 0 <b ≦ 1.0. 제 2 항에 있어서, 상기 염화프라세오디움은 티탄산스트론튬(SrTiO3)에 대하여 0.0005 ∼ 0.01 몰비의 범위로 첨가하는 것을 특징으로 하는 티탄산스트론튬계 적색 형광체의 제조방법.The method of manufacturing a strontium titanate-based red phosphor according to claim 2, wherein the prasedium chloride is added in a range of 0.0005 to 0.01 molar ratio with respect to strontium titanate (SrTiO 3 ). 제 2 항에 있어서, 상기 수산화알루미늄은 티탄산스트론튬(SrTiO3)에 대하여 1 몰비이하의 범위로 첨가하는 것을 특징으로 하는 티탄산스트론튬계 적색 형광체의 제조방법.The method of manufacturing a strontium titanate-based red phosphor according to claim 2, wherein the aluminum hydroxide is added in a range of 1 mol or less with respect to strontium titanate (SrTiO 3 ).
KR1019990007436A 1999-03-06 1999-03-06 A red fluorescent body based SrTiO3and process for preparing them KR20000059660A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019990007436A KR20000059660A (en) 1999-03-06 1999-03-06 A red fluorescent body based SrTiO3and process for preparing them

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019990007436A KR20000059660A (en) 1999-03-06 1999-03-06 A red fluorescent body based SrTiO3and process for preparing them

Publications (1)

Publication Number Publication Date
KR20000059660A true KR20000059660A (en) 2000-10-05

Family

ID=19575747

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019990007436A KR20000059660A (en) 1999-03-06 1999-03-06 A red fluorescent body based SrTiO3and process for preparing them

Country Status (1)

Country Link
KR (1) KR20000059660A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100319764B1 (en) * 1999-12-24 2002-01-09 오길록 A oxide-based red phosphor for fluorescent display and a preparation method thereof
KR100355456B1 (en) * 1999-07-30 2002-10-11 한국전자통신연구원 A red phosphor for fluorescent display and a preparation method thereof
KR100373839B1 (en) * 2000-09-01 2003-02-26 삼성에스디아이 주식회사 Low-voltage red phosphor and method of preparing same
KR100424073B1 (en) * 2001-05-22 2004-03-22 한국과학기술연구원 Fluorene compounds containing various functional groups, their polymers, and el element using the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100355456B1 (en) * 1999-07-30 2002-10-11 한국전자통신연구원 A red phosphor for fluorescent display and a preparation method thereof
KR100319764B1 (en) * 1999-12-24 2002-01-09 오길록 A oxide-based red phosphor for fluorescent display and a preparation method thereof
KR100373839B1 (en) * 2000-09-01 2003-02-26 삼성에스디아이 주식회사 Low-voltage red phosphor and method of preparing same
KR100424073B1 (en) * 2001-05-22 2004-03-22 한국과학기술연구원 Fluorene compounds containing various functional groups, their polymers, and el element using the same

Similar Documents

Publication Publication Date Title
KR100355456B1 (en) A red phosphor for fluorescent display and a preparation method thereof
KR100319488B1 (en) Green fluorescent body based zinc silicate
JP4173057B2 (en) Fluorescent substance and fluorescent display device
KR100336973B1 (en) A red fluorescent body based SrTiO3 used in low voltage and process for preparing them
KR20000059660A (en) A red fluorescent body based SrTiO3and process for preparing them
KR19990085329A (en) Strontium titanate-based red phosphor and its manufacturing method
KR100270409B1 (en) Ared flurorescent body based lanthanum titanate and its preparing method
KR100285274B1 (en) A green fluorescent body based gadolinium aluminate and process for preparing them
KR101496959B1 (en) Red-emitting phosphors with highly enhanced luminescent efficiency and their preparation methods
KR20100120362A (en) Green emitting phosphor for vacuum ultraviolet excited light emitting device, preparation method thereof and light emitting device having the same
KR100361847B1 (en) Oxide fluorescent material and producing methods of the same
KR100348207B1 (en) Fluorescent Material of Lanthanum Gallate and Method for Producing The Same
KR100348967B1 (en) Blue Luminescence comprising thulium for low voltage cathodoluminescence and manufacturing method thereof
KR100364494B1 (en) A red fluorescent body based on gadolinium oxide and methods of preparing the same
KR100658707B1 (en) A red emitting phosphor for low-voltage applications and a method of preparing the same
KR100534017B1 (en) Novel Zirconate Phosphor Compositions
KR100358811B1 (en) green phosphors for low voltage electron excitation
JP5016804B2 (en) Phosphor, method for manufacturing the same, and light emitting device
KR100738404B1 (en) Zinc gallium oxide-based green phosphor and method for the preparation thereof
KR100424864B1 (en) Process for preparing GdOBr green phosphor
KR100439340B1 (en) A red phosphor for fluorescent display and the preparation method thereof
JP2000044943A (en) New green-emitting phosphor
KR20010063937A (en) A oxide-based red phosphor for fluorescent display and a preparation method thereof
KR20000008650A (en) Method for preparing red fluorescent substance made of yttrium oxide derivatives
KR20020025281A (en) A green phosphor for fluorescent display and a preparation method thereof

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E601 Decision to refuse application