JP5659972B2 - ORGANIC ELECTROLUMINESCENT ELEMENT AND LIGHTING DEVICE - Google Patents

Description

  The present invention relates to an organic electroluminescence element and a lighting device.

Organic electroluminescence elements (hereinafter abbreviated as OLED elements, organic EL elements, etc.) can be driven at a low voltage of several volts to several tens of volts, and are self-luminous so that they have a wide viewing angle and visibility. It is a high-quality, thin-film, solid-state device, so it is attracting attention as a display or lighting application from the viewpoints of space saving, energy saving, and portability. Have begun to do.
However, for the realization and widespread use of large screen displays or lighting that replaces cold cathode fluorescent lamps, the luminous efficiency is dramatically higher than the current situation, the luminous lifetime is long, and there are no defects such as discoloration of the luminescent color over time. Development of devices is desired.

In recent years, phosphorescent materials have been actively studied as a technique for increasing luminous efficiency.
Phosphorescent materials are attracting much attention as illumination applications because they may have almost the same luminous efficiency as cold cathode fluorescent lamps. In order to realize the white light necessary for illumination, it is necessary that the light emission efficiency, color purity, light emission lifetime, and the like of materials emitting light of blue, green, and red are balanced at a high level. However, blue light-emitting materials that require high energy for excitation are difficult to design, and no material that satisfies all the required performance has yet been obtained.
On the other hand, silole compounds that are silicon-containing compounds and π-conjugated compounds are expected as light-emitting materials and light-emitting host materials with high electron transport properties. (For example, with respect to 2,5-diarylsilole derivatives, see Non-patent Document 1 and Patent Document 1) However, the silole derivatives have a drawback that their light emission lifetime is remarkably short. In addition, diaromatic condensed siloles composed only of aromatic rings, spirodibenzosilole derivatives (see, for example, Patent Document 2), dibenzosilole derivatives to which a hole transporting substituent such as triarylamine is added (for example, Patent Document 3) In addition, although the triphenylenesilole derivative substituted with an alkoxy group (see, for example, Patent Document 4) and the like have made certain progress in light emission efficiency, satisfactory results have not yet been obtained for the light emission lifetime. On the other hand, a ladder-type spirodibenzosilole (see Patent Document 5) that aims to achieve both high efficiency of light emission and long life has been reported. In particular, when applied to a blue phosphorescent light emitting element, the light emission efficiency However, defects such as emission lifetime and discoloration of the emission color over time were not yet satisfactory.

USP 6051319 JP 2003-243178 A JP 2001-172284 A JP 2010-64976 A JP 2001-210473 A

Chem. Mater. 2001, 13, 2680-2683

  Therefore, the main object of the present invention is to provide an organic electroluminescence element and an illumination device using a diaromatic ring-condensed silole compound that can improve luminous efficiency and luminous lifetime and prevent discoloration of luminescent color over time. There is.

「一般式１中、Ｒ_１、及びＲ_２は水素原子、炭素数６〜２０の芳香族炭化水素環基、炭素数３〜２０の芳香族複素環基を表わす。但し、Ｒ_１とＲ_２が同時に水素原子であることはない。Ｒ_３及びＲ_４は炭素数６〜２０の芳香族炭化水素環基、炭素数３〜２０の芳香族複素環基を表わす。Ｒ_３とＲ_４は互いに結合して環を形成してもよい。Ｑ_１、Ｑ_３、Ｑ_４、及びＱ_６は窒素原子、若しくはＣ−Ｒｘを表わす。Ｒｘは水素原子、炭素数６〜２０の芳香族炭化水素環基、炭素数３〜２０の芳香族複素環基を表わす。Ｑ_２及びＱ_５は窒素原子、若しくはＣ−Ｈを表わす。
一般式２中、Ｒ_５、及びＲ_６は水素原子、炭素数６〜２０の芳香族炭化水素環基、炭素数３〜２０の芳香族複素環基を表わす。但し、Ｒ_５とＲ_６が同時に水素原子であることはない。Ｒ_７及びＲ_８は炭素数６〜２０の芳香族炭化水素環基、炭素数３〜２０の芳香族複素環基を表わす。Ｒ_７とＲ_８は互いに結合して環を形成してもよい。Ｑ_７及びＱ_９は窒素原子、若しくはＣ−Ｒｚを表わす。Ｒｚは水素原子、炭素数６〜２０の芳香族炭化水素環基、炭素数３〜２０の芳香族複素環基を表わす。Ｑ_８、及びＱ_１０は酸素原子、若しくは硫黄原子を表わす。
一般式３において、Ｒ_１、Ｒ_２、及びＱ_１〜Ｑ_６は一般式１におけるものと同義である。Ｒ_９及びＲ_１０は水素原子、炭素数６〜２０の芳香族炭化水素環基、炭素数３〜２０の芳香族複素環基を表わす。
一般式４においてＲ_５、Ｒ_６、及びＱ_７〜Ｑ_１０は一般式２におけるものと同義である。Ｒ_１１及びＲ_１２は水素原子、炭素数６〜２０の芳香族炭化水素環基、炭素数３〜２０の芳香族複素環基を表わす。」 In order to solve the above problems, according to the present invention,
In an organic electroluminescence device having a pair of electrodes and at least one organic layer disposed between the pair of electrodes and including a light emitting layer,
At least one of the organic layers contains at least one diaromatic ring-condensed silole compound represented by the general formulas 1 to 4, and an organic electroluminescence device is provided. The

“In General Formula 1, R ₁ and R ₂ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms, provided that R ₁ and R ₂ There is .R ₃ and _{R 4} not simultaneously hydrogen atoms aromatic hydrocarbon ring group having 6 to 20 carbon atoms, .R ₃ and _{R 4} representing an aromatic heterocyclic group having 3 to 20 carbon atoms with each other Q ₁ , Q ₃ , Q ₄ , and Q _{6 each} represent a nitrogen atom or C—Rx, where Rx is a hydrogen atom or an aromatic hydrocarbon ring having 6 to 20 carbon atoms. Group represents an aromatic heterocyclic group having 3 to 20 carbon atoms, Q ₂ and Q ₅ each represent a nitrogen atom or C—H.
In General Formula 2, R ₅ and R ₆ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. However, R ₅ and R ₆ are not simultaneously hydrogen atoms. R ₇ and R ₈ represent an aromatic hydrocarbon ring group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms. R ₇ and R ₈ may combine with each other to form a ring. Q ₇ and Q ₉ represent a nitrogen atom or C—Rz. Rz represents a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Q ₈ and Q ₁₀ represent an oxygen atom or a sulfur atom.
In General Formula 3, R ₁ , R ₂ , and Q _{1 to} Q ₆ have the same meanings as in General Formula 1. R ₉ and R ₁₀ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
In the general formula 4, R ₅ , R ₆ , and Q _{7 to} Q ₁₀ are the same as those in the general formula 2. R ₁₁ and R ₁₂ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. "

  According to the present invention, it is possible to improve the light emission efficiency and the light emission lifetime, and to prevent discoloration of the emitted color over time.

It is the schematic diagram which showed an example of the display apparatus. It is a schematic diagram of the display part of the display apparatus of FIG. It is the schematic of an illuminating device. It is sectional drawing of the illuminating device of FIG.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

The OLED element of the present invention is an OLED element having at least one organic layer including a light emitting layer between a pair of electrodes (for example, between an anode and a cathode), and at least one of the organic layers. The diaromatic condensed silole compound represented by the general formulas 1 to 4 is contained.
The diaromatic condensed silole compound has an aromatic substituent at a specific site (R ₁ or R ₂ in general formula 1 and general formula 3, or R ₅ or R ₆ in general formula 2 and general formula 4). In general formula 1 and general formula 3, the specific site (Q ₂ and Q ₅ ) is a nitrogen atom or a carbon atom having no substituent.
About the effect obtained by the OLED element of the present invention containing the diaromatic ring-condensed silole compound represented by the general formula 1 to the general formula 4 in at least one layer of the organic layer, the present inventors are as follows. I am thinking.
A conventionally known silole compound used in an OLED element is rigid, has a large molecular distortion, and is unstable in light and heat, whereas the diaromatic ring-condensed silole compound has an appropriate substituent arrangement. Therefore, it is considered that a more stable structure can be formed and the lifetime of OLED element emission can be extended because the aromatic rings of the constituent components have an appropriate dihedral angle with little distortion. .
At the same time, the condensed ring can maintain and maintain the steric structure to an appropriate level, and the conjugation spread can be appropriately adjusted for the π-conjugate. The ring-condensed silole compound has high stability, and when it is contained in an OLED element, it appropriately interacts with the material contained in the same layer or an adjacent layer to optimally control the movement of charges. We estimate that it is possible.
From the above, the present inventors, when using the diaromatic ring-condensed silole compound according to the present invention in an OLED element and a lighting device comprising the same, have high luminous efficiency, long luminous lifetime, and luminescent color over time. It is estimated that defects such as discoloration can be reduced.

《Diaromatic condensed silole compound》
The diaromatic condensed silole compound of the present invention will be described in detail.
The diaromatic condensed silole compound is represented by general formulas 1 to 4.

In General Formula 1, R ₁ and R ₂ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. However, R ₁ and R ₂ are not hydrogen atoms at the same time. R ₃ and R ₄ represent an aromatic hydrocarbon ring group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms. R ₃ and R ₄ may combine with each other to form a ring. Q ₁ , Q ₃ , Q ₄ , and Q ₆ represent a nitrogen atom or C—Rx. Rx represents a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Q ₂ and Q ₅ represent a nitrogen atom or C—H.
In General Formula 2, R ₅ and R ₆ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. However, R ₅ and R ₆ are not simultaneously hydrogen atoms. R ₇ and R ₈ represent an aromatic hydrocarbon ring group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms. R ₇ and R ₈ may combine with each other to form a ring. Q ₇ and Q ₉ represent a nitrogen atom or C—Rz. Rz represents a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Q ₈ and Q ₁₀ represent an oxygen atom or a sulfur atom.
In General Formula 3, R ₁ , R ₂ , and Q _{1 to} Q ₆ are the same as those in General Formula 1. R ₉ and R ₁₀ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
In General Formula 4, R ₅ , R ₆ , and Q _{7 to} Q ₁₀ are the same as those in General Formula 2. R ₁₁ and R ₁₂ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, and an aromatic heterocyclic group having 3 to 20 carbon atoms.
In the general formulas 1 to 4, as the aromatic hydrocarbon ring group represented by R _{1 to} R ₁₂ , for example, phenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, Examples include a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, and a biphenylyl group.
Among them, preferred examples of the aromatic hydrocarbon ring group include a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenyl group, and a fluorenyl group, and particularly preferred are a phenyl group, a naphthyl group, and a fluorenyl group.
These groups may further have a substituent described later.
In the general formulas 1 to 4, examples of the aromatic heterocyclic group represented by R _{1 to} R ₁₂ include a pyridyl group, a pyrimidyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a pyrazinyl group, and a triazolyl group. Group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group)), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group , Furanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group) One replaced with a nitrogen atom), a quinoxalinyl group, Riajiniru group, quinazolinyl group, and phthalazinyl group.
Among them, preferred examples of the aromatic heterocyclic group include a pyridyl group, a pyrimidyl group, an imidazolyl group, a pyrazolyl group, a thienyl group, a quinolyl group, a dibenzofuryl group, a carbazolyl group, a carbolinyl group, and a diazacarbolinyl group. Includes a pyridyl group, a pyrimidyl group, a pyrazolyl group, a dibenzofuryl group, a carbazolyl group, a carbolinyl group, and a diazacarbazolyl group.
These groups may further have a substituent described later.

In the general formulas 1 to 4, the aromatic hydrocarbon ring group and the aromatic heterocyclic group represented by R _{1 to} R ₁₂ may each have an alkyl group (for example, a methyl group) , Ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.) ), Alkenyl groups (eg, vinyl, allyl, 1-propenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, isopropenyl, etc.), alkynyl (eg, ethynyl, propargyl) Group), aromatic hydrocarbon group (aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc., for example, phenyl group, Lorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, triphenylenyl group, biphenylyl group, etc.), aromatic heterocyclic group ( For example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, azacarbazolyl group (carbazole ring of the above carbazolyl group) Any one of carbon atoms constituting one or more carbon atoms is replaced by a nitrogen atom), benzofuryl group, dibenzofuryl group, azadibenzofuryl group (any carbon atom constituting the dibenzofuran ring of the dibenzofuryl group) Benzothienyl group, indolyl group, dibenzothienyl group, benzoimidazolyl group, oxazolyl group, benzoxazolyl group, quinoxalinyl group, isoxazolyl group, isothiazonyl group, indolocarbazolyl Group, hexaazatriphenylenyl group, benzodifuranyl group, benzodithienyl group, phosphor group, silylyl group, boryl group, bipyridyl group, etc., heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.) ), Alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy groups (for example, cyclopentyloxy group, cyclohexyloxy group, etc.) , Aryloxy groups (for example, phenoxy group, naphthyloxy group, etc.), alkylthio groups (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio groups (for example, Cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyl) Oxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfur group) Nyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.) An acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group) Etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, Silcarbonyloxy group, phenylcarbonyloxy group, acryloyl group, methacryloyl group, etc.), amide group (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonyl) Amino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group) Propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexyl Aminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido) Group, dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group) Group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethyl) Sulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), Amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, phenylamino group, diphenylamino group, naphthylamino group, 2 -Pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophene) Cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group), phosphono group, hydroxy group, etc. It is done.
These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

“Q ₁ , Q ₃ , Q ₄ , and Q ₆ ” in the general formulas 1 and 3 represent a nitrogen atom or C—Rx. Rx represents a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Specific examples of Rx are the same as those described for R _{1 to} R ₁₂ above. “Q ₂ and Q ₅ ” in the general formulas 1 and 3 represent a nitrogen atom or C—H. Preferably it represents C—H.
The number of nitrogen atoms represented by Q _{1 to} Q ₆ in General Formula 1 is preferably 0, 1 or 2.
The number of nitrogen atoms represented by Q _{1 to} Q ₆ in the general formula 3 is preferably 0, 2 or 4.
“Q ₇ and Q ₉ ” in the general formulas 2 and 4 represent a nitrogen atom or C—Rz. Rz represents a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Q ₈ and Q ₁₀ represent an oxygen atom or a sulfur atom.
The number of nitrogen atoms represented by Q _{7 to} Q ₁₀ in the general formula 2 is preferably 0 to 4. More preferably, it is 0-2. Most preferably, it is zero.
The number of nitrogen atoms represented by Q _{7 to} Q ₁₀ in the general formula 4 is preferably 0 to 2.

Hereinafter, although the specific example of the diaromatic ring condensed silole type compound of this invention represented by General formula 1-4 is given, this invention is not limited to these.

下記参照文献（ｅ）に従い合成した出発原料（A）３．９１ｇ（１０．０ｍｍｏｌ）を無水エーテルに溶解し、窒素気流下、内温−７８℃に冷却した。次に１．６１ＭのｎＢｕＬｉ／ヘキサン溶液１４．９ｍｌを（２２．０ｍｍｏｌ）内温−７８℃~−７５℃を保ちながらゆっくりと滴下した。滴下後、同温度で２時間撹拌を行った。次いで、ジフェニルジクロロシラン２．６６ｇ（１０．５ｍｍｏｌ）を無水エーテル１０ｍｌに希釈した溶液を内温−７０℃を保ちながら、滴下した。同温度で３時間撹拌したのち、冷却を止め、成り行きで室温まで戻した。溶媒を減圧下に留去し、残さをジクロロメタン−メタノール混合溶媒で再結晶し、中間体（Ｂ）を３．８８ｇ（９４％）得た。次に、（Ｂ）３．５０ｇ（８．４７ｍｍｏｌ）をＤＭＡc３０ｍｌに溶解し、カルバゾール１．４９ｇ（８．８９ｍｍｏｌ）、ＣｕＩ １．６１ｇ（８．４７ｍｍｏｌ）、炭酸カリウム１．１７ｇ（８．４７ｍｍｏｌ）L-ｐｒｏｌｉｎｅ １００ｍｇ（０．８５ｍｍｏｌ）を加え、窒素気流下、内温１４０℃で４時間加熱撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをシリカゲルカラムクロマトグラフィー(展開溶媒＝トルエン：メチレンクロライド＝９：１)にて精製し、Ｓｉ−1の白色粉末を得た。収量３．５９ｇ(収率８５％) 構造は、核磁気共鳴法（^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ等）及びＭＡＳＳスペクトル（質量分析法）にて同定した。 Hereinafter, although the synthesis example of the diaromatic condensed silole type compound of this invention is given, this invention is not limited to these.
<< Synthesis Example 1: Synthesis of Compound Si-1 >>

3.91 g (10.0 mmol) of the starting material (A) synthesized according to the following reference (e) was dissolved in anhydrous ether and cooled to an internal temperature of −78 ° C. under a nitrogen stream. Next, 14.9 ml of a 1.61 M nBuLi / hexane solution (22.0 mmol) was slowly added dropwise while maintaining the internal temperature of -78 ° C to -75 ° C. After dropping, the mixture was stirred at the same temperature for 2 hours. Subsequently, a solution obtained by diluting 2.66 g (10.5 mmol) of diphenyldichlorosilane in 10 ml of anhydrous ether was added dropwise while maintaining an internal temperature of −70 ° C. After stirring for 3 hours at the same temperature, the cooling was stopped and the temperature was returned to room temperature. The solvent was distilled off under reduced pressure, and the residue was recrystallized with a dichloromethane-methanol mixed solvent to obtain 3.88 g (94%) of intermediate (B). Next, 3.50 g (8.47 mmol) of (B) was dissolved in 30 ml of DMAc, and 1.49 g (8.89 mmol) of carbazole, 1.61 g (8.47 mmol) of CuI, 1.17 g (8.47 mmol) of potassium carbonate. 100 mg (0.85 mmol) of L-proline was added, and the mixture was heated and stirred at an internal temperature of 140 ° C. for 4 hours under a nitrogen stream. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent = toluene: methylene chloride = 9: 1) to obtain a white powder of Si-1. Yield 3.59 g (yield 85%) The structure was identified by nuclear magnetic resonance ( ¹ H-NMR, ¹³ C-NMR, etc.) and MASS spectrum (mass spectrometry).

下記参照文献（ｅ）に従い合成した出発原料（A）３．９１ｇ（１０．０ｍｍｏｌ）を無水エーテルに溶解し、窒素気流下、内温−７８℃に冷却した。次に１．６１ＭのｎＢｕＬｉ／ヘキサン溶液１４．９ｍｌを（２２．０ｍｍｏｌ）内温−７８℃~−７５℃を保ちながらゆっくりと滴下した。滴下後、同温度で２時間撹拌を行った。次いで、テトラクロロシラン０．８９ｇ（５．２５ｍｍｏｌ）を無水エーテル１０ｍｌに希釈した溶液を内温−７０℃を保ちながら、滴下した。同温度で４時間撹拌したのち、冷却を止め、成り行きで室温まで戻した。溶媒を減圧下に留去し、残さをジクロロメタン−エタノール混合溶媒で再結晶し、中間体（Ｃ）を３．９８ｇ（８１％）得た。次に、（Ｂ）３．５０ｇ（７．１１ｍｍｏｌ）をＤＭＡc５０ｍｌに溶解し、カルバゾール２．５０ｇ（１４．９ｍｍｏｌ）、ＣｕＩ ２．８４ｇ（１４．９ｍｍｏｌ）、炭酸カリウム２．０６ｇ（１４．９ｍｍｏｌ）L-ｐｒｏｌｉｎｅ １８０ｍｇ（１．６０ｍｍｏｌ）を加え、窒素気流下、内温１４０℃で６時間加熱撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをシリカゲルカラムクロマトグラフィー(展開溶媒＝ヘプタン：メチレンクロライド＝９：１)にて精製し、Ｓｉ−３の白色粉末を得た。収量４．３１ｇ(収率９１％) 構造は、核磁気共鳴法（^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ等）及びＭＡＳＳスペクトル（質量分析法）にて同定した。 << Synthesis Example 2: Synthesis of Compound Si-3 >>

3.91 g (10.0 mmol) of the starting material (A) synthesized according to the following reference (e) was dissolved in anhydrous ether and cooled to an internal temperature of −78 ° C. under a nitrogen stream. Next, 14.9 ml of a 1.61 M nBuLi / hexane solution (22.0 mmol) was slowly added dropwise while maintaining the internal temperature of -78 ° C to -75 ° C. After dropping, the mixture was stirred at the same temperature for 2 hours. Next, a solution obtained by diluting 0.89 g (5.25 mmol) of tetrachlorosilane in 10 ml of anhydrous ether was added dropwise while maintaining the internal temperature at -70 ° C. After stirring at the same temperature for 4 hours, the cooling was stopped and the temperature was returned to room temperature. The solvent was distilled off under reduced pressure, and the residue was recrystallized with a mixed solvent of dichloromethane-ethanol to obtain 3.98 g (81%) of intermediate (C). Next, 3.50 g (7.11 mmol) of (B) was dissolved in 50 ml of DMAc, 2.50 g (14.9 mmol) of carbazole, 2.84 g (14.9 mmol) of CuI, and 2.06 g (14.9 mmol) of potassium carbonate. L-proline (180 mg, 1.60 mmol) was added, and the mixture was stirred with heating at 140 ° C. for 6 hours under a nitrogen stream. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent = heptane: methylene chloride = 9: 1) to obtain a white powder of Si-3. Yield 4.31 g (yield 91%) The structure was identified by nuclear magnetic resonance ( ¹ H-NMR, ¹³ C-NMR, etc.) and MASS spectrum (mass spectrometry).

下記参照文献（ａ）に従い合成した出発原料（D）４．９２ｇ（１０．０ｍｍｏｌ）をＤＭＡc６０ｍｌに溶解し、カルバゾール３．３６ｇ（２０．１ｍｍｏｌ）、ＣｕＩ ３．８５ｇ（２０．１ｍｍｏｌ）、炭酸カリウム２．７８ｇ（２０．１ｍｍｏｌ）L-ｐｒｏｌｉｎｅ ２３０ｍｇ（２．００ｍｍｏｌ）を加え、窒素気流下、内温１５０℃で８時間加熱撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをシリカゲルカラムクロマトグラフィー(展開溶媒＝ヘプタン：酢酸エチル＝１９：１)にて精製し、Ｓｉ−４の白色粉末を得た。収量５．８５ｇ(収率８８％) 構造は、核磁気共鳴法（^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ等）及びＭＡＳＳスペクトル（質量分析法）にて同定した。 << Synthesis Example 3: Synthesis of Compound Si-4 >>

4.92 g (10.0 mmol) of starting material (D) synthesized according to the following reference (a) was dissolved in 60 ml of DMAc, and 3.36 g (20.1 mmol) of carbazole, 3.85 g (20.1 mmol) of CuI, potassium carbonate 2.78 g (20.1 mmol) L-proline 230 mg (2.00 mmol) was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. for 8 hours under a nitrogen stream. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent = heptane: ethyl acetate = 19: 1) to obtain a white powder of Si-4. Yield 5.85 g (yield 88%) The structure was identified by nuclear magnetic resonance ( ¹ H-NMR, ¹³ C-NMR, etc.) and MASS spectrum (mass spectrometry).

下記参照文献（ｂ）に従い合成した出発原料（Ｅ）２．７２ｇ（１０．０ｍｍｏｌ）をＤＭＳO ５０ｍｌに溶解し、ビスジオキサボラン３．８１ｇ（１５．０ｍｍｏｌ）、酢酸カリウム１．９６ｇ（２０．０ｍｍｏｌ）Ｐｄ（ｄｐｐｆ）Ｃｌ_２ ０．４１ｇ（０．５０ｍｍｏｌ）を加え、窒素気流下、１２０℃で５時間加熱撹拌した。反応終了後、室温まで冷却し、水２００ｍｌを加え、有機層を酢酸エチルで抽出した。抽出液を飽和食塩水で洗浄した。有機層を減圧下に留去し、残さをヘプタンで懸濁洗浄することにより、中間体（Ｆ）を３．００ｇ（収率９４％）で得た。次に、（Ｆ）２．５０ｇ（７．８３ｍｍｏｌ）（Ｃ）１．８２ｇ（３．７２ｍｍｏｌ）、炭酸カリウム５．９５ｇ（４３．１ｍｍｏｌ）、Ｐｄ（ｄｂａ）_２ ０．９０ｇ（１．５７ｍｍｏｌ）。ｄｐｐｆ ０．８７ｇ（１．５７ｍｍｏｌ）、水１ｍｌをＤＭＥ１００ｍｌに加えて溶解し、内温１００℃で６時間加熱撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをシリカゲルカラムクリマトグラフィー（展開溶媒＝ヘプタン：酢酸エチル＝９：１）にて精製し、Ｓｉ−２３の白色粉末を得た。収量２．３９ｇ(収率９０％) 構造は、核磁気共鳴法（^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ等）及びＭＡＳＳスペクトル（質量分析法）にて同定した。 << Synthesis Example 4: Synthesis of Compound Si-23 >>

2.72 g (10.0 mmol) of the starting material (E) synthesized according to the following reference (b) was dissolved in 50 ml of DMSO, 3.81 g (15.0 mmol) of bisdioxaborane, 1.96 g of potassium acetate (20.20). 0 mmol) Pd (dppf) Cl ₂ (0.41 g, 0.50 mmol) was added, and the mixture was heated and stirred at 120 ° C. for 5 hours under a nitrogen stream. After completion of the reaction, the reaction mixture was cooled to room temperature, 200 ml of water was added, and the organic layer was extracted with ethyl acetate. The extract was washed with saturated brine. The organic layer was distilled off under reduced pressure, and the residue was suspended and washed with heptane to obtain 3.00 g of intermediate (F) (yield 94%). Next, (F) 2.50 g (7.83 mmol) (C) 1.82 g (3.72 mmol), potassium carbonate 5.95 g (43.1 mmol), Pd (dba) ₂ 0.90 g (1.57 mmol) . dppf 0.87 g (1.57 mmol) and 1 ml of water were dissolved in 100 ml of DME, and the mixture was heated and stirred at an internal temperature of 100 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent = heptane: ethyl acetate = 9: 1) to obtain a white powder of Si-23. Yield 2.39 g (90% yield) The structure was identified by nuclear magnetic resonance ( ¹ H-NMR, ¹³ C-NMR, etc.) and MASS spectrum (mass spectrometry).

下記参照文献（ｂ）に従い合成した出発原料（Ｇ）２．３４ｇ（１０．０ｍｍｏｌ）を酢酸３０ｍｌに溶解し、３０％過酸化水素１１．３ｍｌ（１００ｍｍｏｌ）を加え、９５℃で５時間加熱撹拌した。反応液を減圧下で９０％程度濃縮し、残さに１％重層水１００ｍｌを加え、酢酸エチルで有機層を抽出した。飽和食塩水で有機層を３回洗浄し、有機層を減圧下で濃縮した。残さにクロロホルム３０ｍｌを加え、オキシ臭化リン４．２９ｇ（１５．０ｍｍｏｌ）を加え、加熱還流を３時間行った。溶媒及び過剰のオキシ臭化リンを減圧下に留去し、残さをトルエンにて再結晶し、中間体（Ｈ）を２．５０ｇ（収率８０％）得た。次に（Ｈ）２．５ｇ（７．９９ｍｍｏｌ）を脱水エーテル５０ｍｌに溶解し、内温を−７５℃に冷却した。次に１．６１ＭのｎＢｕＬｉ／ヘキサン溶液 １０．９ｍｌ（１７．６ｍｍｏｌ）を内温−７０℃以下を保ちながらゆっくりと加えた。添加後、２時間同温度下で撹拌したのち、ＳｉＣｌ_４ ０．７１ｇ（４．１９ｍｍｏｌ）を脱水エーテル１０ｍｌに溶解した溶液を内温−６５℃以下を保ちながらゆっくりと加えた。同温度で３時間撹拌したのち、成り行きで室温まで加温し、さらに２時間撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをメチレンクロリドーエタノール混合溶媒で再結晶し、中間体（Ｉ）を１．００ｇ（収率７５％）で得た。次に（Ｉ）１．００ｇ（３．００ｍｍｏｌ）を酢酸１０ｍｌに溶解し、３０％過酸化水素３．３ｍｌ（３０ｍｍｏｌ）を加え、９５℃で５時間加熱撹拌した。反応液を減圧下で９０％程度濃縮し、残さに１％重層水１０ｍｌを加え、酢酸エチルで有機層を抽出した。飽和食塩水で有機層を３回洗浄し、有機層を減圧下で濃縮した。残さにクロロホルム１０ｍｌを加え、オキシ臭化リン２．８６ｇ（１０．０ｍｍｏｌ）を加え、加熱還流を３時間行った。溶媒及び過剰のオキシ臭化リンを減圧下に留去し、残さをトルエンにて再結晶し、中間体（Ｊ）を１．４０ｇ（収率９５％）得た。次に（ｊ）１．００ｇ（２．０３ｍｍｏｌ）をＤＭＡc１０ｍｌに溶解し、カルバゾール０．７５ｇ（４．４７ｍｍｏｌ）、ＣｕＩ ０．８５ｇ（４．４７ｍｍｏｌ）、炭酸カリウム０．６２ｇ（４．４７ｍｍｏｌ）L-ｐｒｏｌｉｎｅ ５０ｍｇ（０．４０ｍｍｏｌ）を加え、窒素気流下、内温１５０℃で６時間加熱撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをシリカゲルカラムクロマトグラフィー(展開溶媒＝ヘプタン：メチレンクロリド＝９：１)にて精製し、Ｓｉ−２６の白色粉末を得た。収量１．０５ｇ(収率７８％) 構造は、核磁気共鳴法（^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ等）及びＭＡＳＳスペクトル（質量分析法）にて同定した。 << Synthesis Example 5: Synthesis of Compound Si-26 >>

2.34 g (10.0 mmol) of the starting material (G) synthesized according to the following reference (b) was dissolved in 30 ml of acetic acid, 11.3 ml (100 mmol) of 30% hydrogen peroxide was added, and the mixture was heated and stirred at 95 ° C. for 5 hours. did. The reaction solution was concentrated about 90% under reduced pressure, 100 ml of 1% multistory water was added to the residue, and the organic layer was extracted with ethyl acetate. The organic layer was washed 3 times with saturated brine, and the organic layer was concentrated under reduced pressure. To the residue, 30 ml of chloroform was added, 4.29 g (15.0 mmol) of phosphorus oxybromide was added, and the mixture was heated to reflux for 3 hours. The solvent and excess phosphorus oxybromide were distilled off under reduced pressure, and the residue was recrystallized from toluene to obtain 2.50 g of intermediate (H) (yield 80%). Next, 2.5 g (7.99 mmol) of (H) was dissolved in 50 ml of dehydrated ether, and the internal temperature was cooled to -75 ° C. Next, 10.9 ml (17.6 mmol) of a 1.61 M nBuLi / hexane solution was slowly added while maintaining the internal temperature at −70 ° C. or lower. After the addition, the mixture was stirred at the same temperature for 2 hours, and then a solution in which 0.71 g (4.19 mmol) of SiCl ₄ was dissolved in 10 ml of dehydrated ether was slowly added while maintaining the internal temperature at −65 ° C. or lower. After stirring at the same temperature for 3 hours, the reaction was allowed to warm to room temperature, followed by further stirring for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was recrystallized with a mixed solvent of methylene chloride ethanol to obtain 1.00 g of intermediate (I) (yield 75%). Next, 1.00 g (3.00 mmol) of (I) was dissolved in 10 ml of acetic acid, 3.3 ml (30 mmol) of 30% hydrogen peroxide was added, and the mixture was heated and stirred at 95 ° C. for 5 hours. The reaction solution was concentrated about 90% under reduced pressure, 10 ml of 1% multistory water was added to the residue, and the organic layer was extracted with ethyl acetate. The organic layer was washed 3 times with saturated brine, and the organic layer was concentrated under reduced pressure. Chloroform 10 ml was added to the residue, phosphorus oxybromide 2.86 g (10.0 mmol) was added, and the mixture was heated to reflux for 3 hours. The solvent and excess phosphorus oxybromide were distilled off under reduced pressure, and the residue was recrystallized from toluene to obtain 1.40 g of intermediate (J) (yield 95%). Next, (j) 1.00 g (2.03 mmol) is dissolved in 10 ml of DMAc, 0.75 g (4.47 mmol) of carbazole, 0.85 g (4.47 mmol) of CuI, 0.62 g (4.47 mmol) of potassium carbonate L -Proline 50 mg (0.40 mmol) was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. for 6 hours under a nitrogen stream. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent = heptane: methylene chloride = 9: 1) to obtain a white powder of Si-26. Yield 1.05 g (Yield 78%) The structure was identified by nuclear magnetic resonance ( ¹ H-NMR, ¹³ C-NMR, etc.) and MASS spectrum (mass spectrometry).

下記参照文献（ｇ）に従い合成した出発原料（Ｋ）３．１８ｇ（１０．０ｍｍｏｌ）をクロロホルム６０ｍｌに溶解し、ＮＢＳ３．９１ｇ（２２．０ｍｍｏｌ）を加え、室温で３時間撹拌を行った。反応終了後、有機層を充分水洗し、溶媒を減圧下に留去した。残さをトルエンから再結晶し、中間体（Ｌ）４．５０ｇ（収率９５％）得た。次に、（Ｌ）４．００ｇ（８．３９ｍｍｏｌ）を脱水エーテル５０ｍｌに溶解し、内温を−７５℃に冷却した。次に１．６１ＭのｎＢｕＬｉ／ヘキサン溶液 １０．９ｍｌ（１７．６ｍｍｏｌ）を内温−７０℃以下を保ちながらゆっくりと加えた。添加後、２時間同温度下で撹拌したのち、ＳｉＣｌ_４ ０．７１ｇ（４．１９ｍｍｏｌ）を脱水エーテル１０ｍｌに溶解した溶液を内温−６５℃以下を保ちながらゆっくりと加えた。同温度で３時間撹拌したのち、成り行きで室温まで加温し、さらに２時間撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをメチレンクロリドーエタノール混合溶媒で再結晶し、中間体（Ｍ）を２．２２ｇ（収率８０％）で得た。次に（Ｍ）２．００ｇ（２．０５ｍｍｏｌ）を酢酸３０ｍｌに溶解し、臭素０．６９ｇ（４．３１ｍｍｏｌ）を加えて室温で５時間撹拌した。溶媒を減圧下に留去し、残さをトルエンで再結晶し、知中間体（Ｎ）を１．８０ｇ（収率９０％)で得た。次に（Ｎ）１．５０ｇ（１．５４ｍｍｏｌ）をＤＭＡc３０ｍｌに溶解し、カルバゾール１．０８ｇ（６．４７ｍｍｏｌ）、ＣｕＩ １．２３ｇ（６．４７ｍｍｏｌ）、炭酸カリウム０．８９ｇ（６．４７ｍｍｏｌ）L-ｐｒｏｌｉｎｅ ７０ｍｇ（０．６０ｍｍｏｌ）を加え、窒素気流下、内温１５０℃で８時間加熱撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをシリカゲルカラムクロマトグラフィー(展開溶媒＝ヘプタン：メチレンクロリド＝１０：１)にて精製し、Ｓｉ−３２の白色粉末を得た。収量１．５３ｇ(収率７５％) 構造は、核磁気共鳴法（^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ等）及びＭＡＳＳスペクトル（質量分析法）にて同定した。 << Synthesis Example 6: Synthesis of Compound Si-32 >>

3.18 g (10.0 mmol) of the starting material (K) synthesized according to the following reference document (g) was dissolved in 60 ml of chloroform, 3.91 g (22.0 mmol) of NBS was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the organic layer was sufficiently washed with water and the solvent was distilled off under reduced pressure. The residue was recrystallized from toluene to obtain 4.50 g of intermediate (L) (yield 95%). Next, 4.00 g (8.39 mmol) of (L) was dissolved in 50 ml of dehydrated ether, and the internal temperature was cooled to -75 ° C. Next, 10.9 ml (17.6 mmol) of a 1.61 M nBuLi / hexane solution was slowly added while maintaining the internal temperature at −70 ° C. or lower. After the addition, the mixture was stirred at the same temperature for 2 hours, and then a solution in which 0.71 g (4.19 mmol) of SiCl ₄ was dissolved in 10 ml of dehydrated ether was slowly added while maintaining the internal temperature at −65 ° C. or lower. After stirring at the same temperature for 3 hours, the reaction was allowed to warm to room temperature, followed by further stirring for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was recrystallized with a mixed solvent of methylene chloride ethanol to obtain 2.22 g of intermediate (M) (yield 80%). Next, 2.00 g (2.05 mmol) of (M) was dissolved in 30 ml of acetic acid, 0.69 g (4.31 mmol) of bromine was added, and the mixture was stirred at room temperature for 5 hours. The solvent was distilled off under reduced pressure, and the residue was recrystallized from toluene to obtain 1.80 g (yield 90%) of the known intermediate (N). Next, 1.50 g (1.54 mmol) of (N) was dissolved in 30 ml of DMAc, 1.08 g (6.47 mmol) of carbazole, 1.23 g (6.47 mmol) of CuI, and 0.89 g (6.47 mmol) of potassium carbonate. -Proline 70 mg (0.60 mmol) was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. for 8 hours under a nitrogen stream. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent = heptane: methylene chloride = 10: 1) to obtain a white powder of Si-32. Yield 1.53 g (yield 75%) The structure was identified by nuclear magnetic resonance ( ¹ H-NMR, ¹³ C-NMR, etc.) and MASS spectrum (mass spectrometry).

中間体（Ｃ）４．９０ｇ（１０．０ｍｍｏｌ）をＤＭＡc７０ｍｌに溶解し、３−フェニルインドール４．０６ｇ（２１．０ｍｍｏｌ）、ＣｕＩ ４．００ｇ（２１．０ｍｍｏｌ）、炭酸カリウム２．９０ｇ（２１．０ｍｍｏｌ）L-ｐｒｏｌｉｎｅ２３０ｍｇ（２．００ｍｍｏｌ）を加え、窒素気流下、内温１５０℃で７時間加熱撹拌を行った。反応終了後、溶媒を減圧下に留去し、残さをシリカゲルカラムクロマトグラフィー(展開溶媒＝ヘプタン：酢酸エチル＝１０：１)にて精製し、Ｓｉ−４６の白色粉末を得た。収量６．２２ｇ(収率８７％) 構造は、核磁気共鳴法（^１Ｈ−ＮＭＲ、^１３Ｃ−ＮＭＲ等）及びＭＡＳＳスペクトル（質量分析法）にて同定した。 << Synthesis Example 7: Synthesis of Compound Si-46 >>

Intermediate (C) 4.90 g (10.0 mmol) was dissolved in DMAc 70 ml, 3-phenylindole 4.06 g (21.0 mmol), CuI 4.00 g (21.0 mmol), potassium carbonate 2.90 g (21. 0 mmol) L-proline (230 mg, 2.00 mmol) was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. for 7 hours under a nitrogen stream. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent = heptane: ethyl acetate = 10: 1) to obtain a white powder of Si-46. Yield 6.22 g (yield 87%) The structure was identified by nuclear magnetic resonance ( ¹ H-NMR, ¹³ C-NMR, etc.) and MASS spectrum (mass spectrometry).

In addition, diaromatic condensed silole compounds other than those shown in Synthesis Examples 1 to 8 were synthesized in the same manner.
In addition, in the synthesis | combination of the diaromatic ring-condensed silole type compound of this invention, the reference literature is enumerated below.
(A) Science 1998, 282, pp. 913-915 (b) J. Org. Org. Chem. , 2002, VOL. 67, pages 9392-9396 (c) J. MoI. Org. Chem. , 2006, VOL. 71, pp. 7826-7834 (d) J. MoI. Am. Chem. Soc. , VOL. 124, no. 1, 2002, pages 49-57 (e) WO 2006/002731, page 15 (f) J. Am. C. S. , [Section] B, Physical Organic 1996, 733-735 (g) Chem. Lett. 1982, pp. 1195-1198

The function of the diaromatic ring-condensed silole compound of the present invention contained in at least one of the organic layers constituting the organic EL device of the present invention is not limited. It may be contained.
The diaromatic ring-condensed silole compound is preferably a light emitting layer or a hole transport layer from the viewpoint of obtaining the effects described in the present invention (high light emission efficiency, long light emission lifetime, no or little discoloration over time). From the viewpoint of being contained in either the electron transport layer or the hole blocking layer and responsible for hole transport, it is preferably contained in the light emitting layer and the hole transport layer, and most preferably contained in the light emitting layer.
In particular, when the diaromatic condensed silole compound is contained in the light emitting layer, the diaromatic condensed silole compound of the present invention is preferably used as a light emitting host compound (also referred to as a host material).
Each organic layer constituting the organic EL device of the present invention may be constituted solely by the diaromatic ring-condensed silole compound of the present invention, or the diaromatic ring-condensed silole compound is mixed with other materials. You may be comprised with the mixture.

<< Constitutional layer of OLED element (organic EL element) >>
The constituent layers of the OLED element (organic EL element) of the present invention will be described.
The OLED element (organic EL element) of the present invention has a pair of electrodes (cathode and anode) on a substrate, and has an organic layer including a light emitting layer between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.
Hereinafter, although the preferable specific example of the layer structure of the OLED element (organic EL element) of this invention is shown below, this invention is not limited to these.
(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode

In the OLED element (organic EL element) of the present invention, the light emitting maximum wavelength of the blue light emitting layer is preferably 430 nm to 480 nm, and the green light emitting layer preferably has a light emitting maximum wavelength of 510 nm to 550 nm, and the red light emitting layer. Is preferably a monochromatic light emitting layer having a light emission maximum wavelength in the range of 600 nm to 640 nm, and is preferably a display element using these.
Further, a white light emitting element may be formed by laminating at least three of these light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers.
The OLED element of the present invention is preferably a white light emitting element, and is preferably a lighting device using these.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May also be the interface between the light emitting layer and the adjacent layer.
The total thickness of the light emitting layer is not particularly limited, but is preferably from the viewpoint of the uniformity of the film and the application of unnecessary high voltage during light emission and the improvement of the stability of the emission color with respect to the driving current. It is adjusted to the range of 2 nm to 5 μm, more preferably adjusted to the range of 2 nm to 200 nm, and particularly preferably adjusted to the range of 10 nm to 40 nm.

The light emitting layer of the OLED device of the present invention contains a light emitting dopant (such as a phosphorescent dopant (also referred to as a phosphorescent dopant group) or a fluorescent dopant) compound and a host compound.
In particular, the light emitting layer preferably contains a blue phosphorescent dopant compound and a host compound.

(1) Luminescent dopant compound A luminescent dopant compound is demonstrated.
As the luminescent dopant compound, a phosphorescent dopant compound or a fluorescent dopant compound can be used. In the present invention, a phosphorescent dopant compound is preferably used, and a blue phosphorescent dopant compound is more preferably used.

(1.1) Phosphorescent dopant compound The phosphorescent dopant compound according to the present invention will be described.
The phosphorescent dopant compound according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant compound is a compound that emits phosphorescence at room temperature (25 ° C.). A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.
The above phosphorescence quantum yield can be measured by the method described in Spectral II, page 398 (1992 edition, Maruzen) of 4th edition Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant compound according to the present invention only needs to achieve the above phosphorescence yield of 0.01 or more in any solvent.

There are two types of emission principles of the phosphorescent dopant compound.
One of them is the recombination of carriers on the host compound to which carriers are transported, generating an excited state of the luminescent host compound, and transferring this energy to the phosphorescent dopant to obtain light emission from the phosphorescent dopant. The energy transfer type.
The other is a carrier trap type in which the phosphorescent dopant compound itself becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant compound is obtained.
In any case, the excited state energy of the phosphorescent dopant compound is lower than the excited state energy of the host compound, which is a condition for obtaining good light emission.

Specific examples of known compounds used as phosphorescent dopants are shown below, but the present invention is not limited thereto.

(1.2) Fluorescent dopant compound Examples of the fluorescent dopant compound include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squarylium dyes, oxobenzoanthracene dyes, fluorescein dyes, rhodamine dyes, Examples include pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

(2) Luminescent host compound (also referred to as host material, host compound, luminescent host, etc.)
The light emitting host compound used in the light emitting layer and the light emitting unit of the OLED device of the present invention is phosphorescent at a room temperature (25 ° C.) with a mass ratio in the layer of 20% or more among the compounds contained in the light emitting layer. The quantum yield is defined as a compound having a value of less than 0.1, and preferably the phosphorescence quantum yield is less than 0.01.
The light emitting host compound preferably has a mass ratio in the layer of 20% or more among the compounds contained in the light emitting layer.
As the host compound, it is preferable to use the diaromatic condensed silole compound of the present invention. The host compound may be composed of one of the diaromatic ring-condensed silole compounds of the present invention alone, or may be composed of a combination of a plurality of the diaromatic ring-condensed silole compounds. .
By using a plurality of types of host compounds, it is possible to adjust the movement of carriers, and the performance of the OLED element can be further increased. In addition, by using a plurality of known compounds used as the phosphorescent dopant, it is possible to mix different light emission, thereby obtaining an arbitrary emission color.
The light emitting host used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). One or a plurality of such compounds may be used.

Conventionally known host compounds may be used in combination with the host compound.
Known light-emitting host compounds typically include those having a basic skeleton such as carbazole derivatives, triarylamine derivatives, aromatic derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, oligoarylene compounds, carboline derivatives, And diazacarbazole derivatives.
A known host compound that may be used in combination is preferably a compound that has a hole transporting ability and an electron transporting ability, prevents a long wavelength of light emission, and has a high Tg (glass transition temperature).
Specific examples of known host compounds include, but are not limited to, compounds described in the following documents.
JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

Next, an injection layer, a blocking layer, a transport layer and the like used as a constituent layer of the OLED element of the present invention will be described.
<Injection layer: electron injection layer, hole transport layer>
The injection layer can be provided as necessary, and includes an electron injection layer and a hole injection layer, and as described above, between the anode and the light emitting layer or the hole transport layer, or between the cathode and the light emitting layer or the electron transport layer. It may be present between.
An injection layer is a layer provided between an electrode and an organic layer to reduce drive voltage and improve light emission brightness. “OLED element and its forefront of industrialization (November 30, 1998, issued by NTS)” Chapter 2 “Electrode Materials” (pages 123 to 166) of the second edition of the same, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45579, JP-A-9-260062, JP-A-8-288069, and the like, and representative examples thereof include copper phthalocyanine. Phthalocyanine buffer layers, oxide buffer layers typified by vanadium oxide, amorphous carbon buffer layers, polymer buffer layers using conductive polymers such as polyaniline (emeraldine) and polythiophene, and the like.
Details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium or aluminum Metal buffer layer represented by lithium fluoride, alkali metal compound buffer layer represented by lithium fluoride, alkaline earth metal compound buffer layer represented by magnesium fluoride, oxide buffer layer represented by aluminum oxide, etc. It is done.
The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

<Blocking layer: hole blocking layer, electron blocking layer>
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film.
The blocking layer is, for example, pages 237 of JP-A Nos. 11-204158 and 11-204359, and “OLED elements and the forefront of industrialization (November 30, 1998, issued by NTS Corporation)”. There is a hole blocking layer (hole blocking layer).
The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons and having a remarkably small ability to transport holes. By blocking hole transport, the recombination probability of electrons and holes can be improved. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.
The hole blocking layer of the OLED element (organic EL element) of the present invention is preferably provided adjacent to the light emitting layer.
The hole blocking layer preferably contains the carbazole derivative, carboline derivative, diazacarbazole derivative, or the like mentioned as the host compound.

Moreover, when it has several light emitting layers from which luminescent color differs, it is preferable that the light emitting layer with the shortest light emission maximum wavelength is the closest to an anode among all the light emitting layers. In such a case, it is preferable to additionally provide a hole blocking layer between the shortest wave light emitting layer and the light emitting layer next to the anode next to the light emitting layer. Further, it is preferable that 50% by mass or more of the compound of the hole blocking layer provided at the position is 0.3 eV or more larger than the ionization potential of the host compound of the shortest wave emitting layer.
The ionization potential is defined as the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by, for example, the following method.
(1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA The ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
(2) It can also be determined by a method of direct measurement by photoelectron spectroscopy. Yes. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki.

On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material having a function of transporting holes and a very small ability to transport electrons, and transporting electrons while transporting holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.
The film thickness of the hole blocking layer and electron blocking layer according to the present invention is preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes. In a broad sense, the hole transport layer and the electron blocking layer can be regarded as being included in the hole transport layer.
The hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers and conductive polymers (polymers and oligomers), particularly thiophene oligomers.

The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Further, the OLED element material of the present invention can also be preferably used.
Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4 '. -Diamine (TPD), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD), 4,4 ', 4 "-tris [N- (3-methylphenyl) ) -N-phenylamino] triphenylamine (MTDATA).
Furthermore, a polymer material in which these materials are introduced into a polymer chain or a polymer main chain can also be used.
Inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole transport material.
JP-A-11-251067, J. Org. Huang et al. A p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.

The hole transport layer is formed by thinning the hole transport material as described above by, for example, a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. be able to.
Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-5 micrometers, Preferably it is 5 nm-200 nm.
Further, the hole transport material may have a single layer structure composed of a plurality of types of materials.
Alternatively, a hole transport layer having a high p property doped with impurities can be used.

《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons. In a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
The electron transport layer can be provided as a single layer or a plurality of layers.
An electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the cathode side with respect to the light emitting layer may have a function of transmitting electrons injected from the cathode to the light emitting layer. As the material, any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthra Examples include quinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, phthalocyanine materials and derivatives thereof can also be preferably used as the electron transport material.
In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm.
The electron transport layer may have a single layer structure composed of one or more of the above materials.
Further, an electron transport layer having a high n property doped with impurities can also be used.

"anode"
As the anode in the OLED element, an electrode material made of a metal, an alloy, an electrically conductive compound and a mixture thereof having a high work function (4 eV or more) is preferably used.
Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.
Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.
For the anode, a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern may be formed through a photolithography method or a mask.
Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used.
When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less.
Further, although the film thickness depends on the material, it is usually in the range of 10 nm to 1000 nm, and preferably in the range of 10 nm to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm.
In order to transmit the emitted light, if either the anode or the cathode of the OLED element is transparent or translucent, the light emission luminance is improved and it is convenient.
Moreover, after producing the said metal by the film thickness of 1 nm-20 nm to a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the OLED device (organic EL device) of the present invention, there is no particular limitation on the type of glass, plastic, etc. It may be transparent or opaque.
When extracting light from the support substrate side, the support substrate is preferably transparent.
Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film.
A particularly preferable support substrate is a resin film capable of giving flexibility to the OLED element (organic EL element).

Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellulose esters (cellulose acetate propionate (CAP), cellulose acetate phthalate (TAC), and cellulose nitrate. Etc.) or derivatives thereof, polyvinylidene chloride, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyethersulfone (PES), polyphenylene sulfide, polysulfones, polyether Imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic Alternatively polyarylates, and cycloolefin resins such as ARTON (manufactured by JSR) or APEL (manufactured by Mitsui Chemicals).
On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987. The permeability is 10 ⁻³ cm ³ / (m ² · 24 h · atm) (1 atm is 1.01325 × 10 ⁵ Pa) or less, and the water vapor permeability is 10 ⁻³ g / (m ² · 24 h) or less. It is preferably a high barrier film, and more preferably has a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less.

As a material for forming the barrier film, any material may be used as long as it has a function of suppressing intrusion of moisture or oxygen that causes deterioration of the element. For example, silicon oxide, silicon dioxide, silicon nitride, or the like is preferably used. it can. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.
The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, and an atmospheric pressure plasma polymerization method is particularly preferable.

Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.
The external extraction quantum efficiency at room temperature of light emission of the OLED element (organic EL element) of the present invention is preferably 1% or more, more preferably 5% or more.
Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the OLED element / the number of electrons sent to the OLED element × 100.
In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the OLED element into multiple colors with a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the OLED element is preferably 480 nm or less.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, or a support substrate with an adhesive agent can be mentioned, for example.
As a sealing member, it should just be arrange | positioned so that the display area | region of an OLED element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.
Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned.
Further, the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less, and conforms to JIS K 7129-1992. The water permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by the method is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less.

Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
In addition, when using a thermosetting adhesive, since an OLED element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.
In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.

Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials.
The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster-ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
In the gap between the sealing member and the display area of the OLED element, it is preferable to inject an inert gas such as nitrogen or argon, an inert liquid such as fluorinated hydrocarbon, or silicon oil in the gas phase and the liquid phase. . A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.
Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.), sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, etc.), metal halides. Perchloric acids and the like, and anhydrous salts are preferably used.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when sealing is performed by the sealing film, it is preferable to provide a protective film and a protective plate.
As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used. It is preferable to use a film.

《Light extraction》
The OLED element emits light inside a layer having a higher refractive index than air (refractive index is about 1.7 to 2.1), and only 15% to 20% of the light generated in the light emitting layer can be extracted. Is generally said.
This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.
As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

In the present invention, these methods can be used in combination with the OLED element of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, a transparent electrode A method of forming a diffraction grating between any of the layers and the light emitting layer (including between the substrate and the outside) can be suitably used. In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.
When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency.
This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction, such as first-order diffraction or second-order diffraction, and light generated from the light-emitting layer. The light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating in any layer or medium (in the transparent substrate or transparent electrode). It is intended to be taken out.
The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.
However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.
As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated. At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.
The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The OLED element of the present invention is processed on the light extraction side of the substrate, for example, by providing a microlens array-like structure, or combined with a so-called condensing sheet, so that the OLED element is arranged in a specific direction, for example, the element light emitting surface. On the other hand, the brightness | luminance in a specific direction can be raised by condensing in a front direction.
As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.
As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<< Production Method of OLED Element (Organic EL Element) >>
As an example of the method for producing the OLED device of the present invention, a method for producing an OLED device comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
First, a desired electrode material, for example, a thin film made of an anode material is formed on an appropriate support substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm. To do.

Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are OLED element materials, is formed thereon.
As a method for forming each of these layers, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above. In view of the above, in the present invention, a wet process is preferable, and film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is particularly preferable.
Examples of the liquid medium for dissolving or dispersing the OLED element material of the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, mesitylene, Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.
Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 nm to 200 nm, and a cathode is provided. Thus, a desired OLED element can be obtained.

Note that it is also possible to produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order by reversing the order of production.
When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Application>
The OLED element (organic EL element) of the present invention can be used as a display device, a display, and various light sources.
For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Examples include, but are not limited to, a light source of a sensor, and the light source can be preferably used for a backlight of a liquid crystal display device and a light source for illumination.
In the OLED element (organic EL element) of the present invention, patterning may be performed by a metal mask, an inkjet printing method, or the like at the time of film formation, if necessary. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.
The light emission color of the OLED element (organic EL element) of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (Edited by the Japan Color Society, University of Tokyo Press, 1985). The color measured when the result measured with a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates is determined.
Further, when the OLED element (organic EL element) of the present invention is a white light emitting element, white means the CIE 1931 color system at 1000 cd / m ² when the front luminance at 2 ° viewing angle is measured by the above method. Is in the region of X = 0.33 ± 0.07, Y = 0.33 ± 0.1.

<< Display device and lighting device >>
An example of a display device (see FIGS. 1 and 2) and an illumination device (see FIGS. 3 and 4) using the OLED element (organic EL element) of the present invention will be described based on the drawings.

FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements.
FIG. 1 is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
As shown in FIG. 1, the display 1 includes a display unit A having a plurality of pixels and a control unit B that performs image scanning of the display unit A based on image information.
The control unit B is electrically connected to the display unit A.
The control unit B sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside, and the pixels for each scanning line sequentially emit light according to the image data signal by the scanning signal to perform image scanning. The image information is displayed on the display unit A.

FIG. 2 is a schematic diagram of the display unit A.
As shown in FIG. 2, the display unit A has a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 on a substrate.
The main members of the display unit A will be described below.
FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
Each of the scanning lines 5 and the plurality of data lines 6 in the wiring portion is made of a conductive material.
The scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice pattern, and are connected to the pixels 3 at the orthogonal positions (details are not shown).
When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.
According to the display unit A, full-color display can be performed by appropriately arranging pixels in which the emission color is a red region, a green region, and a blue region on the same substrate.

FIG. 3 shows a schematic diagram of the illumination device.
As shown in FIG. 3, the organic EL element 101 is covered with a glass cover 102. The sealing operation with the glass cover 102 is preferably a glove box (purity) in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. 99.999% or higher atmosphere of high purity nitrogen gas).
FIG. 4 shows a cross-sectional view of the lighting device.
As shown in FIG. 4, the lighting device includes a cathode 105, an organic EL layer 106, and a glass substrate 107 with a transparent electrode.
In the lighting device, the glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.
In addition, compounds used for manufacturing the device are shown below.

<Production of sample>
(1) OLED element 1-1
Using a substrate in which ITO (indium tin oxide) is formed to a thickness of 200 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm, the ITO film is patterned to obtain a light emitting area of 50 mm × 50 mm, and an anode electrode (ITO) A transparent electrode) was prepared, ultrasonically cleaned with isopropyl alcohol, dried with nitrogen gas, and further subjected to UV ozone cleaning to prepare a transparent support substrate.
This transparent support substrate was put into a commercially available vacuum deposition apparatus, and after reducing the pressure to 4 × 10 ⁻⁴ Pa or less, CuPc (copper phthalocyanine) was deposited as a hole injection layer to provide a 20 nm hole injection layer.
Subsequently, a hole transporting material HT-1 is deposited to a thickness of 20 nm to form a hole transporting layer, on which a diaromatic condensed silole compound Si-1 of the present invention as a host material and a blue phosphorescent dopant D- 1 and a light emitting layer having a dopant concentration of 10% was deposited by 30 nm.
Further, the electron transport material ET-1 was deposited to 30 nm to form an electron transport layer, then lithium fluoride was deposited to 0.5 nm to form an electron injection layer, aluminum 120 nm was deposited to form a cathode, OLED element 1-1 "was produced.

(2) OLED elements 1-2 to 1-27
In the production of the OLED element 1-1, as shown in Table 1, the electron transport material, the host material, and the hole transport material were changed.
Other than that produced "OLED element 1-2-1-27" similarly.

<< Evaluation of Samples (OLED Elements 1-1 to 1-27) >>
In each of the OLED elements 1-1 to 1-27, the non-light-emitting surface is covered with a glass case, the peripheral portion is sealed with an epoxy-based adhesive, and an illumination device (planar lamp) as shown in FIGS. For each element, the following light emission efficiency, light emission lifetime, and discoloration (discoloration of the light emission color over time) were evaluated.

(1) Luminous efficiency About OLED elements 1-1 to 1-27, a constant current of ^2.5 mA / cm ² was applied, and the external extraction quantum efficiency at that time was measured. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used.
In addition, the value of efficiency sets the measured value of the OLED element 1-1 to 100 for the OLED elements 1-1 to 1-14, and the OLED element 1-15 for the OLED elements 1-15-1 to 1-20. Table 1 shows relative values when the measured value of OLED element 1-21 is 100 with respect to OLED elements 1-21 to 1-27.

(2) for emission lifetime OLED element 1-1～1-27, initial luminance 600 cd / ^{m 2} was driven at a constant current at a current giving, to measure the time to be 1/2 (300 cd / ^{m 2)} of the initial luminance, This was taken as a measure of stability.
As in the evaluation of efficiency, the stability value is 100 for the OLED elements 1-1 to 1-14, and the measured value of the OLED elements 1-1 to 1-20 is 100. On the other hand, the measured value of the OLED element 1-15 is 100, and the relative value when the measured value of the OLED element 1-20 is 100 is shown in Table 1 for the OLED elements 1-21 to 1-27. .

(3) The emission color of the color change with time OLED element 1-1～1-27, initial luminance 600 cd / ^{m 2} constant current was driven at a current giving, becomes the initial luminance 2/3 (400 cd / ^{m 2)} The change in emission color was observed visually, and the following four rank evaluations were performed on the observation results. The obtained results are shown in Table 1.
“◎”: No discoloration is observed. “◯”: Slightly yellowish.
“△”: Yellowish.
“×”: remarkably yellowish.

(4) Summary As shown in Table 1, OLED elements 1-1 to 1-7, 1-15 to 1-18, 1-21 to 1-24 and OLED elements 1-8 to 1-14, 1-19 to 1-20, 1-25 to 1-27, OLED elements 1-1 to 1-7, 1-15 to 1-18, 1-21 to 1-24, which are examples of the present invention, It was excellent in all the characteristics of luminous efficiency, luminous lifetime and discoloration (discoloration of luminescent color with time).
From the above, the fact that a diaromatic condensed silole compound is contained in an organic layer such as a hole transport layer, a light emitting layer, or an electron transport layer is useful for improving luminous efficiency, light emitting lifetime, and prevention of discoloration. I understand that.

<< Preparation of White Light-Emitting Element X and White Illuminating Device X >>: Example of the Present Invention As a positive hole injection / transport layer in the same manner as in Example 1 above on a glass substrate with ITO patterned to 20 mm × 20 mm as an anode HT-1 is formed into a film having a thickness of 30 nm, and the diaromatic condensed silole compound Si-3 and dopants D-6 and D-36 are deposited at a deposition rate of 100: 0.5: 8, respectively. The emission layer having a thickness of 40 nm was provided.
Next, 10 nm of BAlq was formed as a hole blocking layer, and then 30 nm of Alq ₃ was formed to provide an electron transport layer.
Subsequently, lithium fluoride was formed to a thickness of 0.5 nm as an electron injection layer, and then 200 nm of aluminum was formed as a cathode to produce “white light emitting element X”.
Next, the non-light-emitting surface of the white light-emitting element X was covered with a glass case and sealed with an epoxy adhesive, and a flat lamp type “white illumination device X” as shown in FIGS. 3 and 4 was produced.
When the white lighting device X was energized, white light with luminous efficiency comparable to that of the cold cathode tube was obtained, and it was found that the white light emitting element X can be used as the lighting device. The light emission life of this lighting device was good, and no discoloration of the emission color over time was observed.

<< Preparation of White Light-Emitting Element Y and White Lighting Device Y >>: Example of the Present Invention On the same glass substrate used for the production of white light-emitting element X and white lighting device X of Example 2, poly (3, 4-Ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083), a pure solution diluted to 70%, was spin-coated at 3000 rpm for 30 seconds, dried, and then positively coated with a film thickness of 30 nm. A hole transport layer was provided.
Further, the substrate with a hole transport layer was transferred to a nitrogen atmosphere, and a diaromatic condensed silole compound Si-46 (150 mg) and dopants D-8 (6.5 mg) and D-34 (4.0 mg) were added. A solution dissolved in 10 ml of toluene was spin-coated at 1000 rpm for 30 seconds, and then dried under reduced pressure at 100 ° C. to obtain a light emitting layer.
Subsequently, this substrate was transferred to a vacuum deposition apparatus, and Alq ₃ was formed to a thickness of 40 nm as an electron transport layer at a degree of vacuum of 4.0 × 10 ⁻⁴ Pa, and subsequently, lithium fluoride was set to a thickness of 0.04 as an electron injection layer. After forming to a thickness of 5 nm, aluminum having a thickness of 150 nm was formed as a cathode to produce “white light emitting element Y”.
Next, the non-light-emitting surface of the white light-emitting element Y was covered with a glass case and sealed with an epoxy adhesive, and a flat lamp type “white illumination device Y” as shown in FIGS. 3 and 4 was produced.
When the white lighting device Y was energized, almost white light was obtained, and it was found that the white light emitting element Y can be used as the lighting device. The light emission life of this lighting device was good, and no discoloration of the emission color over time was observed.

<< Production of Comparative White Light Emitting Elements y1 and y2 and Comparative White Lighting Devices y1 and y2 >>
In the production of the white light-emitting element Y and the white lighting device Y, the diaromatic condensed silole compound Si-23 was replaced with the comparative compound 5 (150 mg) and the comparative compound 6 (150 mg), respectively. Comparative white light-emitting elements y1 and y2 were produced, and then comparative white lighting devices y1 and y2 were produced respectively.
When the white light-emitting elements y1 and y2 for comparison were respectively energized, white light emission was obtained from the white illumination devices y1 and y2, respectively, and the white light-emitting devices y1 and y2 had white light emission efficiency as an example of the present invention. It was found that it was about 80% of the white lighting device Y having the element Y, and the luminescent color changed to yellow over time.
From the above, according to the white light-emitting element Y which is an embodiment of the present invention, the white illumination device is superior in light emission efficiency, light-emission life and discoloration of the emitted color over time as compared with the comparative white light-emitting elements y1 and y2. It is clear that can be provided.

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line A Display part B Control part 101 Organic EL element 102 Glass cover 105 Cathode 106 Organic EL layer 107 Glass substrate with a transparent electrode 108 Nitrogen gas 109 Water trapping agent

Claims (4)

In an organic electroluminescence device having a pair of electrodes and at least one organic layer disposed between the pair of electrodes and including a light emitting layer,
At least one of the diaromatic ring-condensed silole compounds represented by the general formulas 1 to 4 is contained in at least one of the organic layers.

“In General Formula 1, R ₁ and R ₂ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms, provided that R ₁ and R ₂ There is .R ₃ and _{R 4} not simultaneously hydrogen atoms aromatic hydrocarbon ring group having 6 to 20 carbon atoms, .R ₃ and _{R 4} representing an aromatic heterocyclic group having 3 to 20 carbon atoms with each other Q ₁ , Q ₃ , Q ₄ , and Q _{6 each} represent a nitrogen atom or C—Rx, where Rx is a hydrogen atom or an aromatic hydrocarbon ring having 6 to 20 carbon atoms. Group represents an aromatic heterocyclic group having 3 to 20 carbon atoms, Q ₂ and Q ₅ each represent a nitrogen atom or C—H.
In General Formula 2, R ₅ and R ₆ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. However, R ₅ and R ₆ are not simultaneously hydrogen atoms. R ₇ and R ₈ represent an aromatic hydrocarbon ring group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms. R ₇ and R ₈ may combine with each other to form a ring. Q ₇ and Q ₉ represent a nitrogen atom or C—Rz. Rz represents a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. Q ₈ and Q ₁₀ represent an oxygen atom or a sulfur atom.
In General Formula 3, R ₁ , R ₂ , and Q _{1 to} Q ₆ have the same meanings as in General Formula 1. R ₉ and R ₁₀ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms.
In the general formula 4, R ₅ , R ₆ , and Q _{7 to} Q ₁₀ are the same as those in the general formula 2. R ₁₁ and R ₁₂ represent a hydrogen atom, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms. " The organic electroluminescent device according to claim 1,
The organic light-emitting device, wherein the light emitting layer contains at least one diaromatic condensed silole compound represented by the general formulas 1 to 4. In the organic electroluminescent element according to claim 1 or 2,
An organic electroluminescence device, wherein the light emitting layer contains a blue phosphorescent dopant compound.   An illuminating device comprising the organic electroluminescence element according to claim 1.

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