TW201800558A - LED photoluminescence device including red organic-inorganic composite light emitting material - Google Patents

Abstract

The present disclosure relates to an LED photoluminescence device including a red organic-inorganic composite light emitting material, and in particular, to an LED photoluminescence device including a red organic-inorganic composite light emitting material having a composition of the following Chemical Formula 1: [Chemical Formula 1] [(Ax1,Rx2)(L)y(X)]n wherein, in Chemical Formula 1, A includes one or more types of metal ions selected from the group consisting of monovalent metal ions selected from among Li, Na or K, divalent metal ions selected from among Mg, Ca, Sr, Ba or Zn, trivalent metal ions selected from among Al or La and tetravalent metal ions selected from among Zr or Ti, or metal compounds thereof, R includes one type selected from among Eu or Eu compounds, L includes one type selected from among aromatic-based compounds having at least two carboxylic acid groups, X includes one or more types selected from among phenanthroline and derivatives thereof, x1 is 0 ≤ x1 < 2, x2 is 0 < x2 ≤ 2, a sum of x1 and x2 is 0 < x1+x2 ≤ 2, y is 2 or 3, and n is an integer selected from among integers of 1 or greater.

Description

Photoluminescent diode device comprising red organic-inorganic composite luminescent material

The invention relates to a photoluminescence diode device comprising a red organic-inorganic composite luminescent material, in particular to a photoluminescence diode device, comprising a red organic-inorganic composite luminescent material as metal-organic coordination polymerization. To coordinate a metal to an organic luminescent ligand. The red organic-inorganic composite luminescent material has better stability than the existing organic luminescent compound, has better brightness than the inorganic luminescent material due to its narrower half-height width, and is applicable to ultraviolet light (UV). ) and the Blu-ray range.

A white light emitting diode (LED) technically obtained by a combination of phosphors has been widely used commercially by coating yellow and red phosphors on a blue LED wafer to fabricate a device. Get white. As for the yellow fluorescent material generally used, an oxide-based fluorescent material is usually used, and as for the red fluorescent material, a nitride-based fluorescent material is used.

Due to the increasing demand for high color rendering and high color gamut displays, the demand for corresponding luminescent materials has also increased. Existing phosphors have high reliability and high brightness, but have a wide half of the illuminating wavelength. The problem of high width and widening, and the wavelength obtained is limited.

Therefore, recent research has been devoted to deep red phosphors having a narrow half-height width and enhanced brightness, however, these phosphors are fragile to humidity and heat, and have a problem of stability during the manufacturing process.

Further, the existing organic light-emitting material is a high-brightness material in which the obtained wavelength is easily controlled, however, there is still a limit in use due to poor stability.

In view of the problems of existing organic/inorganic luminescent materials, there is a need to develop red phosphors having a narrow half-height width and capable of obtaining red wavelengths. As a result, research and attention have focused on new luminescent materials.

Korean Patent Application Publication No. 10-2014-0059982, entitled "Water Sensitive Fluorescent Material, Its Manufacturing Method, and Reversible Water Detection Sensor Containing Water Sensitive Fluorescent Material" (water sensitive phosphor, manufacturing) The method of reacting and reversible water detection sensor comprises a water sensitive phosphor, relating to a phenanthroline complex, a preparation method thereof, and a reversible water detecting sensor. The quinone-morpholine complex is a water sensitive fluorescent material and can measure trace amounts of water. The reversible water detecting sensor can use the bismuth-morpholine complex as a water-sensitive fluorescent material, and the water permeability can be repeatedly measured by measuring the change in the amount of water in the fluorescent material in the water-sensitive fluorescent material. This patent also incorporates a bismuth complex as shown below as a water sensitive fluorescent material.

Wherein X is a free methyl group (-CH ₃ ), an ethyl group (-CH ₂ CH ₃ ), an isopropyl group (-CH(CH ₃ ) ₂ ), a trifluoromethyl group (-CF ₃ ), a pentafluoroethane A group consisting of (-CF ₂ CF ₃ ) or heptafluoropropyl (-CF ₂ CF ₂ CF ₃ ).

The above patent relates to a method for producing a quinone-morpholine complex which can be used as a water sensitive fluorescent material, measurable water, and related to measuring fluorescence changes in water sensitive fluorescent materials. method. When examined in detail, this patent produces a quinone-phenanthryl compound and uses it as a fluorescent material. However, the above patent differs from the present disclosure in that the compound is manufactured for use as a water sensitive fluorescent material, and although The ruthenium-porphyrin complex itself is formed from molecular species, and the present disclosure synthesizes a coordination polymer phosphor which can be used in LEDs.

Conventional technical documents

Patent document

(Patent Document 1) Korean Patent Application Publication No. 10-2014-0059982.

The present invention is based on the necessity of researching a luminescent material for a metal-organic coordination polymer which is excited in the UV region and the blue region to emit light and has high brightness, and is directed to providing a red organic-inorganic luminescent material. The photoluminescent diode device has higher brightness than existing metal-organic coordination polymers.

The present disclosure relates to a photoluminescent diode device comprising a red organic-inorganic composite luminescent material. One embodiment of the present disclosure provides a photoluminescent diode comprising a red organic-inorganic composite luminescent material having the following chemical formula 1 composition. Device.

[Chemical Formula 1] [(A _x1 , R _x2 )(L) _y (X)] _n

x1<2，x2符合0<x2

2，x1和x2的總和符合0<x1+x2

2；以及y是2或3，n是1或1以上的任一整數。 In Chemical Formula 1, A contains a free monovalent metal ion lithium (Li), sodium (Na) or potassium (K), a divalent metal ion magnesium (Mg), calcium (Ca), strontium (Sr), strontium (Ba). Or one or more metal ions of a group consisting of zinc (Zn), a trivalent metal ion aluminum (Al) or lanthanum (La), and a tetravalent metal ion zirconium (Zr) or titanium (Ti), or a metal compound thereof R includes one selected from the group consisting of Eu (Eu) or a ruthenium compound; L contains one selected from the group consisting of aromatic compounds having at least two carboxylic acid groups; and X includes one or more selected from the group consisting of morpholine and its derivatives; X1 matches 0

X1<2, x2 matches 0<x2

2, the sum of x1 and x2 meets 0<x1+x2

2; and y is 2 or 3, and n is any integer of 1 or more.

Another embodiment of the present disclosure provides a photoluminescence diode device comprising a red organic-inorganic composite luminescent material having the following chemical formula 1 and prepared by a method comprising: Weighing the raw material, which comprises one or more selected from monovalent to tetravalent metal ions or a metal compound thereof, selected from Eu (Eu) or cerium compounds, and selected from aromatic systems having at least two carboxylic acid groups One of the compounds, and one or more selected from the group consisting of phenanthroline or a derivative thereof; the weighed raw material is placed in a solvent of 50 ml to 100 ml to prepare a mixture, and uniformly stirred; and at a temperature of 90 ° C to 210 ° C This mixture was synthesized below.

[Chemical Formula 1] [(A _x1 , R _x2 )(L) _y (X)] _n

x1<2，x2符合0<x2

2，x1和x2的總和符合0<x1+x2

2；以及y是2或3，n是1或1以上的整數。 In Chemical Formula 1, A includes a free monovalent metal ion lithium (Li), sodium (Na) or potassium (K), a divalent metal ion magnesium (Mg), calcium (Ca), strontium (Sr), strontium (Ba). Or one or more metal ions of a group consisting of zinc (Zn), a trivalent metal ion aluminum (Al) or lanthanum (La), and a tetravalent metal ion zirconium (Zr) or titanium (Ti), or a metal compound thereof R includes one selected from the group consisting of Eu (Eu) or a ruthenium compound; L includes one selected from the group consisting of aromatic compounds having at least two carboxylic acid groups; and X includes one or more selected from the group consisting of morpholine and its derivatives; X1 matches 0

X1<2, x2 matches 0<x2

2, the sum of x1 and x2 meets 0<x1+x2

2; and y is 2 or 3, and n is an integer of 1 or more.

The objects and features of the present disclosure will be apparent from the following description of the embodiments and the accompanying drawings in which: FIG. 1 shows a light-excited light (PL) spectrum and a scanning electron microscope (SEM) image according to the present disclosure; 2 shows an X-ray diffraction spectrum (XRD) according to the present disclosure; FIG. 3 shows a comparison of PL peaks according to the present disclosure; and FIG. 4 shows an installation of an ultraviolet light-emitting diode (UV LED) package according to the present disclosure. Evaluation results; Figure 5 shows the evaluation results of the installation of the blue LED package according to the present disclosure; Figure 6 shows the excitation spectrum according to the comparative embodiment of the present disclosure; and Figure 7 shows the luminescence spectrum according to the comparative embodiment of the present disclosure; Figure 8 shows the luminescence spectrum according to Example 12 of the present disclosure.

Hereinafter, the disclosure will be described in detail. However, the following examples are for illustrative purposes only, and the disclosure is not limited thereto.

The present disclosure relates to a photoluminescent diode device comprising a red organic-inorganic composite luminescent material comprising one or more of excitation sources selected from UV LEDs or blue LEDs.

Firstly, a red organic-inorganic composite luminescent material according to an embodiment of the present disclosure is used as a luminescent material of a metal-organic coordination polymer, which is excited by a UV region and a blue region of 350 nm to 450 nm. The red organic-inorganic composite luminescent material exhibits an emission wavelength of from 600 nm to 630 nm, and has a full width at half maximum of 15 nm or less and high brightness.

In detail, a photoluminescent diode comprising a red organic-inorganic composite luminescent material is a red organic-inorganic composite luminescent material based on a structure of an activator added with cerium ions (Eu ³⁺ ), and Its chemical composition is shown in the following Chemical Formula 1.

[Chemical Formula 1] [(A _x1 , R _x2 )(L) _y (X)] _n

x1<2，x2符合0<x2

2，x1和x2的總和符合0<x1+x2

2；y是2或3，n是1或1以上的整數。 In Chemical Formula 1, A contains a free monovalent metal ion lithium (Li), sodium (Na) or potassium (K), a divalent metal ion magnesium (Mg), calcium (Ca), strontium (Sr), strontium (Ba). Or one or more metal ions of a group consisting of zinc (Zn), a trivalent metal ion aluminum (Al) or lanthanum (La), and a tetravalent metal ion zirconium (Zr) or titanium (Ti), or a metal compound thereof ; R comprises one selected from the group consisting of Eu (Eu) or a ruthenium compound; L comprises one selected from the group consisting of aromatic compounds having at least two carboxylic acid groups; X comprises one or more selected from the group consisting of morpholine and its derivatives; X1 matches 0

X1<2, x2 matches 0<x2

2, the sum of x1 and x2 meets 0<x1+x2

2; y is 2 or 3, and n is an integer of 1 or more.

When x1, x2 or y is outside the above numerical range, the synthesis does not proceed normally, and even the luminescence and luminance properties are not good.

As an example of the metal compound of Chemical Formula 1, zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), lanthanum oxide (La ₂ O ₃ ), yttrium oxide (Gd ₂ O ₃ ), aluminum sulfate (Al _{2 ) may be used.} (SO ₄ ) ₃ ), a metal compound in titanium oxide (TiO ₂ ), zinc nitrate (Zn(NO ₃ ) ₂ ), bismuth oxide (Bi ₂ O ₃ ) or manganese carbonate (MnCO ₃ ). However, the scope of the disclosure is not limited to the above examples.

As the ruthenium (Eu) compound which can be used as R in Chemical Formula 1, ruthenium and one or more metal ions and oxides, or a metal oxide containing ruthenium can be used.

Specific examples of the cerium compound may include cerium-doped zinc oxide (ZnO: Eu), cerium-doped cerium oxide (Y ₂ O ₃ :Eu), cerium-doped cerium oxide (La ₂ O ₃ :Eu) or cerium nitrate hydrate. One of (Eu(NO ₃ ) ₃ .xH ₂ O), and Eu(NO ₃ ) ₃ . xH ₂ O where x is an integer of from 1 to select 6.

When a ruthenium or osmium compound is used, a 铕 characteristic peak can be obtained, which when used for a light-emitting diode, has a red color and a narrow full width at half maximum, and has high color reproduction.

The L in Chemical Formula 1 is one selected from the aromatic compounds having at least two carboxylic acid groups, and examples thereof may include the following Chemical Formulas 2 to 8. However, the disclosure is not limited to the following examples.

Regarding X in Chemical Formula 1, one or more selected from the group consisting of morpholine and a derivative thereof, and examples thereof include the compounds represented by the following Chemical Formulas 9 to 12. However, the scope of the disclosure is not limited to the following examples.

R ₁ to R _{10 are} each independently hydrogen, deuterium, halogen, cyano, nitro, amine, substituted or unsubstituted C _1-60 alkyl, C _1-60 haloalkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _1-60 haloalkoxy, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or not Substituted C _6-60 aryl, substituted or unsubstituted C _6-60 aryloxy, or substituted or unsubstituted C _1-60 heterocyclic group including one or more of N, O and S, Q is N or CH.

With respect to still further specific examples of R ₁ to R ₁₀ , R ₁ is hydrogen (H), cyano (-CN) or methyl (CH ₃ ), and R ₂ to R _{7 are} each independently hydrogen (H), Amino (-NH ₂ ), methyl (CH ₃ ) or phenyl, R ₈ is hydrogen (H) or methoxy (-OCH ₃ ), R ₉ is hydrogen (H), C ₁ -C ₆ alkyl , phenyl, nC ₁ -C ₆ alkylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, triethylphenyl, n-nitrophenyl, n-aminobenzene , n-sulfonylphenyl, disulfonylphenyl, nC ₁ -C ₆ alkoxyphenyl, dimethoxyphenyl, diethoxyphenyl, n-pyridyl, pyridyl, Pyrimidyl, furfuryl, naphthyl or pyrenyl, and R ₁₀ is selected from hydrogen (H), C ₁ -C ₆ alkyl, phenyl or nC ₁ -C ₆ alkyl Phenyl.

C ₁ -C ₆ alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyloxy, and n is an integer selected from 2 to 4 and represents o--( O-), m-(m-) and p-(p-).

With regard to further specific examples of the morpholine and its derivatives which can be used in the present disclosure, one or more compounds selected from the following Chemical Formulas 13 to 28 can be used.

The use of such phenanthroline and its derivatives can effectively increase the brightness compared to the absence of phenanthroline and its derivatives.

x1<2，x2較佳為0<x2

2，x1和x2的總和較佳為0<x1+x2

2。而且，相較於只包含A_x1，包含所有A_x1和R_x2之組成或是只包含R_x2的組成具有增強的亮度，並且由於使用較少稀土金屬而具有單元費用降低的優點，且只使用A_x1無法得到發光性質。 In the chemical formula 1, A _x1 and R _x2 , x1 is preferably 0.

X1<2, x2 is preferably 0<x2

2, the sum of x1 and x2 is preferably 0<x1+x2

2. Moreover, the composition containing all of the composition of A _x1 and R _x2 or the composition containing only R _x2 has enhanced brightness compared to only containing A _x1 , and has the advantage of lowering the unit cost due to the use of less rare earth metal, and is only used. A _x1 cannot obtain luminescent properties.

並(pyrazino)[2,3-f][1,10]啡啉)]_n、[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡啶並(pyrido)[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)]_n、[(Al_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡

並[2,3-f][1,10]啡啉)]_n、[(Ti_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡

並[2,3-f][1,10]啡啉)]_n、[(Zn_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡

並[2,3-f][1,10]啡啉)]_n、[(Bi_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡

並[2,3-f][1,10]啡啉)]_n、[(Mn_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡

並[2,3-f][1,10]啡啉)]_n、[(Y₂O₃：Eu)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)]_n、[(La₂O₃：Eu)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)]_n、[(Gd₂O₃：Eu)(4,4’-氧基雙(苯甲酸))₃(吡啶[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)]_n、[(La₂O₃：Eu)(對苯二甲酸)₃(吡

並[2,3-f][1,10]-啡啉-2,3-二腈)]_n、[(Y₂O₃：Eu)(4,4’-氧基雙(苯甲酸))₃(四吡啶並[3,2-a：2’,3’-c：3”,2”-h：2”’,3”-j]啡

(phenazine))]_n、[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)_0.5(1,10-啡啉)_0.5]_n、[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)_0.5(吡

並[2,3-f][1,10]啡啉)_0.5]_n、[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)_0.5(3-甲基吡

並[2,3-f][1,10]啡啉)_0.5]_n、[Eu(1,3,5-三(4-羧基苯基)苯)₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)]_n、[Eu(4,4’-氧基雙(苯甲酸))₃(二吡啶並[3,2-a：2’,3’-c]啡

]_n或[Eu(4,4’-氧基雙(苯甲 酸)₃(11-甲氧基二吡啶並[3,2-a：2’,3’-c]啡

)]_n。 Preferred examples of the red organic-inorganic composite luminescent material according to Chemical Formula 1 in the photoluminescent diode device of the present disclosure may include [(Y _0.5 , Eu _0.5 ) (4,4'-oxybis(benzoic acid) )) ₃ (Pyr

And (pyrazino)[2,3-f][1,10]morpholine)] _n ,[(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyrido (pyrido) )[2',3':5,6]Py

And [2,3-f][1,10]morpholine)] _n , [(Al _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl)

And [2,3-f][1,10]morpholine)] _n , [(Ti _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl)

And [2,3-f][1,10]morpholine)] _n ,[(Zn _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl)

And [2,3-f][1,10]morpholine)] _n , [(Bi _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl)

And [2,3-f][1,10]morpholine)] _n ,[(Mn _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl)

And [2,3-f][1,10]morpholine)] _n , [(Y ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyridine[2', 3':5,6]pyridyl

And [2,3-f][1,10]morpholine)] _n , [(La ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyrido[2', 3':5,6]pyridyl

And [2,3-f][1,10]morpholine)] _n ,[(Gd ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyridine [2',3 ':5,6]Py

And [2,3-f][1,10]morpholine)] _n ,[(La ₂ O ₃ :Eu)(terephthalic acid) ₃ (pyridyl)

And [2,3-f][1,10]-morpholin-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]morphine

(phenazine))] _n , [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyrido[2',3':5,6]pyrr

And [2,3-f][1,10]morpholine) _0.5 (1,10-morpholine) _0.5 ] _n , [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid) ) ₃ (pyrido[2',3':5,6]pyridin

And [2,3-f][1,10]morpholine) _0.5 (pyridyl)

And [2,3-f][1,10]morpholine) _0.5 ] _n , [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyrido[2', 3':5,6]pyridyl

And [2,3-f][1,10]morpholine) _0.5 (3-methylpyridyl)

And [2,3-f][1,10]morpholine) _0.5 ] _n ,[Eu(1,3,5-tris(4-carboxyphenyl)benzene) ₃ (pyrido[2',3': 5,6]pyridyl

And [2,3-f][1,10]morpholine)] _n , [Eu(4,4'-oxybis(benzoic acid)) ₃ (dipyrido[3,2-a:2', 3'-c] brown

_n or [Eu(4,4'-oxybis(benzoic acid) ₃ (11-methoxydipyrido[3,2-a:2',3'-c] brown

)] _n .

According to another embodiment of the present disclosure, a photoluminescence diode device comprising a red organic-inorganic composite luminescent material having the following chemical formula 1 is prepared by the following steps: weighing a unit price of 0.01 mol to 0.19 mol a material selected from one or more of a tetravalent metal ion or a metal compound thereof, a ratio of 0.1 mol to 0.19 mol, selected from Eu (Eu) or a bismuth compound, and a ratio of 0.01 mol to 0.6 mol. The above-mentioned weighed raw material is placed from one of an aromatic compound having at least two carboxylic acid groups, and a raw material selected from one or more of phenanthroline or a derivative thereof in a ratio of 0.01 mol to 0.2 mol. 50 ml to 100 ml of solvent and uniformly stirred to prepare a mixture such as water, propanol, ethanol, methanol, dimethylformamide (DMF) or dimethylacetamide (DMA), and at temperature This mixture is synthesized at 90 ° C to 210 ° C: [Chemical Formula 1] [(A _x1 , R _x2 )(L) _y (X)] _n

x1<2，x2符合0<x2

2，以及x1和x2的總和符合0<x1+x2

2，y是2或3，n是擇自1或1以上的整數。 In Chemical Formula 1, A includes a free monovalent metal ion lithium (Li), sodium (Na) or potassium (K), a divalent metal ion magnesium (Mg), calcium (Ca), strontium (Sr), strontium (Ba). Or one or more metal ions of a group consisting of zinc (Zn), a trivalent metal ion aluminum (Al) or lanthanum (La), and a tetravalent metal ion zirconium (Zr) or titanium (Ti), or a metal compound thereof R includes one selected from the group consisting of ruthenium or osmium compounds, and L includes one selected from the group consisting of aromatic compounds having at least two carboxylic acid groups, and X includes one or more selected from the group consisting of morpholine and its derivatives, and x1 is in accordance with 0.

X1<2, x2 matches 0<x2

2, and the sum of x1 and x2 meets 0<x1+x2

2, y is 2 or 3, and n is an integer selected from 1 or more.

When a single crystal image is detected, an aromatic compound having at least two carboxylic acid groups can be coordinated to three times for one metal, and the morphine and its derivatives are coordinated in the same ratio. When a higher ratio is introduced, crystallinity is affected, and as a result, the luminescent material cannot be synthesized.

Further, when each material has a value outside the above numerical range, the synthesis does not proceed normally, or the brightness of the material is poor when synthesized, and it is not economical due to the generation of unreacted materials.

The weighed raw materials are mixed in a solvent, and the mixture is synthesized at a temperature of from 90 ° C to 210 ° C. When synthesized at a temperature below 90 ° C, a red organic-inorganic composite luminescent material is not formed, and when the temperature is higher than 210 ° C, the luminance of the red organic-inorganic composite luminescent material is reduced.

This preparation method can be represented by the following chemical reaction formula 1.

[Chemical Reaction Formula 1] A, R+L+X->[(A _x1 , R _x2 )(L) _y (X)] _n

A: one or more selected from a monovalent to a tetravalent metal ion or a metal compound thereof

R: a type of compound selected from hydrazine or hydrazine

L: one of aromatic compounds having at least two carboxylic acid groups

X: one or more selected from the group consisting of phenanthroline and its derivatives.

Such as the reaction chemical formula 1, the red organic-inorganic composite hair of the present disclosure The photonic material is doped with a metal cation on Part A, and, unlike the existing metal-organic framework, which is doped only on R, promotes electron transport effects and architectural crystallinity, making it useful when used in LEDs and the like. There are advantages of improved luminescent properties.

The red organic-inorganic composite luminescent material having the chemical formula 1 prepared by the above method exhibits red luminescent material properties of 600 nm to 630 nm illuminating wavelength for excitation light in the UV and blue light regions, and is comparable to existing fluorescent light. Phosphors having a narrow half-height width of 15 nm or less and high brightness.

Thus, the availability of red organic-inorganic composite luminescent materials in photoluminescent diode devices can be identified by using UV or blue LED wafers to detect the luminescent properties of red organic-inorganic composite luminescent materials.

Hereinafter, the present disclosure will be described in detail with reference to the embodiments and comparative examples.

Example

Example 1

[2,3-f][1,10]啡啉(化學式13)，將稱重的原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃之下將混合物合成以製備金屬-有機配位聚合物[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡

[2,3-f][1,10]啡啉)]_n之發光材料。 Weigh 0.1 mol of Y(NO ₃ ) ₃ . 6H ₂ O compound, 0.1 mol ratio of Eu(NO ₃ ) ₃ . 5H ₂ O compound, 0.2 molar ratio of 4,4'-oxybis(benzoic acid) and 0.2 molar ratio of pyridyl

[2,3-f][1,10]morpholine (Formula 13), the weighed material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl)

[2,3-f] [1,10] phenanthroline)] _n of the luminescent material.

Mix 5wt% of luminescent material and silicone package (silicone) Encapsulant (Dow Corning Corporation OE6630A, OE6630B), a mixture of 4.5 mg to 5.0 mg was coated on a 5630 UV LED wafer, and the resultant was cured at 150 ° C for about 2 hours to prepare an LED package.

Example 2

並[2,3-f][1,10]啡啉)]_n之發光材料。 A metal-organic coordination polymer [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl) was prepared in the same manner as in Example 1.

And [2,3-f] [1,10] phenanthroline)] _n of the luminescent material.

A 10 wt% luminescent material and a silicone encapsulant (Dow Corning Corporation OE6630A, OE 6630B) were mixed, and a mixture of 4.5 mg to 5.0 mg was coated on a 5630 UV LED wafer, and the resultant was cured at 150 ° C. In an hour, an LED package is produced.

Example 3

並[2,3-f][1,10]啡啉(化學式17)，將稱重的原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃之下將混合物合成而製備金屬-有機配位聚合物[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)]_n之發光材料。 Weigh 0.1 mol of Y(NO ₃ ) ₃ . 6H ₂ O compound, 0.1 mol ratio of Eu(NO ₃ ) ₃ . 5H ₂ O compound, 0.2 molar ratio of 4,4'-oxybis(benzoic acid) and 0.2 molar ratio of pyrido[2',3':5,6]pyridinium

And [2,3-f][1,10] phenanthroline (Chemical Formula 17), the weighed raw material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridine). And [2', 3': 5, 6]

And [2,3-f] [1,10] phenanthroline)] _n of the luminescent material.

A 10 wt% luminescent material and a silicone encapsulant (Dow Corning Corporation OE6630A, OE 6630B) were mixed, and a mixture of 4.5 mg to 5.0 mg was coated on a 5630 UV LED wafer, and the resultant was cured at 150 ° C. In an hour, an LED package is produced.

Example 4

並[2,3-f][1,10]啡啉(化學式17)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[(Y₂O₃：Eu)(4,4’-氧基雙(苯甲酸))₃(吡啶[2’,3’：5,6]吡

[2,3-f][1,10]啡啉)]_n之有機-無機複合發光材料。 Weighing 0.1 molar ratio of Y ₂ O ₃ :Eu ³⁺ compound, 0.2 molar ratio of 4,4′-oxybis(benzoic acid) and 0.2 molar ratio of pyrido[2′,3′:5 ,6]Pyr

And [2,3-f][1,10] phenanthroline (Chemical Formula 17), the weighed material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(Y ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyridine). [2',3':5,6]Py

An organic-inorganic composite luminescent material of [2,3-f][1,10]morpholine)] _n .

A blue LED package was prepared in the same manner as in Example 3 except that the obtained red luminescent material was used.

Example 5

並[2,3-f][1,10]啡啉(化學式17)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[(La₂O₃：Eu)(4,4’-氧基雙(苯甲酸))₃(吡啶[2’,3’：5,6]吡

[2,3-f][1,10]啡啉)]_n之有機-無機複合發光材料。 Weighing 0.1 molar ratio of La ₂ O ₃ :Eu ³⁺ compound, 0.2 molar ratio of 4,4′-oxybis(benzoic acid) and 0.2 molar ratio of pyrido[2′,3′:5 ,6]Pyr

And [2,3-f][1,10] phenanthroline (Chemical Formula 17), the weighed material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(La ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyridine). [2',3':5,6]Py

An organic-inorganic composite luminescent material of [2,3-f][1,10]morpholine)] _n .

A blue LED package was prepared in the same manner as in Example 3 except that the obtained red luminescent material was used.

Example 6

並[2,3-f][1,10]啡啉(化學式17)，將稱重之原料 置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[(Gd₂O₃：Eu)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)]_n之有機-無機複合發光材料。 Weighing 0.1 molar ratio of Gd ₂ O ₃ :Eu ³⁺ compound, 0.2 molar ratio of 4,4′-oxybis(benzoic acid) and 0.2 molar ratio of pyrido[2′,3′:5 ,6]Pyr

And [2,3-f][1,10] phenanthroline (Chemical Formula 17), the weighed material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(Gd ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyridine). And [2', 3': 5, 6]

And an organic-inorganic composite luminescent material of [2,3-f][1,10]morpholine)] _n .

A blue LED package was prepared in the same manner as in Example 3 except that the obtained red luminescent material was used.

Example 7

並[2,3-f][1,10]-啡啉-2,3-二腈(化學式14)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[(La₂O₃：Eu)(對苯二甲酸)₃(吡

並[2,3-f][1,10]-啡啉-2,3-二腈]_n之有機-無機複合發光材料。 Weighing a 0.1 molar ratio of La ₂ O ₃ :Eu ³⁺ compound, 0.2 molar ratio of terephthalic acid (chemical formula 5), and a molar ratio of 0.2 mol

And [2,3-f][1,10]-phenanthroline-2,3-dicarbonitrile (chemical formula 14), and the weighed raw material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(La ₂ O ₃ :Eu)(terephthalic acid) ₃ (pyridyl)

And an organic-inorganic composite luminescent material of [2,3-f][1,10]-morpholine-2,3-dicarbonitrile] _n .

A blue LED package was prepared in the same manner as in Example 2 except that the obtained red luminescent material was used.

Example 8

(化學式28)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[(Y₂O₃：Eu)(4,4’氧基雙(苯甲酸))₃(四吡啶並[3,2-a：2’,3’-c：3”,2”-h：2”’,3”-j]啡

)]_n.之有機-無機複合發光材料。 Weighing 0.1 molar ratio of Y ₂ O ₃ :Eu compound, 0.2 molar ratio of 4,4′-oxybis(benzoic acid) and 0.2 molar ratio of tetrapyrido[3,2-a:2' , 3'-c: 3", 2"-h: 2"', 3"-j] brown

(Chemical Formula 28), the weighed material was placed in 50 ml of water. After uniformly stirring the resultant, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(Y ₂ O ₃ :Eu)(4,4'oxybis(benzoic acid)) ₃ (tetrapyridine) And [3,2-a:2',3'-c:3",2"-h:2"',3"-j]morphine

.)] Of the _n-organic - inorganic composite luminescent material.

A blue LED package was prepared in the same manner as in Example 2 except The resulting red luminescent material was used.

Example 9

並[2,3-f][1,10]啡啉(化學式17)以及0.1莫耳比例的1,10-啡啉(化學式16)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)_0.5(1,10-啡啉)_0.5]_n之有機-無機複合發光材料。 Weigh 0.1 mol of Y(NO ₃ ) ₃ . 6H ₂ O compound, 0.1 mol ratio of Eu(NO ₃ ) ₃ . 5H ₂ O compound, 0.2 molar ratio of 4,4'-oxybis(benzoic acid), 0.1 molar ratio of pyrido[2',3':5,6]pyridinium

And [2,3-f][1,10]morpholine (chemical formula 17) and 0.1 mol% of 1,10-morpholine (chemical formula 16), and the weighed raw materials were placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridine [2',3':5,6]Py

An organic-inorganic composite luminescent material of [2,3-f][1,10]morpholine) _0.5 (1,10-morpholine) _0.5 ] _n .

A blue LED package was prepared in the same manner as in Example 3 except that the obtained red luminescent material was used.

Example 10

並[2,3-f][1,10]啡啉(化學式17)以及0.1莫耳比例的吡

並[2,3-f][1,10]啡啉(化學式13)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成以製備金屬-有機配位聚合物[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)_0.5(吡嗪並[2,3-f][1,10]啡啉)_0.5]_n.之有機-無機複合發光材料。 Weigh 0.1 mol of Y(NO ₃ ) ₃ . 6H ₂ O compound, 0.1 mol ratio of Eu(NO ₃ ) ₃ . 5H ₂ O compound, 0.2 molar ratio of 4,4'-oxybis(benzoic acid), 0.1 molar ratio of pyrido[2',3':5,6]pyridinium

And [2,3-f][1,10] phenanthroline (chemical formula 17) and a molar ratio of 0.1 mol

And [2,3-f][1,10] phenanthroline (Chemical Formula 13), and the weighed raw material was placed in 50 ml of water. After uniformly stirring the resultant, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridine [2',3':5,6]Py

An organic-inorganic composite luminescent material of [2,3-f][1,10]morpholine) _0.5 (pyrazino[2,3-f][1,10]morpholine) _0.5 ] _n .

A blue LED package was prepared in the same manner as in Example 3 except The resulting red luminescent material was used.

Example 11

並[2,3-f][1,10]啡啉(化學式17)以及0.1莫耳比例的3-甲基吡

並[2,3-f][1,10]啡啉(化學式15)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[(Y_0.5,Eu_0.5)(4,4’-氧基雙(苯甲酸))₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)_0.5(3-甲基吡

並[2,3-f][1,10]啡啉)_0.5]_n.之有機-無機複合發光材料。 Weigh 0.1 mol of Y(NO ₃ ) ₃ . 6H ₂ O compound, 0.1 mol ratio of Eu(NO ₃ ) ₃ . 5H ₂ O compound, 0.2 molar ratio of 4,4'-oxybis(benzoic acid), 0.1 molar ratio of pyrido[2',3':5,6]pyridinium

And [2,3-f][1,10] phenanthroline (chemical formula 17) and 3-methylpyrene in a 0.1 molar ratio

And [2,3-f][1,10] phenanthroline (Chemical Formula 15), the weighed material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridine [2',3':5,6]Py

And [2,3-f][1,10]morpholine) _0.5 (3-methylpyridyl)

An organic-inorganic composite luminescent material of [2,3-f][1,10]morpholine) _0.5 ] _n .

A blue LED package was prepared in the same manner as in Example 3 except that the obtained red luminescent material was used.

Example 12

並[2,3-f][1,10]啡啉(化學式17)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[Eu(1,3,5-三(4-羧基苯基)苯)₃(吡啶並[2’,3’：5,6]吡

並[2,3-f][1,10]啡啉)]_n.之有機-無機複合發光材料。 Weigh 0.1 mol of Eu(NO ₃ ) ₃ . 5H ₂ O compound, 0.2 molar ratio of 1,3,5-tris(4-carboxyphenyl)benzene, and 0.2 molar ratio of pyrido[2',3':5,6]pyridinium

And [2,3-f][1,10] phenanthroline (Chemical Formula 17), the weighed material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [Eu(1,3,5-tris(4-carboxyphenyl)benzene) ₃ (pyridine[2' , 3':5,6]Py

. And [2,3-f] [1,10] phenanthroline)] _n of organic - inorganic composite luminescent material.

A blue LED package was prepared in the same manner as in Example 3 except that the obtained red luminescent material was used.

Example 13

(化學式18)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[Eu(4,4’-氧基雙(苯甲酸))₃(二吡啶並[3,2-a：2’,3’-c]啡

)]_n.之有機-無機複合發光材料。 Weigh 0.1 mol of Eu(NO ₃ ) ₃ . 5H ₃ O compound, 0.2 molar ratio of 4,4'-oxybis(benzoic acid) and 0.2 molar ratio of dipyrido[3,2-a:2',3'-c]morphine

(Chemical Formula 18), the weighed material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [Eu(4,4'-oxybis(benzoic acid)) ₃ (dipyrido[3,2- a: 2', 3'-c] brown

.)] Of the _n-organic - inorganic composite luminescent material.

A blue LED package was prepared in the same manner as in Example 3 except that the obtained red luminescent material was used.

Example 14

(化學式19)，將稱重之原料置於50毫升水中。將所得物均勻攪拌後，在溫度150℃下將混合物合成而製備金屬-有機配位聚合物[Eu(4,4’-氧基雙(苯甲酸))₃(11-甲氧基二吡啶並[3,2-a：2’,3’-c]啡

)]_n.之有機-無機複合發光材料。 Weigh 0.1 mol of Eu(NO ₃ ) ₃ . 5H ₂ O compound, 0.2 molar ratio of 4,4'-oxybis(benzoic acid) and 0.2 molar ratio of 11-methoxydipyrido[3,2-a:2',3'-c ]coffee

(Chemical Formula 19), the weighed material was placed in 50 ml of water. After the resultant was uniformly stirred, the mixture was synthesized at a temperature of 150 ° C to prepare a metal-organic coordination polymer [Eu(4,4'-oxybis(benzoic acid)) ₃ (11-methoxydipyridine). [3,2-a:2',3'-c]morphine

.)] Of the _n-organic - inorganic composite luminescent material.

A blue LED package was prepared in the same manner as in Example 3 except that the obtained red luminescent material was used.

Comparative example

Comparative Example 1

Weigh 0.1 mol of Y(NO ₃ ) ₃ . 6H ₂ O compound, 0.1 mol ratio of Eu(NO ₃ ) ₃ . a 5H ₂ O compound, a 0.1 molar ratio of cerium (III) nitrate pentahydrate, a 0.2 molar ratio of 3,5-pyridinedicarboxylic acid, and a 0.2 molar ratio of morphine, placing the weighed material in 50 In milliliters of water. After uniformly stirring the resultant, the mixture was synthesized at a temperature of 150 ° C to obtain a metal-organic coordination polymer [(Y _0.5 Eu _0.5 )(morpholine)(3,5-dicarboxylic acid) ₂ 2 (H ₂ O )] _n luminescent material.

A 10 wt% luminescent material and a silicone encapsulant (Dow Corning Corporation OE6630A, OE6630B) were mixed, and a mixture of 4.5 mg to 5.0 mg was coated on a 5630 blue LED wafer, and the resultant was cured at 150 ° C for about 2 hours. LED package.

Comparative Example 2

In the same manner as in Comparative Example 1, a luminescent material of a metal-organic coordination polymer [(Y _0.5 Eu _0.5 )(morpholine)(2,4-dicarboxylic acid) ₂ 2(H ₂ O)] _{n was obtained} . In addition to using a 0.2 molar ratio of 2,4-pyridinedicarboxylic acid.

A 10 wt% luminescent material and a silicone encapsulant (Dow Corning Corporation OE6630A, OE6630B) were mixed, and a mixture of 4.5 mg to 5.0 mg was coated on a 5630 blue LED wafer, and the resultant was cured at 150 ° C for about 2 hours. LED package.

Comparative Example 3

In the same manner as in Comparative Example 1, a metal-organic coordination polymer [(Y _0.5 Eu _0.5 )(morpholine) (1,3,5-tris(4-carboxyphenyl)benzene) ₂ 2 (H) was obtained. ₂ O)] _n luminescent material, except that a 0.2 molar ratio of 1,3,5-tris(4-carboxyphenyl)benzene was used.

A 10 wt% luminescent material and a silicone encapsulant (Dow Corning Corporation OE6630A, OE6630B) were mixed, and a mixture of 4.5 mg to 5.0 mg was coated on a 5630 blue LED wafer, and the resultant was cured at 150 ° C for about 2 hours. LED package.

Test example

When the evaluation of the mounting of the organic-inorganic composite luminescent material of the metal-organic coordination polymer prepared according to the present disclosure examples 1 to 3 was carried out using a UV or blue LED wafer, and according to Comparative Examples 1 to 3, Metal-organic coordination polymer [(Y _0.5 ,Eu _0.5 ) phenanthroline (phen)(3,5-pyridinedicarboxylic acid) ₂ (H ₂ O) ₂ ] _n ,[(Y _0.5 ,Eu _0.5 ) Phenol (phen) (2,4-pyridinedicarboxylic acid) ₂ (H ₂ O) ₂ ] _n , [(Y _0.5 ,Eu _0.5 ) phenanthroline (phen) (1,3,5-tris(4-carboxybenzene) The phenyl) ₂ (H ₂ O) ₂ ] _n is different, and the luminescent material of the metal-organic coordination polymer is excited in the UV region and the 450 nm blue region, and thus can be used as an LED luminescent material. .

As shown in Fig. 1, the metal-organic coordination polymer obtained by the method of Example 1 exhibited red luminescent properties at a near UV of about 614.1 nm and had a narrow full width at half maximum of 12.4 nm. In other words, it can be seen that the luminescent material of the present disclosure is a red luminescent material for LEDs having a narrower half-height width and a higher brightness than existing phosphor materials. Fig. 2 is a graph showing the XRD pattern according to Example 1, and it can be seen that this material has crystallinity. Figure 3 is a view showing the PL spectrum of the luminescent material, the existing phosphors CaAlSiN ₃ :Eu ²⁺ and K ₂ SiF ₆ :Mn ⁴⁺ according to the embodiment 1 of the present disclosure, and the present disclosure is compared with the existing phosphor material. The luminescent material has a narrow full width at half maximum and good light intensity in the UV region. Figure 4 shows the pattern and spectrum of the package (PKG) mounting evaluation using the 400 UV wafers according to the disclosed embodiments 1 and 2, and Figure 5 shows the pattern of the PKG mounting evaluation using the 450 UV wafer according to the embodiment 3 of the present disclosure. And spectrum. Fig. 6 shows the excitation spectrum of the comparative example, and Fig. 7 shows the luminescence spectrum of the comparative example.

The metal-organic coordination polymer of the comparative example is not excited at approximately 400 nm and 450 nm, and therefore cannot be used for UV of 400 nm. LED or 450 nm blue LED photoluminescent device.

Compared with the existing metal-organic coordination polymer luminescent material, the red organic-inorganic composite luminescent material included in the photoluminescent diode device has higher brightness and can be in the UV and blue regions. excitation. This is quite effective as a luminescent material for LEDs because the color reproduction range is wide, the half-height width is narrow and 15 nm or less, and the material can be excited in the blue region as well as the UV region.

As described above, the present disclosure has been described with reference to the embodiments. However, it is understood that those skilled in the art can modify and change the disclosure within the scope of the technical concept of the disclosure disclosed in the appended claims.

Claims (21)

A photoluminescence diode device comprising a red organic-inorganic composite luminescent material, the luminescent material having the following chemical formula 1: [Chemical Formula 1] [(A _x1 , R _x2 )(L) _y (X)] _n In Chemical Formula 1, A includes a free monovalent metal ion Li, Na or K, a divalent metal ion Mg, Ca, Sr, Ba or Zn, a trivalent metal ion Al or La, and a tetravalent metal ion Zr or Ti. One or more metal ions of the constituent group, or a metal compound 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 One or more of automorphic morpholine and its derivatives; x1 is in accordance with 0 X1<2, x2 matches 0<x2 2, the sum of x1 and x2 meets 0<x1+x2 2; and y is 2 or 3, and n is an integer selected from 1 or more. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 1, wherein the metal compound comprises ZnO, Y ₂ O ₃ , La ₂ O ₃ , Gd ₂ O _3. Any metal compound of Al ₂ (SO ₄ ) ₃ , TiO ₂ , Zn(NO ₃ ) ₂ , Bi ₂ O ₃ or MnCO ₃ . A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 1, wherein the Eu compound is Eu and one or more of metal ions and oxides, or a metal compound including Eu . A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 3, wherein the Eu compound is selected from the group consisting of ZnO:Eu, Y ₂ O ₃ :Eu, La ₂ O ₃ : Eu or Eu(NO ₃ ) ₃ . One of xH ₂ O, and Eu(NO ₃ ) ₃ . x in xH ₂ O is an integer selected from 1 to 6. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 1, wherein L comprises at least one selected from the following Chemical Formulas 2 to 8: A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 1, wherein X comprises one or more selected from the following Chemical Formulas 9 to 12: Wherein R ₁ to R _{10 are} each independently hydrogen, deuterium, halogen, cyano, nitro, amine, substituted or unsubstituted C _1-60 alkyl, C _1-60 haloalkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _1-60 haloalkoxy, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or Unsubstituted C _6-60 aryl, substituted or unsubstituted C _6-60 aryloxy, or substituted or unsubstituted C _1-60 heterocyclic group including one or more of N, O and S, Q Is N or CH. A photoluminescent diode device comprising a red organic-inorganic composite luminescent material according to claim 6 wherein R ₁ is hydrogen (H), cyano (-CN) or methyl (CH ₃ ), R ₂ to R _{7 are} each independently hydrogen (H), amine (-NH ₂ ), methyl (CH ₃ ) or phenyl, and R ₈ is hydrogen (H) or methoxy (-OCH ₃ ), R ₉ is hydrogen (H), C ₁ -C ₆ alkyl, phenyl, nC ₁ -C ₆ alkylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, triethyl Phenyl, n-nitrophenyl, n-aminophenyl, n-sulfonylphenyl, disulfophenyl, nC ₁ -C ₆ alkoxyphenyl, dimethoxyphenyl, Diethoxyphenyl, n-pyridyl, pyrimidinyl, fluorenyl, naphthyl or anthracenyl, and R ₁₀ is selected from hydrogen (H), C ₁ -C ₆ alkyl, phenyl or nC ₁ -C _{a 6} alkylphenyl group, the C ₁ -C ₆ alkoxy group being a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or a hexyloxy group, and n being selected from 2 to 4 An integer and represents o-, m-, and p-. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 6 wherein X is one or more selected from the following chemical formulas 13 to 27: A photoluminescence diode device comprising a red organic-inorganic complex luminescent material according to claim 1, wherein X is the following chemical formula 28: A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 1, wherein the chemical formula 1 is selected from [(Y _0.5 , Eu _0.5 ) (4, 4'-oxyl double (benzoic acid)) ₃ (pyridyl) And [2,3-f][1,10]morpholine)] _n ,[(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridine[2',3 ':5,6]Py And [2,3-f][1,10]morpholine)] _n , [(Al _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl) And [2,3-f][1,10]morpholine)] _n , [(Ti _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl) And [2,3-f][1,10]morpholine)] _n ,[(Zn _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl) And [2,3-f][1,10]morpholine)] _n , [(Bi _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl) And [2,3-f][1,10]morpholine)] _n ,[(Mn _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl) And [2,3-f][1,10]morpholine)] _n , [(Y ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyridine[2', 3':5,6]pyridyl And [2,3-f][1,10]morpholine)] _n , [(La ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyrido[2', 3':5,6]pyridyl And [2,3-f][1,10]morpholine)] _n , [(Gd ₂ O ₃ :Eu)(4,4'-oxybis(benzoic acid)) ₃ (pyridine[2', 3':5,6]pyridyl And [2,3-f][1,10]morpholine)] _n ,[(La ₂ O ₃ :Eu)(terephthalic acid) ₃ (pyridyl) And [2,3-f][1,10]-morpholin-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]morphine )] _n , [(Y _0.5 ,Eu _0.5 )(4,4'oxybis(benzoic acid)) ₃ (pyridyl) And [2,3-f][1,10]morpholine) _0.5 (1,10-morpholine) _0.5 ] _n , [(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid) ) ₃ (pyrido[2',3':5,6]pyridin And [2,3-f][1,10]morpholine) _0.5 (pyridyl) And [2,3-f][1,10]morpholine) _0.5 ] _n ,[(Y _0.5 ,Eu _0.5 )(4,4'-oxybis(benzoic acid)) ₃ (pyridyl) And [2,3-f][1,10]morpholine) _0.5 (3-methylpyridyl) And [2,3-f][1,10]morpholine) _0.5 ] _n ,[Eu(1,3,5-tris(4-carboxyphenyl)benzene) ₃ (pyrido[2',3': 5,6]pyridyl And [2,3-f][1,10]morpholine)] _n , [Eu(4,4'-oxybis(benzoic acid)) ₃ (dipyrido[3,2-a:2', 3'-c] brown )] _n or [Eu(4,4'-oxybis(benzoic acid)) ₃ (11-methoxydipyrido[3,2-a:2',3'-c] brown )] _n . The photoluminescent diode device comprising the red organic-inorganic composite luminescent material according to claim 1, wherein the red organic-inorganic composite luminescent material having the chemical formula 1 has a full width at half maximum of 15 nm. Or below. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material, the luminescent material having the following chemical formula 1 and prepared by a method comprising: weighing a raw material, the raw material comprising from a unit price to four One or more of a valent metal ion or a metal compound thereof, one selected from Eu or Eu compounds, one selected from an aromatic compound having at least two carboxylic acid groups, and one selected from the group consisting of morpholine or a derivative thereof Or a plurality of; the weighed raw material is placed in a solvent of 50 ml to 100 ml to prepare a mixture, and uniformly stirred; and the mixture is synthesized at a temperature of 90 ° C to 210 ° C: [Chemical Formula 1] [(A _x1 , R _x2 ) (L) _y (X)] _n wherein, in Chemical Formula 1, A includes a free monovalent metal ion Li, Na or K, a divalent metal ion Mg, Ca, Sr, Ba or Zn, a trivalent metal ion Al or La, and one or more metal ions of the group consisting of tetravalent metal ions Zr or Ti, or a metal compound thereof; R comprising one selected from Eu or Eu compounds; L comprising selected from at least two carboxylic acids Aromatic compound Of one; comprising X-phenanthroline and derivatives thereof selected from the one or more; X1 meet 0 X1<2, x2 matches 0<x2 2, and the sum of x1 and x2 meets 0<x1+x2 2; and y is 2 or 3, and n is an integer of 1 or more. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 12, wherein the monovalent to tetravalent metal ion or a metal thereof is weighed from 0.01 mol to 0.19 mol. One or more of the compounds, one selected from the group consisting of Eu or Eu compounds in a ratio of 0.1 mol to 0.19 mol, and an aromatic compound having at least two carboxylic acid groups in a ratio of 0.01 mol to 0.6 mol. One of the materials, and a raw material selected from one or more of morpholine or a derivative thereof, in a ratio of 0.01 mole to 0.2 mole. A photoluminescent diode device comprising a red organic-inorganic composite luminescent material according to claim 12, wherein the solvent is water, propanol, ethanol, methanol, dimethylformamide (DMF) or Dimethylacetamide (DMA). A photoluminescent diode device comprising a red organic-inorganic composite luminescent material according to claim 12, wherein the metal compound comprises ZnO, Y ₂ O ₃ , La ₂ O ₃ , Gd ₂ O _{3, Al 2 (SO 4)} 3, TiO 2, metal compound, _{Zn (NO 3) 2, Bi} 2 O 3 MnCO ₃ or any one of. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 12, wherein the Eu compound is selected from the group consisting of ZnO:Eu, Y ₂ O ₃ :Eu, La ₂ O ₃ : Eu or Eu(NO ₃ ) ₃ . One of xH ₂ O, and Eu(NO ₃ ) ₃ . x in xH ₂ O is an integer selected from 1 to 6. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 12, wherein L comprises at least one selected from the following Chemical Formulas 2 to 8: A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 12, wherein X comprises one or more selected from the following Chemical Formulas 9 to 12: Wherein R ₁ to R _{10 are} each independently hydrogen, deuterium, halogen, cyano, nitro, amine, substituted or unsubstituted C _1-60 alkyl, C _1-60 haloalkyl, substituted or unsubstituted C _1-60 alkoxy, substituted or unsubstituted C _1-60 haloalkoxy, substituted or unsubstituted C _3-60 cycloalkyl, substituted or unsubstituted C _2-60 alkenyl, substituted or Unsubstituted C _6-60 aryl, substituted or unsubstituted C _6-60 aryloxy, or substituted or unsubstituted C _1-60 heterocyclic group including one or more of N, O and S, Q Is N or CH. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 18, wherein R ₁ is hydrogen (H), cyano (-CN) or methyl (CH ₃ ), R ₂ to R _{7 are} each independently hydrogen (H), amine (-NH ₂ ), methyl (CH ₃ ) or phenyl, and R ₈ is hydrogen (H) or methoxy (-OCH ₃ ), R ₉ is hydrogen (H), C ₁ -C ₆ alkyl, phenyl, nC ₁ -C ₆ alkylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, triethyl Phenyl, n-nitrophenyl, n-aminophenyl, n-sulfonylphenyl, disulfophenyl, nC ₁ -C ₆ alkoxyphenyl, dimethoxyphenyl, Diethoxyphenyl, n-pyridyl, pyrimidinyl, fluorenyl, naphthyl or anthracenyl, and R ₁₀ is selected from hydrogen (H), C ₁ -C ₆ alkyl, phenyl or nC ₁ -C _{a 6} alkylphenyl group, the C ₁ -C ₆ alkoxy group being a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or a hexyloxy group, and n being selected from 2 to 4 An integer and represents o-, m-, and p-. A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 18, wherein X is one or more selected from the following Chemical Formulas 13 to 27: A photoluminescence diode device comprising a red organic-inorganic composite luminescent material according to claim 12, wherein X is the following chemical formula 28: