WO2017138765A1 - Led light emitting device comprising red organic-inorganic composite light emitting material - Google Patents

Led light emitting device comprising red organic-inorganic composite light emitting material Download PDF

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WO2017138765A1
WO2017138765A1 PCT/KR2017/001474 KR2017001474W WO2017138765A1 WO 2017138765 A1 WO2017138765 A1 WO 2017138765A1 KR 2017001474 W KR2017001474 W KR 2017001474W WO 2017138765 A1 WO2017138765 A1 WO 2017138765A1
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formula
light emitting
phenanthroline
inorganic composite
emitting material
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PCT/KR2017/001474
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French (fr)
Korean (ko)
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임서영
고다현
김영식
류정곤
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주식회사 효성
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • 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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

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  • the present invention relates to an LED light emitting device including a red organic-inorganic composite light emitting material, more specifically, an organic metal coordination polymer in which a metal is coordinated with an organic light emitting ligand, which is more stable than an existing organic light emitting compound and has a half width than an inorganic light emitting material.
  • the present invention relates to an LED light emitting device comprising a red organic-inorganic composite light emitting material which is narrow in size and excellent in luminance and capable of excitation in UV and blue regions.
  • yellow is realized by applying yellow and red phosphors to a blue LED chip to manufacture a device.
  • yellow phosphors are mainly oxide-based phosphors
  • red phosphors are nitride-based phosphors.
  • the existing organic light emitting material is a material of high brightness that is easy to control the wavelength of the implementation, but is still vulnerable to stability due to restrictions on use.
  • X is -CH 3 , -CH 2 CH 3 , -CH (CH 3) 2 , -CF 3 , -CF 2 CF 3 or -CF 2 CF 2 CF 3 It is selected from the group consisting of.
  • the patent relates to a method of preparing a europium-phenanthroline complex compound as a moisture-sensitive fluorescent material capable of measuring moisture, and to measuring the fluorescence change of the water-sensitive fluorescent substance.
  • the europium-phenanthroline complex itself is made of a molecular material, but the present invention has a difference in synthesizing a coordinating polymeric fluorescent substance that can be utilized as an LED.
  • Patent Document 1 Korean Patent Publication No. 10-2014-0059982
  • the present invention has been completed in response to the need for research on the organometallic coordination polymer of the light emitting material having excitation in the UV region and the blue region, and emit light, and compared to the light emitting material of the conventional organic metal coordination polymer
  • An object of the present invention is to provide an LED light emitting device having a high brightness and including a red organic-inorganic composite light emitting material.
  • the present invention relates to an LED light emitting device including a red organic-inorganic composite light emitting material, and provides an LED light emitting device including a red organic-inorganic composite light emitting material having a composition of Formula 1 below.
  • A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti
  • R includes at least one selected from Eu or Eu compounds
  • L is an aromatic having at least two carboxylic acid groups Including one selected from the group compounds
  • X includes one or more selected from phenanthroline (phenanthroline) and derivatives thereof
  • x1 is 0 ⁇ x1 ⁇ 2
  • x2 is 0 ⁇ x2 ⁇ 2
  • the sum of x1 and x2 is 0 ⁇ x 1 + x 2 ⁇ 2 ⁇ 2 y is 2 or 3, and n is an integer selected from one or more integers.
  • one or more selected from monovalent to tetravalent metal ions or metal compounds thereof, one selected from Eu or Eu compounds, one selected from aromatic compounds having at least two carboxylic acid groups, and phenane Weighing at least one raw material selected from trolline and derivatives thereof, preparing the mixture by uniformly mixing the weighed raw material in 50-100 ml of solvent, and synthesizing the mixture at a temperature of 90-210 ° C. It provides an LED light emitting device comprising a red organic-inorganic composite light emitting material having a composition of the formula (1) prepared including the step.
  • A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti
  • R includes at least one selected from Eu or Eu compounds
  • L is an aromatic having at least two carboxylic acid groups Including one selected from the group compounds
  • X includes one or more selected from phenanthroline (phenanthroline) and derivatives thereof
  • x1 is 0 ⁇ x1 ⁇ 2
  • x2 is 0 ⁇ x2 ⁇ 2
  • the sum of x1 and x2 is 0 ⁇ x 1 + x 2 ⁇ 2 ⁇ 2 y is 2 or 3, and n is an integer selected from one or more integers.
  • the red organic-inorganic composite light emitting material included in the LED light emitting device of the present invention has a higher luminance than the light emitting material of the conventional organic metal coordination polymer, and is a material capable of excitation in the UV and blue regions. This has a significant effect as a luminescent material for LEDs because it has a free range of colors, a half width of 15 nm or less and can be excited especially in the UV and blue regions.
  • FIG. 1 shows a PL spectral graph and SEM image according to the present invention.
  • Figure 4 shows the UV LED package mounting evaluation results according to the present invention.
  • Example 8 shows an emission spectrum according to Example 12 of the present invention.
  • the present invention is an LED light emitting device in which the red organic-inorganic composite light emitting material includes one or more excitation sources selected from UV LEDs or Blue LEDs.
  • the red organic-inorganic composite light emitting material according to the embodiment of the present invention is a light emitting material of an organic metal coordination polymer, and is excited by a UV region and a blue region of 350 to 450 nm to exhibit an emission wavelength of 600 to 630 nm, and 15 nm. It has the following half width and high brightness.
  • the LED light emitting device including the red organic-inorganic composite light emitting material is based on the structure that Eu 3 + is added as an activator of the red organic-inorganic composite light emitting material, the chemical composition is as shown in the formula (1).
  • A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti At least one metal ion selected from the group consisting of tetravalent metal ions or metal compounds thereof,
  • R includes one selected from Eu or Eu compounds
  • L includes one selected from aromatic compounds having at least two carboxylic acid groups
  • X includes at least one selected from phenanthroline and its derivatives
  • x1 is 0 ⁇ x1 ⁇ 2
  • x2 is 0 ⁇ x2 ⁇ 2
  • the sum of x1 and x2 is 0 ⁇ x 1+ x 2 ⁇ 2
  • y is 2 or 3
  • n is an integer chosen from the integer of 1 or more.
  • the metal compound in Chemical Formula 1 may be, for example, ZnO, Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Y (NO 3 ) 3 , Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 Or a metal compound containing MnCO 3 may be used, but the scope of the present invention is not limited only to the above examples.
  • Eu As the Eu compound which may be used as R in Formula 1, Eu and one or more metal ions and oxides, or metal oxides containing Eu may be used.
  • Eu compound may be one selected from ZnO: Eu, Y 2 O 3 : Eu, La 2 O 3 : Eu or Eu (NO 3 ) 3 xH 2 O, and Eu (NO 3 ) from 3 ⁇ xH 2 O x is an integer selected from 1-6.
  • Eu or Eu compounds When Eu or Eu compounds are used, they have an Eu characteristic peak, which has a narrow half width of red, and when used in an LED, high color reproduction is possible.
  • L may be used as one selected from aromatic compounds having at least two carboxylic acid groups.
  • Chemical Formulas 2 to 8 may be used, but the scope of the present invention is not limited only to the following examples. .
  • X in Formula 1 may be used at least one selected from phenanthroline (phenanthroline) and derivatives thereof, for example, a compound represented by the following formulas 9 to 12 may be used, the scope of the present invention only by the following examples Is not limited.
  • R 1 to R 10 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C 1 -60 alkyl; 1- C 60 haloalkyl; Substituted or unsubstituted C 1 -60 alkoxy; Substituted or unsubstituted C 1 -60 haloalkoxy; Substituted or unsubstituted C 3 -60 cycloalkyl; A substituted or unsubstituted C 2- 60 alkenyl; Substituted or unsubstituted C 6- 60 aryl; Substituted or unsubstituted C 6-60 aryloxy; Or a C 1- 60 heterocyclic group, including a substituted or unsubstituted N, O, and S 1 out of the above, Q is N or CH.
  • R 1 to R 10 R 1 is hydrogen (H), cyano group (-CN) or methyl group (CH 3 ), and R 2 to R 7 are each independently hydrogen (H), Amino group (-NH 2 ), methyl group (CH 3 ) or phenyl, R 8 is hydrogen (H) or methoxy (-OCH 3 ), R 9 is hydrogen (H), C 1 -C 6 alkyl group , phenyl, (phenyl), nC 1 ⁇ C 6 alkyl phenyl (nC 1 ⁇ C 6 alkylphenyl) , dimethylphenyl (dimethylphenyl), trimethylphenyl (trimethylphenyl), diethyl phenyl (diethylphenyl), triethyl phenyl (triethylphenyl), n- Nitrophenyl (n-nitrophenyl), n-aminophenyl (n-aminophenyl), n-sulfon
  • the C 1 ⁇ C 6 alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy, n is any integer selected from 2 to 4, o-, m-, p- it means.
  • phenanthroline and its derivatives that may be used in the present invention, one or more compounds selected from the following Chemical Formulas 13 to 28 may be used.
  • phenanthroline and its derivatives are effective in improving the luminance as compared with the case where the phenanthroline and its derivatives are not used.
  • the red organic-inorganic composite light emitting material according to Chemical Formula 1 included in the LED light emitting device of the present invention is [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (paragino [2,3- f] [1,10] phenanthroline)] n, [(. Y 0.
  • a solvent such as water (H 2 O), propanol, ethanol, methanol, dimethylformamide (DMF, dimethylformamide) or dimethylacetamide (DMA, dimethyacetamide) and mixed uniformly.
  • a solvent such as water (H 2 O), propanol, ethanol, methanol, dimethylformamide (DMF, dimethylformamide) or dimethylacetamide (DMA, dimethyacetamide)
  • It comprises a red organic-inorganic composite light emitting material having a composition of Formula 1 prepared by the step of synthesizing the mixture at a temperature of 90 ⁇ 210 °C.
  • A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti At least one metal ion selected from the group consisting of tetravalent metal ions or metal compounds thereof,
  • R includes one selected from Eu or Eu compounds
  • L includes one selected from aromatic compounds having at least two carboxylic acid groups
  • X includes at least one selected from phenanthroline and its derivatives
  • x1 is 0 ⁇ x1 ⁇ 2
  • x2 is 0 ⁇ x2 ⁇ 2
  • the sum of x1 and x2 is 0 ⁇ x 1+ x 2 ⁇ 2
  • y is 2 or 3
  • n is an integer chosen from the integer of 1 or more.
  • the single crystal image indicates that aromatic compounds having at least two carboxylic acid groups in one metal are coordinated up to three times, and phenanthroline and its derivatives are coordinated in the same ratio. Given, the correct light emitting material is not synthesized.
  • Each weighed raw material can be mixed with a solvent and synthesized at a temperature of 90-210 ° C., if it is synthesized at a temperature below 90 ° C., a red organic-inorganic composite luminescent material is not formed and exceeds 210 ° C. The luminance of the red organic-inorganic composite light emitting material is reduced.
  • A, R, L, and X are the same as A, R, L, and X of Formula 1, and the red organic-inorganic composite luminescent material of the present invention has a conventional metal-organic skeleton by doping a cationic metal in the A portion. Unlike the Si doped with only Eu to R, the effect of electron transfer and crystallinity of the skeleton structure are improved, and thus, when used in an LED lamp, there is an advantage of improving light emission characteristics.
  • the red organic-inorganic composite luminescent material having the formula (1) prepared by the above method has a light emission wavelength of 600 to 630 nm for excitation light in the UV and blue regions, and has a red color having a narrow half width and a high brightness of 15 nm or less compared with a conventional phosphor. The characteristics of the light emitting material are shown.
  • the red organic-inorganic composite light emitting material can be used in the LED light emitting device by examining the light emission characteristics by using the UV or Blue LED chip.
  • Group composite light emitting material [(Y 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [ 1,10] phenanthroline)] n was prepared.
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • Group composite light emitting material [(La 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [ 1,10] phenanthroline)] n was prepared.
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • Group composite light emitting material [(Gd 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [ 1,10] phenanthroline)] n was prepared.
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • a UV LED package was manufactured in the same manner as in Example 2, except that the prepared red light emitting material was used.
  • Phenazine (Formula 28) is weighed, the weighed raw material is placed in 50 ml of water (H 2 O) and mixed uniformly. The mixture was synthesized at a temperature of 150 ° C.
  • organic-inorganic composite light emitting material [(Y 2 O 3 : Eu) (4,4′-oxybis (benzoic acid)) 3 (tetrapyrido [3,2-a: 2 ′, 3 '-C: 3', 2'-h: 2 '', 3'-j] phenazine)] n .
  • a UV LED package was manufactured in the same manner as in Example 2, except that the prepared red light emitting material was used.
  • organic-inorganic composite light emitting material (Y 0.5 , Eu 0.5 ) (4,4 '-Oxybis (benzoic acid)) 3 (pyrido [2', 3 ': 5,6] pyrazino [2,3-f] [1,10] phenanthroline) 0.5 (1,10-phenanthroline 0.5 ] n was prepared.
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • H 2 O water
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • a blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
  • a light emitting material [(Y 0.5 Eu 0.5 ) (phenanthroline) (2,4-) of the organic metal coordination polymer was prepared in the same manner as in Comparative Example 1, except that 0.2 mol ratio of 2,4-pyridine dicarboxylic acid was used. Dicarboxylic acid) 2 2 (H 2 O)] n .
  • a light emitting material [(Y 0.5 Eu 0.5 ) (phenanthrol) of organic metal coordination polymer was prepared in the same manner as in Comparative Example 1 except that 0.2 mol ratio of 1,3,5-tris (4-carboxyphenyl) benzene was used. Lean) (1,3,5-tris (4-carboxyphenyl) benzene) 2 2 (H 2 O)] n was obtained.
  • the organic metal coordination polymer prepared according to Comparative Examples 1 to 3 [(Y 0.5 Eu 0.5 ) (phen) (3,5-pyridine dicarboxylic acid) 2 (H 2 O) 2 ] n , [(Y 0.5 Eu 0.5 ) (phen) (2,4-pyridine dicarboxylic acid) 2 ( H 2 O) 2 ] n , [(Y 0.5 Eu 0.5 ) (phen) (1,3,5-Tris (4-carboxy phenyl) benzene) 2 (H 2 O) 2 ] n Unlike UV and 450 nm It is excited in blue area and can be used as LED light emitting material.
  • the organometallic coordination polymer prepared by the method of Example 1 exhibits a red emission characteristic of about 614.1 nm in nearUV and a narrow half width of 12.4 nm as shown in FIG. 1. That is, it can be seen that it is a red light emitting material for LEDs having a narrow half width and high brightness as compared to the conventional phosphor.
  • Figure 2 is a graph showing the XRD pattern according to Example 1 it can be seen that the material is crystalline.
  • Figure 3 is a light-emitting material and a conventional phosphor CaAlSiN 3 according to the first embodiment of the present invention: a narrow full width at half maximum in the UV region that shows the PL spectrum graph of the Mn 4 +, compared to traditional fluorescent substance: Eu 2 +, K 2 SiF 6
  • the light intensity is good.
  • 4 shows graphs and spectra of PKG mounting evaluation using 400 UV chips according to Examples 1 and 2 of the present invention
  • FIG. 5 shows PKG using a Blue chip of 450 according to Example 3 of the present invention.
  • the graphs and spectra of the implementation evaluations are shown.
  • 6 shows an excitation spectrum of a comparative example
  • FIG. 7 shows an emission spectrum of a comparative example. Since the organometallic coordination polymer of the comparative example is not excited near 400 nm-450 nm, it cannot be used in a 400 nm UV LED or a 450 nm Blue LED light emitting device.

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Abstract

The present invention relates to an LED light emitting device comprising a red organic-inorganic composite light emitting material having a composition of the following chemical formula (1): [chemical formula 1] [(A x1,Rx2)(L)y(X)]n, wherein A comprises at least one metal ion or a metal compound thereof selected from the group consisting of a monovalent metal ion selected from Li, Na or K, a bivalent metal ion selected from Mg, Ca, Sr, Ba or Zn, a trivalent metal ion selected from Al or La, or a tetravalent metal ion selected from Zr or Ti; R comprises at least one selected from Eu or an Eu compound; L comprises at least one selected from aromatic compounds having at least two carboxylic acid groups; X comprises at least one selected from phenanthroline and derivatives thereof; 0≤x1<2; 0<x2≤2; the sum of x1 and x2 is 0<x1+x2≤2; y is 2 or 3; and n is an integer selected from integers of 1 or more.

Description

적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치LED light emitting device comprising red organic-inorganic composite light emitting material
본 발명은 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치에 관한 것으로, 더욱 상세하게 유기 발광 리간드에 금속을 배위시킨 유기 금속 배위 고분자로서 기존 유기발광 화합물보다 안정성이 우수하고, 무기 발광재료보다 반치폭이 좁아 휘도가 우수하며, UV 및 블루 영역에서 여기가 가능한 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치에 관한 것이다.The present invention relates to an LED light emitting device including a red organic-inorganic composite light emitting material, more specifically, an organic metal coordination polymer in which a metal is coordinated with an organic light emitting ligand, which is more stable than an existing organic light emitting compound and has a half width than an inorganic light emitting material. The present invention relates to an LED light emitting device comprising a red organic-inorganic composite light emitting material which is narrow in size and excellent in luminance and capable of excitation in UV and blue regions.
종래 상업적으로 광범위하게 사용되는 백색 LED 구현 기술의 형광체 조합으로는 Blue LED 칩에 황색 및 적색 형광체를 도포하여 소자를 제조함으로써 백색을 구현하고 있다. 일반적으로 사용되는 황색 형광체는 산화물계 형광체가 주로 사용되고 있고, 적색 형광체는 질화물계 형광체가 사용되고 있다. In the phosphor combination of the conventional white LED implementation technology widely used commercially, yellow is realized by applying yellow and red phosphors to a blue LED chip to manufacture a device. In general, yellow phosphors are mainly oxide-based phosphors, and red phosphors are nitride-based phosphors.
현재 고연색성 조명 및 고색재현 디스플레이의 수요가 증가함에 따라 이에 대응하는 발광 재료의 니즈가 증가하고 있는데, 기존 무기 발광재료는 고 신뢰성 및 고 휘도를 갖는 재료이지만, 발광 파장의 반치폭이 넓고 구현 파장이 제한되는 문제가 있다. As the demand for high color rendering and high color reproduction displays increases, the needs of corresponding light emitting materials are increasing. Existing inorganic light emitting materials have high reliability and high brightness, but the half wavelength of emission wavelength is wide and the implementation wavelength is high. There is a limited problem.
따라서, 최근에 이의 한계를 극복하고자 Deep Red의 반치폭이 좁고 휘도가 향상된 형광체가 연구되고 있으나 수분 및 열에 취약하고, 제조 과정의 안정성에 문제가 있다. Therefore, recently, to overcome this limitation, phosphors having a half width of Deep Red and improved luminance have been studied, but are vulnerable to moisture and heat, and have problems in stability of the manufacturing process.
또한, 기존 유기 발광재료는 구현 파장 조절이 쉬운 고 휘도의 재료이나, 여전히 안정성 취약으로 사용에 제약에 따른다. In addition, the existing organic light emitting material is a material of high brightness that is easy to control the wavelength of the implementation, but is still vulnerable to stability due to restrictions on use.
따라서 기존의 유/무기 발광재료의 문제를 해소하기 위해, 반치폭이 좁으며 Red 파장을 구현할 수 있는 적색 형광체에 대한 개발이 요구되며 그에 따라 새로운 발광 재료에 대한 관심과 연구가 집중되고 있다.Therefore, in order to solve the problem of the existing organic / inorganic light emitting material, the development of a red phosphor that can realize a red wavelength with a half width is required, and the interest and research on the new light emitting material is attracting accordingly.
'수분 민감성 형광체, 그의 제조방법 및 수분 민감성 형광체를 포함하는 가역적 수분 검출 센서'를 발명의 명칭으로 하는 한국공개특허 제10-2014-0059982호에 의하면, 극미량의 수분에 대하여도 측정이 가능한 수분 민감성 형광체로서의 유로퓸-페난트롤린 착화합물, 그의 제조방법 및 상기 수분 민감성 형광체로서의 유로퓸-페난트롤린 착화합물을 이용하여 수분량에 따른 수분 민감성 형광체의 형광변화를 측정함으로써 수분 투과도를 반복적으로 측정할 수 있는 가역적 수분 검출 센서에 관한 것으로서, 상기 수분 민감성 형광체는 하기 와 같이 표시되는 유로퓸 착화합물을 소개하고 있다. According to Korean Patent Laid-Open No. 10-2014-0059982 entitled "Moisture Sensitive Phosphor, its manufacturing method and a reversible moisture detection sensor comprising a moisture sensitive phosphor", it is possible to measure moisture sensitivity even when the trace amount of moisture is extremely low. Reversible moisture capable of repeatedly measuring the moisture permeability by measuring the fluorescence change of the moisture sensitive phosphor according to the amount of moisture using the europium-phenanthroline complex as a phosphor, a method of manufacturing the same, and the europium-phenanthroline complex as the moisture sensitive phosphor. Regarding the detection sensor, the moisture sensitive phosphor introduces a europium complex compound represented as follows.
Figure PCTKR2017001474-appb-I000001
Figure PCTKR2017001474-appb-I000001
상기 X는 -CH3, -CH2CH3, -CH(CH3)2, -CF3, -CF2CF3 또는 -CF2CF2CF3 로 이루어지는 군으로부터 선택된 것이다. X is -CH 3 , -CH 2 CH 3 , -CH (CH 3) 2 , -CF 3 , -CF 2 CF 3 or -CF 2 CF 2 CF 3 It is selected from the group consisting of.
상기 특허는 수분에 대한 측정이 가능한 수분 민감형 형광체로 유로퓸-페난트롤린 착화합물의 제조 방법 및 수분 민감성 형광체의 형광 변화 측정에 관한 것으로, 종합적으로 본다면, 유로퓸-페난트롤린 화합물을 제조 및 이를 형광체로 사용하고 있지만, 수분 민감형 형광체로 사용하기 위해 제조되었고, 유로퓸-페난트롤린 착화합물 자체가 분자성 물질로 이루어져 있으나, 본 발명은 LED로 활용 가능한 배위 고분자성 형광체를 합성한 데 차이점이 있다.The patent relates to a method of preparing a europium-phenanthroline complex compound as a moisture-sensitive fluorescent material capable of measuring moisture, and to measuring the fluorescence change of the water-sensitive fluorescent substance. Although used as a water-sensitive phosphor, the europium-phenanthroline complex itself is made of a molecular material, but the present invention has a difference in synthesizing a coordinating polymeric fluorescent substance that can be utilized as an LED.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 한국공개특허 제10-2014-0059982호(Patent Document 1) Korean Patent Publication No. 10-2014-0059982
본 발명은 UV 영역 및 블루(Blue)영역에서 여기하여 발광하고, 고휘도를 갖는 발광 재료의 유기 금속 배위 고분자에 대한 연구가 필요하다는 요구에 따라 완성된 것으로, 기존의 유기 금속 배위 고분자의 발광 재료보다 고 휘도를 갖고, 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치를 제공하는데 그 목적이 있다. The present invention has been completed in response to the need for research on the organometallic coordination polymer of the light emitting material having excitation in the UV region and the blue region, and emit light, and compared to the light emitting material of the conventional organic metal coordination polymer An object of the present invention is to provide an LED light emitting device having a high brightness and including a red organic-inorganic composite light emitting material.
본 발명은 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치에 관한 것으로, 아래 화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치를 제공한다.The present invention relates to an LED light emitting device including a red organic-inorganic composite light emitting material, and provides an LED light emitting device including a red organic-inorganic composite light emitting material having a composition of Formula 1 below.
[화학식 1][Formula 1]
[(A x1,Rx2)(L)y(X)]n [(A x1 , R x2 ) (L) y (X)] n
화학식 1에서, A는 Li, Na 또는 K 중에서 선택된 1가 금속이온 또는, Mg, Ca, Sr, Ba 또는 Zn 중에서 선택된 2가 금속이온 또는, Al 또는 La 중에서 선택된 3가 금속이온 또는, Zr 또는 Ti 중에서 선택된 4가 금속이온으로 이루어진 군으로부터 선택되는 1종 이상의 금속이온 또는 그의 금속화합물을 포함하고, R은 Eu 또는 Eu화합물 중에서 선택되는 1종을 포함하며, L은 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종을 포함하고, X는 페난트롤린(phenanthroline) 및 그 유도체 중에서 선택되는 1종 이상을 포함하며, x1은 0≤x1<2이고, x2는 0<x2≤2이며, x1과 x2의 합은 0<x1+x2≤2 이고, y는 2 또는 3이며, n은 1 이상의 정수에서 선택되는 정수이다.In Formula 1, A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti At least one metal ion selected from the group consisting of tetravalent metal ions selected from the group or a metal compound thereof, R includes at least one selected from Eu or Eu compounds, L is an aromatic having at least two carboxylic acid groups Including one selected from the group compounds, X includes one or more selected from phenanthroline (phenanthroline) and derivatives thereof, x1 is 0≤x1 <2, x2 is 0 <x2≤2, The sum of x1 and x2 is 0 <x 1 + x 2 ≤ 2, y is 2 or 3, and n is an integer selected from one or more integers.
또한, 1가 내지 4가 금속이온 또는 그의 금속화합물 중에서 선택되는 1종 이상과, Eu 또는 Eu화합물 중에서 선택되는 1종과, 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종과, 페난트롤린 및 그 유도체 중에서 선택되는 1종 이상의 원료를 칭량하는 단계와, 칭량된 원료를 50~100 ml 용매에 넣고 균일하게 혼합하여 혼합물을 제조하는 단계와, 혼합물을 90~210 ℃ 온도에서 합성하는 단계를 포함하여 제조된 하기 화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치를 제공한다. In addition, one or more selected from monovalent to tetravalent metal ions or metal compounds thereof, one selected from Eu or Eu compounds, one selected from aromatic compounds having at least two carboxylic acid groups, and phenane Weighing at least one raw material selected from trolline and derivatives thereof, preparing the mixture by uniformly mixing the weighed raw material in 50-100 ml of solvent, and synthesizing the mixture at a temperature of 90-210 ° C. It provides an LED light emitting device comprising a red organic-inorganic composite light emitting material having a composition of the formula (1) prepared including the step.
[화학식 1][Formula 1]
[(A x1,Rx2)(L)y(X)]n [(A x1 , R x2 ) (L) y (X)] n
화학식 1에서, A는 Li, Na 또는 K 중에서 선택된 1가 금속이온 또는, Mg, Ca, Sr, Ba 또는 Zn 중에서 선택된 2가 금속이온 또는, Al 또는 La 중에서 선택된 3가 금속이온 또는, Zr 또는 Ti 중에서 선택된 4가 금속이온으로 이루어진 군으로부터 선택되는 1종 이상의 금속이온 또는 그의 금속화합물을 포함하고, R은 Eu 또는 Eu화합물 중에서 선택되는 1종을 포함하며, L은 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종을 포함하고, X는 페난트롤린(phenanthroline) 및 그 유도체 중에서 선택되는 1종 이상을 포함하며, x1은 0≤x1<2이고, x2는 0<x2≤2이며, x1과 x2의 합은 0<x1+x2≤2 이고, y는 2 또는 3이며, n은 1 이상의 정수에서 선택되는 정수이다.In Formula 1, A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti At least one metal ion selected from the group consisting of tetravalent metal ions selected from the group or a metal compound thereof, R includes at least one selected from Eu or Eu compounds, L is an aromatic having at least two carboxylic acid groups Including one selected from the group compounds, X includes one or more selected from phenanthroline (phenanthroline) and derivatives thereof, x1 is 0≤x1 <2, x2 is 0 <x2≤2, The sum of x1 and x2 is 0 <x 1 + x 2 ≤ 2, y is 2 or 3, and n is an integer selected from one or more integers.
본 발명의 LED 발광 장치에 포함되는 적색 유무기 복합 발광 재료는 기존 유기 금속 배위 고분자의 발광 재료보다 고 휘도를 갖고, UV 및 블루 영역에서 여기가 가능한 재료이다. 이는 색 구현 범위가 자유롭고, 반치폭이 15 nm 이하로 좁으며 특히 UV 및 블루 영역에서 여기될 수 있으므로, LED 용 발광 재료로 상당한 효과가 있다.The red organic-inorganic composite light emitting material included in the LED light emitting device of the present invention has a higher luminance than the light emitting material of the conventional organic metal coordination polymer, and is a material capable of excitation in the UV and blue regions. This has a significant effect as a luminescent material for LEDs because it has a free range of colors, a half width of 15 nm or less and can be excited especially in the UV and blue regions.
도 1은 본 발명에 따른 PL 스펙트럼 그래프 및 SEM 이미지를 나타낸 것이다.1 shows a PL spectral graph and SEM image according to the present invention.
도 2 는 본 발명에 따른 XRD를 나타낸 것이다.2 shows an XRD according to the present invention.
도 3 은 본 발명에 따른 PL peak 비교를 나타낸 것이다.3 shows a PL peak comparison according to the present invention.
도 4는 본 발명에 따른 UV LED 패키지 실장 평가 결과를 나타낸 것이다. Figure 4 shows the UV LED package mounting evaluation results according to the present invention.
도 5는 본 발명에 따른 BLUE LED 패키지 실장 평가 결과를 나타낸 것이다. 5 shows the evaluation results of the BLUE LED package mounting according to the present invention.
도 6은 본 발명의 비교예에 따른 여기 스펙트럼을 나타낸 것이다.6 shows an excitation spectrum according to a comparative example of the present invention.
도 7은 본 발명의 비교예에 따른 발광 스펙트럼을 나타낸 것이다. 7 shows an emission spectrum according to a comparative example of the present invention.
도 8은 본 발명의 실시예 12에 따른 발광 스펙트럼을 나타낸 것이다.8 shows an emission spectrum according to Example 12 of the present invention.
이와 같은 본 발명을 다음에서 상세하게 설명하기로 하며, 다음의 구현예는 단지 예시하기 위한 것으로 본 발명이 반드시 이에 한정되는 것은 아니다.The present invention will be described in detail in the following, and the following embodiments are merely to illustrate, but the present invention is not necessarily limited thereto.
본 발명은 적색 유무기 복합 발광 재료가 UV LED 또는 Blue LED에서 선택되는 1종 이상의 여기원을 포함하는 LED 발광 장치이다.The present invention is an LED light emitting device in which the red organic-inorganic composite light emitting material includes one or more excitation sources selected from UV LEDs or Blue LEDs.
먼저, 본 발명의 한 구현예에 따른 적색 유무기 복합 발광재료는 유기 금속 배위 고분자의 발광재료로서 350 내지 450 nm의 UV 영역 및 Blue 영역에 의해 여기되어 600~630 nm 발광 파장을 나타내며, 15 nm 이하의 반치폭과 고휘도를 갖는다.First, the red organic-inorganic composite light emitting material according to the embodiment of the present invention is a light emitting material of an organic metal coordination polymer, and is excited by a UV region and a blue region of 350 to 450 nm to exhibit an emission wavelength of 600 to 630 nm, and 15 nm. It has the following half width and high brightness.
구체적으로, 상기 적색 유무기 복합 발광재료를 포함하는 LED 발광 장치는 적색 유무기 복합 발광재료의 활성제로 Eu3 +가 첨가된 구조를 기본으로 하며, 그 화학식 조성은 아래 화학식 1과 같다.Specifically, the LED light emitting device including the red organic-inorganic composite light emitting material is based on the structure that Eu 3 + is added as an activator of the red organic-inorganic composite light emitting material, the chemical composition is as shown in the formula (1).
[화학식 1][Formula 1]
[(A x1,Rx2)(L)y(X)]n [(A x1 , R x2 ) (L) y (X)] n
화학식 1에서, A는 Li, Na 또는 K 중에서 선택된 1가 금속이온 또는, Mg, Ca, Sr, Ba 또는 Zn 중에서 선택된 2가 금속이온 또는, Al 또는 La 중에서 선택된 3가 금속이온 또는, Zr 또는 Ti 중에서 선택된 4가 금속이온으로 이루어진 군으로부터 선택되는 1종 이상의 금속이온 또는 그의 금속화합물을 포함하고, In Formula 1, A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti At least one metal ion selected from the group consisting of tetravalent metal ions or metal compounds thereof,
R은 Eu 또는 Eu화합물 중에서 선택되는 1종을 포함하며, R includes one selected from Eu or Eu compounds,
L은 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종을 포함하고, L includes one selected from aromatic compounds having at least two carboxylic acid groups,
X는 페난트롤린(phenanthroline) 및 그 유도체 중에서 선택되는 1종 이상을 포함하며,X includes at least one selected from phenanthroline and its derivatives,
x1은 0≤x1<2이고, x2는 0<x2≤2이며, x1과 x2의 합은 0<x1+x2≤2 이고, x1 is 0 ≦ x1 <2, x2 is 0 <x2 ≦ 2, the sum of x1 and x2 is 0 <x 1+ x 2 ≤ 2,
y는 2 또는 3이며, n은 1 이상의 정수에서 선택되는 정수이다.y is 2 or 3, and n is an integer chosen from the integer of 1 or more.
만약, 상기 x1, x2 또는 y의 수치범위를 벗어나게 될 경우 합성이 제대로 안되거나 합성이 된다 하더라도 발광 및 휘도 특성이 좋지 못한 현상을 보인다.If it is out of the numerical range of x 1 , x 2 or y, the light emission and luminance characteristics are poor even if the synthesis is not properly performed or synthesized.
상기 화학식 1에서 금속화합물은 예를들면, ZnO, Y2O3, La2O3, Gd2O3, Y(NO3)3, Al2(SO4)3, TiO2, Zn(NO3)2, Bi2O3 또는 MnCO3을 포함하는 금속화합물이 사용될 수 있으나, 상기 예들로만 본 발명의 범위가 한정되는 것은 아니다.The metal compound in Chemical Formula 1 may be, for example, ZnO, Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Y (NO 3 ) 3 , Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 Or a metal compound containing MnCO 3 may be used, but the scope of the present invention is not limited only to the above examples.
상기 화학식 1에서 R로 사용될 수 있는 Eu 화합물은 Eu과 1종 이상의 금속이온 및 산화물, 또는 Eu이 포함된 금속산화물이 사용될 수 있다.As the Eu compound which may be used as R in Formula 1, Eu and one or more metal ions and oxides, or metal oxides containing Eu may be used.
Eu화합물의 구체예로는 ZnO:Eu, Y2O3:Eu, La2O3:Eu 또는 Eu(NO3)3·xH2O중에서 선택되는 1종이 사용 될 수 있으며, Eu(NO3)3·xH2O에서 x는 1 내지 6에서 선택되는 정수이다.Specific examples of the Eu compound may be one selected from ZnO: Eu, Y 2 O 3 : Eu, La 2 O 3 : Eu or Eu (NO 3 ) 3 xH 2 O, and Eu (NO 3 ) from 3 · xH 2 O x is an integer selected from 1-6.
Eu 또는 Eu 화합물을 사용하면 Eu 특성 피크(characteristic peak)를 갖게 되는데, 이는 적색의 좁은 반치폭을 갖게 하여 LED에 사용하게 되면 고색 재현이 가능하게 된다.When Eu or Eu compounds are used, they have an Eu characteristic peak, which has a narrow half width of red, and when used in an LED, high color reproduction is possible.
상기 화학식 1의 L은 카르복실산기를 적어도 두개 갖는 방향족계 화합물에서 선택되는 1종이 사용될 수 있으며, 예를들면 하기 화학식 2 내지 8 이 사용될 수 있으나, 하기 예들로만 본 발명의 범위가 한정되는 것은 아니다.In Formula 1, L may be used as one selected from aromatic compounds having at least two carboxylic acid groups. For example, the following Chemical Formulas 2 to 8 may be used, but the scope of the present invention is not limited only to the following examples. .
[화학식 2][Formula 2]
Figure PCTKR2017001474-appb-I000002
Figure PCTKR2017001474-appb-I000002
[화학식 3][Formula 3]
Figure PCTKR2017001474-appb-I000003
Figure PCTKR2017001474-appb-I000003
[화학식 4][Formula 4]
Figure PCTKR2017001474-appb-I000004
Figure PCTKR2017001474-appb-I000004
[화학식 5][Formula 5]
Figure PCTKR2017001474-appb-I000005
Figure PCTKR2017001474-appb-I000005
[화학식 6][Formula 6]
Figure PCTKR2017001474-appb-I000006
Figure PCTKR2017001474-appb-I000006
[화학식 7][Formula 7]
Figure PCTKR2017001474-appb-I000007
Figure PCTKR2017001474-appb-I000007
[화학식 8][Formula 8]
Figure PCTKR2017001474-appb-I000008
Figure PCTKR2017001474-appb-I000008
상기 화학식 1의 X는 페난트롤린(phenanthroline) 및 그 유도체 중에서 선택되는 1종 이상이 사용될 수 있으며, 예를들면 하기 화학식 9 내지 12 로 표시되는 화합물이 사용될 수 있고, 하기 예들로만 본 발명의 범위가 한정되는 것은 아니다. X in Formula 1 may be used at least one selected from phenanthroline (phenanthroline) and derivatives thereof, for example, a compound represented by the following formulas 9 to 12 may be used, the scope of the present invention only by the following examples Is not limited.
[화학식 9][Formula 9]
Figure PCTKR2017001474-appb-I000009
Figure PCTKR2017001474-appb-I000009
[화학식 10][Formula 10]
Figure PCTKR2017001474-appb-I000010
Figure PCTKR2017001474-appb-I000010
[화학식 11][Formula 11]
Figure PCTKR2017001474-appb-I000011
Figure PCTKR2017001474-appb-I000011
[화학식 12][Formula 12]
Figure PCTKR2017001474-appb-I000012
Figure PCTKR2017001474-appb-I000012
상기 R1 내지 R10은 각각 독립적으로 수소; 중수소; 할로겐; 시아노; 니트로; 아미노; 치환 또는 비치환된 C1- 60알킬; C1- 60할로알킬; 치환 또는 비치환된 C1- 60알콕시; 치환 또는 비치환된 C1- 60할로알콕시; 치환 또는 비치환된 C3- 60사이클로알킬; 치환 또는 비치환된 C2- 60알케닐; 치환 또는 비치환된 C6- 60아릴; 치환 또는 비치환된 C6-60아릴옥시; 또는 치환 또는 비치환된 N, O 및 S 중 1개 이상을 포함하는 C1- 60헤테로고리기이며, Q는 N 또는 CH 이다.R 1 to R 10 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C 1 -60 alkyl; 1- C 60 haloalkyl; Substituted or unsubstituted C 1 -60 alkoxy; Substituted or unsubstituted C 1 -60 haloalkoxy; Substituted or unsubstituted C 3 -60 cycloalkyl; A substituted or unsubstituted C 2- 60 alkenyl; Substituted or unsubstituted C 6- 60 aryl; Substituted or unsubstituted C 6-60 aryloxy; Or a C 1- 60 heterocyclic group, including a substituted or unsubstituted N, O, and S 1 out of the above, Q is N or CH.
상기 R1 내지 R10을 보다 구체적으로 예를 들자면, R1은 수소(H), 시아노기(-CN) 또는 메틸기(CH3)이고, R2 내지 R7은 각각 독립적으로 수소(H), 아미노기(-NH2), 메틸기(CH3)또는 페닐(phenyl)이며, R8은 수소(H) 또는 메톡시(-OCH3)이고, R9는 수소(H), C1~C6알킬기, 페닐(phenyl), n-C1~C6알킬페닐(n-C1~C6alkylphenyl), 디메틸페닐(dimethylphenyl), 트리메틸페닐(trimethylphenyl), 디에틸페닐(diethylphenyl), 트리에틸페닐(triethylphenyl), n-니트로페닐(n-nitrophenyl), n-아미노페닐(n-aminophenyl), n-설포닐페닐(n-sulfonylphenyl), 디설포닐페닐(disulfonylphenyl), n-C1~C6알콕시페닐(n-C1~C6alkoxyphenyl), 디메톡시페닐(dimethoxyphenyl), 디에톡시페닐(diethoxyphenyl), n-피리딜(n-pyridyl), 프리미딜(pyrimidyl), 퍼퓨릴(furfuryl), 나프탈레닐(naphthalenyl) 또는 피레닐(pyrenyl)이며, R10은 수소(H), C1~C6알킬기, 페닐(phenyl) 또는 n-C1~C6알킬페닐(n-C1~C6alkylphenyl)중에서 선택되는 것을 사용할 수 있다.More specifically, for example, R 1 to R 10 , R 1 is hydrogen (H), cyano group (-CN) or methyl group (CH 3 ), and R 2 to R 7 are each independently hydrogen (H), Amino group (-NH 2 ), methyl group (CH 3 ) or phenyl, R 8 is hydrogen (H) or methoxy (-OCH 3 ), R 9 is hydrogen (H), C 1 -C 6 alkyl group , phenyl, (phenyl), nC 1 ~ C 6 alkyl phenyl (nC 1 ~ C 6 alkylphenyl) , dimethylphenyl (dimethylphenyl), trimethylphenyl (trimethylphenyl), diethyl phenyl (diethylphenyl), triethyl phenyl (triethylphenyl), n- Nitrophenyl (n-nitrophenyl), n-aminophenyl (n-aminophenyl), n-sulfonylphenyl (n-sulfonylphenyl), disulfonylphenyl, nC 1 to C 6 alkoxyphenyl (nC 1 to C 6 alkoxyphenyl ), Dimethoxyphenyl, diethoxyphenyl, n-pyridyl, n-pyridyl, pyrimidyl, furfuryl, naphthalenyl or pyrenyl R 10 is hydrogen (H), C 1 ~ C 6 alkyl group, phenyl ) Or nC 1 ~ C 6 alkyl phenyl (nC 1 ~ C 6 alkylphenyl) may be selected from is selected from.
상기 C1~C6알콕시는 메톡시, 에톡시, 프로폭시, 부톡시, 펜틸옥시 또는 헥실옥시이며, n은 2 내지 4 중에서 선택되는 어느 하나의 정수이며, o-, m-, p-를 의미한다.The C 1 ~ C 6 alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy, n is any integer selected from 2 to 4, o-, m-, p- it means.
본 발명에서 사용될 수 있는 상기 페난트롤린 및 그 유도체를 보다 더 구체적으로 예를 들자면, 하기 화학식 13 내지 28 중에서 선택되는 1종 이상의 화합물을 사용할 수 있다.To be more specific examples of the phenanthroline and its derivatives that may be used in the present invention, one or more compounds selected from the following Chemical Formulas 13 to 28 may be used.
[화학식 13][Formula 13]
Figure PCTKR2017001474-appb-I000013
Figure PCTKR2017001474-appb-I000013
[화학식 14][Formula 14]
Figure PCTKR2017001474-appb-I000014
Figure PCTKR2017001474-appb-I000014
[화학식 15][Formula 15]
Figure PCTKR2017001474-appb-I000015
Figure PCTKR2017001474-appb-I000015
[화학식 16][Formula 16]
Figure PCTKR2017001474-appb-I000016
Figure PCTKR2017001474-appb-I000016
[화학식 17][Formula 17]
Figure PCTKR2017001474-appb-I000017
Figure PCTKR2017001474-appb-I000017
[화학식 18][Formula 18]
Figure PCTKR2017001474-appb-I000018
Figure PCTKR2017001474-appb-I000018
[화학식 19][Formula 19]
Figure PCTKR2017001474-appb-I000019
Figure PCTKR2017001474-appb-I000019
[화학식 20][Formula 20]
Figure PCTKR2017001474-appb-I000020
Figure PCTKR2017001474-appb-I000020
[화학식 21][Formula 21]
Figure PCTKR2017001474-appb-I000021
Figure PCTKR2017001474-appb-I000021
[화학식 22][Formula 22]
Figure PCTKR2017001474-appb-I000022
Figure PCTKR2017001474-appb-I000022
[화학식 23][Formula 23]
Figure PCTKR2017001474-appb-I000023
Figure PCTKR2017001474-appb-I000023
[화학식 24][Formula 24]
Figure PCTKR2017001474-appb-I000024
Figure PCTKR2017001474-appb-I000024
[화학식 25][Formula 25]
Figure PCTKR2017001474-appb-I000025
Figure PCTKR2017001474-appb-I000025
[화학식 26][Formula 26]
Figure PCTKR2017001474-appb-I000026
Figure PCTKR2017001474-appb-I000026
[화학식 27][Formula 27]
Figure PCTKR2017001474-appb-I000027
Figure PCTKR2017001474-appb-I000027
[화학식 28][Formula 28]
Figure PCTKR2017001474-appb-I000028
Figure PCTKR2017001474-appb-I000028
이와 같은 페난트롤린 및 그 유도체를 사용하게 되면 페난트롤린 및 그 유도체를 사용하지 않은 경우에 비해서 휘도 향상에 효과가 있다.The use of such phenanthroline and its derivatives is effective in improving the luminance as compared with the case where the phenanthroline and its derivatives are not used.
상기 화학식 1에서 A x1, Rx2 에서, x1은 0≤x1<2이고, x2는 0<x2≤2이며, x1과 x2의 합은 0<x1+x2≤2인 것이 바람직한데, Ax1과 Rx2 모두를 포함하는 구성 또는 Rx2만 포함하는 구성은 A x1 만 포함하는 구성에 비해 휘도가 향상되고, 희토류 금속을 적게 사용하기 때문에 단가 절감에 대한 이점을 갖으며, Ax1만으로는 발광특성을 나타낼 수 없다.In Formula 1, A x1 , R x2 Where x1 is 0 ≦ x1 <2, x2 is 0 <x2 ≦ 2, and the sum of x1 and x2 is preferably 0 <x 1+ x 2 ≤ 2, wherein the configuration includes both A x1 and R x2 Or a configuration containing only R x2 is A Compared with the configuration containing only x1 , the luminance is improved, and the use of less rare earth metals has the advantage of cost reduction, and A x1 alone does not exhibit light emission characteristics.
본 발명의 LED 발광 장치에 포함되는 상기 화학식 1에 따른 적색 유무기 복합 발광재료는 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(파라지노[2,3-f][1,10]페난트롤린)]n, [(Y0. 5,Eu0 . 5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]파라지노[2,3-f][1,10]페난트롤린)]n, [(Al0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Ti0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Zn0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Bi0 . 5,Eu0 . 5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Mn0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Y2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n, [(La2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n, [(Gd2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n, [(La2O3:Eu)(테레프탈릭 에시드)3(피라지노[2,3-f][1,10]-페난트롤린-2,3-다이카보나이트릴)]n, [(Y2O3:Eu)(4,4’-옥시비스(벤조산))3(테트라피리도[3,2-a:2´,3´-c:3´´,2´´-h:2´´´,3´´-j]페나진)]n, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(1,10-페난트롤린)0.5]n, [(Y0. 5,Eu0 . 5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(피라지노[2,3-f][1,10]페난트롤린)0.5]n, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(3-메틸피라지노[2,3-f][1,10]페난트롤린)0.5]n, [Eu(1,3,5-트리스(4-카복시페닐)벤젠)3(피리도[2’,3’:5,6]파라지노[2,3-f][1,10]페난트롤린)]n, [Eu(4,4’-옥시비스(벤조산))3(dipyrido[3,2-a:2´,3´-c]phenzine)]n 또는 [Eu(4,4’-옥시비스(벤조산))3(11-methoxydipyrido[3,2-a:2',3'-c]phenazine)]n을 바람직한 예로 들 수 있다.The red organic-inorganic composite light emitting material according to Chemical Formula 1 included in the LED light emitting device of the present invention is [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (paragino [2,3- f] [1,10] phenanthroline)] n, [(. Y 0. 5, Eu 0 5) (4,4'- oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5 , 6] paragino [2,3-f] [1,10] phenanthroline)] n , [(Al 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2 , 3-f] [1,10] phenanthroline)] n , [(Ti 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1 , 10] phenanthroline)] n , [(Zn 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline) ] n, [(Bi 0. 5, Eu 0. 5) (4,4'- oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n, [(Mn 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n , [(Y 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline)] n , [(La 2 O 3: Eu ) (4,4'- oxybis (benzoic acid)) 3 ( Lido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline)] n, [(Gd 2 O 3: Eu) (4,4'- oxybis (Benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline)] n , [(La 2 O 3 : Eu) ( Terephthalic acid) 3 (pyrazino [2,3-f] [1,10] -phenanthroline-2,3-dicarbonitrile)] n , [(Y 2 O 3 : Eu) (4,4 ' Oxybis (benzoic acid)) 3 (tetrapyrido [3,2-a: 2´, 3´-c: 3´´, 2´´-h: 2´´´, 3´´-j] phenazine )] n , [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1 , 10] phenanthroline) 0.5 (1,10-phenanthroline) 0.5] n, [(Y 0. 5, Eu 0. 5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline) 0.5 (pyra Gino [2,3-f] [1,10] phenanthroline) 0.5 ] n , [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3 ': 5,6] pyrazino [2,3-f] [1,10] phenanthroline) 0.5 (3-methylpyrazino [2,3-f] [1,10] phenanthroline) 0.5 ] n , [Eu (1,3,5-tris (4-carboxyphenyl) benzene) 3 (pyrido [2 ', 3': 5,6] paragino [2,3-f] [1,10] phenanthrol Lin)] n , [Eu (4,4′-oxybis (benzoic acid)) 3 (dipyrido [3,2-a: 2 ′, 3′-c] phenzine)] n or [Eu (4,4'- Oxybis (benzoic acid)) 3 (11-methoxydipyrido [3,2-a: 2 ', 3'-c] phenazine)] n is a preferable example.
본 발명의 또 다른 구현예에 따른 LED 발광 장치는,LED light emitting device according to another embodiment of the present invention,
먼저, 0.01 내지 0.19 mol 비의 1가 내지 4가 금속이온 또는 그의 금속화합물 중에서 선택되는 1종 이상과, 0.1 내지 0.19 mol 비의 Eu 또는 Eu화합물 중에서 선택되는 1종과, 0.01 내지 0.6 mol비의 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종과, 0.01 내지 0.2 mol비의 페난트롤린 및 그 유도체 중에서 선택되는 1종 이상의 원료를 칭량하는 단계와,First, at least one selected from 0.01 to 0.19 mol ratio of monovalent to tetravalent metal ions or a metal compound thereof, at least one selected from 0.1 to 0.19 mol ratio of Eu or Eu compound, and 0.01 to 0.6 mol ratio of Weighing at least one raw material selected from aromatic compounds having at least two carboxylic acid groups, phenanthroline at 0.01 to 0.2 mol ratio and derivatives thereof, and
상기와 같이 칭량된 원료 50~100 ml를 물(H2O),프로판올, 에탄올, 메탄올, 디메틸포름아마이드(DMF, dimethylformamide) 또는 디메틸아세트아마이드(DMA, dimethyacetamide)와 같은 용매에 넣고 균일하게 혼합하여 혼합물을 제조하는 단계와,50-100 ml of the weighed raw material as above is added to a solvent such as water (H 2 O), propanol, ethanol, methanol, dimethylformamide (DMF, dimethylformamide) or dimethylacetamide (DMA, dimethyacetamide) and mixed uniformly. Preparing a mixture,
혼합물을 90~210 ℃ 온도에서 합성하는 단계를 포함하여 제조된 하기 화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료를 포함한다. It comprises a red organic-inorganic composite light emitting material having a composition of Formula 1 prepared by the step of synthesizing the mixture at a temperature of 90 ~ 210 ℃.
[화학식 1][Formula 1]
[(A x1,Rx2)(L)y(X)]n [(A x1 , R x2 ) (L) y (X)] n
화학식 1에서, A는 Li, Na 또는 K 중에서 선택된 1가 금속이온 또는, Mg, Ca, Sr, Ba 또는 Zn 중에서 선택된 2가 금속이온 또는, Al 또는 La 중에서 선택된 3가 금속이온 또는, Zr 또는 Ti 중에서 선택된 4가 금속이온으로 이루어진 군으로부터 선택되는 1종 이상의 금속이온 또는 그의 금속화합물을 포함하고,In Formula 1, A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti At least one metal ion selected from the group consisting of tetravalent metal ions or metal compounds thereof,
R은 Eu 또는 Eu화합물 중에서 선택되는 1종을 포함하며, R includes one selected from Eu or Eu compounds,
L은 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종을 포함하고, L includes one selected from aromatic compounds having at least two carboxylic acid groups,
X는 페난트롤린(phenanthroline) 및 그 유도체 중에서 선택되는 1종 이상을 포함하며,X includes at least one selected from phenanthroline and its derivatives,
x1은 0≤x1<2이고, x2는 0<x2≤2이며, x1과 x2의 합은 0<x1+x2≤2 이고, x1 is 0 ≦ x1 <2, x2 is 0 <x2 ≦ 2, the sum of x1 and x2 is 0 <x 1+ x 2 ≤ 2,
y는 2 또는 3이며, n은 1 이상의 정수에서 선택되는 정수이다.y is 2 or 3, and n is an integer chosen from the integer of 1 or more.
만약, 단결정 이미지를 확인할 경우 하나의 금속에 카르복실산기를 적어도 두개 갖는 방향족계 화합물은 3배까지, 페난트롤린 및 그 유도체는 동일한 비율로 배위됨을 나타내고, 그 이상의 비율이 들어갈 경우 결정성에 영향을 주어 제대로 된 발광재료가 합성되지 않는다.If the single crystal image is confirmed, it indicates that aromatic compounds having at least two carboxylic acid groups in one metal are coordinated up to three times, and phenanthroline and its derivatives are coordinated in the same ratio. Given, the correct light emitting material is not synthesized.
또한, 각각의 원료의 이 범위를 벗어날 경우에 제대로 합성이 되지 않거나, 합성이 되었을 경우 물질의 휘도가 좋지 아니하며, 미반응물이 생겨서 경제적이지 못하다.In addition, if it is out of this range of each raw material is not properly synthesized, or when synthesized, the brightness of the material is not good, and unreacted substances are not economical.
칭량된 각각의 원료를 용매와 혼합하여, 90~210 ℃ 온도에서 합성할 수 있는데, 만약 90 ℃ 미만의 온도에서 합성할 경우 적색 유무기 복합 발광 재료가 형성이 되지 않고, 210 ℃를 초과할 경우 적색 유무기 복합 발광 재료의 휘도가 저하되는 현상을 보인다. Each weighed raw material can be mixed with a solvent and synthesized at a temperature of 90-210 ° C., if it is synthesized at a temperature below 90 ° C., a red organic-inorganic composite luminescent material is not formed and exceeds 210 ° C. The luminance of the red organic-inorganic composite light emitting material is reduced.
이와 같은 제조 방법을 반응식 1로 나타내면 다음과 같다.Such a manufacturing method is shown in Scheme 1 as follows.
[반응식 1]Scheme 1
Figure PCTKR2017001474-appb-I000029
Figure PCTKR2017001474-appb-I000029
상기 반응식 1에서 A, R, L, X는 화학식 1의 A, R, L, X와 동일하고, 본 발명의 적색 유무기 복합 발광 재료는 A 부분에 양이온 금속을 도핑하므로서 기존의 금속-유기 골격체가 R에 Eu만 도핑한 것과는 다르게 전자 이동의 효과 및 골격 구조의 결정성을 향상하여 LED등에 사용하면 발광 특성을 향상시킬 수 있는 장점이 있다. In Scheme 1, A, R, L, and X are the same as A, R, L, and X of Formula 1, and the red organic-inorganic composite luminescent material of the present invention has a conventional metal-organic skeleton by doping a cationic metal in the A portion. Unlike the Si doped with only Eu to R, the effect of electron transfer and crystallinity of the skeleton structure are improved, and thus, when used in an LED lamp, there is an advantage of improving light emission characteristics.
상기 방법으로 제조된 화학식 1 조성을 갖는 적색 유무기 복합 발광 재료는 UV 및 블루 영역의 여기 광에 대한 발광 파장이 600 ~ 630 nm이며, 기존의 형광체에 비해서 15 nm 이하의 좁은 반치폭과 고휘도를 갖는 적색 발광 재료의 특성을 보이게 된다.The red organic-inorganic composite luminescent material having the formula (1) prepared by the above method has a light emission wavelength of 600 to 630 nm for excitation light in the UV and blue regions, and has a red color having a narrow half width and a high brightness of 15 nm or less compared with a conventional phosphor. The characteristics of the light emitting material are shown.
따라서, 상기 적색 유무기 복합 발광 재료를 UV 또는 Blue LED 칩을 이용하여 발광 특성을 살펴봄으로써 LED 발광 장치에 사용 가능함을 확인할 수 있다.Therefore, it can be seen that the red organic-inorganic composite light emitting material can be used in the LED light emitting device by examining the light emission characteristics by using the UV or Blue LED chip.
이하 본 발명을 실시예 및 비교예를 들어 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.
실시예Example
실시예 1Example 1
0.1 mol비의 Y(NO3)3·6H2O화합물, 0.1 mol비의 Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비즈(벤조산), 0.2 mol비의 피라지노[2,3-f][1,10]페난트롤린(화학식 13)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 발광 재료 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of Y (NO 3 ) 3 · 6H 2 O compound, 0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O compound, 0.2 mol ratio of 4,4'-oxybeads (benzoic acid), 0.2 mol ratio Pyrazino [2,3-f] [1,10] phenanthroline (Formula 13) was weighed, the weighed raw material was poured into 50 ml of water (H 2 O), mixed uniformly, and the mixture was then heated to 150 ° C. Synthesis at temperature gave light emitting material [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n It was.
발광재료 5 wt% 와 실리콘 봉지재(다우 코닝사 OE6630A, OE6630B)를 혼합하여 5630 UV LED 칩 위에 4.5-5.0 mg을 도포한 후 150 도에서 약 2시간 경화시켜 LED 패키지를 제조하였다.  5 wt% of the luminescent material and the silicon encapsulant (Dow Corning Co., Ltd. OE6630A, OE6630B) were mixed to apply 4.5-5.0 mg on a 5630 UV LED chip, and then cured at 150 degrees for about 2 hours to manufacture an LED package.
실시예Example 2 2
유기 금속 배위 고분자의 발광 재료 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n 은 실시예 1과 같은 방법으로 제조하였다.Light emitting material [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n of an organometallic coordination polymer It was prepared in the same manner as in Example 1.
발광재료 10 wt% 와 실리콘 봉지재(다우 코닝사 OE6630A, OE6630B)를 혼합하여 5630 UV LED 칩 위에 4.5-5.0 mg을 도포한 후 150 도에서 약 2 시간 경화시켜 LED 패키지를 제조하였다.10 wt% of the luminescent material and the silicon encapsulant (Dow Corning Co., Ltd. OE6630A, OE6630B) were mixed to apply 4.5-5.0 mg on a 5630 UV LED chip, and then cured at 150 degrees for about 2 hours to manufacture an LED package.
실시예Example 3 3
0.1 mol비의 Y(NO3)3·6H2O화합물, 0.1 mol비의 Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.2 mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합발광 재료 [(Y0. 5,Eu0 . 5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of Y (NO 3 ) 3 · 6H 2 O compound, 0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O compound, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.2 mol ratio Pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline (Formula 17) was weighed and the weighed raw material was weighed in 50 ml of water (H 2 O ) was added and uniformly mixed, and then the composite light-emitting material group synthesized by the presence or absence and the mixture temperature at 150 ℃ [(. Y 0. 5, Eu 0 5) (4,4'- oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline)] n was prepared.
발광재료 10 wt% 와 실리콘 봉지재(다우 코닝사 OE6630A, OE6630B)를 혼합하여 5630 Blue LED 칩 위에 4.5-5.0 mg을 도포한 후 150도에서 약 2시간 경화시켜 LED 패키지를 제조하였다.10 wt% of the luminescent material and the silicon encapsulant (Dow Corning Co., Ltd. OE6630A, OE6630B) were mixed to apply 4.5-5.0 mg on a 5630 Blue LED chip, and then cured at 150 degrees for about 2 hours to manufacture an LED package.
실시예Example 4 4
0.1 mol비의 Y2O3:Eu3 +화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.2 mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [(Y2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of Y 2 O 3 : Eu 3 + compound, 0.2 mol ratio of 4,4'-oxybis (benzoic acid), 0.2 mol ratio of pyrido [2 ', 3': 5,6] pyrazino [2 , 3-f] [1,10] phenanthroline (Formula 17) was weighed, and the weighed raw material was poured into 50 ml of water (H 2 O), mixed uniformly, and then the mixture was synthesized at 150 ° C. Group composite light emitting material [(Y 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [ 1,10] phenanthroline)] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다. A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
실시예Example 5 5
0.1 mol비의 La2O3:Eu3 +화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.2 mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [(La2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of La 2 O 3: Eu 3 + compound, 0.2 mol ratio of the 4,4'-oxybis (benzoic acid), 0.2 mol of the non-pyrido also [2 ', 3': 5,6] pyrazino [2 , 3-f] [1,10] phenanthroline (Formula 17) was weighed, and the weighed raw material was poured into 50 ml of water (H 2 O), mixed uniformly, and then the mixture was synthesized at 150 ° C. Group composite light emitting material [(La 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [ 1,10] phenanthroline)] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다. A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
실시예Example 6 6
0.1 mol비의 Gd2O3:Eu3 +화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.2 mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [(Gd2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of Gd 2 O 3 : Eu 3 + compound, 0.2 mol ratio of 4,4'-oxybis (benzoic acid), 0.2 mol ratio of pyrido [2 ', 3': 5,6] pyrazino [2 , 3-f] [1,10] phenanthroline (Formula 17) was weighed, and the weighed raw material was poured into 50 ml of water (H 2 O), mixed uniformly, and then the mixture was synthesized at 150 ° C. Group composite light emitting material [(Gd 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [ 1,10] phenanthroline)] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다. A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
실시예Example 7 7
0.1 mol비의 La2O3:Eu3 +화합물, 0.2 mol비의 테레프탈릭 에시드 (화학식 5), 0.2 mol비의 피라지노[2,3-f][1,10]-페난트롤린-2,3-다이카보나이트릴(화학식 14)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [(La2O3:Eu)(테레프탈릭 에시드)3(피라지노[2,3-f][1,10]-페난트롤린-2,3-다이카보나이트릴)]n 을 제조하였다.0.1 mol ratio of La 2 O 3 : Eu 3 + compound, 0.2 mol ratio of terephthalic acid (Formula 5), 0.2 mol ratio of pyrazino [2,3-f] [1,10] -phenanthroline-2 , 3-dicarbonitrile (Formula 14) was weighed, the weighed raw material was placed in 50 ml of water (H 2 O), mixed uniformly, and the mixture was synthesized at 150 ° C. to yield an organic-inorganic composite light emitting material [(La 2 O 3 : Eu) (terephthalic acid) 3 (pyrazino [2,3-f] [1,10] -phenanthroline-2,3-dicarbonitrile)] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 2와 동일하게 실시하여 UV LED 패키지를 제조하였다. A UV LED package was manufactured in the same manner as in Example 2, except that the prepared red light emitting material was used.
실시예Example 8 8
0.1 mol비의 Y2O3:Eu 화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.2 mol비의 테트라피리도[3,2-a:2´,3´-c:3´´,2´´-h:2´´´,3´´-j]페나진(화학식 28)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [(Y2O3:Eu)(4,4’-옥시비스(벤조산))3(테트라피리도[3,2-a:2´,3´-c:3´´,2´´-h:2´´´,3´´-j]페나진)]n 을 제조하였다.0.1 mol ratio of Y 2 O 3 : Eu compound, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.2 mol ratio of tetrapyrido [3,2-a: 2 ′, 3′-c: 3 ´´, 2´´-h: 2´´´, 3´´-j] Phenazine (Formula 28) is weighed, the weighed raw material is placed in 50 ml of water (H 2 O) and mixed uniformly. The mixture was synthesized at a temperature of 150 ° C. to yield an organic-inorganic composite light emitting material [(Y 2 O 3 : Eu) (4,4′-oxybis (benzoic acid)) 3 (tetrapyrido [3,2-a: 2 ′, 3 '-C: 3', 2'-h: 2 '', 3'-j] phenazine)] n .
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 2와 동일하게 실시하여 UV LED 패키지를 제조하였다. A UV LED package was manufactured in the same manner as in Example 2, except that the prepared red light emitting material was used.
실시예Example 9 9
0.1 mol비의 Y(NO3)3·6H2O화합물, 0.1 mol비의　Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.1 mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)과 0.1 mol 비의 1,10-페난트롤린(화학식 16)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(1,10-페난트롤린)0.5]n을 제조하였다. 0.1 mol ratio of Y (NO 3 ) 3 · 6H 2 O compound, 0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O compound, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.1 mol ratio Pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline (Formula 17) with 0.1 mol ratio of 1,10-phenanthroline (Formula 16) ), The weighed raw material is placed in 50 ml of water (H 2 O), uniformly mixed, and the mixture is synthesized at 150 ° C. to yield an organic-inorganic composite light emitting material [(Y 0.5 , Eu 0.5 ) (4,4 '-Oxybis (benzoic acid)) 3 (pyrido [2', 3 ': 5,6] pyrazino [2,3-f] [1,10] phenanthroline) 0.5 (1,10-phenanthroline 0.5 ] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다. A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
실시예Example 10 10
0.1 mol비의 Y(NO3)3·6H2O화합물, 0.1 mol비의　Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.1 mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)과 0.1 mol 비의 피라지노[2,3-f][1,10]페난트롤린(화학식 13)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(피라지노[2,3-f][1,10]페난트롤린)0.5]n을 제조하였다. 0.1 mol ratio of Y (NO 3 ) 3 · 6H 2 O compound, 0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O compound, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.1 mol ratio Pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline (Formula 17) with pyrazino [2,3-f] [ 1,10] Phenanthroline (Formula 13) is weighed, the weighed raw material is placed in 50 ml of water (H 2 O), mixed uniformly, and then the mixture is synthesized at a temperature of 150 ° C. Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline ) 0.5 (pyrazino [2,3-f] [1,10] phenanthroline) 0.5 ] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다. A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
실시예Example 11 11
0.1 mol비의 Y(NO3)3·6H2O화합물, 0.1 mol비의 Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.1 mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)과 0.1mol 비의 3-메틸피라지노[2,3-f][1,10]페난트롤린 (화학식 15)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(3-메틸피라지노[2,3-f][1,10]페난트롤린)0.5]n을 제조하였다.0.1 mol ratio of Y (NO 3 ) 3 · 6H 2 O compound, 0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O compound, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.1 mol ratio Pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline (Formula 17) with 3-methylpyrazino [2,3- in 0.1 mol ratio f] [1,10] phenanthroline (Formula 15) is weighed, the weighed raw material is placed in 50 ml of water (H 2 O), uniformly mixed, and the mixture is synthesized at a temperature of 150 ° C. to emit an organic-inorganic complex. Material [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] Phenanthroline) 0.5 (3-methylpyrazino [2,3-f] [1,10] phenanthroline) 0.5 ] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다. A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
실시예Example 12 12
0.1 mol비의 Eu(NO3)3·5H2O화합물, 0.2 mol비의 1,3,5-트리스(4-카복시페닐)벤젠, 0.2 mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유무기 복합 발광 재료 [Eu(1,3,5-트리스(4-카복시페닐)벤젠)3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of Eu (NO 3 ) 3 .5H 2 O compound, 0.2 mol ratio of 1,3,5-tris (4-carboxyphenyl) benzene, 0.2 mol ratio of pyrido [2 ', 3': 5, 6] Pyrazino [2,3-f] [1,10] phenanthroline (Formula 17) is weighed, the weighed raw material is placed in 50 ml of water (H 2 O), uniformly mixed, and the mixture is 150 Organic-inorganic composite luminescent material [Eu (1,3,5-tris (4-carboxyphenyl) benzene) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-) f] [1,10] phenanthroline)] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다. A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
실시예Example 13 13
0.1 mol비의 Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.2 mol비의 디피리도[3,2-a:2´,3´-c]페나진 (화학식 18)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유기 금속 배위 고분자의 유무기 복합 발광 재료 [Eu(4,4’-옥시비스(벤조산))3(디피리도[3,2-a:2´,3´-c]페나진)]n 을 제조하였다.0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O compound, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.2 mol ratio of dipyrido [3,2-a: 2 ′, 3´- c] Phenazine (Formula 18) is weighed, the weighed raw material is placed in 50 ml of water (H 2 O) and uniformly mixed, and then the mixture is synthesized at 150 ° C. to synthesize an organic-inorganic coordination polymer organic-inorganic composite light emitting material. [Eu (4,4'-oxybis (benzoic acid)) 3 (dipyrido [3,2-a: 2 ', 3'-c] phenazine)] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다. A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
실시예Example 14 14
0.1 mol비의 Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.2 mol비의 11-methoxydipyrido[3,2-a:2',3'-c]phenazine(화학식 19)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유기 금속 배위 고분자의 유무기 복합 발광 재료 [Eu(4,4’-옥시비스(벤조산))3(11-메톡시디피리도[3,2-a:2',3'-c]페나진)]n 을 제조하였다.0.1 mol ratio of Eu (NO 3 ) 3 .5H 2 O compound, 0.2 mol ratio of 4,4'-oxybis (benzoic acid), 0.2 mol ratio of 11-methoxydipyrido [3,2-a: 2 ', 3' -c] phenazine (Formula 19) was weighed, and the weighed raw material was placed in 50 ml of water (H 2 O), mixed uniformly, and then the mixture was synthesized at a temperature of 150 ° C. to form an organic-inorganic composite light emitting material of an organic metal coordination polymer. [Eu (4,4'-oxybis (benzoic acid)) 3 (11-methoxydipyrido [3,2-a: 2 ', 3'-c] phenazine)] n was prepared.
제조된 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 3과 동일하게 실시하여 블루 LED 패키지를 제조하였다.A blue LED package was manufactured in the same manner as in Example 3, except that the prepared red light emitting material was used.
비교예Comparative example
비교예Comparative example 1 One
0.1 mol비의 Y(NO3)3·6H2O화합물, 0.1 mol비의 Eu(NO3)3·5H2O화합물, 0.1 mol비의 유로피엄(III) 니트레이트 펜타하이드레이트(Europium(III) nitrate pentahydrate), 0.2 mol비의 3,5-피리딘 디카복시산, 0.2 mol 비의 페난트롤린을 칭량하고 이를 물 50 ml를 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 유기 금속 배위 고분자의 발광 재료 [(Y0.5Eu0.5)(페난트롤린)(3,5-디카르복시산)22(H2O)]n을 수득하였다.0.1 mol ratio of Y (NO 3 ) 3 · 6H 2 O compound, 0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O compound, 0.1 mol of europium (III) nitrate pentahydrate (Europium (III) nitrate pentahydrate), 0.2 mol ratio of 3,5-pyridine dicarboxylic acid, 0.2 mol ratio of phenanthroline, weighed 50 ml of water, mixed uniformly, and then the mixture was synthesized at 150 ° C. to coordinate organic metal. A light emitting material [(Y 0.5 Eu 0.5 ) (phenanthroline) (3,5-dicarboxylic acid) 2 2 (H 2 O)] n of a polymer was obtained.
발광재료 10 wt% 와 실리콘 봉지재(다우 코닝사 OE6630A, OE6630B)를 혼합하여 5630 Blue LED 칩 위에 4.5-5.0 mg을 도포한 후 150도에서 약 2시간 경화시켜 LED 패키지를 제조하였다.10 wt% of the luminescent material and the silicon encapsulant (Dow Corning Co., Ltd. OE6630A, OE6630B) were mixed to apply 4.5-5.0 mg on a 5630 Blue LED chip, and then cured at 150 degrees for about 2 hours to manufacture an LED package.
비교예Comparative example 2 2
0.2 mol비의 2,4-피리딘 디카르복시산을 사용한 것을 제외하고는 비교예 1과 같은 방법으로 제조하여 유기 금속 배위 고분자의 발광 재료[(Y0.5Eu0.5)(페난트롤린)(2,4-디카르복시산)22(H2O)]n을 수득하였다.A light emitting material [(Y 0.5 Eu 0.5 ) (phenanthroline) (2,4-) of the organic metal coordination polymer was prepared in the same manner as in Comparative Example 1, except that 0.2 mol ratio of 2,4-pyridine dicarboxylic acid was used. Dicarboxylic acid) 2 2 (H 2 O)] n .
발광재료 10 wt% 와 실리콘 봉지재(다우 코닝사 OE6630A, OE6630B)를 혼합하여 5630 Blue LED 칩 위에 4.5-5.0 mg을 도포한 후 150도에서 약 2시간 경화시켜 LED 패키지를 제조하였다.10 wt% of the luminescent material and the silicon encapsulant (Dow Corning Co., Ltd. OE6630A, OE6630B) were mixed to apply 4.5-5.0 mg on a 5630 Blue LED chip, and then cured at 150 degrees for about 2 hours to manufacture an LED package.
비교예Comparative example 3 3
0.2 mol비의 1,3,5-트리스(4-카복시페닐)벤젠을 사용한 것을 제외하고는 비교예 1과 같은 방법으로 제조하여 유기 금속 배위 고분자의 발광 재료[(Y0.5Eu0.5)(페난트롤린)(1,3,5-트리스(4-카복시페닐)벤젠)22(H2O)]n을 수득하였다.A light emitting material [(Y 0.5 Eu 0.5 ) (phenanthrol) of organic metal coordination polymer was prepared in the same manner as in Comparative Example 1 except that 0.2 mol ratio of 1,3,5-tris (4-carboxyphenyl) benzene was used. Lean) (1,3,5-tris (4-carboxyphenyl) benzene) 2 2 (H 2 O)] n was obtained.
발광재료 10 wt% 와 실리콘 봉지재(다우 코닝사 OE6630A, OE6630B)를 혼합아여 5630 Blue LED 칩 위에 4.5-5.0 mg을 도포한 후 150도에서 약 2시간 경화시켜 LED 패키지를 제조하였다.10 wt% of the luminescent material and the silicon encapsulant (Dow Corning Corporation OE6630A, OE6630B) were mixed to apply 4.5-5.0 mg on a 5630 Blue LED chip, and then cured at 150 ° C. for about 2 hours to manufacture an LED package.
실험예Experimental Example
본 발명의 실시예 1 내지 3에 따라서 제조된 유기 금속 배위 고분자의 유무기 복합 발광 재료를 UV 또는 Blue LED칩을 이용하여 실장 평가를 한 결과, 비교예 1 내지 3에 따라서 제조된 유기 금속 배위 고분자 [(Y0.5Eu0.5)(phen)(3,5-pyridine dicarboxylic acid)2(H2O)2]n, [(Y0.5Eu0.5)(phen)(2,4-pyridine dicarboxylic acid)2(H2O)2]n, [(Y0.5Eu0.5)(phen)(1,3,5-Tris(4-carboxy phenyl)benzene)2(H2O)2]n과 달리 UV 및 450 nm의 Blue영역에서 여기되어 LED 발광 재료로 사용이 가능하다.As a result of mounting evaluation of the organic-inorganic composite light emitting material of the organic metal coordination polymer prepared according to Examples 1 to 3 of the present invention using UV or Blue LED chip, the organic metal coordination polymer prepared according to Comparative Examples 1 to 3 [(Y 0.5 Eu 0.5 ) (phen) (3,5-pyridine dicarboxylic acid) 2 (H 2 O) 2 ] n , [(Y 0.5 Eu 0.5 ) (phen) (2,4-pyridine dicarboxylic acid) 2 ( H 2 O) 2 ] n , [(Y 0.5 Eu 0.5 ) (phen) (1,3,5-Tris (4-carboxy phenyl) benzene) 2 (H 2 O) 2 ] n Unlike UV and 450 nm It is excited in blue area and can be used as LED light emitting material.
실시예 1의 방법으로 제조된 유기 금속 배위 고분자는 도 1에 표시한 바와 같이 nearUV에서 약 614.1nm의 적색 발광 특성을 보이며 12.4nm 의 좁은 반치폭을 갖는다. 즉, 기존의 형광체에 비해서 좁은 반치폭과 고휘도의 LED용 적색 발광 재료임을 알 수 있다. 도 2는 실시예 1에 따른 XRD 패턴을 나타낸 그래프로 결정성이 있는 재료임을 알 수 있다. 도 3은 본 발명의 실시예 1에 따른 발광 재료와 기존 형광체 CaAlSiN3:Eu2 +, K2SiF6:Mn4 +과의 PL 스펙트럼 그래프를 나타낸 것으로 UV 영역에서 기존의 형광체에 비해 반치폭이 좁고 빛의 강도가 좋음을 나타낸다. 도 4는 본 발명의 실시예 1 내지 2에 따른 400의 UV 칩을 이용하여 PKG 실장 평가를 한 그래프와 스펙트럼을 나타내고, 도 5는 본 발명의 실시예 3에 따른 450의 Blue 칩을 이용하여 PKG 실장 평가를 한 그래프와 스펙트럼을 나타낸 것이다. 도 6은 비교예의 여기 스펙트럼을 나타내고, 도 7은 비교예의 발광 스펙트럼을 나타낸 것이다. 비교예의 유기 금속 배위 고분자는 400nm-450nm 부근에서 여기되지 못하기 때문에 400nm의 UV LED 또는 450nm의 Blue LED 발광 장치에 사용되지 못한다.The organometallic coordination polymer prepared by the method of Example 1 exhibits a red emission characteristic of about 614.1 nm in nearUV and a narrow half width of 12.4 nm as shown in FIG. 1. That is, it can be seen that it is a red light emitting material for LEDs having a narrow half width and high brightness as compared to the conventional phosphor. Figure 2 is a graph showing the XRD pattern according to Example 1 it can be seen that the material is crystalline. Figure 3 is a light-emitting material and a conventional phosphor CaAlSiN 3 according to the first embodiment of the present invention: a narrow full width at half maximum in the UV region that shows the PL spectrum graph of the Mn 4 +, compared to traditional fluorescent substance: Eu 2 +, K 2 SiF 6 The light intensity is good. 4 shows graphs and spectra of PKG mounting evaluation using 400 UV chips according to Examples 1 and 2 of the present invention, and FIG. 5 shows PKG using a Blue chip of 450 according to Example 3 of the present invention. The graphs and spectra of the implementation evaluations are shown. 6 shows an excitation spectrum of a comparative example, and FIG. 7 shows an emission spectrum of a comparative example. Since the organometallic coordination polymer of the comparative example is not excited near 400 nm-450 nm, it cannot be used in a 400 nm UV LED or a 450 nm Blue LED light emitting device.
이상에서 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허청구범위에 기재된 본 발명의 기술적 사상으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다Although described with reference to the embodiments above, those skilled in the art can understand that the present invention can be variously modified and changed without departing from the spirit of the invention described in the claims below. There will be

Claims (21)

  1. 하기 화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.An LED light emitting device comprising a red organic-inorganic composite light emitting material having a composition of Formula 1.
    [화학식 1][Formula 1]
    [(A x1,Rx2)(L)y(X)]n [(A x1 , R x2 ) (L) y (X)] n
    화학식 1에서, A는 Li, Na 또는 K 중에서 선택된 1가 금속이온 또는, Mg, Ca, Sr, Ba 또는 Zn 중에서 선택된 2가 금속이온 또는, Al 또는 La 중에서 선택된 3가 금속이온 또는, Zr 또는 Ti 중에서 선택된 4가 금속이온으로 이루어진 군으로부터 선택되는 1종 이상의 금속이온 또는 그의 금속화합물을 포함하고, In Formula 1, A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti At least one metal ion selected from the group consisting of tetravalent metal ions or metal compounds thereof,
    R은 Eu 또는 Eu화합물 중에서 선택되는 1종을 포함하며, R includes one selected from Eu or Eu compounds,
    L은 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종을 포함하고, L includes one selected from aromatic compounds having at least two carboxylic acid groups,
    X는 페난트롤린(phenanthroline) 및 그 유도체 중에서 선택되는 1종 이상을 포함하며,X includes at least one selected from phenanthroline and its derivatives,
    x1은 0≤x1<2이고, x2는 0<x2≤2이며, x1과 x2의 합은 0<x1+x2≤2 이고,x1 is 0 ≦ x1 <2, x2 is 0 <x2 ≦ 2, the sum of x1 and x2 is 0 <x 1+ x 2 ≤ 2,
    y는 2 또는 3이며, n은 1 이상의 정수에서 선택되는 정수이다.y is 2 or 3, and n is an integer chosen from the integer of 1 or more.
  2. 제1항에 있어서,The method of claim 1,
    금속화합물은 ZnO, Y2O3, La2O3, Gd2O3, Al2(SO4)3, TiO2, Zn(NO3)2, Bi2O3 또는 MnCO3 중에서 선택되는 어느 하나를 포함하는 금속화합물인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.Metal compounds include ZnO, Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 Or a red and organic-inorganic composite light emitting material, characterized in that the metal compound including any one selected from MnCO 3 .
  3. 제1항에 있어서,The method of claim 1,
    Eu 화합물은 Eu과 1종 이상의 금속이온 및 산화물, 또는 Eu이 포함된 금속산화물인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.An Eu compound includes a red organic-inorganic composite light emitting material, characterized in that the Eu and at least one metal ion and oxide, or a metal oxide containing Eu.
  4. 제3항에 있어서,The method of claim 3,
    Eu 화합물은 ZnO:Eu, Y2O3:Eu, La2O3:Eu 또는 Eu(NO3)3·xH2O중에서 선택되는 1종이며, Eu(NO3)3·xH2O에서 x는 1 내지 6에서 선택되는 정수인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.The Eu compound is one selected from ZnO: Eu, Y 2 O 3 : Eu, La 2 O 3 : Eu, or Eu (NO 3 ) 3 xH 2 O, and in Eu (NO 3 ) 3 xH 2 O LED light emitting device comprising a red organic-inorganic composite light emitting material, characterized in that the integer selected from 1 to 6.
  5. 제1항에 있어서,The method of claim 1,
    L은 하기 화학식 2 내지 8 중에서 선택되는 것을 포함하는 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.L is a LED light emitting device comprising a red organic-inorganic composite light emitting material characterized in that it comprises one selected from the following formula (2).
    [화학식 2][Formula 2]
    Figure PCTKR2017001474-appb-I000030
    Figure PCTKR2017001474-appb-I000030
    [화학식 3][Formula 3]
    Figure PCTKR2017001474-appb-I000031
    Figure PCTKR2017001474-appb-I000031
    [화학식 4][Formula 4]
    Figure PCTKR2017001474-appb-I000032
    Figure PCTKR2017001474-appb-I000032
    [화학식 5][Formula 5]
    Figure PCTKR2017001474-appb-I000033
    Figure PCTKR2017001474-appb-I000033
    [화학식 6][Formula 6]
    Figure PCTKR2017001474-appb-I000034
    Figure PCTKR2017001474-appb-I000034
    [화학식 7][Formula 7]
    Figure PCTKR2017001474-appb-I000035
    Figure PCTKR2017001474-appb-I000035
    [화학식 8][Formula 8]
    Figure PCTKR2017001474-appb-I000036
    Figure PCTKR2017001474-appb-I000036
  6. 제1항에 있어서,The method of claim 1,
    X는 하기 화학식 9 내지 12 로 표시되는 것 중에서 선택되는 1종 이상을 포함하는 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.X is a LED light emitting device comprising a red organic-inorganic composite light emitting material, characterized in that it comprises one or more selected from those represented by the formulas (9) to (12).
    [화학식 9][Formula 9]
    Figure PCTKR2017001474-appb-I000037
    Figure PCTKR2017001474-appb-I000037
    [화학식 10][Formula 10]
    Figure PCTKR2017001474-appb-I000038
    Figure PCTKR2017001474-appb-I000038
    [화학식 11][Formula 11]
    Figure PCTKR2017001474-appb-I000039
    Figure PCTKR2017001474-appb-I000039
    [화학식 12][Formula 12]
    상기 R1 내지 R10은 각각 독립적으로 수소; 중수소; 할로겐; 시아노; 니트로; 아미노; 치환 또는 비치환된 C1- 60알킬; C1- 60할로알킬; 치환 또는 비치환된 C1- 60알콕시; 치환 또는 비치환된 C1- 60할로알콕시; 치환 또는 비치환된 C3- 60사이클로알킬; 치환 또는 비치환된 C2- 60알케닐; 치환 또는 비치환된 C6- 60아릴; 치환 또는 비치환된 C6-60아릴옥시; 또는 치환 또는 비치환된 N, O 및 S 중 1개 이상을 포함하는 C1- 60헤테로고리기이며, Q는 N 또는 CH 이다.R 1 to R 10 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C 1 -60 alkyl; 1- C 60 haloalkyl; Substituted or unsubstituted C 1 -60 alkoxy; Substituted or unsubstituted C 1 -60 haloalkoxy; Substituted or unsubstituted C 3 -60 cycloalkyl; A substituted or unsubstituted C 2- 60 alkenyl; Substituted or unsubstituted C 6- 60 aryl; Substituted or unsubstituted C 6-60 aryloxy; Or a C 1- 60 heterocyclic group, including a substituted or unsubstituted N, O, and S 1 out of the above, Q is N or CH.
  7. 제6항에 있어서,The method of claim 6,
    상기 R1은 수소(H), 시아노기(-CN) 또는 메틸기(CH3)이고, R2 내지 R7은 각각 독립적으로 수소(H), 아미노기(-NH2), 메틸기(CH3)또는 페닐(phenyl)이며, R8은 수소(H) 또는 메톡시(-OCH3)이고, R9는 수소(H), C1~C6알킬기, 페닐(phenyl), n-C1~C6알킬페닐(n-C1~C6alkylphenyl), 디메틸페닐(dimethylphenyl), 트리메틸페닐(trimethylphenyl), 디에틸페닐(diethylphenyl), 트리에틸페닐(triethylphenyl), n-니트로페닐(n-nitrophenyl), n-아미노페닐(n-aminophenyl), n-설포닐페닐(n-sulfonylphenyl), 디설포닐페닐(disulfonylphenyl), n-C1~C6알콕시페닐(n-C1~C6alkoxyphenyl), 디메톡시페닐(dimethoxyphenyl), 디에톡시페닐(diethoxyphenyl), n-피리딜(n-pyridyl), 프리미딜(pyrimidyl), 퍼퓨릴(furfuryl), 나프탈레닐(naphthalenyl) 또는 피레닐(pyrenyl)이며, R10은 수소(H), C1~C6알킬기, 페닐(phenyl) 또는 n-C1~C6알킬페닐(n-C1~C6alkylphenyl)중에서 선택될 수 있고, 상기 C1~C6알콕시는 메톡시, 에톡시, 프로폭시, 부톡시, 펜틸옥시 또는 헥실옥시이며, n은 2 내지 4 중에서 선택되는 어느 하나의 정수이며, o-, m-, p-를 의미하는 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.R 1 is hydrogen (H), cyano group (-CN) or methyl group (CH 3 ), and R 2 to R 7 are each independently hydrogen (H), amino group (-NH 2 ), methyl group (CH 3 ) or Phenyl, R 8 is hydrogen (H) or methoxy (-OCH 3 ), R 9 is hydrogen (H), a C 1 to C 6 alkyl group, phenyl, nC 1 to C 6 alkylphenyl (nC 1 ~ C 6 alkylphenyl), dimethylphenyl, trimethylphenyl, diethylphenyl, triethylphenyl, n-nitrophenyl, n-aminophenyl ( n-aminophenyl), n-sulfonylphenyl, disulfonylphenyl, nC 1 to C 6 alkoxyphenyl (nC 1 to C 6 alkoxyphenyl), dimethoxyphenyl, diethoxyphenyl ( diethoxyphenyl, n-pyridyl, pyrimidyl, furfuryl, naphthalenyl or pyrenyl, R 10 is hydrogen (H), C 1- the C 6 alkyl, phenyl, (phenyl) or nC 1 ~ C 6 alkyl phenyl (nC 1 ~ C 6 alkylphenyl) May be selected, wherein the C 1 ~ C 6 alkoxy are methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy it is oxy, n is an integer of any one selected from 2 to 4, o-, m -An LED light-emitting device comprising a red organic-inorganic composite light emitting material, characterized in that p-.
  8. 제6항에 있어서,The method of claim 6,
    X는 하기 화학식 13 내지 27 중에서 선택되는 1종 이상인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치. X is a LED light emitting device comprising a red organic-inorganic composite light emitting material, characterized in that at least one selected from the formulas (13) to (27).
    [화학식 13][Formula 13]
    Figure PCTKR2017001474-appb-I000041
    Figure PCTKR2017001474-appb-I000041
    [화학식 14][Formula 14]
    Figure PCTKR2017001474-appb-I000042
    Figure PCTKR2017001474-appb-I000042
    [화학식 15][Formula 15]
    Figure PCTKR2017001474-appb-I000043
    Figure PCTKR2017001474-appb-I000043
    [화학식 16][Formula 16]
    Figure PCTKR2017001474-appb-I000044
    Figure PCTKR2017001474-appb-I000044
    [화학식 17][Formula 17]
    Figure PCTKR2017001474-appb-I000045
    Figure PCTKR2017001474-appb-I000045
    [화학식 18][Formula 18]
    Figure PCTKR2017001474-appb-I000046
    Figure PCTKR2017001474-appb-I000046
    [화학식 19][Formula 19]
    Figure PCTKR2017001474-appb-I000047
    Figure PCTKR2017001474-appb-I000047
    [화학식 20][Formula 20]
    Figure PCTKR2017001474-appb-I000048
    Figure PCTKR2017001474-appb-I000048
    [화학식 21][Formula 21]
    Figure PCTKR2017001474-appb-I000049
    Figure PCTKR2017001474-appb-I000049
    [화학식 22][Formula 22]
    Figure PCTKR2017001474-appb-I000050
    Figure PCTKR2017001474-appb-I000050
    [화학식 23][Formula 23]
    Figure PCTKR2017001474-appb-I000051
    Figure PCTKR2017001474-appb-I000051
    [화학식 24][Formula 24]
    Figure PCTKR2017001474-appb-I000052
    Figure PCTKR2017001474-appb-I000052
    [화학식 25][Formula 25]
    Figure PCTKR2017001474-appb-I000053
    Figure PCTKR2017001474-appb-I000053
    [화학식 26][Formula 26]
    Figure PCTKR2017001474-appb-I000054
    Figure PCTKR2017001474-appb-I000054
    [화학식 27][Formula 27]
    Figure PCTKR2017001474-appb-I000055
    Figure PCTKR2017001474-appb-I000055
  9. 제1항에 있어서,The method of claim 1,
    X는 하기 화학식 28인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.X is a LED light emitting device comprising a red organic-inorganic composite light emitting material characterized in that the formula (28).
    [화학식 28][Formula 28]
    Figure PCTKR2017001474-appb-I000056
    Figure PCTKR2017001474-appb-I000056
  10. 제1항에 있어서,The method of claim 1,
    상기 화학식 1은 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(파라지노[2,3-f][1,10]페난트롤린)]n, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]파라지노[2,3-f][1,10]페난트롤린)]n, [(Al0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Ti0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Zn0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Bi0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Mn0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Y2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n, [(La2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n, [(Gd2O3:Eu)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n, [(La2O3:Eu)(테레프탈릭 에시드)3(피라지노[2,3-f][1,10]-페난트롤린-2,3-다이카보나이트릴)]n, [(Y2O3:Eu)(4,4’-옥시비스(벤조산))3(테트라피리도[3,2-a:2´,3´-c:3´´,2´´-h:2´´´,3´´-j]페나진)]n, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(1,10-페난트롤린)0.5]n, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(피라지노[2,3-f][1,10]페난트롤린)0.5]n, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)0.5(3-메틸피라지노[2,3-f][1,10]페난트롤린)0.5]n, [Eu(1,3,5-트리스(4-카복시페닐)벤젠)3(피리도[2’,3’:5,6]파라지노[2,3-f][1,10]페난트롤린)]n, [Eu(4,4’-옥시비스(벤조산))3(dipyrido[3,2-a:2´,3´-c]phenzine)]n 또는 [Eu(4,4’-옥시비스(벤조산))3(11-methoxydipyrido[3,2-a:2',3'-c]phenazine)]n 중에서 선택되는 화합물인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.Formula 1 is [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (paragino [2,3-f] [1,10] phenanthroline)] n , [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] paragino [2,3-f] [1,10] phenanthroline) ] n , [(Al 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n , [(Ti 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n , [(Zn 0.5 , Eu 0.5 ) (4, 4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n , [(Bi 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid )) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n , [(Mn 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [ 2,3-f] [1,10] phenanthroline)] n , [(Y 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline)] n , [(La 2 O 3 : Eu) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline)] n, [(Gd 2 O 3: Eu) (4,4'- oxybis ( Premature birth)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline)] n, [(La 2 O 3: Eu), (terephthaloyl Ric acid) 3 (pyrazino [2,3-f] [1,10] -phenanthroline-2,3-dicarbonitrile)] n , [(Y 2 O 3 : Eu) (4,4'- Oxybis (benzoic acid)) 3 (tetrapyrido [3,2-a: 2´, 3´-c: 3´´, 2´´-h: 2´´´, 3´´-j] phenazine) ] n , [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1, 10] phenanthroline) 0.5 (1,10-phenanthroline) 0.5 ] n , [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3' : 5,6] pyrazino [2,3-f] [1,10] phenanthroline) 0.5 (pyrazino [2,3-f] [1,10] phenanthroline) 0.5 ] n , [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline) 0.5 (3-methylpyrazino [2,3-f] [1,10] phenanthroline) 0.5 ] n , [Eu (1,3,5-tris (4-carboxyphenyl) benzene) 3 (pyrido [ 2 ', 3': 5,6] paragino [2,3-f] [1,10] phenanthroline)] n , [Eu (4,4'-oxybis (benzoic acid)) 3 (dipyrido [3 , 2-a: 2 , 3'-c] phenzine)] n or [Eu (4,4'- oxybis (benzoic acid)) 3 (11-methoxydipyrido [ 3,2-a: from 2 ', 3'-c] phenazine )] n An LED light-emitting device comprising a red organic-inorganic composite light emitting material, characterized in that the compound selected.
  11. 제1항에 있어서,The method of claim 1,
    화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료는 반치폭이 15 nm 이하인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.The red organic-inorganic composite luminescent material having the composition of Formula 1 has a half-width of 15 nm or less LED light emitting device comprising a red organic-inorganic composite luminescent material.
  12. 제1항에 따른 적색 유무기 복합 발광 재료를 제조하기 위해서,In order to manufacture the red organic-inorganic composite luminescent material according to claim 1,
    1가 내지 4가 금속이온 또는 그의 금속화합물 중에서 선택되는 1종 이상과, Eu 또는 Eu화합물 중에서 선택되는 1종과, 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종과, 페난트롤린 및 그 유도체 중에서 선택되는 1종 이상의 원료를 칭량하는 단계; One or more selected from monovalent to tetravalent metal ions or metal compounds thereof, one selected from Eu or Eu compounds, one selected from aromatic compounds having at least two carboxylic acid groups, and phenanthroline And weighing at least one raw material selected from the derivatives thereof;
    칭량된 원료 50~100ml를 용매에 넣고 균일하게 혼합하여 혼합물을 제조하는 단계;50 to 100 ml of a weighed raw material is put in a solvent and mixed uniformly to prepare a mixture;
    혼합물을 90~210 ℃ 온도에서 합성하는 단계;를 포함하여 제조된 하기 화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.Synthesizing the mixture at a temperature of 90 ~ 210 ℃; LED light-emitting device comprising a red organic-inorganic composite light emitting material having a composition of Formula 1 prepared, including.
    [화학식 1][Formula 1]
    [(A x1,Rx2)(L)y(X)]n [(A x1 , R x2 ) (L) y (X)] n
    화학식 1에서, A는 Li, Na 또는 K 중에서 선택된 1가 금속이온 또는, Mg, Ca, Sr, Ba 또는 Zn 중에서 선택된 2가 금속이온 또는, Al 또는 La 중에서 선택된 3가 금속이온 또는, Zr 또는 Ti 중에서 선택된 4가 금속이온으로 이루어진 군으로부터 선택되는 1종 이상의 금속이온 또는 그의 금속화합물을 포함하고, In Formula 1, A is a monovalent metal ion selected from Li, Na or K, or a divalent metal ion selected from Mg, Ca, Sr, Ba or Zn, or a trivalent metal ion selected from Al or La, or Zr or Ti At least one metal ion selected from the group consisting of tetravalent metal ions or metal compounds thereof,
    R은 Eu 또는 Eu화합물 중에서 선택되는 1종을 포함하며, R includes one selected from Eu or Eu compounds,
    L은 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종을 포함하고, L includes one selected from aromatic compounds having at least two carboxylic acid groups,
    X는 페난트롤린(phenanthroline) 및 그 유도체 중에서 선택되는 1종 이상을 포함하며,X includes at least one selected from phenanthroline and its derivatives,
    x1은 0≤x1<2이고, x2는 0<x2≤2이며, x1과 x2의 합은 0<x1+x2≤2 이고,x1 is 0 ≦ x1 <2, x2 is 0 <x2 ≦ 2, the sum of x1 and x2 is 0 <x 1+ x 2 ≤ 2,
    y는 2 또는 3이며, n은 1 이상의 정수에서 선택되는 정수이다.y is 2 or 3, and n is an integer chosen from the integer of 1 or more.
  13. 제12항에 있어서, The method of claim 12,
    0.01 내지 0.19 mol비의 1가 내지 4 금속이온 또는 그의 금속화합물 중에서 선택되는 1종 이상과, 0.1 내지 0.19 mol비의 Eu 또는 Eu화합물 중에서 선택되는 1종과, 0.01 내지 0.6 mol비의 카르복실산기를 적어도 두개 갖는 방향족계 화합물 중에서 선택되는 1종과, 0.01 내지 0.2 mol비의 페난트롤린 및 그 유도체 중에서 선택되는 1종 이상의 원료를 칭량하는 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.One or more selected from 0.01 to 0.19 mol ratio of monovalent to four metal ions or metal compounds thereof, one selected from 0.1 to 0.19 mol ratio of Eu or Eu compounds, and 0.01 to 0.6 mol ratio of carboxylic acid groups LED comprising a red organic-inorganic composite light emitting material, characterized in that one selected from the aromatic compounds having at least two and at least one raw material selected from 0.01 to 0.2 mol ratio of phenanthroline and its derivatives Light emitting device.
  14. 제12항에 있어서,The method of claim 12,
    용매는 H2O, 프로판올, 에탄올, 메탄올, 디메틸포름아마이드(DMF; dimethylformamide), 디메틸아세트아마이드(DMA; dimethyacetamide) 인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.A solvent is H 2 O, propanol, ethanol, methanol, dimethylformamide (DMF; dimethylformamide), dimethylacetamide (DMA; dimethyacetamide) LED light emitting device comprising a red organic-inorganic composite light emitting material, characterized in that.
  15. 제12항에 있어서,The method of claim 12,
    금속화합물은 ZnO, Y2O3, La2O3, Gd2O3, Al2(SO4)3, TiO2, Zn(NO3)2, Bi2O3 또는 MnCO3 중에서 선택되는 어느 하나를 포함하는 금속화합물인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.Metal compounds include ZnO, Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 Or a red and organic-inorganic composite light emitting material, characterized in that the metal compound including any one selected from MnCO 3 .
  16. 제12항에 있어서,The method of claim 12,
    Eu 화합물은 ZnO:Eu, Y2O3:Eu, La2O3:Eu 또는 Eu(NO3)3·xH2O중에서 선택되는 1종이며, Eu(NO3)3·xH2O에서 x는 1 내지 6에서 선택되는 정수인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.The Eu compound is one selected from ZnO: Eu, Y 2 O 3 : Eu, La 2 O 3 : Eu, or Eu (NO 3 ) 3 xH 2 O, and in Eu (NO 3 ) 3 xH 2 O LED light emitting device comprising a red organic-inorganic composite light emitting material, characterized in that the integer selected from 1 to 6.
  17. 제12항에 있어서,The method of claim 12,
    L은 하기 화학식 2 내지 8중에서 선택되는 적어도 어느 하나를 포함하는 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.L is a LED light emitting device comprising a red organic-inorganic composite light emitting material, characterized in that it comprises at least any one selected from the following formula (2).
    [화학식 2][Formula 2]
    Figure PCTKR2017001474-appb-I000057
    Figure PCTKR2017001474-appb-I000057
    [화학식 3][Formula 3]
    Figure PCTKR2017001474-appb-I000058
    Figure PCTKR2017001474-appb-I000058
    [화학식 4][Formula 4]
    Figure PCTKR2017001474-appb-I000059
    Figure PCTKR2017001474-appb-I000059
    [화학식 5][Formula 5]
    Figure PCTKR2017001474-appb-I000060
    Figure PCTKR2017001474-appb-I000060
    [화학식 6][Formula 6]
    Figure PCTKR2017001474-appb-I000061
    Figure PCTKR2017001474-appb-I000061
    [화학식 7][Formula 7]
    Figure PCTKR2017001474-appb-I000062
    Figure PCTKR2017001474-appb-I000062
    [화학식 8][Formula 8]
    Figure PCTKR2017001474-appb-I000063
    Figure PCTKR2017001474-appb-I000063
  18. 제12항에 있어서,The method of claim 12,
    X는 하기 화학식 9 내지 12 로 표시되는 것 중에서 선택되는 1종 이상을 포함하는 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.X is a LED light emitting device comprising a red organic-inorganic composite light emitting material, characterized in that it comprises one or more selected from those represented by the formulas (9) to (12).
    [화학식 9][Formula 9]
    Figure PCTKR2017001474-appb-I000064
    Figure PCTKR2017001474-appb-I000064
    [화학식 10][Formula 10]
    Figure PCTKR2017001474-appb-I000065
    Figure PCTKR2017001474-appb-I000065
    [화학식 11][Formula 11]
    Figure PCTKR2017001474-appb-I000066
    Figure PCTKR2017001474-appb-I000066
    [화학식 12][Formula 12]
    Figure PCTKR2017001474-appb-I000067
    Figure PCTKR2017001474-appb-I000067
    상기 R1 내지 R10은 각각 독립적으로 수소; 중수소; 할로겐; 시아노; 니트로; 아미노; 치환 또는 비치환된 C1- 60알킬; C1- 60할로알킬; 치환 또는 비치환된 C1- 60알콕시; 치환 또는 비치환된 C1- 60할로알콕시; 치환 또는 비치환된 C3- 60사이클로알킬; 치환 또는 비치환된 C2- 60알케닐; 치환 또는 비치환된 C6- 60아릴; 치환 또는 비치환된 C6-60아릴옥시; 또는 치환 또는 비치환된 N, O 및 S 중 1개 이상을 포함하는 C1- 60헤테로고리기이며, Q는 N 또는 CH 이다.R 1 to R 10 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C 1 -60 alkyl; 1- C 60 haloalkyl; Substituted or unsubstituted C 1 -60 alkoxy; Substituted or unsubstituted C 1 -60 haloalkoxy; Substituted or unsubstituted C 3 -60 cycloalkyl; A substituted or unsubstituted C 2- 60 alkenyl; Substituted or unsubstituted C 6- 60 aryl; Substituted or unsubstituted C 6-60 aryloxy; Or a C 1- 60 heterocyclic group, including a substituted or unsubstituted N, O, and S 1 out of the above, Q is N or CH.
  19. 제18항에 있어서,The method of claim 18,
    상기 R1은 수소(H), 시아노기(-CN) 또는 메틸기(CH3)이고, R2 내지 R7은 각각 독립적으로 수소(H), 아미노기(-NH2), 메틸기(CH3) 또는 페닐(phenyl)이며, R8은 수소(H) 또는 메톡시(-OCH3)이고, R9는 수소(H), C1~C6알킬기, 페닐(phenyl), n-C1~C6알킬페닐(n-C1~C6alkylphenyl), 디메틸페닐(dimethylphenyl), 트리메틸페닐(trimethylphenyl), 디에틸페닐(diethylphenyl), 트리에틸페닐(triethylphenyl), n-니트로페닐(n-nitrophenyl), n-아미노페닐(n-aminophenyl), n-설포닐페닐(n-sulfonylphenyl), 디설포닐페닐(disulfonylphenyl), n-C1~C6알콕시페닐(n-C1~C6alkoxyphenyl),디메톡시페닐(dimethoxyphenyl), 디에톡시페닐(diethoxyphenyl), n-피리딜(n-pyridyl), 프리미딜(pyrimidyl), 퍼퓨릴(furfuryl), 나프탈레닐(naphthalenyl) 또는 피레닐(pyrenyl)이며, R10은 수소(H), C1~C6알킬기, 페닐(phenyl) 또는 n-C1~C6알킬페닐(n-C1~C6alkylphenyl)중에서 선택될 수 있고, 상기 C1~C6알콕시는 메톡시, 에톡시, 프로폭시, 부톡시, 펜틸옥시 또는 헥실옥시이며, n은 2 내지 4 중에서 선택되는 어느 하나의 정수이며, o-, m-, p-를 의미하는 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.R 1 is hydrogen (H), cyano group (-CN) or methyl group (CH 3 ), and R 2 to R 7 are each independently hydrogen (H), amino group (-NH 2 ), methyl group (CH 3 ) or Phenyl, R 8 is hydrogen (H) or methoxy (-OCH 3 ), R 9 is hydrogen (H), a C 1 to C 6 alkyl group, phenyl, nC 1 to C 6 alkylphenyl (nC 1 ~ C 6 alkylphenyl), dimethylphenyl, trimethylphenyl, diethylphenyl, triethylphenyl, n-nitrophenyl, n-aminophenyl ( n-aminophenyl), n-sulfonylphenyl, disulfonylphenyl, nC 1 to C 6 alkoxyphenyl (nC 1 to C 6 alkoxyphenyl), dimethoxyphenyl, diethoxyphenyl ( diethoxyphenyl, n-pyridyl, pyrimidyl, furfuryl, naphthalenyl or pyrenyl, R 10 is hydrogen (H), C 1- the C 6 alkyl, phenyl, (phenyl) or nC 1 ~ C 6 alkyl phenyl (nC 1 ~ C 6 alkylphenyl) May be selected, wherein the C 1 ~ C 6 alkoxy are methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy it is oxy, n is an integer of any one selected from 2 to 4, o-, m -An LED light-emitting device comprising a red organic-inorganic composite light emitting material, characterized in that p-.
  20. 제18항에 있어서,The method of claim 18,
    X는 하기 화학식 13 내지 27 중에서 선택되는 1종 이상인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치. X is a LED light emitting device comprising a red organic-inorganic composite light emitting material, characterized in that at least one selected from the formulas (13) to (27).
    [화학식 13][Formula 13]
    Figure PCTKR2017001474-appb-I000068
    Figure PCTKR2017001474-appb-I000068
    [화학식 14][Formula 14]
    Figure PCTKR2017001474-appb-I000069
    Figure PCTKR2017001474-appb-I000069
    [화학식 15][Formula 15]
    Figure PCTKR2017001474-appb-I000070
    Figure PCTKR2017001474-appb-I000070
    [화학식 16][Formula 16]
    Figure PCTKR2017001474-appb-I000071
    Figure PCTKR2017001474-appb-I000071
    [화학식 17][Formula 17]
    Figure PCTKR2017001474-appb-I000072
    Figure PCTKR2017001474-appb-I000072
    [화학식 18][Formula 18]
    Figure PCTKR2017001474-appb-I000073
    Figure PCTKR2017001474-appb-I000073
    [화학식 19][Formula 19]
    Figure PCTKR2017001474-appb-I000074
    Figure PCTKR2017001474-appb-I000074
    [화학식 20][Formula 20]
    Figure PCTKR2017001474-appb-I000075
    Figure PCTKR2017001474-appb-I000075
    [화학식 21][Formula 21]
    Figure PCTKR2017001474-appb-I000076
    Figure PCTKR2017001474-appb-I000076
    [화학식 22][Formula 22]
    Figure PCTKR2017001474-appb-I000077
    Figure PCTKR2017001474-appb-I000077
    [화학식 23][Formula 23]
    Figure PCTKR2017001474-appb-I000078
    Figure PCTKR2017001474-appb-I000078
    [화학식 24][Formula 24]
    Figure PCTKR2017001474-appb-I000079
    Figure PCTKR2017001474-appb-I000079
    [화학식 25][Formula 25]
    Figure PCTKR2017001474-appb-I000080
    Figure PCTKR2017001474-appb-I000080
    [화학식 26][Formula 26]
    Figure PCTKR2017001474-appb-I000081
    Figure PCTKR2017001474-appb-I000081
    [화학식 27][Formula 27]
    Figure PCTKR2017001474-appb-I000082
    Figure PCTKR2017001474-appb-I000082
  21. 제12항에 있어서,The method of claim 12,
    X는 하기 화학식 28인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 LED 발광 장치.X is a LED light emitting device comprising a red organic-inorganic composite light emitting material characterized in that the formula (28).
    [화학식 28][Formula 28]
    Figure PCTKR2017001474-appb-I000083
    Figure PCTKR2017001474-appb-I000083
PCT/KR2017/001474 2016-02-12 2017-02-10 Led light emitting device comprising red organic-inorganic composite light emitting material WO2017138765A1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012028874A1 (en) * 2010-09-01 2012-03-08 University Of Sheffield Cytotoxic luminescent metal complexes

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Publication number Priority date Publication date Assignee Title
WO2012028874A1 (en) * 2010-09-01 2012-03-08 University Of Sheffield Cytotoxic luminescent metal complexes

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Title
LI, W.-L.: "The preparation and luminescence of Eu(III) activated o-phenanthroline containing Gd(III) succinate phosphors", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 206, no. 2, 1994, pages 195 - 199, XP024176712, DOI: doi:10.1016/0925-8388(94)90035-3 *
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