WO2017150831A1 - Blue led device for display, comprising red organic-inorganic composite light-emitting material - Google Patents

Blue led device for display, comprising red organic-inorganic composite light-emitting material Download PDF

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WO2017150831A1
WO2017150831A1 PCT/KR2017/001766 KR2017001766W WO2017150831A1 WO 2017150831 A1 WO2017150831 A1 WO 2017150831A1 KR 2017001766 W KR2017001766 W KR 2017001766W WO 2017150831 A1 WO2017150831 A1 WO 2017150831A1
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formula
phenanthroline
inorganic composite
emitting material
light emitting
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PCT/KR2017/001766
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French (fr)
Korean (ko)
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고다현
임서영
김영식
류정곤
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주식회사 효성
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements

Definitions

  • the present invention relates to a blue LED device for a display comprising a red organic-inorganic composite light emitting material. More specifically, the emission wavelength of the excitation light in the UV and blue regions is 600 to 630 nm, and a high color is obtained by applying a new red light emitting material of an organometallic coordination polymer having a narrow half-width and a high luminance of 15 nm or less compared to conventional phosphors.
  • the present invention relates to a blue LED device for display that can be reproduced.
  • a phosphor combination of a representative blue LED package is represented by a combination of green and red phosphors on a blue LED.
  • the color reproducibility is determined by the color coordinates of blue, green, and red that pass through the color filter, and the area percentage value of the area of the National Television System Committee (NTSC) color coordinates is called a color reproducibility.
  • NTSC National Television System Committee
  • phosphor combination One of the important factors in determining the color reproducibility in such a backlight unit is phosphor combination.
  • a combination of blue LED, LSN (yellow phosphor), and SCASN (nitride-based red phosphor) is applied to a general blue LED backlight unit, but color reproducibility is limited to being applied to a premium display.
  • red phosphors have mainly developed sulfide-based, oxide-based, or nitride-based phosphors. However, this is difficult to implement a half-width of 20 nm or less, there is a problem such as a patent to apply.
  • the quantum dot and OLED materials have a narrow half-width and have excellent color reproducibility.
  • these materials are vulnerable to moisture environments and thus have limitations in application to displays.
  • An object of the present invention is to provide a novel red light-emitting material of an organometallic coordination polymer having an emission wavelength of 600 to 630 nm with respect to excitation light in the UV and blue regions, and having a narrow half-value width and high brightness of 15 nm or less compared to conventional phosphors. It is done.
  • an object of the present invention is to provide a blue LED device for a display to which an existing green phosphor is applied.
  • the present inventors have found the possibility of producing a premium-class display through multi-wavelength shift in the future with a material that is not conventionally present.
  • the present invention relates to a blue LED device for a display including a red organic-inorganic composite light emitting material, and provides a blue LED device for a display including a red organic-inorganic composite light emitting material having a composition of the following Chemical 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
  • 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 ml to 100 ml of solvent, and mixing the mixture at a temperature of 90 to 210 ° C. It provides a blue LED device for a display comprising a red organic-inorganic composite light emitting material having a composition of the formula (1) prepared including the step of synthesizing.
  • 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 of the present invention is a light emitting material of an organic metal coordination polymer, and has a higher luminance than a light emitting material of an existing organic metal coordination polymer and is capable of excitation in the UV and blue regions. This has a significant effect as a light emitting material for LEDs since the color implementation range is free, the half width is narrow to 15 nm or less and can be excited especially in the blue region.
  • FIG. 1 shows a PL spectral graph and an SEM image according to an embodiment of the present invention.
  • FIG. 3 and 4 show excitation spectra of the red organic-inorganic composite luminescent material according to the present invention (X axis represents wavelength, Y axis represent emission intensity).
  • FIG. 5 shows the emission spectra of FIGS. 3 and 4 (X-axis represents wavelength and Y-axis represents emission intensity).
  • 6 is a red organic-inorganic composite light emitting material synthesized by changing A of Formula 1 according to the present invention to Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 , MnCO 3 in addition to yttrium Is a graph showing the emission wavelength spectrum.
  • FIG. 7 is a red organic-inorganic composite light emitting material synthesized by changing A of Formula 1 according to the present invention into Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 , MnCO 3 in addition to yttrium EDS graph of.
  • FIGS. 8, 9, and 10 show an image of a single crystal structure of the red organic-inorganic composite light emitting material according to the present invention, and FIGS. 8, 9, and 10 show [(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 .
  • Example 11 is a graph showing excitation and emission spectra according to Example 10 of the present invention.
  • Example 12 is a graph showing excitation and emission spectra according to Example 11 of the present invention.
  • Example 13 is a graph showing excitation and emission spectra according to Example 12 of the present invention.
  • Example 14 is a graph showing excitation and emission spectra according to Example 13 of the present invention.
  • Example 15 is a graph showing excitation and emission spectra according to Example 14 of the present invention.
  • 16 is a graph showing emission spectra according to Examples 15-17 of the present invention.
  • Example 17 is a graph showing an emission spectrum according to Example 18 of the present invention.
  • Example 18 is a graph showing an emission spectrum according to Example 19 of the present invention.
  • Example 19 is a graph showing an emission spectrum according to Example 20 of the present invention.
  • 20 is a graph showing emission spectra of commercially used phosphors.
  • 21 is a graph showing an emission spectrum according to the present invention.
  • the present invention relates to a blue LED device for a display comprising a red organic-inorganic composite light emitting material.
  • the red organic-inorganic composite light emitting material included in the blue LED device for display according to the present invention is a light emitting material of an organic metal coordination polymer, and is excited by a UV region of 350 to 450 nm and a blue region to emit a 600 to 630 nm emission wavelength. It has a full width at half maximum of 15 nm or less.
  • the red organic-inorganic composite light emitting material is based on a structure in which Eu 3 + is added as an activator, the chemical composition is as shown in the following 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 of 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 that 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 ) 3 X in xH 2 O is an integer selected from 1 to 6.
  • Eu or Eu compound it has Eu characteristic peak, which has a narrow half width of red, and when used in 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 blue LED device for display of the present invention is [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2, 3-f] [1,10] phenanthroline)] 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)] 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 ] Phenanthro
  • the blue LED device for display of the present invention is the blue LED device for display of the present invention.
  • One or more selected from 0.01 to 0.19 mol ratio of monovalent to tetravalent 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 carboxyl Weighing one kind selected from aromatic compounds having at least two acid groups, and one raw material selected from phenanthroline and derivatives thereof in a ratio of 0.01 to 0.2 mol, and
  • the raw materials weighed as above are mixed in 50-100 ml of water (H 2 O), propanol, ethanol, methanol, dimethylformamide (DMF, dimethylformamide) or dimethylacetamide (DMA, dimethyacetamide) and mixed uniformly. Preparing a mixture by mixing the same solvent and uniformly mixing the same;
  • 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 the excitation light in the UV and blue regions, and has a narrow half width and a high brightness of 15 nm or less compared to the conventional phosphor.
  • the characteristic of the red light emitting material is shown. This can be confirmed through FIG. 1.
  • Example 2 It was prepared in the same manner as in Example 1 except that it was synthesized at 170 °C temperature.
  • Phenanthroline (Formula 13) is weighed, the weighed raw material is placed in 50 ml of water (H 2 O), mixed uniformly, and the mixture is synthesized at a temperature of 150 ° C. to give a red organic-inorganic composite luminescent material [(Al 0.5 , Eu 0.5 ) (4,4′-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n was prepared.
  • Phenanthroline (Formula 13) is weighed, the weighed raw material is placed in 50 ml of water (H 2 O), mixed uniformly, and the mixture is synthesized at 150 ° C. to give a red organic-inorganic composite luminescent material [(Zn 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n was prepared.
  • Organic-inorganic 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.
  • Organic-inorganic 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.
  • Organic-inorganic 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.
  • 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 150 ° C.
  • red organic-inorganic composite luminescent 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 .
  • red organic-inorganic composite luminescent 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-phenanthrole Lean) 0.5 ] n .
  • red 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] phenanthrol Lean) 0.5 (pyrazino [2,3-f] [1,10] phenanthroline) 0.5 ] n was prepared.
  • H 2 O water
  • Luminescent 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.
  • each LED chip is mounted on the lead frame, and then attached using a bonding wire of gold wire for electrical connection, and the red organic-inorganic composite light emitting material obtained in Example 1 [ (Y 0.5 , Eu 0.5 ) (4,4′-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n and conventional green phosphors as (Sr, Ba) 2 SiO 4 :
  • An LED package was prepared by coating an encapsulant made of a methyl-based resin to which Eu was added.
  • the LED package manufactured by the above method is mounted on a PCB substrate to manufacture a LED bar, the LED bar is installed on the light guide plate, and the optical sheet, the diffusion and prism sheet, and the protective sheet are placed in a conventional manner, and then connected to an inverter to make a BLU. Was prepared.
  • a blue LED backlight unit was manufactured in the same manner as in Example 21, except that the red light emitting material prepared in Comparative Example 1 was used.
  • the red luminescent material prepared by the method of the example shows a red luminescence property 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.
  • a blue (blue) LED device (backlight unit) for display is manufactured based on the red light emitting materials prepared in Examples 1 to 20 and Comparative Example 1.
  • FIG. 2 is a spectrum graph when it synthesize
  • n is the excitation spectrum. According to this figure, it turns out that it has strong excitation light in about 360-400 nm.
  • Figure 5 is a red light emitting material having a red emission characteristics of 613 nm, [(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 shows an excitation spectrum.
  • FIGS. 8 to 10 show a single crystal image of the red light emitting material according to the present invention. 8, 9, 10 all of [(Y 0.
  • Figure 20 is SCASN commercially used as: the full width at half maximum (FWHM) in the graph of ((Sr, Ca) AlSiN 3 Eu 2 +) fluorescent material has a 75 nm.
  • Figure 21 shows the spectrum of the LED package according to the present invention.
  • LED package is added by adding 5 ⁇ 10% by weight of the conventional green phosphor and the prepared red light emitting material to a silicone resin (a mixture of OE 6630 A and OE 6630 B in a 1: 4 ratio), and then homogenizing it into a homogenizer and encapsulating it. Ash compositions were prepared. The weight percent is added in the ratio that x, y coordinates satisfy (0.27, 0.24) when the combined LED PKG passes the color filter.
  • a silicone resin a mixture of OE 6630 A and OE 6630 B in a 1: 4 ratio
  • FIG. 22 shows the actual NTSC simulation results based on the combination of the conventional green phosphor and the new red light emitting material of the present invention as shown in Table 1 below.

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Abstract

The present invention relates to a blue LED device for a display, comprising a red organic-inorganic composite light-emitting material allowing high color reproduction and, specifically, to a blue LED device for a display, comprising a red organic-inorganic composite light-emitting material having a composition of chemical formula 1 below. [Chemical formula 1] [(Ax1,Rx2)(L)y(X)]n wherein in chemical formula 1, A includes at least one metal ion or a metal compound thereof, the metal ion being 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 includes one selected from Eu or an Eu compound; L includes one selected from aromatic compounds having at least two carboxylic acid groups; X includes at least one selected from phenanthroline and a derivative thereof; x1 satisfies 0≤x1<2; x2 satisfies 0<x2≤2; the sum of x1 and x2 satisfies 0<x1 +x2≤2; y is 2 or 3; and n is an integer selected from integers of 1 or greater.

Description

적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치Blue LED device for display containing red organic-inorganic composite light emitting material
본 발명은 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치에 관한 것이다. 더욱 상세하게, UV 및 블루 영역의 여기광에 대한 발광 파장이 600 내지 630 nm이며, 기존의 형광체에 비해서 15 nm 이하의 좁은 반치폭과 고휘도를 갖는 유기 금속 배위 고분자의 새로운 적색 발광재료를 적용하여 고색재현이 가능한 디스플레이용 블루 LED 장치에 관한 것이다.The present invention relates to a blue LED device for a display comprising a red organic-inorganic composite light emitting material. More specifically, the emission wavelength of the excitation light in the UV and blue regions is 600 to 630 nm, and a high color is obtained by applying a new red light emitting material of an organometallic coordination polymer having a narrow half-width and a high luminance of 15 nm or less compared to conventional phosphors. The present invention relates to a blue LED device for display that can be reproduced.
발광다이오드(Light-Emitting Diode: LED)의 백라이트 유닛(Back Light Unit: BLU)에서 대표적인 블루(Blue) LED 패키지의 형광체 조합은 블루 LED에 녹색과 적색 형광체의 조합으로 표현된다. In the back light unit (BLU) of a light-emitting diode (LED), a phosphor combination of a representative blue LED package is represented by a combination of green and red phosphors on a blue LED.
색 재현율은 컬러 필터(Color Filter)를 통과한 청색, 녹색, 적색의 색 좌표로 결정되고 NTSC(National Television System Committee) 색 좌표의 면적대비 면적 백분율 값을 색 재현율이라 칭한다. The color reproducibility is determined by the color coordinates of blue, green, and red that pass through the color filter, and the area percentage value of the area of the National Television System Committee (NTSC) color coordinates is called a color reproducibility.
이러한 백라이트 유닛에서 색 재현율을 결정하는 중요한 요소 중 하나는 형광체 조합이다. 현재 일반적인 블루 LED 백라이트 유닛에는 블루 LED, LSN(황색 형광체), SCASN(질화물계 적색 형광체) 조합을 적용하고 있으나 색 재현율은 프리미엄급 디스플레이에 적용하는데는 한계가 있다. One of the important factors in determining the color reproducibility in such a backlight unit is phosphor combination. Currently, a combination of blue LED, LSN (yellow phosphor), and SCASN (nitride-based red phosphor) is applied to a general blue LED backlight unit, but color reproducibility is limited to being applied to a premium display.
종래 기술은 광 스펙트럼 분포상 녹색과 적색 사이의 구분이 모호하여 혼색되어 있었으며, 따라서 LCD 디스플레이를 구현했을 때 색 재현 특성이 좋지 못하다는 문제점이 있었다. In the prior art, the distinction between green and red is ambiguous due to the light spectrum distribution, and therefore, there is a problem in that color reproduction characteristics are not good when the LCD display is implemented.
이를 해결하고자 반치폭(FWHM: 최대 발광 강도의 1/2의 강도를 가진 두 파장 사이의 간격- 반치폭이 적을수록 사람의 색감각과의 차이가 적다)이 30 nm를 갖는 좁은 반치폭의 녹색 및 적색 형광체로 색 재현율을 향상시키는 연구가 진행되고 있다. To solve this problem, narrow half-width green and red phosphors with 30 nm of half width (FWHM: spacing between two wavelengths with half the maximum luminous intensity-the smaller the half width is, the smaller the difference with human color sense) Research to improve the color reproduction rate is underway.
종래 적색 형광체는 주로 황화물계 또는 산화물계, 질화물계 형광체가 개발되고 있다. 그러나, 이는 20 nm 이하의 반치폭 구현에 어려움이 있고, 적용하기에 특허 등의 문제점이 있다. Conventionally, red phosphors have mainly developed sulfide-based, oxide-based, or nitride-based phosphors. However, this is difficult to implement a half-width of 20 nm or less, there is a problem such as a patent to apply.
또한 양자점(Quamtum dot)과 OLED의 재료는 좁은 반치폭으로 색 재현율이 우수하나, 이는 수분 환경에 취약하여 디스플레이에 적용하기에 한계가 있었다. In addition, the quantum dot and OLED materials have a narrow half-width and have excellent color reproducibility. However, these materials are vulnerable to moisture environments and thus have limitations in application to displays.
따라서, 이러한 문제점을 극복하기 위해 새로운 발광 재료가 필요한 실정이다.Therefore, a new light emitting material is needed to overcome this problem.
본 발명은 UV 및 블루 영역의 여기 광에 대한 발광 파장이 600 내지 630 nm이며, 기존의 형광체에 비해서 15 nm 이하의 좁은 반치폭과 고휘도를 갖는 유기 금속 배위 고분자의 새로운 적색 발광 재료를 제공하는 것을 목적으로 한다. An object of the present invention is to provide a novel red light-emitting material of an organometallic coordination polymer having an emission wavelength of 600 to 630 nm with respect to excitation light in the UV and blue regions, and having a narrow half-value width and high brightness of 15 nm or less compared to conventional phosphors. It is done.
이와 함께 기존의 녹색 형광체가 함께 적용된 디스플레이용 블루 LED 장치를 제공하는 것을 목적으로 한다.Along with this, an object of the present invention is to provide a blue LED device for a display to which an existing green phosphor is applied.
이로써 종래에는 없는 물질로 장래에 다파장 이동을 통하여 프리미엄급 디스플레이를 생산할 수 있는 가능성을 발견한 것이다.As a result, the present inventors have found the possibility of producing a premium-class display through multi-wavelength shift in the future with a material that is not conventionally present.
본 발명은 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치에 관한 것으로, 하기 화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치를 제공한다.The present invention relates to a blue LED device for a display including a red organic-inorganic composite light emitting material, and provides a blue LED device for a display including a red organic-inorganic composite light emitting material having a composition of the following Chemical 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, 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 ml~100 ml의 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 디스플레이용 블루 LED 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 ml to 100 ml of solvent, and mixing the mixture at a temperature of 90 to 210 ° C. It provides a blue LED device for a display comprising a red organic-inorganic composite light emitting material having a composition of the formula (1) prepared including the step of synthesizing.
[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 적색 유무기 복합 발광 재료는 유기 금속 배위 고분자의 발광 재료로서 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 블루 영역에서 여기될 수 있으므로, LED 용 발광 재료로 상당한 효과가 있다.The red organic-inorganic composite light emitting material of the present invention is a light emitting material of an organic metal coordination polymer, and has a higher luminance than a light emitting material of an existing organic metal coordination polymer and is capable of excitation in the UV and blue regions. This has a significant effect as a light emitting material for LEDs since the color implementation range is free, the half width is narrow to 15 nm or less and can be excited especially in the blue region.
또한 종래에는 없는 물질로 장래에 다파장 이동을 통하여 프리미엄급 디스플레이를 생산이 가능할 것으로 예상되어 산업적인 이용 가능성이 높다.In addition, it is expected that it will be possible to produce a premium-class display through multi-wavelength movement in the future as a material that does not exist in the past, and thus is highly industrially available.
도 1은 본 발명의 실시예에 따른 PL 스펙트럼 그래프 및 SEM 이미지를 나타낸다.1 shows a PL spectral graph and an SEM image according to an embodiment of the present invention.
도 2는 본 발명의 실시예 및 비교예에 따른 발광 스펙트럼 그래프이다.2 is a light emission spectrum graph according to Examples and Comparative Examples of the present invention.
도 3과 4는 본 발명에 따른 적색 유무기 복합 발광재료의 여기 스펙트럼을 나타낸 것이다(X축은 파장을, Y축은 발광강도를 나타낸다). 3 and 4 show excitation spectra of the red organic-inorganic composite luminescent material according to the present invention (X axis represents wavelength, Y axis represent emission intensity).
도 5는 도 3과 도 4의 발광 스펙트럼을 나타낸 것이다(X축은 파장을, Y축은 발광강도를 나타낸다). FIG. 5 shows the emission spectra of FIGS. 3 and 4 (X-axis represents wavelength and Y-axis represents emission intensity).
도 6은 본 발명에 따른 화학식 1의 A를 이트륨 이외에 Al2(SO4)3, TiO2, Zn(NO3)2, Bi2O3, MnCO3로 변경하여 합성한 적색 유무기 복합 발광재료의 발광 파장 스펙트럼을 나타낸 그래프이다.6 is a red organic-inorganic composite light emitting material synthesized by changing A of Formula 1 according to the present invention to Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 , MnCO 3 in addition to yttrium Is a graph showing the emission wavelength spectrum.
도 7은 본 발명에 따른 화학식 1의 A를 이트륨 이외에 Al2(SO4)3, TiO2, Zn(NO3)2, Bi2O3, MnCO3로 변경하여 합성한 적색 유무기 복합 발광재료의 EDS 그래프이다. FIG. 7 is a red organic-inorganic composite light emitting material synthesized by changing A of Formula 1 according to the present invention into Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 , MnCO 3 in addition to yttrium EDS graph of.
도 8 내지 도 10은 본 발명에 따른 적색 유무기 복합 발광재료의 단결정 구조의 이미지를 나타낸 것으로, 도 8, 도 9, 도 10 모두 [(Y0.5,Eu0.5)(4,4'-옥시비스(벤조산))3(피리도[2',3':5,6]피라지노[2,3-f][1,10]페난트롤린)]n 의 경우의 이미지이다.8 to 10 show an image of a single crystal structure of the red organic-inorganic composite light emitting material according to the present invention, and FIGS. 8, 9, and 10 show [(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 .
도 11은 본 발명 실시예 10에 따른 여기 및 발광 스펙트럼을 나타낸 그래프이다.11 is a graph showing excitation and emission spectra according to Example 10 of the present invention.
도 12는 본 발명 실시예 11에 따른 여기 및 발광 스펙트럼을 나타낸 그래프이다.12 is a graph showing excitation and emission spectra according to Example 11 of the present invention.
도 13은 본 발명 실시예 12에 따른 여기 및 발광 스펙트럼을 나타낸 그래프이다.13 is a graph showing excitation and emission spectra according to Example 12 of the present invention.
도 14는 본 발명 실시예 13에 따른 여기 및 발광 스펙트럼을 나타낸 그래프이다.14 is a graph showing excitation and emission spectra according to Example 13 of the present invention.
도 15는 본 발명 실시예 14에 따른 여기 및 발광 스펙트럼을 나타낸 그래프이다.15 is a graph showing excitation and emission spectra according to Example 14 of the present invention.
도 16은 본 발명 실시예 15-17에 따른 발광 스펙트럼을 나타낸 그래프이다.16 is a graph showing emission spectra according to Examples 15-17 of the present invention.
도 17은 본 발명 실시예 18에 따른 발광 스펙트럼을 나타낸 그래프이다.17 is a graph showing an emission spectrum according to Example 18 of the present invention.
도 18은 본 발명 실시예 19에 따른 발광 스펙트럼을 나타낸 그래프이다.18 is a graph showing an emission spectrum according to Example 19 of the present invention.
도 19는 본 발명 실시예 20에 따른 발광 스펙트럼을 나타낸 그래프이다.19 is a graph showing an emission spectrum according to Example 20 of the present invention.
도 20은 상업적으로 사용되는 형광체의 발광 스펙트럼을 나타낸 그래프이다.20 is a graph showing emission spectra of commercially used phosphors.
도 21은 본 발명에 따른 발광 스펙트럼을 나타낸 그래프이다.21 is a graph showing an emission spectrum according to the present invention.
도 22는 본 발명에 따른 NTSC 실측치 결과를 나타낸 그래프이다.22 is a graph showing NTSC measured results according to 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 재료를 포함하는 디스플레이용 블루 LED 장치에 관한 것이다.The present invention relates to a blue LED device for a display comprising a red organic-inorganic composite light emitting material.
먼저, 본 발명에 따른 디스플레이용 블루 LED 장치에 포함되는 적색 유무기 복합 발광 재료는 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 included in the blue LED device for display according to the present invention is a light emitting material of an organic metal coordination polymer, and is excited by a UV region of 350 to 450 nm and a blue region to emit a 600 to 630 nm emission wavelength. It has a full width at half maximum of 15 nm or less.
구체적으로, 상기 적색 유무기 복합 발광 재료는 활성제로 Eu3 +가 첨가된 구조를 기본으로 하며, 그 화학식 조성은 아래 화학식 1과 같다.Specifically, the red organic-inorganic composite light emitting material is based on a structure in which Eu 3 + is added as an activator, the chemical composition is as shown in the following 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 synthesis is not properly performed or synthesized.
상기 화학식 1의 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 of 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 1의 R로 사용될 수 있는 Eu 화합물은 Eu과 1종 이상의 금속이온 및 산화물, 또는 Eu이 포함된 금속산화물이 사용 될 수 있다.As the Eu compound that 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·xH2O 중에서 선택되는 1종이 사용될 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 ) 3 X in xH 2 O is an integer selected from 1 to 6.
Eu 또는 Eu 화합물을 사용하면 Eu 특성 피크(characteristic peak)를 갖게 되는데, 이는 적색의 좁은 반치폭을 갖게 하여 LED에 사용하게 되면 고색재현이 가능하게 된다.If Eu or Eu compound is used, it has Eu characteristic peak, which has a narrow half width of red, and when used in 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 PCTKR2017001766-appb-I000001
Figure PCTKR2017001766-appb-I000001
[화학식 3][Formula 3]
Figure PCTKR2017001766-appb-I000002
Figure PCTKR2017001766-appb-I000002
[화학식 4][Formula 4]
Figure PCTKR2017001766-appb-I000003
Figure PCTKR2017001766-appb-I000003
[화학식 5][Formula 5]
Figure PCTKR2017001766-appb-I000004
Figure PCTKR2017001766-appb-I000004
[화학식 6][Formula 6]
Figure PCTKR2017001766-appb-I000005
Figure PCTKR2017001766-appb-I000005
[화학식 7][Formula 7]
Figure PCTKR2017001766-appb-I000006
Figure PCTKR2017001766-appb-I000006
[화학식 8][Formula 8]
Figure PCTKR2017001766-appb-I000007
Figure PCTKR2017001766-appb-I000007
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 PCTKR2017001766-appb-I000008
Figure PCTKR2017001766-appb-I000008
[화학식 10][Formula 10]
Figure PCTKR2017001766-appb-I000009
Figure PCTKR2017001766-appb-I000009
[화학식 11][Formula 11]
Figure PCTKR2017001766-appb-I000010
Figure PCTKR2017001766-appb-I000010
[화학식 12][Formula 12]
Figure PCTKR2017001766-appb-I000011
Figure PCTKR2017001766-appb-I000011
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, pyrimidyl, furfuryl, naphthalenyl or pyrenyl R 10 is hydrogen (H), C 1 ~ C 6 alkyl group, phenyl (pheny l), or 1 ~ C 6 alkyl phenyl nC (can be used is selected from nC 1 ~ C 6 alkylphenyl).
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 PCTKR2017001766-appb-I000012
Figure PCTKR2017001766-appb-I000012
[화학식 14][Formula 14]
Figure PCTKR2017001766-appb-I000013
Figure PCTKR2017001766-appb-I000013
[화학식 15][Formula 15]
Figure PCTKR2017001766-appb-I000014
Figure PCTKR2017001766-appb-I000014
[화학식 16][Formula 16]
Figure PCTKR2017001766-appb-I000015
Figure PCTKR2017001766-appb-I000015
[화학식 17][Formula 17]
Figure PCTKR2017001766-appb-I000016
Figure PCTKR2017001766-appb-I000016
[화학식 18][Formula 18]
Figure PCTKR2017001766-appb-I000017
Figure PCTKR2017001766-appb-I000017
[화학식 19][Formula 19]
Figure PCTKR2017001766-appb-I000018
Figure PCTKR2017001766-appb-I000018
[화학식 20][Formula 20]
Figure PCTKR2017001766-appb-I000019
Figure PCTKR2017001766-appb-I000019
[화학식 21][Formula 21]
Figure PCTKR2017001766-appb-I000020
Figure PCTKR2017001766-appb-I000020
[화학식 22][Formula 22]
Figure PCTKR2017001766-appb-I000021
Figure PCTKR2017001766-appb-I000021
[화학식 23][Formula 23]
Figure PCTKR2017001766-appb-I000022
Figure PCTKR2017001766-appb-I000022
[화학식 24][Formula 24]
Figure PCTKR2017001766-appb-I000023
Figure PCTKR2017001766-appb-I000023
[화학식 25][Formula 25]
Figure PCTKR2017001766-appb-I000024
Figure PCTKR2017001766-appb-I000024
[화학식 26][Formula 26]
Figure PCTKR2017001766-appb-I000025
Figure PCTKR2017001766-appb-I000025
[화학식 27][Formula 27]
Figure PCTKR2017001766-appb-I000026
Figure PCTKR2017001766-appb-I000026
[화학식 28][Formula 28]
Figure PCTKR2017001766-appb-I000027
Figure PCTKR2017001766-appb-I000027
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 디스플레이용 블루 LED 장치에 포함되는 상기 화학식 1에 따른 적색 유무기 복합 발광재료는 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[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]피라지노[2,3-f][1,10]페난트롤린)]n, [Eu(4,4’-옥시비스(벤조산))3(디피리도[3,2-a:2´,3´-c]페나진)]n 또는 [Eu(4,4’-옥시비스(벤조산))3(11-메톡시디피리도[3,2-a:2',3'-c]페나진)]n을 바람직한 예로 들 수 있다.The red organic-inorganic composite light emitting material according to Chemical Formula 1 included in the blue LED device for display of the present invention is [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2, 3-f] [1,10] phenanthroline)] 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)] 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 (ben) Acid)) 3 (pyrido [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 (pyri Degree [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 (pyrimidin [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline)] n, [Eu (4,4'- oxybis (benzoic acid)) 3 (Diffie Lido [3,2-a: 2 ', 3'-c] phenazine)] 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 디스플레이용 블루 LED 장치는, The blue LED device for display of the present invention,
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 1종의 원료를 칭량하는 단계와,One or more selected from 0.01 to 0.19 mol ratio of monovalent to tetravalent 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 carboxyl Weighing one kind selected from aromatic compounds having at least two acid groups, and one raw material selected from phenanthroline and derivatives thereof in a ratio of 0.01 to 0.2 mol, and
상기와 같이 칭량된 원료를 50~100 ml의 물(H2O), 프로판올, 에탄올, 메탄올, 디메틸포름아마이드(DMF, dimethylformamide) 또는 디메틸아세트아마이드(DMA, dimethyacetamide)와 같은 용매에 넣고 균일하게 혼합하여 혼합물을 제조하는 단계와, 같은 용매에 넣고 균일하게 혼합하여 혼합물을 제조하는 단계와,The raw materials weighed as above are mixed in 50-100 ml of water (H 2 O), propanol, ethanol, methanol, dimethylformamide (DMF, dimethylformamide) or dimethylacetamide (DMA, dimethyacetamide) and mixed uniformly. Preparing a mixture by mixing the same solvent and uniformly mixing the same;
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 PCTKR2017001766-appb-I000028
Figure PCTKR2017001766-appb-I000028
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.
또한, 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. 이는 도 1을 통해 확인할 수 있다.In addition, 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 the excitation light in the UV and blue regions, and has a narrow half width and a high brightness of 15 nm or less compared to the conventional phosphor. The characteristic of the red light emitting material is shown. This can be confirmed through FIG. 1.
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.
실시예 Example
실시예 1Example 1
0.1 mol비의　Y(NO3)3·6H2O, 0.1 mol비의 Eu(NO3)3·5H2O, 0.2 mol비의 4,4’-옥시비스(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 적색 유무기 복합 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, 0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.2 mol ratio of pyra Gino [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 the mixture at 150 ° C. Synthesized red organic-inorganic composite luminescent material [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n Was prepared.
실시예 2Example 2
170 ℃ 온도에서 합성한 것을 제외하고는 실시예 1과 같은 방법으로 제조하였다.It was prepared in the same manner as in Example 1 except that it was synthesized at 170 ℃ temperature.
실시예 3Example 3
190 ℃ 온도에서 합성한 것을 제외하고는 실시예 1과 같은 방법으로 제조하였다.It was prepared in the same manner as in Example 1 except that it was synthesized at 190 ° C.
실시예Example 4 4
0.1 mol비의 Y(NO3)3·6H2O, 0.1 mol비의 Eu(NO3)3·5H2O, 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 적색 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)]n 을 제조하였다.0.1 mol ratio of Y (NO 3 ) 3 · 6H 2 O, 0.1 mol ratio of Eu (NO 3 ) 3 · 5H 2 O, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.2 mol ratio of pyri [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline (Formula 17) is weighed and the weighed raw material is poured into 50 ml water (H 2 O). The mixture was mixed uniformly, and then the mixture was synthesized at a temperature of 150 ° C. to give a red 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)] n was prepared.
실시예 5Example 5
0.1 mol비의　Al2(SO4)3, 0.1 mol비의 Eu 화합물, 0.2 mol비의 4,4’-옥시비스(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 적색 유무기 복합 발광 재료 [(Al0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of Al 2 (SO 4 ) 3 , 0.1 mol ratio of Eu compound, 0.2 mol ratio of 4,4′-oxybis (benzoic acid), 0.2 mol ratio of 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 the mixture is synthesized at a temperature of 150 ° C. to give a red organic-inorganic composite luminescent material [(Al 0.5 , Eu 0.5 ) (4,4′-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n was prepared.
실시예 6Example 6
0.1 mol비의 TiO2, 0.1 mol비의 Eu 화합물, 0.2 mol비의 4,4’-옥시비스(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 적색 유무기 복합 발광 재료 [(Ti0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of TiO 2 , 0.1 mol ratio of Eu compound, 0.2 mol ratio of 4,4'-oxybis (benzoic acid), 0.2 mol ratio of pyrazino [2,3-f] [1,10] phenanthroline Weighing Formula 13 is carried out, and the weighed raw material is placed in 50 ml of water (H 2 O), mixed uniformly, and then the mixture is synthesized at 150 ° C. to give a red organic-inorganic composite light emitting material [(Ti 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n was prepared.
실시예 7Example 7
0.1 mol비의 Zn(NO3)2, 0.1 mol비의 Eu 화합물, 0.2 mol비의 4,4’-옥시비스(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 적색 유무기 복합 발광 재료 [(Zn0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of Zn (NO 3 ) 2 , 0.1 mol ratio of Eu compound, 0.2 mol ratio of 4,4'-oxybis (benzoic acid), 0.2 mol ratio of 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 the mixture is synthesized at 150 ° C. to give a red organic-inorganic composite luminescent material [(Zn 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n was prepared.
실시예 8Example 8
0.1 mol비의 Bi2O3, 0.1 mol비의 Eu 화합물, 0.2 mol비의 4,4’-옥시비스(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 적색 유무기 복합 발광 재료 [(Bi0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of Bi 2 O 3 , 0.1 mol ratio of Eu compound, 0.2 mol ratio of 4,4'-oxybis (benzoic acid), 0.2 mol ratio of pyrazino [2,3-f] [1,10] phenan Weigh out the trolline (Formula 13), mix the weighed stock in 50 ml water (H 2 O), mix uniformly and synthesize the mixture at 150 ° C to give a red organic-inorganic composite luminescent material [(Bi 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n was prepared.
실시예 9Example 9
0.1 mol비의 MnCO3, 0.1 mol비의 Eu 화합물, 0.2 mol비의 4,4’-옥시비스(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 적색 유무기 복합 발광 재료 [(Mn0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n 을 제조하였다.0.1 mol ratio of MnCO 3 , 0.1 mol ratio of Eu compound, 0.2 mol ratio of 4,4'-oxybis (benzoic acid), 0.2 mol ratio of pyrazino [2,3-f] [1,10] phenanthroline (13), the weighed raw material is placed in 50 ml of water (H 2 O), uniformly mixed, and then the mixture is synthesized at 150 ° C. to give a red organic-inorganic composite light emitting material [(Mn 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n was prepared.
실시예 10Example 10
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 적색 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, 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 give red color. Organic-inorganic 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.
실시예 11Example 11
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 적색 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, 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 give red color. Organic-inorganic 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.
실시예 12Example 12
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 적색 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, 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 give red color. Organic-inorganic 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.
실시예 13Example 13
0.1 mol비의 La2O3:Eu3 +화합물, 0.2 mol비의 테레프탈릭 에시드, 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 적색 유무기 복합 발광 재료 [(La2O3:Eu)(테레프탈릭 에시드)3(피라지노[2,3-f][1,10]-페난트롤린-2,3-다이카보나이트릴)]n 을 제조하였다.0.1 in mol ratio La 2 O 3: Eu 3 + compound, of terephthalic Acid rigs, 0.2 mol ratio of 0.2 mol ratio pyrazino [2,3-f] [1,10] - 2,3-phenanthroline Carbonitril (formula 14) 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 give a red 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.
실시예 14Example 14
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 적색 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 150 ° C. to give a red organic-inorganic composite luminescent 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 .
실시예 15Example 15
0.1 mol비의　Y(NO3)3·6H2O화합물, 0.1 mol비의　Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.1mol비의 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린(화학식 17)과 0.1mol 비의 1,10-페난트롤린(화학식 16)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 적색 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 Of pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline (Formula 17) and 1,10-phenanthroline (Formula 16) in 0.1 mol ratio ), 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 give a red organic-inorganic composite luminescent 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-phenanthrole Lean) 0.5 ] n .
실시예 16Example 16
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 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 적색 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 0.1 mol ratio of pyrazino [2,3-f] [ 1,10] Phenanthroline (Formula 13) is weighed, and the weighed raw material is placed in 50 ml of water (H 2 O), mixed uniformly, and the mixture is synthesized at a temperature of 150 ° C. to give a red 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] phenanthrol Lean) 0.5 (pyrazino [2,3-f] [1,10] phenanthroline) 0.5 ] n was prepared.
실시예 17Example 17
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 적색 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), mixed uniformly, and the mixture is synthesized at a temperature of 150 ° C. to form a red organic-inorganic compound. Luminescent 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.
실시예 18Example 18
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 적색 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 Red 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.
실시예 19Example 19
0.1 mol비의 Eu(NO3)3·5H2O화합물, 0.2 mol비의 4,4’-옥시비스(벤조산), 0.2 mol비의 dipyrido[3,2-a:2´,3´-c]phenzine (화학식 18)을 칭량하고, 칭량된 원료를 50 ml 물(H2O)에 넣고 균일하게 혼합한 다음 상기 혼합물을 150 ℃ 온도에서 합성하여 적색 유무기 복합 발광 재료 [Eu(4,4’-옥시비스(벤조산))3(dipyrido[3,2-a:2´,3´-c]phenzine)]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 ] phenzine (Formula 18) is weighed, and the weighed raw material is poured into 50 ml of water (H 2 O), mixed uniformly, and the mixture is synthesized at a temperature of 150 ° C. to form a red organic-inorganic composite light emitting material [Eu (4,4 '-Oxybis (benzoic acid)) 3 (dipyrido [3,2-a: 2', 3'-c] phenzine)] n was prepared.
실시예 20Example 20
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 적색 유무기 복합 발광 재료 [Eu(4,4’-옥시비스(벤조산))3(11-methoxydipyrido[3,2-a:2',3'-c]phenazine)]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 poured into 50 ml of water (H 2 O), mixed uniformly, and then the mixture was synthesized at 150 ° C. to give a red organic-inorganic composite light emitting material [Eu (4). , 4'-oxybis (benzoic acid)) 3 (11-methoxydipyrido [3,2-a: 2 ', 3'-c] phenazine)] n was prepared.
실시예 21Example 21
세라믹 기판의 리드프레임에 접착제를 도포하고, 상기 리드프레임에 낱개의 LED 칩을 장착한 후에 전기적 연결이 되도록 금선의 본딩 와이어를 사용하여 부착하고, 실시예 1에서 얻은 적색 유무기 복합 발광 재료인 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n 와 종래의 녹색 형광체로서 (Sr,Ba)2SiO4:Eu가 첨가된 메틸계의 수지로된 봉지재를 피복하여 LED 패키지를 제조하였다. An adhesive is applied to the lead frame of the ceramic substrate, and each LED chip is mounted on the lead frame, and then attached using a bonding wire of gold wire for electrical connection, and the red organic-inorganic composite light emitting material obtained in Example 1 [ (Y 0.5 , Eu 0.5 ) (4,4′-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n and conventional green phosphors as (Sr, Ba) 2 SiO 4 : An LED package was prepared by coating an encapsulant made of a methyl-based resin to which Eu was added.
상기 방법으로 제조된 LED 패키지를 PCB 기판에 복수개 실장하여 LED 바를 제조하고, 상기 LED 바를 도광판에 설치하고, 통상적인 방법으로 광학시트, 확산 및 프리즘 시트, 보호 시트를 위치시킨 후에 인버터와 연결하여 BLU를 제조하였다. The LED package manufactured by the above method is mounted on a PCB substrate to manufacture a LED bar, the LED bar is installed on the light guide plate, and the optical sheet, the diffusion and prism sheet, and the protective sheet are placed in a conventional manner, and then connected to an inverter to make a BLU. Was prepared.
실시예 22Example 22
적색 유무기 복합 발광 재료로서 실시예 2에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다. An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 2.
실시예 23Example 23
적색 유무기 복합 발광 재료로서 실시예 3에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다. An LED package and a BLU were manufactured in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 3.
실시예 24Example 24
적색 유무기 복합 발광 재료로서 실시예 4에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다. An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 4.
실시예 25Example 25
적색 유무기 복합 발광 재료로서 실시예 5에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다. An LED package and a BLU were manufactured in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 5.
실시예 26Example 26
적색 유무기 복합 발광 재료로서 실시예 6에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다. An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 6.
실시예 27Example 27
적색 유무기 복합 발광 재료로서 실시예 7에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were manufactured in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 7.
실시예 28Example 28
적색 유무기 복합 발광 재료로서 실시예 8에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 8.
실시예 29Example 29
적색 유무기 복합 발광 재료로서 실시예 9에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 9.
실시예 30Example 30
적색 유무기 복합 발광 재료로서 실시예 10에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were manufactured in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 10.
실시예 31Example 31
적색 유무기 복합 발광 재료로서 실시예 11에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 11.
실시예 32Example 32
적색 유무기 복합 발광 재료로서 실시예 12에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were manufactured in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 12.
실시예 33Example 33
적색 유무기 복합 발광 재료로서 실시예 13에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were manufactured in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 13.
실시예 34Example 34
적색 유무기 복합 발광 재료로서 실시예 14에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 14.
실시예 35Example 35
적색 유무기 복합 발광 재료로서 실시예 15에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 15.
실시예 36Example 36
적색 유무기 복합 발광 재료로서 실시예 16에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 16.
실시예 37Example 37
적색 유무기 복합 발광 재료로서 실시예 17에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 17.
실시예 38Example 38
적색 유무기 복합 발광 재료로서 실시예 18에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 18.
실시예 39Example 39
적색 유무기 복합 발광 재료로서 실시예 19에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 19.
실시예 40Example 40
적색 유무기 복합 발광 재료로서 실시예 20에서 제조한 것을 사용하는 것 외에는 상기 실시예 21과 동일하게 실시하여 LED 패키지와 BLU를 제조하였다.An LED package and a BLU were prepared in the same manner as in Example 21, except that the red organic-inorganic composite light emitting material was prepared in Example 20.
비교예Comparative example
비교예 1Comparative Example 1
상업적으로 사용되고 있는 SCASN((Sr,Ca)AlSiN3:Eu2 +)형광체는 시중에서 구입하여 사용하였으며, 이의 그래프는 도 20과 같이 반치폭(FWHM)은 75 nm를 갖는다.SCASN commercially used as ((Sr, Ca) AlSiN 3 : Eu 2 +) phosphor was purchased from the market, its graph has a 75 nm full width at half maximum (FWHM) is as shown in Fig.
비교예 2Comparative Example 2
비교예 1에서 제조한 적색 발광 재료를 사용하는 것 이외에는 상기 실시예 21과 동일하게 실시하여 블루 LED 백라이트 유닛을 제조하였다. A blue LED backlight unit was manufactured in the same manner as in Example 21, except that the red light emitting material prepared in Comparative Example 1 was used.
실험예Experimental Example
실시예의 방법으로 제조된 적색 발광 재료는 도 1에 표시한 바와 같이 nearUV에서 약 614.1 nm의 적색 발광 특성을 보이며 12.4 nm 의 좁은 반치폭을 갖는다. 즉, 기존의 형광체에 비해서 좁은 반치폭과 고휘도의 LED용 적색 발광 재료임을 알 수 있다.The red luminescent material prepared by the method of the example shows a red luminescence property 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.
상기 실시예 1 내지 20과 비교예 1에서 제조한 적색 발광 재료를 기반으로 하여 디스플레이용 블루(청색) LED 장치(백라이트 유닛)를 제조한다. A blue (blue) LED device (backlight unit) for display is manufactured based on the red light emitting materials prepared in Examples 1 to 20 and Comparative Example 1.
한편, 도 2는 150 ℃에서 210 ℃ 까지 20 ℃ 간격으로 합성을 했을 경우의 스펙트럼 그래프이다. 이 도면에 의하면 150 ℃에서 210 ℃ 까지는 유사한 휘도를 갖는 반면에 210 ℃ 이상에서는 발광재료의 휘도 저하 현상이 나타나는 것을 알 수 있다.2 is a spectrum graph when it synthesize | combines by 20 degreeC interval from 150 degreeC to 210 degreeC. According to this drawing, it can be seen that the brightness of the light emitting material is lowered at 210 ° C. while the brightness is similar from 150 ° C. to 210 ° C.
도 3은 614.1 nm의 적색 발광 특성을 보이는 본 발명에 따른 적색 발광 재료, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n의 여기 스펙트럼이다. 이 도면에 의하면, 약 360~400 nm에서 강한 여기광을 갖는다는 것을 알 수 있다. 3 is a red light emitting material according to the present invention showing a red light emission characteristic of 614.1 nm, [(Y 0.5 , Eu 0.5 ) (4,4′-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] n is the excitation spectrum. According to this figure, it turns out that it has strong excitation light in about 360-400 nm.
도 4에 의하면, 피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린을 포함하는 경우 Blue(약 450 nm) 여기광원을 갖고, 약 613 nm에서 강한 적색 발광 파장을 갖는다. 즉, Blue LED용으로 사용 가능한 적색 발광 재료라는 것을 알 수 있다. According to Figure 4, in the case of containing pyrido [2 ', 3': 5,6] pyrazino [2,3-f] [1,10] phenanthroline, it has a Blue (about 450 nm) excitation light source, It has a strong red light emission wavelength at about 613 nm. That is, it can be seen that it is a red light emitting material that can be used for the Blue LED.
도 5는 613 nm의 적색 발광 특성을 갖는 적색 발광 재료, [(Y0. 5,Eu0 . 5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n의 여기 스펙트럼을 나타낸 것이다. Figure 5 is a red light emitting material having a red emission characteristics of 613 nm, [(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 shows an excitation spectrum.
도 6은 본 발명에 따른 화학식 1의 A를 이트륨 이외에 Al2(SO4)3, TiO2, Zn(NO3)2, Bi2O3, MnCO3로 변경하여 합성한 적색 발광 재료의 발광 파장 스펙트럼을 나타낸 그래프이고, 도 7은 본 발명에 따른 화학식 1의 A를 이트륨 이외에 Al2(SO4)3, TiO2, Zn(NO3)2, Bi2O3, MnCO3로 변경하여 합성한 적색 발광 재료의 EDS 그래프이며, 도 8 내지 10은 본 발명에 따른 적색 발광 재료의 단결정 이미지를 나타낸 것이다. 도 8, 도 9, 도 10 모두 [(Y0. 5,Eu0 . 5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[2,3-f][1,10]페난트롤린)]n 의 이미지이다. 6 is a light emission wavelength of a red light emitting material synthesized by changing A of Formula 1 according to the present invention to Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 , MnCO 3 in addition to yttrium Figure 7 is a graph showing the spectrum, Figure 7 synthesized by changing the A of Formula 1 according to the present invention Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 , MnCO 3 in addition to yttrium EDS graph of the red light emitting material, FIGS. 8 to 10 show a single crystal image of the red light emitting material according to the present invention. 8, 9, 10 all of [(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 .
도 20은 상업적으로 사용되고 있는 SCASN((Sr,Ca)AlSiN3:Eu2 +)형광체의 그래프로 반치폭(FWHM)은 75 nm를 갖는다.Figure 20 is SCASN commercially used as: the full width at half maximum (FWHM) in the graph of ((Sr, Ca) AlSiN 3 Eu 2 +) fluorescent material has a 75 nm.
도 21은 본 발명에 따른 LED 패키지의 스펙트럼을 표시한 것이다.Figure 21 shows the spectrum of the LED package according to the present invention.
LED 패키지는 실리콘계 수지 (OE 6630 A 와 OE 6630 B를 1:4 비율로 섞은 것)에 종래 녹색 형광체와 제조된 적색 발광 재료를 5~10 중량% 첨가한 후 이를 호모게나이저에 넣어 균질화 시켜 봉지재 조성물을 제조하였다. 중량%는 조합된 LED PKG가 color filter를 통과 하였을 경우 x, y 좌표가 (0.27, 0.24)를 만족하는 비율로 첨가 한다.LED package is added by adding 5 ~ 10% by weight of the conventional green phosphor and the prepared red light emitting material to a silicone resin (a mixture of OE 6630 A and OE 6630 B in a 1: 4 ratio), and then homogenizing it into a homogenizer and encapsulating it. Ash compositions were prepared. The weight percent is added in the ratio that x, y coordinates satisfy (0.27, 0.24) when the combined LED PKG passes the color filter.
도 22는 종래 녹색 형광체와 본 발명의 새로운 적색 발광물질을 다음 표 1과 같이 조합하여 실측치 기반 NTSC 시뮬레이션 결과를 도시한 것이다.FIG. 22 shows the actual NTSC simulation results based on the combination of the conventional green phosphor and the new red light emitting material of the present invention as shown in Table 1 below.
Figure PCTKR2017001766-appb-T000001
Figure PCTKR2017001766-appb-T000001
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 것이다.Although 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 디스플레이용 블루 LED 장치.Blue LED device for a display comprising a red organic-inorganic composite light emitting material having a composition of 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, and 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 디스플레이용 블루 LED 장치.Metal compounds include ZnO, Y 2 O 3 , La 2 O 3 , Red organic-inorganic composite light emitting, characterized in that the metal compound containing any one selected from Gd 2 O 3 , Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 or MnCO 3 Blue LED device for display comprising the material.
  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 디스플레이용 블루 LED 장치.The Eu compound is a blue LED device for a display comprising 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·xH2O 중에서 선택되는 1종이며, Eu(NO3)3·xH2O 에서 x는 1 내지 6에서 선택되는 정수인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 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 Eu (NO 3 ) 3 · xH 2 O to x Blue LED device for a display 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 디스플레이용 블루 LED 장치.L is a blue LED device for a display comprising a red organic-inorganic composite light emitting material, characterized in that it comprises one selected from the formula 2 to 8.
    [화학식 2][Formula 2]
    Figure PCTKR2017001766-appb-I000029
    Figure PCTKR2017001766-appb-I000029
    [화학식 3][Formula 3]
    Figure PCTKR2017001766-appb-I000030
    Figure PCTKR2017001766-appb-I000030
    [화학식 4][Formula 4]
    Figure PCTKR2017001766-appb-I000031
    Figure PCTKR2017001766-appb-I000031
    [화학식 5][Formula 5]
    Figure PCTKR2017001766-appb-I000032
    Figure PCTKR2017001766-appb-I000032
    [화학식 6][Formula 6]
    Figure PCTKR2017001766-appb-I000033
    Figure PCTKR2017001766-appb-I000033
    [화학식 7][Formula 7]
    Figure PCTKR2017001766-appb-I000034
    Figure PCTKR2017001766-appb-I000034
    [화학식 8][Formula 8]
    Figure PCTKR2017001766-appb-I000035
    Figure PCTKR2017001766-appb-I000035
  6. 제1항에 있어서,The method of claim 1,
    X는 하기 화학식 9 내지 12 로 표시되는 것 중에서 선택되는 1종 이상을 포함하는 것을 특징으로 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치.X is a blue LED device for a display 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 PCTKR2017001766-appb-I000036
    Figure PCTKR2017001766-appb-I000036
    [화학식 10][Formula 10]
    Figure PCTKR2017001766-appb-I000037
    Figure PCTKR2017001766-appb-I000037
    [화학식 11][Formula 11]
    Figure PCTKR2017001766-appb-I000038
    Figure PCTKR2017001766-appb-I000038
    [화학식 12][Formula 12]
    Figure PCTKR2017001766-appb-I000039
    Figure PCTKR2017001766-appb-I000039
    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; A 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, R9 는 수소(H), C1~C6 알킬기, 페닐(phenyl), n-C1~C6 알킬페닐(n-C1~C6 alkylphenyl), 디메틸페닐(dimethylphenyl), 트리메틸페닐(trimethylphenyl), 디에틸페닐(diethylphenyl), 트리에틸페닐(triethylphenyl), n-니트로페닐(n-nitrophenyl), n-아미노페닐(n-aminophenyl), n-설포닐페닐(n-sulfonylphenyl), 디설포닐페닐(disulfonylphenyl), n-C1~C6 알콕시페닐(n-C1~C6 alkoxyphenyl), 디메톡시페닐(dimethoxyphenyl), 디에톡시페닐(diethoxyphenyl), n-피리딜(n-pyridyl), 프리미딜(pyrimidyl), 퍼퓨릴(furfuryl), 나프탈레닐(naphthalenyl) 또는 피레닐(pyrenyl)이며, R10은 수소(H), C1~C6 알킬기, 페닐(phenyl) 또는 n-C1~C6 알킬페닐(n-C1~C6 alkylphenyl) 중에서 선택될 수 있고, 상기 C1~C6 알콕시는 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 디스플레이용 블루 LED 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- C 6 alkyl, phenyl, (phenyl) or nC 1 ~ C 6 alkyl phenyl (nC 1 ~ C 6 alkylphenyl) of Document may be selected, wherein the C 1 ~ C 6 alkoxy are methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy is oxy, n is an integer of any one selected from 2 to 4, o-, A blue LED device for a display comprising a red organic-inorganic composite light emitting material, characterized by m-, 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 디스플레이용 블루 LED 장치.X is a blue LED device for a display 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 PCTKR2017001766-appb-I000040
    Figure PCTKR2017001766-appb-I000040
    [화학식 14][Formula 14]
    Figure PCTKR2017001766-appb-I000041
    Figure PCTKR2017001766-appb-I000041
    [화학식 15][Formula 15]
    Figure PCTKR2017001766-appb-I000042
    Figure PCTKR2017001766-appb-I000042
    [화학식 16][Formula 16]
    Figure PCTKR2017001766-appb-I000043
    Figure PCTKR2017001766-appb-I000043
    [화학식 17][Formula 17]
    Figure PCTKR2017001766-appb-I000044
    Figure PCTKR2017001766-appb-I000044
    [화학식 18][Formula 18]
    Figure PCTKR2017001766-appb-I000045
    Figure PCTKR2017001766-appb-I000045
    [화학식 19][Formula 19]
    Figure PCTKR2017001766-appb-I000046
    Figure PCTKR2017001766-appb-I000046
    [화학식 20][Formula 20]
    Figure PCTKR2017001766-appb-I000047
    Figure PCTKR2017001766-appb-I000047
    [화학식 21][Formula 21]
    Figure PCTKR2017001766-appb-I000048
    Figure PCTKR2017001766-appb-I000048
    [화학식 22][Formula 22]
    Figure PCTKR2017001766-appb-I000049
    Figure PCTKR2017001766-appb-I000049
    [화학식 23][Formula 23]
    Figure PCTKR2017001766-appb-I000050
    Figure PCTKR2017001766-appb-I000050
    [화학식 24][Formula 24]
    Figure PCTKR2017001766-appb-I000051
    Figure PCTKR2017001766-appb-I000051
    [화학식 25][Formula 25]
    Figure PCTKR2017001766-appb-I000052
    Figure PCTKR2017001766-appb-I000052
    [화학식 26][Formula 26]
    Figure PCTKR2017001766-appb-I000053
    Figure PCTKR2017001766-appb-I000053
    [화학식 27][Formula 27]
    Figure PCTKR2017001766-appb-I000054
    Figure PCTKR2017001766-appb-I000054
  9. 제1항에 있어서,The method of claim 1,
    X는 하기 화학식 28인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치.X is a blue LED device for a display comprising a red organic-inorganic composite light emitting material, characterized in that the formula (28).
    [화학식 28][Formula 28]
    Figure PCTKR2017001766-appb-I000055
    Figure PCTKR2017001766-appb-I000055
  10. 제1항에 있어서,The method of claim 1,
    상기 화학식 1은 [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피라지노[2,3-f][1,10]페난트롤린)]n, [(Y0.5,Eu0.5)(4,4’-옥시비스(벤조산))3(피리도[2’,3’:5,6]피라지노[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]피라지노[2,3-f][1,10]페난트롤린)]n, [Eu(4,4’-옥시비스(벤조산))3(디피리도[3,2-a:2´,3´-c]페나진)]n 또는 [Eu(4,4’-옥시비스(벤조산))3(11-메톡시디피리도[3,2-a:2',3'-c]페나진)]n 중에서 선택되는 화합물인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치.Formula 1 is [(Y 0.5 , Eu 0.5 ) (4,4'-oxybis (benzoic acid)) 3 (pyrazino [2,3-f] [1,10] phenanthroline)] 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) ] 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] pyrazino [2,3-f] [1,10] phenanthroline)] n , [Eu (4,4'-oxybis (benzoic acid)) 3 (dipyrido [ 3,2- a: 2 ', 3'-c] phenazine)] n or [Eu (4,4'-oxybis (benzoic acid)) 3 (11-methoxydipyrido [3,2-a: 2', 3 ' -c] phenazine)] A blue LED device for a display, comprising a red organic-inorganic composite light emitting material, characterized in that the compound selected from n .
  11. 제1항에 있어서,The method of claim 1,
    화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료는 반치폭이 15 nm 이하인 것을 특징으로 하는 고색재현이 가능한 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치.Red organic-inorganic composite light-emitting material having a composition of Formula 1 is a blue LED device for a display comprising a red organic-inorganic composite light-emitting material capable of high color, characterized in that the half-value width is 15 nm or less.
  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 원료를 50~100ml의 용매에 넣고 균일하게 혼합하여 혼합물을 제조하는 단계;Preparing a mixture by uniformly mixing the weighed raw material in 50-100 ml of a solvent;
    혼합물을 90~210 ℃ 온도에서 합성하는 단계;를 포함하여 제조된 하기 화학식 1의 조성을 갖는 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치.Synthesis of the mixture at a temperature of 90 ~ 210 ℃; Blue LED device for a display comprising a red organic-inorganic composite light emitting material having a composition of the 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, and the sum of x1 and x2 is 0 < x 1 + x 2 ≤ 2,
    y는 2 또는 3이며, n은 1이상의 정수에서 선택되는 정수이다.y is 2 or 3, and n is an integer selected from the integer of 1 or more.
  13. 제12항에 있어서, The method of claim 12,
    0.01 내지 0.19 mol비의 1가 내지 4가 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 디스플레이용 블루 LED 장치.One or more selected from 0.01 to 0.19 mol ratio of monovalent to tetravalent 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 carboxyl A red organic-inorganic composite luminescent material comprising at least one raw material selected from aromatic compounds having at least two acid groups and at least one raw material selected from 0.01 to 0.2 mol ratio of phenanthroline and its derivatives Blue LED device for display.
  14. 제12항에 있어서,The method of claim 12,
    용매는 H2O, 프로판올, 에탄올, 메탄올, 디메틸포름아마이드(DMF, dimethylformamide), 디메틸아세트아마이드(DMA, dimethyacetamide) 인 것을 특징으로 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치.The solvent is H 2 O, propanol, ethanol, methanol, dimethylformamide (DMF, dimethylformamide), dimethylacetamide (DMA, dimethyacetamide), characterized in that the blue LED device for a display comprising a red organic-inorganic composite light emitting material.
  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 적색 발광 재료를 적용한 디스플레이용 블루 LED 장치.Metal compounds include ZnO, Y 2 O 3 , La 2 O 3 , A display using a red light-emitting material, characterized in that the metal compound containing any one selected from Gd 2 O 3 , Al 2 (SO 4 ) 3 , TiO 2 , Zn (NO 3 ) 2 , Bi 2 O 3 or MnCO 3 Blue LED device.
  16. 제12항에 있어서,The method of claim 12,
    Eu 화합물은 ZnO:Eu, Y2O3:Eu, La2O3:Eu 또는 Eu(NO3)3·xH2O 중에서 선택되는 1종이며, Eu(NO3)3·xH2O 에서 x는 1 내지 6에서 선택되는 정수인 것을 특징으로 적색 발광 재료를 적용한 디스플레이용 블루 LED 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 Eu (NO 3 ) 3 · xH 2 O to x Is an integer selected from 1 to 6, the blue LED device for a display to which the red light emitting material is applied.
  17. 제12항에 있어서,The method of claim 12,
    L은 하기 화학식 2 내지 8 중에서 선택되는 어느 하나를 포함하는 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치.L is a blue LED device for a display comprising a red organic-inorganic composite light emitting material, characterized in that it comprises any one selected from the following formula (2).
    [화학식 2][Formula 2]
    Figure PCTKR2017001766-appb-I000056
    Figure PCTKR2017001766-appb-I000056
    [화학식 3][Formula 3]
    Figure PCTKR2017001766-appb-I000057
    Figure PCTKR2017001766-appb-I000057
    [화학식 4][Formula 4]
    Figure PCTKR2017001766-appb-I000058
    Figure PCTKR2017001766-appb-I000058
    [화학식 5][Formula 5]
    Figure PCTKR2017001766-appb-I000059
    Figure PCTKR2017001766-appb-I000059
    [화학식 6][Formula 6]
    Figure PCTKR2017001766-appb-I000060
    Figure PCTKR2017001766-appb-I000060
    [화학식 7][Formula 7]
    Figure PCTKR2017001766-appb-I000061
    Figure PCTKR2017001766-appb-I000061
    [화학식 8][Formula 8]
    Figure PCTKR2017001766-appb-I000062
    Figure PCTKR2017001766-appb-I000062
  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 디스플레이용 블루 LED 장치.X is a blue LED device for a display comprising a red organic-inorganic composite light emitting material, characterized in that it comprises at least one selected from those represented by the following formulas (9) to (12).
    [화학식 9][Formula 9]
    Figure PCTKR2017001766-appb-I000063
    Figure PCTKR2017001766-appb-I000063
    [화학식 10][Formula 10]
    Figure PCTKR2017001766-appb-I000064
    Figure PCTKR2017001766-appb-I000064
    [화학식 11][Formula 11]
    Figure PCTKR2017001766-appb-I000065
    Figure PCTKR2017001766-appb-I000065
    [화학식 12][Formula 12]
    Figure PCTKR2017001766-appb-I000066
    Figure PCTKR2017001766-appb-I000066
    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; A 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, R9 는 수소(H), C1~C6 알킬기, 페닐(phenyl), n-C1~C6 알킬페닐(n-C1~C6 alkylphenyl), 디메틸페닐(dimethylphenyl), 트리메틸페닐(trimethylphenyl), 디에틸페닐(diethylphenyl), 트리에틸페닐(triethylphenyl), n-니트로페닐(n-nitrophenyl), n-아미노페닐(n-aminophenyl), n-설포닐페닐(n-sulfonylphenyl), 디설포닐페닐(disulfonylphenyl), n-C1~C6 알콕시페닐(n-C1~C6 alkoxyphenyl), 디메톡시페닐(dimethoxyphenyl), 디에톡시페닐(diethoxyphenyl), n-피리딜(n-pyridyl), 프리미딜(pyrimidyl), 퍼퓨릴(furfuryl), 나프탈레닐(naphthalenyl) 또는 피레닐(pyrenyl)이며, R10은 수소(H), C1~C6 알킬기, 페닐(phenyl) 또는 n-C1~C6 알킬페닐(n-C1~C6 alkylphenyl) 중에서 선택될 수 있고, 상기 C1~C6 알콕시는 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 디스플레이용 블루 LED 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- C 6 alkyl, phenyl, (phenyl) or nC 1 ~ C 6 alkyl phenyl (nC 1 ~ C 6 alkylphenyl) of Document may be selected, wherein the C 1 ~ C 6 alkoxy are methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy is oxy, n is an integer of any one selected from 2 to 4, o-, A blue LED device for a display comprising a red organic-inorganic composite light emitting material, characterized by m-, 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 디스플레이용 블루 LED 장치.X is a blue LED device for a display 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 PCTKR2017001766-appb-I000067
    Figure PCTKR2017001766-appb-I000067
    [화학식 14][Formula 14]
    Figure PCTKR2017001766-appb-I000068
    Figure PCTKR2017001766-appb-I000068
    [화학식 15][Formula 15]
    Figure PCTKR2017001766-appb-I000069
    Figure PCTKR2017001766-appb-I000069
    [화학식 16][Formula 16]
    Figure PCTKR2017001766-appb-I000070
    Figure PCTKR2017001766-appb-I000070
    [화학식 17][Formula 17]
    Figure PCTKR2017001766-appb-I000071
    Figure PCTKR2017001766-appb-I000071
    [화학식 18][Formula 18]
    Figure PCTKR2017001766-appb-I000072
    Figure PCTKR2017001766-appb-I000072
    [화학식 19][Formula 19]
    Figure PCTKR2017001766-appb-I000073
    Figure PCTKR2017001766-appb-I000073
    [화학식 20][Formula 20]
    Figure PCTKR2017001766-appb-I000074
    Figure PCTKR2017001766-appb-I000074
    [화학식 21][Formula 21]
    Figure PCTKR2017001766-appb-I000075
    Figure PCTKR2017001766-appb-I000075
    [화학식 22][Formula 22]
    Figure PCTKR2017001766-appb-I000076
    Figure PCTKR2017001766-appb-I000076
    [화학식 23][Formula 23]
    Figure PCTKR2017001766-appb-I000077
    Figure PCTKR2017001766-appb-I000077
    [화학식 24][Formula 24]
    Figure PCTKR2017001766-appb-I000078
    Figure PCTKR2017001766-appb-I000078
    [화학식 25][Formula 25]
    Figure PCTKR2017001766-appb-I000079
    Figure PCTKR2017001766-appb-I000079
    [화학식 26][Formula 26]
    Figure PCTKR2017001766-appb-I000080
    Figure PCTKR2017001766-appb-I000080
    [화학식 27][Formula 27]
    Figure PCTKR2017001766-appb-I000081
    Figure PCTKR2017001766-appb-I000081
  21. 제12항에 있어서,The method of claim 12,
    X는 하기 화학식 28인 것을 특징으로 하는 적색 유무기 복합 발광 재료를 포함하는 디스플레이용 블루 LED 장치.X is a blue LED device for a display comprising a red organic-inorganic composite light emitting material, characterized in that the formula (28).
    [화학식 28][Formula 28]
    Figure PCTKR2017001766-appb-I000082
    Figure PCTKR2017001766-appb-I000082
PCT/KR2017/001766 2016-02-29 2017-02-17 Blue led device for display, comprising red organic-inorganic composite light-emitting material WO2017150831A1 (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

Patent 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

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LI, W . -L. ET AL.: "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 *
LI, X. -X. ET AL.: "A New L anthanide Coordination Polymer with 4,4'-oxybis- (Benzoic Acid) Ligand: Hydrothermal Synthesis, Crystal Structure and Photoluminescence", JOURNAL OF CHEMICAL CRYSTALLOGRAPHY, vol. 41, 2011, pages 757 - 761, XP019892202 *
SHU, W. -Y. ET AL.: "Fluorescence of Complexes of Eu III with Aromatic Carboxylic Acid-1,10-phenanthroline", TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA, vol. 11, no. 5, 2001, pages 806 - 809 *
WAN, Y. ET AL.: "High-dimensional Architectures from the Self-assembly of Lanthanide Ions with Benzenedicarboxylates and 1,10-phenanthroline", INORGANIC CHEMISTRY, vol. 42, no. 16, 2003, pages 4985 - 4994, XP055412505 *

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