JPH09227861A - Production of luminescent rare earth complex material introduced into solid matrix - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-performance luminescent material which is kept out of contact with the open air and has both toughness and moldability by introducing a rare earth complex synthesized from a rare earth ion and an org. ligand having a conjugated system similar to an arom. ring into a solid matrix by the sol-gel method. SOLUTION: A rare earth complex synthesized from a rare earth ion and an org. ligand having a conjugated system similar to an arom. ring (e.g. bipyridine, terpyridine, phenanthroline, phthalocyanine, pyridine, quinoline, urotropin, a β-diketone, dibenzoic acid, a crown ether, cryptand, or an aminpolycarboxylate) is introduced by the sol-gel method into an org.-inorg. composite matrix formed by partially substituting the three-dimensional structure of silica with an org. silane [e.g. 3-(trimethoxysilyl)propyl acrylate, diethoxydimethylsilane, or diethoxydiphenylsilane] and heated at 50-350 deg.C to give a high-performance luminescent material. Figure 1 shows the production process.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides a rare earth complex, which is easily deactivated by the influence of humidity in the air, into a solid matrix by the sol-gel method to effectively shield it from the outside air, which is an excellent property of the rare earth complex. It is a technology for producing a light-emitting material that has both strong toughness and moldability due to a solid matrix in addition to excellent fluorescent properties.

[0002]

2. Description of the Related Art Conventional rare earth luminescent materials are produced by activating rare earth ions in an inorganic compound or glass, and these are usually used in the form of powder.

[0003]

Conventional inorganic phosphors have good fluorescent properties but are inferior in terms of processing. Therefore, molding into fiber cables used for optical communication or substrates with complicated shapes is difficult. Uniform application was difficult. Therefore, it is necessary to develop a light emitting material that has a fluorescent property equal to or higher than that of the inorganic phosphor and that is excellent in moldability.

[0004]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the phosphor has excellent fluorescent characteristics equal to or higher than that of an inorganic phosphor, and has moldability like plastic and toughness like glass. The development of materials with In the present invention, a rare earth complex having good fluorescence characteristics is introduced into an organic-inorganic composite matrix (ORMOSIL) by a sol-gel method, and heat-treated in a temperature range of 50 ° C to 350 ° C to obtain high-performance luminescence. It is characterized by manufacturing the material.

[0005]

In the present invention, it is possible to produce a luminescent material in which a rare earth complex is introduced into a solid matrix without impairing the original excellent fluorescence characteristics.

The production is carried out by adding a predetermined amount of a rare earth complex dissolved in an organic solvent to a mixed solution of an alkoxide of silicon and an organic silane refluxed in the presence of an acid catalyst, aging and drying at room temperature, and further heating at a temperature of 50 ° C to 350 ° C. It can be performed by heat treatment in the area.

Further, unlike the melting method conventionally used for producing glass, the synthesis can be carried out at a relatively low temperature of 350 ° C. or lower, and deterioration due to decomposition of the rare earth complex hardly progresses. It is possible to manufacture a light emitting material with a composition according to the charged ratio without deteriorating the characteristics of the rare earth complex of.

[0008]

EXAMPLE A light emitting material in which a rare earth complex is introduced into an ORMOSIL matrix can be manufactured by the manufacturing process shown in FIG.

The production was carried out using 2,2'-bipyridine (bpy) and 1,10
-Ln (bpy) ₂ Cl ₃ and Ln (phen) ₂ Cl ₃ (Ln, which are rare earth complexes of phenanthroline (phen) with Eu ³⁺ and Tb ³⁺ ions
= Eu, Tb) was introduced into the ORMOSIL matrix (formula 1 and formula 2) by the sol-gel method, and heat treatment was performed at a temperature (350 ° C or lower) at which these were not decomposed. As a result, we succeeded in obtaining a rare earth complex composite light emitting material having sufficient mechanical strength and good transparency.

[0010]

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[0011]

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FIG. 2 shows a sample in which 10 mol% of Tb (bpy) ₂ Cl ₃ was introduced into an ORMOSIL matrix containing TMSPM as an oligomer unit, and Eu in an ORMOSIL matrix containing DEDPS.
Fig. 7 shows the heat treatment temperature dependence of the relative fluorescence intensity in a sample in which 10 mol% of (phen) ₂ Cl ₃ is introduced. Relative fluorescence intensities of 103% and 80% were observed for the practical phosphors in the samples heat-treated in air at 150 ° C for 5 hours.

FIG. 3 shows the time course of the relative fluorescence intensity of the obtained ORMOSIL complex, together with the results of the rare earth complex Tb (bpy) ₂ Cl ₃ itself. The relative fluorescence intensity of the rare earth complex itself decreased sharply with the passage of time, whereas the fluorescence intensity of the ORMOSIL composite-type luminescent material did not decrease at all even after several days, so the rare earth complex was completely removed by the solid matrix. It was revealed that it was shielded from the outside air and retained good fluorescence characteristics.

[0014]

Industrial Applicability According to the present invention, since it is synthesized by the sol-gel method, it is extremely easy to mold it into a bulk body, a thin film, a fiber, and the like, and, in addition, it has a good fluorescent property equivalent to or better than that of a commercially available inorganic phosphor. A light emitting material having Therefore, it is possible to manufacture a high-brightness light emitting material having excellent moldability, which has been considered difficult until now. Further, in the rare earth complex introduced without decomposition, the ligand efficiently absorbs the excitation energy and transfers it to the rare earth ion. Therefore, by selecting those ligands, the excitation light of a specific wavelength (energy) can be obtained. It is also effective in producing a high-brightness light emitting material that selectively responds to.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram of an ORMOSIL complex.

FIG. 2 is a diagram showing heat treatment temperature dependency of relative fluorescence intensity in an ORMOSIL complex. However, (a) consists of TMSPM
A sample in which 10 mol% of Tb (bpy) ₂ Cl ₃ was introduced into the ORMOSIL matrix, (b) was Eu (ph) in the ORMOSIL matrix composed of DEDPS.
This is a sample into which 10 mol% of en) ₂ Cl ₃ is introduced. Also, (a) and
To calculate the relative fluorescence intensity of (b), LaP was used as a standard phosphor.
O ₄ : Ce, Tb and Y (P, V) O ₄ : Eu were used, respectively.

FIG. 3 is a diagram showing a change in relative fluorescence intensity over time in an ORMOSIL complex together with that of a rare earth complex Tb (bpy) ₂ Cl ₃ alone. Where I _o is the ORMOSIL complex and Tb (bpy) ₂ C
Relative fluorescence intensity immediately after heat treatment of l ₃ at 150 ° C., I is a value after a predetermined time has elapsed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuji Tsutsumi 1-5-18 Hotaruikenakacho, Toyonaka-shi, Osaka Maison Toyonaka Part15 Room 207

Claims (1)

[Claims] 1. An organic ligand having a conjugated system portion similar to a rare earth ion and an aromatic ring (for example, bipyridine, terpyridine, phenanthroline, phthalocyanine, pyridine, quinoline, utropine, β-diketone, dibenzoic acid, crown ether, cryptand, Amine polycarboxylic acid,
Diphenyl acid, naphthalic acid, phthalic acid, pyrocatechol, pyrogallol, salicylic acid, and their derivatives) are used as a rare earth complex to partially convert the three-dimensional structure of silica to 3- (trimethoxysilyl) propyl acrylate (TMSPM), After introducing by sol-gel method into organic-inorganic hybrid matrix (ORMOSIL) substituted with organic silane such as diethoxydimethylsilane (DEDMS) and diethoxydiphenylsilane (DEDPS), heat treatment in the temperature range of 50 ° C to 350 ° C Technology for manufacturing high-performance light-emitting materials by doing so.