TWI245586B - Phosphorescent solid body, organic electroluminescent element, and organic electroluminescent device - Google Patents

Phosphorescent solid body, organic electroluminescent element, and organic electroluminescent device Download PDF

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TWI245586B
TWI245586B TW093108735A TW93108735A TWI245586B TW I245586 B TWI245586 B TW I245586B TW 093108735 A TW093108735 A TW 093108735A TW 93108735 A TW93108735 A TW 93108735A TW I245586 B TWI245586 B TW I245586B
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light
item
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Tasuku Satoh
Wataru Sotoyama
Norio Sawatari
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Fujitsu Ltd
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
    • C09K11/7492—Arsenides; Nitrides; Phosphides
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/89—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing mercury
    • C09K11/892—Chalcogenides
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission

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Abstract

Disclosed is a phosphorescence emitting solid comprising an organometallic complex which has a tridentate ligand coordinating to a central metal through two nitrogen atoms and one carbon atom positioning between said two nitrogen atoms and binding with said two nitrogen atoms via bonds and has a halogen atom as a ligand; a luminescent element using the solid; and an organic EL device using the element. The phosphorescence emitting solid can emit a phosphorescence having very high intensity in a solid state, and thus, the use of the solid in an organic EL element allows the significant improvement of the luminous efficiency, which results in the reduction of electric power consumption in an organic EL device.

Description

1245586 玫、發明說明： I：發明戶斤屬之技術領域】 本發明是有關於含有具特定配位子之磷光發光性有機金 屬錯合物之磷光發光固體；使用該磷光發光固體之發光元件， 5特別是有機電致發光元件（以下將「電致發光」略稱為EL); 及使用该有機EL元件之有機EL顯示器、有機el照明裝置等 有機EL裝置。 C mr u 自仗積層正電洞輸送性與電子輸送性之各個有機薄膜之 1〇 積層型元件之報告（例如 C.W.Tang and S.A.Vanslyke，Applied1245586 Rose, description of invention: I: Technical field of the invention] The present invention relates to a phosphorescent light-emitting solid containing a phosphorescent light-emitting organic metal complex with a specific ligand; a light-emitting element using the phosphorescent light-emitting solid, 5 In particular, organic electroluminescence elements (hereinafter, "electroluminescence" is abbreviated as EL); and organic EL devices such as organic EL displays and organic el lighting devices using the organic EL elements. C mr u Report of 10-layered components of each organic thin film from the organic hole transportability and electron transportability of laminated layers (eg C.W.Tang and S.A. Vanslyke, Applied

Physics Letters，第51卷?1) 91351987年）以來，有機虹元件即 以具有自發光、高速回應等特徵之顯示元件而期待其可適用於 平板顯示器，特別受到注目的是作為以1〇v以下之低電壓發光 之大面積發光元件。 15 積層型有機EL元件基本上具有陽極/正電洞輸送層/發光 層/電子輸送層/陰極之構成。其中，發光層可如上述之Tang andPhysics Letters, Vol. 51? 1) Since 91351987), organic rainbow elements are expected to be suitable for flat panel displays with self-luminous, high-speed response and other display elements. They have been particularly noticed as being below 10V. Low-voltage light-emitting large-area light-emitting element. 15 A multilayer organic EL element basically has a structure of an anode / positive hole transport layer / light emitting layer / electron transport layer / cathode. Wherein, the light emitting layer may be as described in Tang and

Vanslyke之2層型元件之情況，構成為使正電洞輸送層或電子 輪送層兼具其機能。 如、為了得到高發光效率之有機EL元件，發光層必須具有高 0發光效率。發光層之構造可為以1種材料形成單獨膜，再加上 於主成分之主體材料中摻雜少量作為客體之螢光發光性高之In the case of Vanslyke's two-layer element, the positive hole transport layer or the electronic carousel layer is configured to have both functions. For example, in order to obtain an organic EL element with high light emitting efficiency, the light emitting layer must have high light emitting efficiency. The structure of the light-emitting layer can be a single film formed by one material, and a small amount of doping as a guest is added to the host material of the main component.

C.W.Tang5S.AW CH.Chen Journal of Applied Physics，第 65 卷 p361〇i989 年）。 又，近年來，已有利用來自分子之激光三重態之發光之石舞 1245586 來取代上述螢光材料， 而受到注目（M.A.Baldo A.Baldo 等，Applied 光材料作為有機EL元件之發光材料， 藉此可提高有機EL元件之發光效率， 等，Nature,第 395 卷，p.151,1998 年； Physics Letters，第 75 卷，p,4，1999 年）。 5 在室溫下發出填光之有機金屬錯合物之有機EL元件 之習知例子可舉特開2002-363552號公報中所記載之具有三座 配位子之金屬錯合物為其-例。該習知例中，揭示了以具有三 座配位子（NIC)之有機金屬錯合物作為有機el元件之發 光材料來使用之技術，該三座配位子乃是藉以翻與氣形成的兩 1〇個配位鍵及鉑與碳之間之一個配位鍵所形成，且該兩個氮與碳 以N，N，C之順序鍵結（NWC)。然而，該錯合物之磷光發光 在室溫下並不充足，因此，前述習知例之有機EL元件發光效 率低。 另一方面，關於在室溫下發出磷光之有機金屬錯合物之一 15 般研究，J.A.G.WUliams等報告中指出，具有n^CTN变三座配 位子構造之有機金屬錯合物，在溶液中可發出比型更 強的磷光（Inorg.Chem·，第 42 卷，p.8609-8611，2003 年）。 來自有機物之發光依據引起發光之激光狀態之性質而可 分為螢光和填光兩大類。目前為止，由於一般的有機物不發出 20 磷光，故有機EL元件中皆利用螢光發光。但是，從EL發光機 構可預測磷光發光狀態係以螢光發光狀態的4倍之機率生成， 故近年來，在室溫下引起磷光發光之重金屬錯合物適用於發光 材料，就成為EL元件之高效率化裝置而受到注目。然而，在 室溫下發出強烈磷光之材料非常少，材料之選擇範圍狭窄是目 1245586 前最大的問題點。 t發明内容】 本發明檢討適用於有機EL元件之磷光發光材料，而目的 在於提供發光效率高之磷光發光固體、利用該磷光發光固體之 5 有機EL元件及有機EL裝置。本發明之其他目的及優點可從以 下說明而清楚明瞭。 為了解決課題而做各種檢討，結果發現，具有特定之三座 配位子與ii素原子作為配位子之金屬錯合物，在固體狀態下尤 其可發出強烈磷光，而將之作為發光材料使用之有機EL元件 10 可高效率發光。 藉本發明之一態樣，可提供一種磷光發光固體，該磷光發 光固體含有分別配位一個以上之三座配位子與i素原子而形 成之有機金屬錯合物，且該三座配位子係以兩個氮原子、與位 於該兩個氮原子間且透過鍵與該兩個氮原子鍵結之一個碳原 15 子來配位鍵結於中心金屬原子。 本發明之磷光發光固體宜具有下述特徵，即： 磷光發光固體含有具有以下式（1)表示之構造之有機金屬錯 合物：C.W.Tang5S.AW CH.Chen Journal of Applied Physics, Vol. 65, p361〇i989). In addition, in recent years, the use of the light-emitting three-state light-emitting stone dance 1245586 from the molecule to replace the above fluorescent materials has attracted attention (MABaldo A. Baldo et al., Applied light materials have been used as light-emitting materials for organic EL devices. This can improve the luminous efficiency of organic EL elements, etc., Nature, Vol. 395, p.151, 1998; Physics Letters, Vol. 75, p. 4, 1999). 5 As a conventional example of an organic EL device that emits a light-filled organometallic complex at room temperature, the metal complex having three ligands described in JP-A-2002-363552 can be cited as an example. . This conventional example discloses a technique using an organometallic complex having three ligands (NIC) as a light-emitting material of an organic el element. The three ligands are formed by transversal energy. Two 10 coordination bonds and one coordination bond between platinum and carbon are formed, and the two nitrogen and carbon are bonded in the order of N, N, C (NWC). However, the phosphorescent luminescence of this complex is not sufficient at room temperature, and therefore, the organic EL element of the aforementioned conventional example has a low luminous efficiency. On the other hand, regarding one of the general studies of organometallic complexes that emit phosphorescence at room temperature, JAGWUliams et al. Reported that organometallic complexes with a three-ligand structure of n ^ CTN change in solution. It can emit stronger phosphorescence than the type (Inorg. Chem., Vol. 42, p. 8609-8611, 2003). Luminescence from organic substances can be divided into two categories, fluorescent and filling, depending on the nature of the state of the laser that causes it to emit light. Up to now, since ordinary organic substances do not emit 20 phosphorescence, organic EL devices have used fluorescent light to emit light. However, it can be predicted from the EL light-emitting mechanism that the phosphorescent light-emitting state is generated with a four times the probability of the fluorescent light-emitting state. Therefore, in recent years, a heavy metal complex that causes phosphorescent light emission at room temperature is suitable for a light-emitting material and has become an EL element High-efficiency devices have attracted attention. However, there are very few materials that emit strong phosphorescence at room temperature, and the narrow choice of materials is the biggest problem before heading 1245586. SUMMARY OF THE INVENTION The present invention reviews a phosphorescent light-emitting material suitable for an organic EL element, and aims to provide a phosphorescent light-emitting solid with high luminous efficiency, an organic EL element using the phosphorescent light-emitting solid, and an organic EL device. Other objects and advantages of the present invention will be apparent from the following description. In order to solve the problem, various reviews were conducted. As a result, it was found that a metal complex having a specific three ligands and a ii prime atom as ligands can emit strong phosphorescence in a solid state, and use it as a light-emitting material. The organic EL element 10 can emit light with high efficiency. According to one aspect of the present invention, a phosphorescent solid can be provided. The phosphorescent solid contains an organometallic complex formed by coordinating one or more three ligands and an i element atom, and the three complexes are coordinated. The child is coordinated to the central metal atom with two nitrogen atoms and a carbon atom 15 located between the two nitrogen atoms and bonded to the two nitrogen atoms through a bond. The phosphorescent light-emitting solid of the present invention preferably has the following characteristics, that is, the phosphorescent light-emitting solid contains an organometallic complex having a structure represented by the following formula (1):

Μ-—X 20 (式（1)中，Μ表示金屬原子，X表示鹵素原子，Ar·1，Ar2， Ar3各自獨立地表示可具有取代基之環狀構造，Ar1 — Αι·2及Ar2 1245586 一之Ar3鍵可為單鍵或雙鍵，Μ與Ar1及Μ與Ar3具有Μ — N之配位 鍵，Μ與Ar2具有M—C之直接鍵，Ar1，Ar2，Ar3之取代基可分 別在Ar1，Ar2，Ar3上互相鍵結形成環狀構造，以及分別在Ar] 與Ar2相互間、及Ar2與Αι·3相互間互相鍵結形成環狀構造）。 5 又，該磷光發光固體含有有機金屬錯合物，該有機金屬錯合物 係分別配位一個以上之三座配位子與鹵素原子而形成者，且該 三座配位子係以兩個氮原子與一個碳原子配位鍵結於中心金 屬原子，又，該兩個氮原子、一個碳原子及中心金屬原子具有 兩個5員環縮合之形狀之構造部分，且該兩個5員環共用該碳原 10 子與中心金屬原子之鍵。又，前述有機金屬錯合物具有以下式 (2)表示之構造部分：M—X 20 (In the formula (1), M represents a metal atom, X represents a halogen atom, Ar · 1, Ar2, and Ar3 each independently represent a cyclic structure which may have a substituent, and Ar1 — Α · 2 and Ar2 1245586 The Ar3 bond can be a single bond or a double bond, M and Ar1 and M and Ar3 have M — N coordination bonds, M and Ar2 have a direct bond of M — C, the substituents of Ar1, Ar2, and Ar3 can be respectively Ar1, Ar2, and Ar3 are bonded to each other to form a ring structure, and Ar] and Ar2 are bonded to each other, and Ar2 and Al · 3 are bonded to each other to form a ring structure). 5 Also, the phosphorescent solid contains an organometallic complex, and the organometallic complex is formed by coordinating one or more three ligands and a halogen atom, and the three ligands are formed by two A nitrogen atom and a carbon atom are coordinated and bonded to a central metal atom, and the two nitrogen atoms, one carbon atom, and the central metal atom have two 5-membered ring-condensed structural parts, and the two 5-membered rings The bond between the carbon atom and the central metal atom is shared. The organometallic complex has a structural portion represented by the following formula (2):

(式（2)中，Μ與X同式（1)，Y為相互獨立地表示碳原子或 氮原子，Ν — Υ鍵結部分構成前述式（1)中之Ar1或Ar3之一部 15 份，苯核可具有取代基，且配位子與中心金屬原子之鍵以外之 鍵可為單鍵亦可為雙鍵。） 又，前述有機金屬錯合物具有以下式（3)表示之構造部分：(In the formula (2), M and X are the same as in the formula (1), Y is a carbon atom or a nitrogen atom independently of each other, and the N—Υ bond portion constitutes 15 parts of Ar1 or Ar3 in the formula (1). The benzene nucleus may have a substituent, and the bond other than the bond between the ligand and the central metal atom may be a single bond or a double bond.) Further, the organometallic complex has a structural portion represented by the following formula (3) :

(式（3)中，Μ與X同式（1)，苯核可相互獨立地具有取代基， 1245586 取代基可在同一環上或鄰接之環之間相互鍵結。） 又，前述Ar1與Ar3相互獨立地含有單環或多環之芳香環。又， 前述Ar1與Ar3相同。又，前述有機金屬錯合物係由一個三座配 位子、一個鹵素原子與一個中心金屬原子形成。又，前述有機 5 金屬錯合物在固體狀態下為電中性。又，前述有機金屬錯合物 可藉真空蒸鍍形成膜。又，前述磷光發光固體係使用純度99.5 重量％以上之前述有機金屬錯合物而形成者。又，前述中心金 屬原子為鉑。又，前述磷光發光固體至少含有各一個之前述有 機金屬錯合物、與具有高於前述有機金屬錯合物之第一激光三 10 重態激光能量之有機材料。又，前述有機材料含有可具有取代 基之咔唑或其衍生物。 藉本發明之磷光發光固體，可實現在固體狀態下非常強烈 之石粦光。 藉有關本發明之其他態樣，可提供利用上述磷光發光固體 15 所形成之有機電致發光元件。 本發明之有機電致發光元件宜具有下述特徵，即：有機電 致發光元件係在發光層内含有前述構光發光固體。又，前述石粦 光發光固體係作為主體或客體產生機能。又，前述發光層中含 有前述磷光發光固體與低分子主體材料。又，前述發光層中含 20 有前述磷光發光固體與高分子主體材料。又，有機電致發光元 件係在色變換層内含有前述磷光發光固體。 藉本發明，可實現發光效率獲得大幅改善之有機EL元件。 藉有關本發明之另一態樣，可提供利用上述有機電致發光 元件而形成之有機電致發光裝置，更具體來說，可提供有機電 1245586 致發光顯示器或有機電致發光照明裝置。 藉本發明，可實現在固體狀態下非常強之磷光，將之使用 在有機EL元件，可大幅改善發光效率，使用該有機EL元件之 有機EL裝置可省電。 5 圖式簡單說明 第1圖是例示以式（4)表示之構造部分之圖。 第2圖是顯示Ar1及Ar3之例之圖。 第3圖是顯示Ar2之例之圖。(In formula (3), M and X are the same as in formula (1), the benzene nucleus may have a substituent independently of each other, and the 1245586 substituents may be bonded to each other on the same ring or adjacent rings.) Further, the aforementioned Ar1 and Ar3 independently contains a monocyclic or polycyclic aromatic ring. The Ar1 and Ar3 are the same. The organometallic complex is formed of one three-segment ligand, one halogen atom, and one central metal atom. The organic 5-metal complex is electrically neutral in a solid state. The organic metal complex can be formed into a film by vacuum evaporation. The phosphorescent light-emitting solid is formed using the organometallic complex compound having a purity of 99.5% by weight or more. The central metal atom is platinum. The phosphorescent light-emitting solid contains at least one of the organic metal complex and an organic material having a first laser triplet laser energy higher than that of the organic metal complex. The organic material contains a carbazole or a derivative thereof which may have a substituent. By means of the phosphorescent luminescent solid of the present invention, it is possible to achieve very strong oscillating light in a solid state. According to another aspect of the present invention, an organic electroluminescence element formed using the phosphorescent light-emitting solid 15 described above can be provided. The organic electroluminescence element of the present invention preferably has a feature that the organic electroluminescence element contains the aforementioned light-emitting solid in a light-emitting layer. In addition, the above-mentioned light-emitting solid-state light emitting system functions as a host or an object. The light-emitting layer contains the phosphorescent light-emitting solid and a low-molecular host material. The light-emitting layer contains 20 of the phosphorescent light-emitting solid and a polymer host material. The organic electroluminescence element contains the aforementioned phosphorescent light-emitting solid in a color conversion layer. According to the present invention, an organic EL device having a greatly improved luminous efficiency can be realized. According to another aspect of the present invention, an organic electroluminescence device formed by using the above-mentioned organic electroluminescence element can be provided. More specifically, an organic electroluminescence display or an organic electroluminescence device can be provided. According to the present invention, very strong phosphorescence in a solid state can be realized. When it is used in an organic EL element, the luminous efficiency can be greatly improved, and an organic EL device using the organic EL element can save power. 5 Brief Description of Drawings Figure 1 is a diagram illustrating the structural part represented by the formula (4). Fig. 2 is a diagram showing examples of Ar1 and Ar3. Fig. 3 is a diagram showing an example of Ar2.

第4圖是例示低分子系主體材料之圖。 10 第5圖是例示17卡峻化合物之圖。 第6圖是例示第5圖中之Ar之圖。 第7圖是例示第6圖中之連結基R。 第8圖是顯示CBP之構造之圖。 第9圖是例示高分子系主體材料之圖。 15 第10圖是顯示星狀放射胺（starburstamine)之構造之圖。 第11圖是顯示TPD之構造之圖。FIG. 4 is a diagram illustrating a low-molecular-based host material. 10 FIG. 5 is a diagram illustrating the 17 Cajun compound. FIG. 6 is a diagram illustrating Ar in FIG. 5. FIG. 7 illustrates the linking group R in FIG. 6. Fig. 8 is a diagram showing the structure of CBP. Fig. 9 is a view illustrating a polymer-based host material. 15 Figure 10 is a diagram showing the structure of starburstamine. Fig. 11 is a diagram showing the structure of the TPD.

第12圖是顯示Alq之構造之圖。 第13圖是例示光吸收端較有關本發明之磷光發光固體更 為短波長之材料之圖。 20 第14圖是顯示DCJTB之構造之圖。 第15圖是有機EL元件之模式側截面圖。 第16圖是有機EL元件之其他模式側截面圖。 第17圖是顯示dpt之合成路徑之圖。 第18圖是顯示Pt (dpt) C1之合成路徑之圖。 10 1245586 第19圖是顯示磷光量子獲率之測定法之圖。 第20圖是顯示比較例中所使用之有機金屬錯合物之分子 構造之圖。 第21圖是表示有機EL元件之EL光譜之圖。 5 第22圖是標示有機EL元件之電流密度與外部量子效率之 關係之圖表。 第23圖是顯示將關於本發明之有機EL元件使用於被動矩 陣顯示器時之模式立體圖。 第24圖是顯示將關於本發明之有機EL元件使用於動態矩 10 陣顯示器時之模式立體圖。 C實施方式3 以下，利用圖、表、式、實施例等來說明本發明之實施型 態。又，這些圖、表、式、實施例等及說明乃是例示本發明者， 並不會限制本發明之範圍。只要與本發明之主旨一致，其他實 15 施型態也屬於本發明之範疇。又，圖中，就相同元件賦予同一 符號。 合成以鉑系有機金屬錯合物為首之多種類有機金屬錯合 物，進行其物性之評價，結果發現，具有ΝΛ(ΤΝ型三座配位 子之有機金屬錯合物若以碳光發光固體使用而不是溶液，則可 20 發出非常強烈的磷光，該磷光發光固體顯示出良好的真空蒸鍍 性，且藉真空蒸鍍可製作僅由具有Ν~(ΤΝ型三座配位子之有 機金屬錯合物形成之平滑膜、或含有具有>Γ(ΤΝ型三座配位 子之有機金屬錯合物之塗料膜，所製作之膜同樣顯示出平坦且 良好之發光特性，從而想出本發明。 1245586Fig. 12 is a diagram showing the structure of Alq. Fig. 13 is a diagram illustrating a material having a light absorption end having a shorter wavelength than the phosphorescent light-emitting solid of the present invention. 20 Figure 14 is a diagram showing the structure of DCJTB. Fig. 15 is a schematic side sectional view of an organic EL element. Fig. 16 is a sectional side view of another mode of the organic EL element. Fig. 17 is a diagram showing a synthetic path of dpt. Fig. 18 is a diagram showing a synthetic path of Pt (dpt) C1. 10 1245586 Fig. 19 is a diagram showing a method for measuring the quantum yield of phosphorescence. Fig. 20 is a diagram showing a molecular structure of an organometallic complex used in a comparative example. Fig. 21 is a diagram showing an EL spectrum of an organic EL element. 5 Figure 22 is a graph showing the relationship between the current density of an organic EL element and the external quantum efficiency. Fig. 23 is a perspective view showing a mode when the organic EL element of the present invention is used in a passive matrix display. Fig. 24 is a perspective view showing a mode when the organic EL element of the present invention is used in a dynamic momentary 10-array display. C Embodiment 3 Hereinafter, embodiments of the present invention will be described using drawings, tables, formulas, and examples. In addition, these figures, tables, formulas, examples, etc. and descriptions are illustrative of the present inventors, and do not limit the scope of the present invention. As long as it is consistent with the gist of the present invention, other implementation forms also belong to the scope of the present invention. In the drawings, the same elements are assigned the same symbols. A variety of organometallic complexes led by platinum-based organometallic complexes were synthesized and evaluated for their physical properties. As a result, it was found that organometallic complexes with ΝΛ (ΤΝ type three-seat ligands) are carbon-luminescent solids. Using instead of solution, it can emit very strong phosphorescence. The phosphorescent solid shows good vacuum evaporation, and the vacuum evaporation can be used to produce organometallic materials with only three N-type ligands. The smooth film formed by the complex, or the coating film containing an organometallic complex with the > Γ (TN type three-segment ligands, the film produced also shows flat and good luminescence characteristics, so the idea of this Invention.

有關本發明之磷光發光固體，含有分別配位一個以上之三 座配位子與鹵素原子而形成之有機金屬錯合物，且該三座配位 子係以兩個氮原子、與位於該兩個氮原子間且透過鍵與該兩個 氮原子鍵結之一個碳原子來配位鍵結於中心金屬原子。該有機 5 金屬錯合物中，與金屬配位鍵結之上述兩個碳原子與碳原子係 以N，C，N之順序結合。亦即，該有機金屬錯體具有N'CTN型 三座配位子。「~」是表示N與C或C與N之間存在有鍵之符 號。有關本發明之三座配位子多為與中心金屬Μ —起在實質上 形成同一平面者，當然除此之外之空間配置者也屬於本發明之 10 範田壽。 有關本發明之磷光發光固體可以僅由該有機金屬錯合物 形成，亦可含有其他成分，也包含以整體固體狀態者、與如有 機EL元件之發光層般呈膜狀者。如有機EL元件之發光層般為 膜狀時，包含了平滑膜之狀況、以及以有機金屬錯合物作為主 15 體或客體含於發光層中之情況之膜。The phosphorescent light-emitting solid of the present invention contains an organometallic complex formed by coordinating one or more three ligands and a halogen atom, and the three ligands are formed by two nitrogen atoms and One nitrogen atom is bonded to the central metal atom through two carbon atoms and a carbon atom bonded to the two nitrogen atoms. In the organic 5-metal complex, the above-mentioned two carbon atoms and carbon atoms bonded to the metal are bonded in the order of N, C, and N. That is, the organometallic complex has a N'CTN type three-seat ligand. "~" Is a symbol indicating that there is a bond between N and C or between C and N. Most of the three ligands related to the present invention are those which form substantially the same plane as the central metal M, of course, those who arrange other spaces also belong to the 10 Fan Tianshou of the present invention. The phosphorescent light-emitting solid according to the present invention may be formed only from the organometallic complex, may contain other components, and may also include those in a solid state as a whole and those having a film-like shape as a light-emitting layer of an organic EL element. When the film is like a light emitting layer of an organic EL device, the film includes a smooth film and a film containing an organometallic complex as a host or a guest in the light emitting layer.

有關本發明之磷光發光固體，更具體來說，以含有具有以 下式（1)表示之構造之有機金屬錯合物為佳。Regarding the phosphorescent light-emitting solid of the present invention, more specifically, it is preferable to contain an organometallic complex having a structure represented by the following formula (1).

…⑴ 式（1 )中，Μ表示金屬原子，X表示鹵素原子，Ai*i，Ar2， 20 Ar3各自獨立地表示可具有取代基之環狀構造，Ar1 —Ar2及Ar2 一 Ar3之鍵可為單鍵或雙鍵。雙鍵亦可與其他雙鍵共軛。Μ與 12 1245586... ⑴ In formula (1), M represents a metal atom, X represents a halogen atom, Ai * i, Ar2, 20 Ar3 each independently represents a cyclic structure which may have a substituent, and the bond of Ar1 to Ar2 and Ar2 to Ar3 may be Single or double bond. Double bonds can also be conjugated with other double bonds. M and 12 1245586

Ar1及Μ與Ar3具有Μ —N之配位鍵，Μ與Ar2具有M—C之 直接鍵，Ar1，Ar2，Ar3之取代基可分別在Ar1，Ar2，Ar3上互 相鍵結形成環狀構造，以及分別在Ar1與Ar2相互間、及Ar2 與Ar3相互間互相鍵結形成環狀構造。 5 Μ是有關本發明之有機金屬錯合物之中心金屬原子，可使 用之金屬並無特別限制，可舉Fe，Co，Ni，Ru，Rh，Pd，Os， Ir，Pt等。其中又以Pt尤佳。Ar1 and M and Ar3 have M—N coordination bonds, M and Ar2 have M—C direct bonds. The substituents of Ar1, Ar2, and Ar3 can be bonded to each other on Ar1, Ar2, and Ar3 to form a ring structure. And, Ar1 and Ar2 are bonded to each other, and Ar2 and Ar3 are bonded to each other to form a ring structure. 5M is the central metal atom of the organometallic complex of the present invention, and the metal to be used is not particularly limited, and examples thereof include Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt. Among them, Pt is particularly preferred.

X表示鹵素原子，可舉F，Cl，Br，I等。選擇時宜以三座 配位子與X來滿足中心金屬原子之安定配位數，並使錯合物全 10 體呈電中性。 上述環狀構造以含有芳香環為佳。亦可含有縮合環或雜 環。以Ar1，Ar2，Ar3皆含有芳香環為佳。X represents a halogen atom, and examples thereof include F, Cl, Br, I and the like. In the selection, three ligands and X should be used to satisfy the stable coordination number of the central metal atom and make the complex of all 10 bodies electrically neutral. The cyclic structure preferably contains an aromatic ring. It may contain a condensed ring or a hetero ring. It is preferred that Ar1, Ar2, and Ar3 all contain aromatic rings.

關於上述N~CTN鍵結，N與C或C與N之間之鍵結，通 常也包含有其他原子介於其間之情況。上述式（1)中之Ar1 — 15 Ar2及Ar2 — Ar3之鍵結即相當於有其他原子介於其間之情況。 只要不違反本發明之主旨，可使用任何原子來作為其他原子， 不過以碳原子為佳。ίΤ(ΓΝ之鍵結中，N與C及/或C與N之 間之鍵結，宜為介在有兩個碳原子之鍵。 >rcrN之鍵結中，Ν與C及C與Ν之間之鍵結是有兩個 20 原子介於其間之鍵結時，係如式（4)所例示，有關本發明之 填光發光固體包含有有機金屬錯合物，其中該有機金屬錯合物 係分別配位一個以上之三座配位子與鹵素原子而形成者，且該 三座配位子係以兩個氮原子與一個碳原子配位鍵結於中心金 屬原子，又，該兩個氮原子、一個碳原子及中心金屬原子具有 13 1245586 兩個5員環縮合之形狀之構造部分，且該兩個5員環共用該碳 原子與中心金屬原子之鍵。藉該構造部分，可輕易得到非常強 烈的磷光。又，式（4 )中，配位子與中心金屬原子之鍵以外 之鍵，可為單鍵或雙鍵。雙鍵亦可與其他雙鍵共軛。配位子與 5 中心金屬原子之鍵以外之鍵中，當然也包含式（4 )中所省略 之鍵結部分。具體來說，可例示第1圖之構造部分。 d \ / C — M——X …⑷Regarding the above-mentioned N ~ CTN bonding, the bonding between N and C or between C and N also usually includes other atoms in between. The bonding of Ar1-15 Ar2 and Ar2-Ar3 in the above formula (1) is equivalent to the case where other atoms are interposed. As long as it does not violate the gist of the present invention, any atom may be used as the other atom, but a carbon atom is preferred. In the bond of Γ (ΓΝ, the bond between N and C and / or C and N is preferably a bond between two carbon atoms. > In the bond of rcrN, N and C and C and N The intermolecular bond is a bond having two 20 atoms in between, as exemplified by formula (4). The light-filled luminescent solid of the present invention contains an organometallic complex, wherein the organometallic complex It is formed by coordination of one or more three ligands and a halogen atom, and the three ligands are coordinated by two nitrogen atoms and one carbon atom and are bonded to the central metal atom. In addition, the two The nitrogen atom, a carbon atom, and the central metal atom have a structural part in the shape of 13 1245586 two 5-membered rings condensed, and the two 5-membered rings share the bond between the carbon atom and the central metal atom. With this structural part, it can be easily Very strong phosphorescence is obtained. Also, in formula (4), the bond other than the bond between the ligand and the central metal atom may be a single bond or a double bond. The double bond may also be conjugated with other double bonds. The ligand and 5 Bonds other than the bond of the central metal atom, of course, also include the bond omitted in formula (4) . Specifically, the structural part of Fig. 1 can be exemplified. D \ / C — M——X… ⑷

VNVN

Ar1〜Ar3以後述之組合尤佳，而配位子之分子構造之對稱性 很大則更佳。又，本發明中，配位子之分子構造對稱性很大係 10 指：Ar2除去或包含其取代基而就M—C之鍵結軸線具有對稱 構造之情況，或Ar1與Ar3之關係除去或包含其取代基而就Μ 一 C之鍵結軸線對稱之情況，或同時滿足上述兩者之情況。上 述分子構造之對稱性大，則錯合物之磷光發光強度變強。 依據這個觀點，上述兩個5員環縮合之形狀之構造部分若 15 為以下式（2)表示之構造部分，則分子構造之對稱性變大， 更為適宜。Ar1 to Ar3 are particularly preferred, and the molecular structure of the ligand is more symmetrical. In addition, in the present invention, the molecular structure of the ligand is highly symmetrical. 10 refers to a case where Ar2 is removed or contains a substituent and has a symmetrical structure with respect to the M—C bond axis, or the relationship between Ar1 and Ar3 is removed or In the case where the substituent is included and the axis of the M-C bond is symmetrical, or both of the above are satisfied. The greater the symmetry of the molecular structure, the stronger the phosphorescence intensity of the complex. According to this view, if the structural part of the shape of the two 5-membered rings condensed above is a structural part represented by the following formula (2), the symmetry of the molecular structure becomes larger, which is more suitable.

…⑵ 式（2)中，Μ與X同式（1)，Υ為相互獨立地表示碳原 子或氮原子，Ν—Υ鍵結部分構成前述式（1)中之Αι·1或Ar3 14 1245586 之一部份，構成Αι·2之一部份之苯核可具有取代基。配位子與 中心金屬原子之鍵以外之鍵可為單鍵亦可為雙鍵。雙鍵可與其 他雙鍵共軛。配位子與中心金屬原子之鍵以外之鍵也包含式 (2)中省略之鍵結部分。 5 關於Ar1與八:^以相互獨立地含有單環或多環之芳香環為 佳。又，Ar1與Ar3以相同為佳。這時，上述兩個5員環縮合之 形狀之構造部分若為以下式（3)表示之構造部分，則分子構 造之對稱性變得更大，更為適宜。... ⑵ In formula (2), M and X are the same as in formula (1), Υ represents a carbon atom or a nitrogen atom independently of each other, and the N-Υ bonding portion constitutes A ·· 1 or Ar3 14 1245586 in the foregoing formula (1). As a part, the benzene nucleus constituting a part of Aι · 2 may have a substituent. The bond other than the bond between the ligand and the central metal atom may be a single bond or a double bond. Double bonds can be conjugated with other double bonds. The bond other than the bond between the ligand and the central metal atom also includes a bond portion omitted in the formula (2). 5 Regarding Ar1 and VIII: ^ It is preferable that the aromatic ring contains a monocyclic or polycyclic ring independently of each other. Ar1 and Ar3 are preferably the same. At this time, if the structural part of the shape in which the two 5-membered rings are condensed is a structural part represented by the following formula (3), the symmetry of the molecular structure becomes larger and more suitable.

10 (式（3)中，Μ與X同式（1)，苯核可相互獨立地具有 取代基，且取代基可在同一環上或鄰接之環之間相互鍵結。） 關於上述Ar1，Ar2及Ar3，其環狀構造之任意位置可被取 代。關於Ar1與Ar3可舉第2圖之構造或其鏡像構造，關於Ar2 可舉第3圖之構造。各記號與式（1)之記號具有相同意義。 15 又，Ar1，Ar2，Ar3之構造係第2、3圖中以〇框住之部分。 第2、3圖中，環之氫可為取代基所取代。取代基可舉例 如鹵素原子、氰基、烧氧基、胺基、烧基、烧基乙酸S旨基、環 烧基、芳基、芳氧基等，而該等可更被取代。更，Ar1，Ar2， Ar3之取代基可分別在Ar1，Ar2，Ar3上互相鍵結形成環狀構造， 20 以及分別在Ar1與Ar2相互間、及Ar2與Ar3相互間互相鍵結形 成環狀構造。 1245586 有關本發明之有機金屬錯合物，係如二聚物等所例示的， 亦可含有多數個三座配位子、中心金屬Μ或鹵素原子X，不過 以由一個三座配位子、一個鹵素原子及一個中心金屬原子所形 成者為佳。具有容易製造蒸鍍膜等優點。 5 關於容易製造蒸鍍膜這一點，有機金屬錯合物以在固體狀 態下呈電中性或接近電中性為佳。而以中性較佳。該中性可由 有機金屬錯合物實質上不帶離子性、不具極化性或帶極小之極 化性來判斷。 有關本發明之磷光發光固體以使用純度99.5重量％以上之 10 有機金屬錯合物而形成者為佳，如此可容易得到發出強烈磷光 之磷光發光固體。而使用純度99.8重量％以上之有機金屬錯合 物形成則更佳。又，這裡所謂有機金屬錯合物之純度，在有關 本發明之磷光發光固體是由多數成分形成之情況時，並非指磷 光發光固體中之有機金屬錯合物之濃度，而是指為了構成磷光 15 發光固體所使用之有機金屬錯合物之純度。 有機EL元件用於全彩顯示器之方法之一是準備紅、綠、 藍各色之有機EL元件，將這三個的組合作為1個畫素使用， 這種方法廣為實行。有關本發明之磷光發光固體，可藉由使所 含之有機金屬錯合物之三座配位子之分子構造變化，來調節發 20 光色，故可將這種多數發光色作為發光材料等來適當使用於必 要之用途。特別是可適用於有機EL元件。 又，以下只要未特別強調，有關本發明之磷光發光固體即 為有關本發明之有機金屬錯合物之固體，主要是針對形成膜等 前之大塊狀態，不過如上所述的，有關本發明之磷光發光固 16 1245586 體，以大塊狀態含有本發明之有機金屬錯合物以外成分之情 況、在形成為膜等後之狀態下由有關本發明之有機金屬錯合物 之固體形成之情況、在形成為膜等後之狀態下含有有關本發明 之有機金屬錯合物以外成分之情況，皆屬於本發明之範疇。 5 有關本發明之磷光發光固體宜含在有機EL元件中作為發 光材料，亦可含於發光層，亦可含於發光層兼電子輸送層、發 光層兼電洞輸送層等。填光發光固體含於發光層時，發光層可 以磷光發光固體單獨成膜來形成，或亦可含有其他材料來形 成。又，由於本發明之有機EL元件中所使用之磷光發光固體 10 在室溫下可發出強烈磷光，故若為色變換方式之有機EL元件， 可作為含於色變換層之發光材料來使用。 有關本發明之磷光發光固體可作為客體或主體來產生機 能。又，亦可與其他主體材料或客體材料共存。共存之其他主 體材料為低分子者或高分子者。低分子者宜為數平均分子量在 15 1，000以下者，高分子者宜為數平均分子量20,000以上者。使 其為主體材料之第一激光三重態激光能量高於所含之有機金 屬錯合物之第一激光三重態激光能量之材料更佳。 低分子系主材料係如第4圖所示，可舉4,4’-雙（2,2’_二苯 乙烯基）-U，-聯苯（DPVBi)、p-六苯基（p-SP)、1，3,6,8-四苯 20 基芘（tppy ) ( l，3,6,8，tetraphenylpyrene )、N，N’-二萘基-N，N’-二苯基_[1，1’_聯苯]_4,4’_二胺（NPD)、可具有取代基之咔唑基 或其衍生物或該等之混合物等。 可具有取代基之咔σ坐基或其衍生物，亦即味。坐化合物，可 舉第5圖所示之化合物。第5圖中，R1，R2表示可賦予在環狀 17 1245586 構造之任意位置之取代基，可各自獨立地表示氫原子、鹵素原 子、烷氧基、胺基、烷基、環烷基、可含有氮原子或硫原子之 芳基、芳氧基，該等更可被取代。又，R1，R2可相互結合、形 成可含有氮原子、硫原子、氧原子之芳香環，該等可更被取代。 5 R1，R2就各個環狀構造存在1〜3個。第5圖中，Ar表示2,3價 之芳香族基或雜環式芳香族基。可舉第6圖所示之基為例。環 構造中之氫原子可被取代。又，這當中可舉第7圖之例來作為 連結基R。 上述u卡。坐化合物與本發明之有機金屬錯合物混合時，由於 10 與錯合物之相互作用很小，故對錯合物本來之發光特性影響很 小，作為主體材料特別有效。以該式表示之咔唑化合物之一例 可舉第8圖所示之雙（9-咔唑基）-聯苯（CBP)。 又，高分子系主材料以第9圖所示之聚對亞苯基亞乙烯 (PPV)、聚噻吩（PAT)、聚對亞苯（ΡΡΡ)、聚乙烯咔唑（PVC)、 15 聚芴（PF)、聚乙炔（PA)衍生物適合。環構造中之氫原子可 被取代。 有機EL元件具有在陽極與陰極之間爽著電洞注入層、電 洞輸送層、發光層、電子輸送層、電子注入層等之構成。這些 層當中，有時電洞注入層、電洞輸送層、電子輸送層、電子注 20 入層不存在。亦可包含其他層。亦可使一層具有多數機能。通 常，是在由玻璃等形成之透明基板上構成上述積層體。有關本 發明之有機EL元件亦可包含該透明基板。採用色變換層時， 多在陰極上（基板之相反側）設置色變換層。第15、16圖是 顯示有機EL元件之構成之模式側截面圖，第15圖是不具色變 18 1245586 換層之情況，第16圖是具有色變換層之情況。第15圖中顯示 了基板1，陽極2,電洞輸送層3,發光層4,電子輸送層5,陰極6， 而第16圖顯示除上述之外再加上色變換層161。 顯示層之構成例，則可舉如下所述者。 5 *陽極/電洞注入層/電洞輸送層/發光層/電子輸送層/電子 注入層/陰極 •陽極/電洞注入層/電洞輸送層/發光層/電子輸送層/陰極 •陽極/電洞輸送層/發光層/電子輸送層/電子注入層/陰極 •陽極/電洞輸送層/發光層/電子輸送層/陰極 10 •陽極/電洞注入層/電洞輸送層/發光層兼電子輸送層/電 子注入層/陰極 •陽極/電洞注入層/電洞輸送層/發光層兼電子輸送層/陰 極 •陽極/電洞輸送層/發光層兼電子輸送層/電子注入層/陰 15 極 •陽極/電洞輸送層/發光層兼電子輸送層/陰極 •陽極/電洞注入層/電洞輸送層兼發光層/電子輸送層/電 子注入層/陰極 •陽極/電洞注入層/電洞輸送層兼發光層/電子輸送層/陰 20 極 •陽極/電洞輸送層兼發光層/電子輸送層/電子注入層/陰 極 •陽極/電洞輸送層兼發光層/電子輸送層/陰極 •陽極/電洞輸送層兼電子輸送層兼發光層/陰極 19 1245586 又，各層所使用之材料、各層之膜厚及製造方法例示如下。 •陽極 陽極之材料並無特別限制，可因應目的適當選擇，可舉例 如金屬、合金、金屬乳化物、電傳導性化合物、該專之混合物 5 等，這當中又以功函數4eV以上之材料為佳。 陽極之材料之具體例可舉：氧化錫、氧化鋅、氧化銦、銦 錫氧化物（ITO)等之導電性金屬氧化物、金、銀、鉻、鎳等 金屬、該等金屬與導電性金屬氧化物之混合物或積層物、硬化 銅、硫化銅等無機導電性物質、聚苯胺、聚噻吩、聚咄咯等有 · 10 機導電性材料、該等與ITO之積層物等。這些可單獨使用，亦 可並用2種以上。當中又以導電性金屬氧化物為佳，從生產性、 高導電性、透明性等觀點來看尤以IT〇為佳。 陽極之厚度並無特別限制，可依據材料等適當選擇，一般 以1〜5000nm為佳，20〜200nm更佳。 15 陽極通常形成於鹼石灰玻璃、無鹼玻璃等玻璃、透明樹脂 等基板上。利用玻璃作為基板時，基於減少從玻璃溶出離子之 觀點，故以無驗玻璃、二氧化秒、施以障壁塗膜之驗石灰玻㉟ φ 為佳。 鼓 板之居度/、要疋可保持機械性強度之充分厚度即可，並 〇無特別限制，而利用玻璃作為基材時，通常在0.2mm以上，又 以0.7mm以上為佳。 反鹿陽極可藉例如讀法、濕式製膜法、電子束法、滅射法、 义、射法、MBE (分子線蟲晶）法、簽離子束法、離子喷 法、雷骑 水聚合法（高周波激光離子噴鍍法）、分子積層法、 20 1245586 印刷法、轉印法、化學反應法（溶膠一凝膠法等）塗布汀〇等 之分散物之方法等來適當形成。 陽極可藉進行洗淨、其他處理使有機EL元件之驅動電壓 降低，提高發光效率。所謂其他處理在例如前述陽極之素材為 5 ιτο時，可適當舉UV—臭氧處理、電漿處理等。 •電洞注入層 電洞注入層之材料並無特別限制，可因應目的適當選擇， 可適备舉例如第10圖所示之星狀放射胺（S加狀） (4,4’，4”一參[3—曱基苯基（苯基）胺基]三苯基胺邱一 10 MTDATA ( 4,4\4- - tris[3 - methylphenyl ( phenyl ) amin〇]triphenylamine，m —MTDATA))、銅酞菁、聚苯胺等。 電洞注入層之厚度並無特別限制，可因應目的適當選擇， 例如以1〜lOOOnm為佳，5〜500nm更佳。 電洞主入層可藉例如条鑛法、濕式製膜法、電子束法、賤 Μ射法、反應性濺射法、咖法、簇離子束法、離子噴鍵法、電 漿聚合法（高周波激光離子噴鍵法）、分子積層法、⑶法、印 刷法、轉印法等適當形成。 •電洞輸送層 2010 (In formula (3), M and X are the same as in formula (1), the benzene nuclei may have substituents independently of each other, and the substituents may be bonded to each other on the same ring or adjacent rings.) Regarding the above-mentioned Ar1, Ar2 and Ar3 may be substituted at any position in the ring structure. For Ar1 and Ar3, the structure shown in Fig. 2 or its mirror structure can be mentioned, and for Ar2, the structure shown in Fig. 3 can be used. Each symbol has the same meaning as the symbol of formula (1). 15 In addition, the structures of Ar1, Ar2, and Ar3 are parts enclosed by 0 in Figs. In Figures 2 and 3, the hydrogen of the ring may be substituted by a substituent. Examples of the substituent include a halogen atom, a cyano group, an alkoxy group, an amine group, an alkynyl group, an alkynyl acetate group, a cycloalkyl group, an aryl group, an aryloxy group, and the like, and these may be further substituted. Furthermore, the substituents of Ar1, Ar2, and Ar3 can be bonded to each other to form a cyclic structure on Ar1, Ar2, and Ar3, and 20 and each of Ar1 and Ar2 can be bonded to each other, and Ar2 and Ar3 can be bonded to each other to form a cyclic structure. . 1245586 The organometallic complex of the present invention is exemplified by a dimer and the like, and may also contain a plurality of three-segment ligands, a central metal M, or a halogen atom X. A halogen atom and a central metal atom are preferred. It has advantages such as being easy to produce a vapor-deposited film. 5 With regard to the ease of producing a vapor-deposited film, the organometallic complex is preferably electrically neutral or close to electrically neutral in a solid state. And neutral is better. The neutrality can be judged from the fact that the organometallic complex is substantially free of ionicity, polarization, or minimal polarizability. The phosphorescent light-emitting solid of the present invention is preferably formed by using an organometallic complex with a purity of 99.5% by weight or more. In this way, a phosphorescent light-emitting solid that emits intense phosphorescence can be easily obtained. It is more preferable to use an organometallic complex with a purity of 99.8% by weight or more. The purity of the organometallic complex here refers to the concentration of the organometallic complex in the phosphorescent light-emitting solid when the phosphorescent light-emitting solid of the present invention is formed from a large number of components, but refers to the phosphorescence 15 Purity of organometallic complexes used in luminescent solids. One method of using organic EL elements for full-color displays is to prepare organic EL elements of red, green, and blue colors, and use a combination of these three as one pixel. This method is widely practiced. Regarding the phosphorescent light-emitting solid of the present invention, the light emitting color can be adjusted by changing the molecular structure of the three ligands of the contained organometallic complex, so that the majority of light-emitting colors can be used as a light-emitting material, etc To properly use for necessary purposes. In particular, it is applicable to organic EL elements. In addition, unless specifically emphasized below, the phosphorescent light-emitting solid of the present invention is a solid of the organometallic complex of the present invention, and is mainly directed to the bulk state before the film is formed. The phosphorescent light-emitting solid 16 1245586 body, when it contains components other than the organometallic complex of the present invention in a bulk state, and when it is formed into a film or the like from a solid state of the organometallic complex of the present invention In the case where a component other than the organometallic complex of the present invention is contained in a state after being formed into a film or the like, it belongs to the scope of the present invention. 5 The phosphorescent light-emitting solid according to the present invention is preferably contained in an organic EL element as a light-emitting material, and may also be contained in a light-emitting layer, a light-emitting layer and an electron transport layer, a light-emitting layer and a hole transport layer, and the like. When the light-filled light-emitting solid is contained in the light-emitting layer, the light-emitting layer may be formed by forming a phosphorescent light-emitting solid alone as a film, or may be formed by containing other materials. In addition, since the phosphorescent light-emitting solid 10 used in the organic EL device of the present invention can emit strong phosphorescence at room temperature, if it is a color conversion type organic EL device, it can be used as a light-emitting material included in the color conversion layer. The phosphorescent light-emitting solid of the present invention can function as an object or host. It can also coexist with other host materials or guest materials. The other coexisting host materials are low molecular or high molecular. Those with a low molecular weight should preferably have a number average molecular weight of 15 1,000 or less, and those with a high molecular weight should have a number average molecular weight of 20,000 or more. The material which makes the first laser triplet laser energy of the host material higher than the first laser triplet laser energy of the organic metal complex is more preferable. As shown in Fig. 4, the main material of the low molecular system is 4,4'-bis (2,2'_distyryl) -U, -biphenyl (DPVBi), p-hexaphenyl (p- SP), 1,3,6,8-tetraphenyl 20 hydrazone (tppy) (l, 3,6,8, tetraphenylpyrene), N, N'-dinaphthyl-N, N'-diphenyl_ [ 1,1'_biphenyl] _4,4'_ diamine (NPD), a carbazolyl group or a derivative thereof which may have a substituent, or a mixture thereof. A carbazo group or a derivative thereof which may have a substituent, that is, odor. As the compound, the compound shown in Fig. 5 can be mentioned. In Figure 5, R1 and R2 represent substituents that can be given at any position in the cyclic 17 1245586 structure, and each independently represent a hydrogen atom, a halogen atom, an alkoxy group, an amine group, an alkyl group, a cycloalkyl group, Aryl groups and aryloxy groups containing nitrogen or sulfur atoms may be substituted. Furthermore, R1 and R2 may be combined with each other to form an aromatic ring which may contain a nitrogen atom, a sulfur atom, and an oxygen atom, and these may be further substituted. 5 R1 and R2 have 1 to 3 ring structures. In Fig. 5, Ar represents a 2,3-valent aromatic group or a heterocyclic aromatic group. Take the base shown in Figure 6 as an example. Hydrogen atoms in the ring structure can be replaced. Here, the linking group R can be taken as an example in FIG. 7. The above u card. When the base compound is mixed with the organometallic complex of the present invention, since the interaction between 10 and the complex is small, it has little effect on the original luminescence characteristics of the complex, and is particularly effective as a host material. An example of the carbazole compound represented by this formula is bis (9-carbazolyl) -biphenyl (CBP) shown in Fig. 8. The main polymer materials are polyparaphenylene vinylene (PPV), polythiophene (PAT), polyparaphenylene (PP), polyvinylcarbazole (PVC), and 15 polyfluorene as shown in FIG. 9. (PF) and polyacetylene (PA) derivatives are suitable. The hydrogen atom in the ring structure may be replaced. The organic EL element has a structure in which a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like are interposed between the anode and the cathode. Among these layers, the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer sometimes do not exist. Other layers may also be included. It is also possible to make the first layer have most functions. The laminated body is usually formed on a transparent substrate made of glass or the like. The organic EL device according to the present invention may include the transparent substrate. When a color conversion layer is used, a color conversion layer is often provided on the cathode (the opposite side of the substrate). Figures 15 and 16 are schematic side cross-sectional views showing the structure of the organic EL element. Figure 15 is a case without color change 18 1245586. Layer 16 is a case with color conversion layer. Fig. 15 shows a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a cathode 6, and Fig. 16 shows a color conversion layer 161 in addition to the above. Examples of the structure of the display layer include the following. 5 * Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode • anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode • anode / Hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode • Anode / hole transport layer / light emitting layer / electron transport layer / cathode 10 • Anode / hole injection layer / hole transport layer / light emitting layer Electron transport layer / electron injection layer / cathode • anode / hole injection layer / hole transport layer / light emitting layer and electron transport layer / cathode • anode / hole transport layer / light emitting layer and electron transport layer / electron injection layer / cathode 15 poles • anode / hole transport layer / light emitting layer and electron transport layer / cathode • anode / hole injection layer / hole transport layer and light emitting layer / electron transport layer / electron injection layer / cathode • anode / hole injection layer / Hole transport layer and light emitting layer / electron transport layer / cathode 20 poles • anode / hole transport layer and light emitting layer / electron transport layer / electron injection layer / cathode • anode / hole transport layer and light emitting layer / electron transport layer / Cathode / anode / hole transport layer and electron transport layer and light emitting layer / cathode 19 12 45586 The materials used for each layer, the film thickness of each layer, and the manufacturing method are exemplified below. • The material of the anode is not particularly limited, and it can be appropriately selected according to the purpose. Examples include metals, alloys, metal emulsions, electrically conductive compounds, and special mixtures of 5. Among them, materials with a work function of 4eV or more are used. good. Specific examples of the material of the anode include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), metals such as gold, silver, chromium, and nickel, and these metals and conductive metals. Mixtures or laminates of oxides, inorganic conductive materials such as hardened copper, copper sulfide, polyaniline, polythiophene, polyfluorene and other organic conductive materials, such as those laminated with ITO. These may be used alone or in combination of two or more. Among them, conductive metal oxides are preferred, and from the viewpoints of productivity, high conductivity, and transparency, IT0 is particularly preferred. The thickness of the anode is not particularly limited, and may be appropriately selected according to materials and the like, and generally is preferably 1 to 5000 nm, and more preferably 20 to 200 nm. 15 The anode is usually formed on glass such as soda-lime glass, alkali-free glass, and transparent resin. When glass is used as the substrate, from the viewpoint of reducing the leaching of ions from the glass, it is preferable to use lime glass ㉟ φ without glass inspection, dioxide seconds, and a barrier coating film. The dwelling of the drum plate may be sufficient to maintain a sufficient thickness of the mechanical strength, and there is no particular limitation. When glass is used as the base material, it is usually 0.2 mm or more and preferably 0.7 mm or more. The anti-deer anode can be used, for example, reading method, wet film forming method, electron beam method, extinction method, meaning, radiation method, MBE (molecular nematode) method, signed ion beam method, ion spray method, and thunder water polymerization method. (High-frequency laser ion plating method), molecular lamination method, 20 1245586 printing method, transfer method, chemical reaction method (sol-gel method, etc.) and a method of applying a dispersion such as tin oxide, etc., are appropriately formed. The anode can be cleaned and other processed to reduce the driving voltage of the organic EL element and improve the luminous efficiency. For the other treatments, for example, when the material of the anode is 5 ιτο, UV-ozone treatment, plasma treatment, and the like can be appropriately adopted. • Hole injection layer The material of the hole injection layer is not particularly limited, and can be appropriately selected according to the purpose. For example, a star-shaped radioactive amine (S plus shape) as shown in FIG. 10 (4,4 ', 4 ” [Refer to [3-Phenylphenyl (phenyl) amino] triphenylamine QIU-1 MTDATA (4,4 \ 4--tris [3 -methylphenyl (phenyl) amin〇] triphenylamine, m —MTDATA)) , Copper phthalocyanine, polyaniline, etc. The thickness of the hole injection layer is not particularly limited, and can be appropriately selected according to the purpose, for example, 1 to 100 nm is preferred, and 5 to 500 nm is more preferred. Method, wet film-forming method, electron beam method, low-level emission method, reactive sputtering method, coffee method, cluster ion beam method, ion spray bonding method, plasma polymerization method (high-frequency laser ion spraying method), molecules The lamination method, the CD method, the printing method, the transfer method, etc. are appropriately formed. • Hole transport layer 20

電洞輪运層之材料並無特別限制，可因應目的適當選擇， 可舉例如芳香族胺化合物、啼 ,Λ t , 卜土米°坐、三唾、σ惡口坐、。惡二唾、 聚芳基烧、”冰林_、笨二胺、芳絲、胺基取代查 耳酉同、苯乙稀酮、腙1、魏類、苯乙烯基胺、芳 香矢亞曱基化合物、4啦系化合物、聚石夕烧系化合物、聚（Ν 烯基卡坐）苯月*系共聚物、。塞吩寡聚物及聚合物、聚。塞 21 1245586 吩等導電性高分子寡聚物及聚合物、石墨膜等。又，將這些電 洞輸送層之材料與發光層材料混合製膜，則可形成電洞輸送層 兼發光層。 該等可單獨使用，亦可併用2種以上，這當中又以芳香族 5 胺化合物為佳。具體來說，以第11圖所示之N，N’一二苯基一 N，N’一雙（3—甲基苯基）一[1，Γ —聯苯]—4,45 —二胺（TPD) 或NPD等芳香族胺更佳。 電洞輸送層之厚度並無特別限制，可因應目的適當選擇， 通常為1〜500nm，而以5〜lOOnm為佳。 10 電洞輸送層之形成可利用與電洞注入層同樣的方法，並適 當變更原料或條件。 •電子輸送層 電子輸送層之材料並無特別限制，可因應目的適當選擇， 可舉例如第12圖所示之三（8—羥基喳啉）鋁（Alq)等羥基 15 °奎°林金屬錯合物、鋁經基林一聯苯氧基錯合物（BAlq)等經 基。奎°林一芳氧基錯合物、σ惡二嗤化合物、三唾化合物、啡琳化 合物、苑化合物、吼σ定化合物、定化合物、ϋ奎4σ林化合物、 二苯基苯醌化合物、硝基取代场化合物等。又，將該等電子輸 送層之材料與發光層之材料混合製膜，可形成發光層兼電子輸 20 送層，更進一步，若更混合電洞輸送層之材料製膜，則可形成 電洞輸送層兼發光層兼電子輸送層。 電子輸送層之厚度並無特別限制，可因應目的適當選擇， 例如通常為1〜500nm，又以10〜50nm為佳。 電子輸送層可以是2層以上之構成。這時，若利用光吸收 22 1245586 端較有關本發明之磷光發光固體更為短波長之材料來作為鄰 接於發光層之電子輸送層材料，則元件中之發光領域可限定在 發光層，可防止發自電子輸送層之多餘發光，故很適宜。 這種光吸收端較有關本發明之磷光發光固體更為短波長 5 之材料，可舉經基唆σ林一芳氧基錯合物、p非琳化合物、σ惡二吐 化合物、***化合物、以8—喳啉酚乃至其化合物為配位子之 有機金屬錯合物等。特別是以Balq及第13圖中所表示之化合 物為佳。The material of the hole transport layer of the hole is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include aromatic amine compounds, cyanide, Λt, burtami, trisal, sigma, etc. Dioxal, polyarylate, "Binglin_, bendiamine, aromatic silk, amine substituted chalcone, acetophenone, fluorene 1, Wei class, styrylamine, aromatic arylene group Compounds, 4La series compounds, polylithium compounds, poly (N alkenyl carding) benzene month copolymers,. Phenene oligomers and polymers, poly. Plug 21 1245586 benzene and other conductive polymers An oligomer, a polymer, a graphite film, etc. In addition, by mixing the materials of the hole transporting layer with the material of the light emitting layer to form a film, the hole transporting layer and the light emitting layer can be formed. These can be used alone or in combination. Among them, an aromatic 5 amine compound is preferred. Specifically, N, N'-diphenyl-N, N'-bis (3-methylphenyl)- [1, Γ-biphenyl] -4,45-diamine (TPD) or aromatic amines such as NPD are more preferred. The thickness of the hole transport layer is not particularly limited and can be appropriately selected according to the purpose, usually 1 to 500 nm. 5 ~ 100nm is preferred. 10 The hole transport layer can be formed by the same method as the hole injection layer, and the raw materials or conditions can be changed as appropriate. The material of the electron transporting layer of the sub-transporting layer is not particularly limited, and can be appropriately selected according to the purpose. For example, the 15 (quinoline) metal complex such as the three (8-hydroxyxanthroline) aluminum (Alq) shown in Figure 12 can be used. Compounds, aluminum via kelin-biphenoxy complex (BAlq), etc. quinoline-aryloxy complex, sigma-oxadioxine compound, sialyl compound, phlenyl compound, garden compound, sigma Compounds, fixed compounds, quaternary quaternary sigmaine compounds, diphenylbenzoquinone compounds, nitro-substituted field compounds, etc. In addition, the materials of these electron transport layers and the materials of the light-emitting layer are mixed to form a film to form a light-emitting layer and electrons. If the material of the hole transporting layer is mixed into a film, the hole transporting layer and the light emitting layer and the electron transporting layer can be formed. The thickness of the electron transporting layer is not particularly limited, and it can be appropriately selected according to the purpose. For example, it is usually 1 to 500 nm, and preferably 10 to 50 nm. The electron transport layer may be composed of two or more layers. At this time, if light absorption 22 is used, the 1245586 end has a shorter wavelength than the phosphorescent solid material of the present invention. Come As the material of the electron transport layer adjacent to the light-emitting layer, the light-emitting area in the element can be limited to the light-emitting layer, which can prevent unnecessary light emission from the electron-transport layer, so it is very suitable. Materials with a shorter wavelength of 5 can be based on sigma-lin-aryloxy complexes, p-filin compounds, sigmaoxetine compounds, triazole compounds, and 8-quinolinol and its compounds as ligands. Organometallic complexes, etc. Especially Balq and the compounds shown in Fig. 13 are preferred.

又，第13圖中，前端未記載化學基之3根分叉表示tert 10 — 丁基。 電子輸送層之形成，可利用與電洞注入層同樣的方法，並 適當變更原料或條件。 •電子注入層In addition, in FIG. 13, three branches with no chemical group at the front end indicate tert 10 -butyl. The formation of the electron transport layer can be performed by the same method as the hole injection layer, and the materials or conditions can be appropriately changed. • Electron injection layer

電子注入層之材料並無特別限制，可因應目的適當選擇， 15 可適當使用例如氟化鋰等鹼金屬氟化物、氟化锶等鹼土類金屬 氟化物等。電子注入層之厚度並無特別限制，可因應目的適當 選擇，例如通常為0.1〜10nm，而以0.5〜2nm為佳。 電子注入層可藉例如蒸鍍法、電子束法、濺射法等適當形 成。 20 •陰極 陰極的材料並無特別限制，可因應與前述電子輸送層、前 述發光層等與陰極鄰接之層或分子之密著性、離子電勢、安定 性等來適當選擇，可舉例如金屬、合金、金屬氧化物、電傳導 性化合物、該等之混合物等。 23 1245586 陰極之材料之具體例可舉鹼金屬（例如Li、Na、K、Cs等）、 驗土類金屬（例如Mg、Ca等）、金、銀、叙、銘、納一鉀合金 或該等之混合金屬、經一紹合金或該等之混合金屬、錢一銀合 金或該等之混合金屬、銦、镱等稀土類金屬、該等之合金等。 5 該等可單獨使用，亦可併用2種以上。該等當中又以工作函數 4eV以下之材料為佳，鋁、鋰一鋁合金或該等之混合金屬、鎂 —銀合金或該等之混合金屬等更佳。 陰極之厚度並無特別限制，可因應陰極之材料等適當選 擇，而以1〜lOOOOnm為佳，20〜200nm更佳。 10 陰極可藉例如蒸鍍法、濕式製膜法、電子束法、濺射法、 反應性濺射法、MBE法、簇離子束法、離子喷鍍法、電漿聚合 法（高周波激光離子喷鍍法）、印刷法、轉印法等適當形成。 併用2種以上作為陰極之材料時，可同時蒸鍍2種以上之 材料來形成合金電極等，亦可蒸鍍事先調製之合金來形成合金 15 電極等。 •其他層 本發明之有機EL元件亦可因應目的而具有適當選擇之其 他層。該其他層可舉例如電洞阻擋層或保護層等。 電洞阻擋層配置於發光層與電子輸送層之間。有機EL元 20 件若具有電洞阻擋層，則可以電洞阻擋層阻擋住從陽極側輸送 之電洞，從陰極輸送之電子通過電洞阻擋層到達發光層，藉此 電子與電洞可在發光層有效率地產生再結合。因此，可防止電 洞與電子在發光層以外之有機薄膜層再結合，可有效率地得到 目的之發光色素之發光，在色純度等點上很有利。電洞阻擋層 24 1245586 之材料並無特別限制，可因應目的，從與電子輸送層之材料相 同之材料適當選擇。 電洞阻擋層之厚度並無特別限制，可因應目的適當選擇， 例如通常為1〜500nm，又以5〜50nm為佳。前述電洞阻擔層可 5 以是單層構造，亦可為積層構造。 電洞阻擋層可藉例如蒸鍍法、濕式製膜法、電子束法、濺 射法、反應性濺射法、MBE法、簇離子束法、離子喷鍍法、電 漿聚合法（高周波激光離子喷鍍法）、分子積層法、LB法、印 刷法、轉印法等適當形成。 10 保護層是保護有機EL元件不受到外界影響之層，係形成 為包住由上述各層形成之積層物。保護層之材料並無特別限 制，可因應目的適當選擇，以例如可抑制水分或氧等會促進有 機EL元件低劣化之分子或物質侵入有機EL元件内之材料為 佳。 15 保護層之材料可舉例如：In、Sn、Cu、A卜Ti、Ni等金屬；The material of the electron injection layer is not particularly limited, and may be appropriately selected according to the purpose. 15 For example, alkali metal fluorides such as lithium fluoride and alkaline earth metal fluorides such as strontium fluoride can be appropriately used. The thickness of the electron injection layer is not particularly limited, and can be appropriately selected according to the purpose. For example, it is usually 0.1 to 10 nm, and preferably 0.5 to 2 nm. The electron injection layer can be appropriately formed by, for example, a vapor deposition method, an electron beam method, a sputtering method, or the like. 20 • The material of the cathode is not particularly limited, and it can be appropriately selected according to the adhesion, ion potential, and stability of the layer or molecule adjacent to the cathode such as the aforementioned electron transport layer and the aforementioned light-emitting layer. Examples include metals, Alloys, metal oxides, electrically conductive compounds, mixtures of these, and the like. 23 1245586 Specific examples of the material of the cathode include alkali metals (such as Li, Na, K, Cs, etc.), soil testing metals (such as Mg, Ca, etc.), gold, silver, Syria, Ming, Na-K alloy or the And other mixed metals, Jing-Shao alloys or mixed metals, Qian-Silver alloys or mixed metals, rare earth metals such as indium, thorium, and alloys of these. 5 These can be used alone or in combination of two or more. Among these, materials with a work function of 4 eV or less are preferred, and aluminum, lithium-aluminum alloy, or a mixed metal thereof, magnesium-silver alloy, or a mixed metal thereof is more preferable. The thickness of the cathode is not particularly limited, and may be appropriately selected in accordance with the material of the cathode, etc., but is preferably 1 to 1000 nm, and more preferably 20 to 200 nm. 10 The cathode can be formed by, for example, a vapor deposition method, a wet film forming method, an electron beam method, a sputtering method, a reactive sputtering method, a MBE method, a cluster ion beam method, an ion spraying method, and a plasma polymerization method (high-frequency laser ionization). Thermal spraying method), printing method, transfer method and the like are appropriately formed. When two or more kinds of materials are used as a cathode material, two or more kinds of materials can be vapor-deposited simultaneously to form alloy electrodes, etc., or alloys prepared in advance can be vapor-deposited to form alloy 15 electrodes, etc. • Other layers The organic EL element of the present invention may have other layers appropriately selected depending on the purpose. The other layer may be, for example, a hole blocking layer or a protective layer. The hole blocking layer is disposed between the light emitting layer and the electron transporting layer. If the organic EL element has a hole blocking layer, the hole blocking layer can block the hole transported from the anode side, and the electrons transported from the cathode pass through the hole blocking layer to the light-emitting layer. The light emitting layer is efficiently recombined. Therefore, recombination of holes and electrons in an organic thin film layer other than the light emitting layer can be prevented, and the luminescence of the intended luminescent pigment can be efficiently obtained, which is advantageous in terms of color purity and the like. The material of the hole blocking layer 24 1245586 is not particularly limited, and it can be appropriately selected from the same material as the material of the electron transport layer according to the purpose. The thickness of the hole blocking layer is not particularly limited, and can be appropriately selected according to the purpose. For example, it is usually 1 to 500 nm, and preferably 5 to 50 nm. The hole supporting layer can be a single-layer structure or a laminated structure. The hole blocking layer may be, for example, a vapor deposition method, a wet film formation method, an electron beam method, a sputtering method, a reactive sputtering method, an MBE method, a cluster ion beam method, an ion spray method, or a plasma polymerization method (high frequency). Laser ion plating method), molecular lamination method, LB method, printing method, transfer method, etc. are appropriately formed. 10 The protective layer is a layer that protects the organic EL element from external influences, and is formed to surround the laminate formed of the above-mentioned layers. The material of the protective layer is not particularly limited, and may be appropriately selected according to the purpose, and for example, a material that can inhibit the intrusion of molecules or substances that promote low degradation of the organic EL element, such as moisture or oxygen, into the organic EL element is preferable. 15 The material of the protective layer may include, for example, metals such as In, Sn, Cu, Ab, Ti, Ni;

MgO、SiO、Si〇2、AI2O3、GeO、NiO、CaO、BaO、Fe2〇3、 Y2〇3、Ti02等金屬氧化物；SiN、SiNxOy等氮化物；MgF2、LiF、 A1F3、CaF2等金屬氟化物；聚乙烯、聚丙烯、聚曱基甲基丙烯 酸酯、聚醯胺、聚尿素、聚四氟乙烯、聚氯三氟乙烯、聚二氯 20 二氟乙烯、氣三氟乙烯與二氯二氟乙烯之共聚物、使含有四氟 乙烯與至少1種共聚用單體之單體混合物共聚合而得之共聚 物、共聚主鏈上具有環狀構造之含氟共聚物、吸水率1重量％ 以上之吸水性物質、吸水率0.1重量％以下之防潮性物質等。 保護層可藉例如蒸鍍法、濕式製膜法、濺射法、反應性濺 25 1245586 射法、MBE法、簇離子束法、離子喷鍍法、電漿聚合法（高周 波激光離子噴鍍法）、印刷法、轉印法等適當形成。 •色變換層 本發明之有機EL元件可因應目的具有適當選擇之色變換 5 層，該色變換層内可含有本發明之磷光發光固體。色變換層係 如特開平第3-152897號公報所記載的，係吸收來自有機EL元 件之發光變更其波長並放出之層，例如製作在藍色單色之有機 EL元件之光取出側基板與ITO電極之間，將藍色變換為綠色 或紅色後放出，可使顯示裝置多色化。色變換層只要可充分吸 10 收被變換光並將之變換為所希望之波長，則任何厚度、材質、 製法皆可，典型為0.01 // m〜100/z m，更適宜具有1 // m〜50// m 之厚度，以藉光刻法等製作為佳。 在此，說明關於發光層之製作，可依據已知方法形成，例 如藉真空蒸鍍等蒸鍍法、濕式製膜法、MBE法、簇離子束法、 15 分子積層法、LB法、印刷法、轉印法等適當形成。這當中， 從不需使用有機溶劑而無廢水處理問題、可低成本、簡便且有 效率地製作這幾點來看，以蒸鍍法為佳，而以單層構造設計發 光層時，例如使發光層作為電洞輸送層兼發光層兼電子輸送層 等來形成時，以濕式製膜法為佳。 20 蒸鍍法並無特別限制，可因應目的從已知者當中適當選 擇，可舉例如真空蒸鍍法、電陰加熱蒸鍍法、化學蒸鍍法、物 理蒸鍍法等。化學蒸鍍法可舉例如電漿CVD法、雷射CVD法、 熱CVD法、氣體源（gas source) CVD法等。 濕式製膜法可在溶劑中混合主體及/或聚合物等形成之膠 26 1245586 黏劑與有關本發明之鱗光發光固體，藉旋轉塗膜法、喷墨法、 浸塗法、«塗抹法㈣式製料法塗布。料，為了提高發 光層之電何輸賴’若將上述所舉作為電洞輸送層材料及電子 輸送層材料之上述材料同時混合人溶液中來製膜，則可使發光 層中具有f簡送層或電子輸送輕能mu層構成電洞 輸曰兼t光層、或發光層兼電子輸送層、錢浦送層兼發 光層兼電子輸送層。 ❿’可使用之膠黏劑之例可舉聚乙婦基心坐、聚碳酸Metal oxides such as MgO, SiO, Si〇2, AI2O3, GeO, NiO, CaO, BaO, Fe2 03, Y2 03, and Ti02; nitrides such as SiN and SiNxOy; metal fluorides such as MgF2, LiF, A1F3, and CaF2 ; Polyethylene, polypropylene, polymethylmethacrylate, polyamide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichloro20 difluoroethylene, trifluoroethylene and dichlorodifluoro Copolymer of ethylene, copolymer obtained by copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer, fluorinated copolymer having a cyclic structure on the main chain of copolymerization, and a water absorption of 1% by weight or more Water-absorbing substances, moisture-proof substances having a water absorption of 0.1% by weight or less, and the like. The protective layer can be formed by, for example, a vapor deposition method, a wet film formation method, a sputtering method, a reactive sputtering method 25 1245586, an MBE method, a cluster ion beam method, an ion spray method, a plasma polymerization method (high-frequency laser ion sputtering). Method), printing method, transfer method, and the like. • Color conversion layer The organic EL element of the present invention may have five layers of color conversion appropriately selected according to the purpose, and the color conversion layer may contain the phosphorescent light-emitting solid of the present invention. The color conversion layer is a layer that absorbs light emitted from an organic EL element and changes its wavelength, as described in Japanese Patent Application Laid-Open No. 3-152897. For example, a light-emitting-side substrate made of a blue-colored organic EL element and Between ITO electrodes, blue is converted to green or red, and the display device is multicolored. As long as the color conversion layer can sufficiently absorb 10 converted light and convert it to a desired wavelength, any thickness, material, and manufacturing method are acceptable, typically 0.01 // m to 100 / zm, and more preferably 1 // m Thickness of ~ 50 // m is best made by photolithography. Here, it is explained that the production of the light-emitting layer can be formed according to known methods, such as a vacuum evaporation method, a wet film formation method, a MBE method, a cluster ion beam method, a 15-molecular layer method, an LB method, and printing. It is suitably formed by a method, a transfer method, or the like. Among these, from the point of not using an organic solvent and having no waste water treatment problem, and being able to be produced at a low cost, simply and efficiently, the vapor deposition method is preferred, and when the light emitting layer is designed with a single layer structure, for example, When the light emitting layer is formed as a hole transporting layer, a light emitting layer, an electron transporting layer, etc., a wet film forming method is preferred. 20 The vapor deposition method is not particularly limited, and may be appropriately selected from known ones according to the purpose, and examples thereof include a vacuum vapor deposition method, an electro-cavity heating vapor deposition method, a chemical vapor deposition method, and a physical vapor deposition method. Examples of the chemical vapor deposition method include a plasma CVD method, a laser CVD method, a thermal CVD method, and a gas source CVD method. The wet film-forming method can mix the glue formed by the main body and / or polymer in a solvent. 26 1245586 Adhesive and the scale-emitting light-emitting solid of the present invention, by spin coating method, inkjet method, dip coating method, Coated by the French method. In order to increase the electricity of the light-emitting layer, if the materials mentioned above as the hole transport layer material and the electron transport layer material are mixed into a solution to form a film, the light-emitting layer can have f The layer or the electron transport light energy mu layer constitutes a hole transporting layer and a light layer, or a light emitting layer and an electron transporting layer, a Qianpu transporting layer and a light emitting layer and an electron transporting layer. ❿ ’Examples of adhesives that can be used include polyethene, carbonic acid

西曰水亂乙稀、聚笨乙稀、聚甲基甲基丙烤酸醋、聚醋、聚石風、 10 ♦亞本基氧化物、聚丁二烯、經樹脂、崎脂、苯氧基樹脂、 聚醯胺、乙基纖維素、醋酸乙婦、ABS樹脂、聚胺甲酸醋、三 聚氰胺樹脂、不餘和聚賴脂、醇酸樹脂、環氧樹脂、聚石夕氧 樹脂等。 藉3色發光法之面板，需要各自發出紅、、綠、青3色光之 15有機EL元件部分，這種情況之各色發光元件部分可例示下述 組合。Xi Yue Shui Chao Ethylene, Polybenzyl Ester, Polymethyl Methyl Propionate Sour Vinegar, Poly Vinegar, Polylithic Wind, 10Adenyl Oxide, Polybutadiene, Resin, Zinc Grease, Phenoxy Base resin, polyamide, ethyl cellulose, ethyl acetate, ABS resin, polyurethane, melamine resin, Yuyao and polylysine, alkyd resin, epoxy resin, polylithic resin, etc. The three-color light-emitting panel requires 15 organic EL element portions that emit red, green, and cyan light, respectively. In this case, the light-emitting element portions of each color can be exemplified by the following combinations.

•綠色發光元件部分 其構成係將有關本發明之磷光發光固體作為單獨或客體 使用（參考實施例4)。 2〇 •紅色發光元件部分 ITO (陽極）/NPD (電洞輸送層）/含有i重量％之第14 圖所示之4-二氰基亞曱基-6-cp-久洛尼啶基苯乙烯基三級丁 基-4H-哌。南（4-dkyan〇methyleneicp_juloilidin〇styryl_2_tert_b utyMH-pyran) (DCJTB)之Alq (電子輸送層兼發光層）/Alq/ 27 1245586• Green light-emitting element portion The phosphor light-emitting solid according to the present invention is used alone or as a guest (refer to Example 4). 2〇 • Red light-emitting element part ITO (anode) / NPD (hole transport layer) / 4-dicyanofluorenylene-6-cp-giolonidinylbenzene as shown in Fig. 14 containing i% by weight Vinyl tertiary butyl-4H-piper. South (4-dkyan〇methyleneicp_juloilidin〇styryl_2_tert_b utyMH-pyran) (DCJTB) Alq (electron transport layer and light emitting layer) / Alq / 27 1245586

Al —Li (陰極） •藍色發光元件部分 ITO (陽極）/NPD/A卜Li (陰極） 利用有關本發明之有機EL元件之有機EL顯示器，可期待 5其發光效率南、驅動壽命長、可安定地驅動。該有機EL元件 可作為被動矩陣面板或動態矩陣面板來使用（例如 日經工b夕 卜口二夕只，2000年3月13日號，第765號，ρ·55〜62)。將有關 本發明之有機EL几件使用於被動矩陣顯示器之情況顯示於第 23圖。第23圖是陽極/電洞輸送層/發光層/電子輸送層/陰極之 10構成例。第23圖中，有機元件係於玻璃製基板1上積層有： 由ITO形成之陽極2、電洞輸送層3、發光層4、電子輸送層5、 由金屬形成之陰極6。由IT〇形成之陽極2為行列電極 (row-electrodes )，由金屬形成之陰極6為柱狀電極（c〇lunmar- electrodes)。該圖中，藉由改變用於發光層4之發光層形成材 15料，可實現紅色發光7、綠色發光8、藍色發光9。 將有關本發明之有機EL元件使用於動態矩陣顯示器之情 況顯示於第24圖。第24圖也是陽極/電洞輸送層/發光層/電子 輸送層/陰極之構成例。第24圖中，有機EL元件係於玻璃製 基板1上積層有··驅動電路2卜TFT(ThinFilmTransist〇r)電 20路22、由1TO形成之陽極2、電洞輸送層3、發光層4、電子 輸送層5、由金屬形成之陰極6。該圖中，也可藉由改變用於 發光層4之發光層形成材料，實現紅色發光7、綠色發光8、 藍色發光9。 以下’針對本發明之例子說明。 28 1245586 本發明之實施例中所使用之三座配位子係藉Stille偶合 法，依據文獻 〇rganometallics (D.J.Cardenas 及 A.M.Echavarre n，第18卷，P.3337 ( 1999年））之方法合成。該等三座配位子亦 可藉由鈐木偶合法（參考文獻：M.D.Sindkhedkar，H.R.Mulla5M. 5 A.Wurth 及 A.Cammers-Goodwin，Tetrahedron，第 57 卷，（2001 年））合成。又，利用三座配位子之金屬錯合物之合成，係依 據文獻 Organometallics (D.J.Cardenas 及 A.M.Echavarren，第 18 卷，p.3337 ( 1999年））之方法進行。 [合成例 1] (Pt (3,5—二（2—咄啶基）甲苯）Cl (Pt (3,5 10 一 di ( 2 —pyridyl) toluene) C1 (以下略稱為：Pt ( dpt) C1)之 合成） (1) 三座配位子3,5 —二（2—。比啶基）甲苯（3,5 — di (2 — pyridyl) toluene，以下略稱為（dpt))之合成（參考第17圖） 將3,5·二漠曱苯（6.9g，20mmoL)、2-三-η-丁基甲錫烧基π比 15 啶（26.9g，73mmoL)、雙（三苯基-膦）二氯化鈀（1.55g，2.2mmoL) 及氯化链（ll_7g，276mmoL )加入130mL之甲苯中，回流2天。 放冷後，加入KF飽和水溶液50mL，藉過濾取出析出之固 體’以少量之冷卻曱苯（20mLx3)洗淨，將之真空乾燥。將所 得到之固體放入二氣曱烷與NaHC03之混合溶液中充分洗淨。 2〇 分取有機層，以MgS04粉末使之乾燥後，以蒸發裝置蒸發除去 溶劑。之後，以二氣曱烷再結晶，得到灰色固體之dpt2.2g。獲 率 45%。 (2) Pt (dpt) C1之合成（參考第18圖） 將 dpt ( 300mg，1.2mmoL)與 K2[PtCl]4 ( 550mg，1.3mmoL) 29 1245586 加入脫氣之醋酸（30mL)中，在130°C下回流2天。放冷後會 析出淡黃色結晶，故過濾取出。以曱醇、水、二***將濾取之 固體充分洗淨，將之真空乾燥。藉二氯甲烷將所得到之粗粉末 再結晶，得到黃色粉末之Pt (dpt) Cl，436mg。獲率77%。 5 [合成例 2] (Pt (3,5—二（2 —喳啉基）甲苯）Cl (Pt (3,5 —di ( 2 — quinolyl ) toluene ) C1 (以下略稱為：Pt ( dqt) C1) 之合成） 三座配位子3,5—二（2—喳啉基）甲苯（3,5 — di (2 — quinolyl ) toluene )(以下略稱為（dqt))係藉由以2 —三一 η-ΐΟ 丁基曱錫烧基σί：σ林取代2—三一η —丁基甲錫烧基吼唆，除此之 外與合成例1同樣做法合成。獲率54%。又，Pt (dqt) C1係將 配位子從dpt換成dqt，除此之外與合成例1同樣做法合成。獲 率 42%。 [合成例 3] (Pt (3,5— 二（2—吡啶基）呲啶）Cl (Pt (3,5 15 — di ( 2 — pyridyl) pyridine) C1 (以下略稱為：Pt ( dppr) C1) 之合成） 三座配位子3,5 —二（2 —吼咬基）吼°定（3,5 — di( 2 —pyridyl ) pyridine，以下略稱為dppr)係藉由將3,5 —二溴曱苯以3,5 — 二溴咄啶取代，除此之外與合成例1同樣做法合成。獲率36%。 20 又，將配位子從dpt換成dppr，除此之外與合成例1同樣做法， 進行有機金屬錯合物Pt (dppr) C1之合成。獲率14%。 [實施例1] 在石英玻璃基板上藉共蒸鍍製作出將合成例1所合成之Pt (dpt) Cl於CBP摻雜2重量％之薄膜。厚度為50nm。又，藉 30 1245586 〜鉸製作f光量子獲率為已知之Alq之單獨膜，作為基準使用。 又，以基準之Alq薄膜之螢光量子獲率作為22%求得本發 明之磷光發光固體（薄膜）之磷光量子獲率。測定係如下進行。 5亦即，第19圖之裝置中，利用365nm之定常光191作為激光， 面以光電二極體192 (濱松水卜二夕只製—ph〇t〇sens〇r 719)監控經由鏡子194,195在樣本196之激光透過量與反射 里 面藉分光放射輝度計193 ( 5夕瓜夕社製cs—1〇〇〇)測 ;本4膜之發光光譜。將激光之每草位吸收量之發光強度與Al — Li (cathode) • Blue light-emitting element part ITO (anode) / NPD / Ab Li (cathode) With the organic EL display of the organic EL element of the present invention, it can be expected that its luminous efficiency is long, its driving life is long, Stable driving. The organic EL element can be used as a passive matrix panel or a dynamic matrix panel (for example, Nikkei Kobuki, Bukou Erxi only, March 13, 2000, No. 765, ρ 55 ~ 62). Fig. 23 shows a case where several organic EL devices according to the present invention are used in a passive matrix display. Fig. 23 is a configuration example of the anode / hole transport layer / light-emitting layer / electron transport layer / cathode. In FIG. 23, the organic elements are laminated on the glass substrate 1. The anode 2, the hole transport layer 3, the light emitting layer 4, the electron transport layer 5, and the cathode 6 made of metal are formed of ITO. The anode 2 formed of IT0 is a row-electrodes, and the cathode 6 formed of a metal is a columnar electrode. In this figure, by changing the light-emitting layer forming material 15 used for the light-emitting layer 4, red light emission 7, green light emission 8, and blue light emission 9 can be realized. Fig. 24 shows a case where the organic EL element of the present invention is used in a dynamic matrix display. Fig. 24 is also a configuration example of the anode / hole transporting layer / light emitting layer / electron transporting layer / cathode. In FIG. 24, the organic EL element is laminated on a glass substrate 1. The driving circuit 2 includes 20 TFT (ThinFilmTransistor) circuits 22, an anode formed of 1TO2, a hole transport layer 3, and a light emitting layer 4. An electron transport layer 5 and a cathode 6 formed of a metal. In this figure, red light emission 7, green light emission 8, and blue light emission 9 can be realized by changing the light emitting layer forming material used for the light emitting layer 4. The following 'is an example of the present invention. 28 1245586 The three ligands used in the examples of the present invention were synthesized by the method of Stille coupling according to the method of Organometallics (D.J. Cardenas and A.M.Echavarren, Vol. 18, P.3337 (1999)). These three ligands can also be synthesized by puppetry (References: M.D. Sindkhedkar, H.R. Mulla 5M. 5 A. Wurth and A. Cammers-Goodwin, Tetrahedron, Vol. 57 (2001)). Furthermore, the synthesis of metal complexes using three ligands was performed according to the method of the document Organometallics (D.J. Cardenas and A.M. Echavarren, Vol. 18, p. 3337 (1999)). [Synthesis Example 1] (Pt (3,5-bis (2-pyridinyl) toluene) Cl) (Pt (3,5 10-di (2-pyridyl) toluene) C1 (hereinafter abbreviated as: Pt (dpt)) Synthesis of C1) (1) Synthesis of three ligands 3,5-bis (2-.pyridyl) toluene (3,5-di (2-pyridyl) toluene, hereinafter abbreviated as (dpt)) (Refer to Fig. 17) 3,5 · Dioxobenzene (6.9g, 20mmoL), 2-tri-n-butylmethyltin π to 15 pyridine (26.9g, 73mmoL), bis (triphenyl-phosphine) ) Palladium dichloride (1.55g, 2.2mmoL) and chlorinated chain (11-7g, 276mmoL) were added to 130mL of toluene and refluxed for 2 days. After cooling, 50mL of KF saturated aqueous solution was added, and the precipitated solid was removed by filtration. The cooled toluene (20 mL x 3) was washed and dried under vacuum. The obtained solid was thoroughly washed in a mixed solution of dioxane and NaHC03. 20 The organic layer was separated and dried with MgS04 powder. The solvent was removed by evaporation with an evaporation device. After that, it was recrystallized with dioxane to obtain 2.2 g of dpt as a gray solid. The yield was 45%. (2) Synthesis of Pt (dpt) C1 (refer to Figure 18) 300mg, 1.2mmoL) and K2 [PtCl] 4 (550mg, 1.3mmoL) 29 1245586 was added to degassed acetic acid (30mL) and refluxed at 130 ° C for 2 days. After cooling, pale yellow crystals would precipitate, so it was taken out by filtration. With methanol and water The diethyl ether was used to thoroughly wash the filtered solid and dried under vacuum. The obtained crude powder was recrystallized by using dichloromethane to obtain Pt (dpt) Cl as a yellow powder, 436 mg. The yield was 77%. 5 [Synthesis Example 2] (Pt (3,5-di (2-pyridinyl) toluene) Cl) (Pt (3,5-di (2-quinolyl) toluene) C1 (hereinafter abbreviated as: Pt (dqt) C1) Synthesis) The three ligands 3,5-bis (2-fluorinyl) toluene (3,5-di (2-quinolyl) toluene) (hereinafter abbreviated as (dqt)) are obtained by using 2-trinyl η-ΐΟ Butyl tin tin alkyl σί: σ Lin was substituted for 2-trin η-butyl methyltin tin alkyl, except that it was synthesized in the same manner as in Synthesis Example 1. The yield was 54%. Also, Pt (dqt) C1 was changed from dpt to dqt except that it was synthesized in the same manner as in Synthesis Example 1. The yield was 42%. [Synthesis Example 3] (Pt (3,5-bis (2-pyridyl) pyridine) ) Cl (Pt (3,5 15 — di (2 — pyridyl) pyridine ) C1 (hereinafter abbreviated as: Synthesis of Pt (dppr) C1)) three ligands 3,5-two (2-roaring bite) 定 ° (3,5-di (2 -pyridyl) pyridine, This is hereinafter abbreviated as dppr). It was synthesized in the same manner as in Synthesis Example 1 except that 3,5-dibromofluorene was substituted with 3,5-dibromopyridine. The yield is 36%. 20 In addition, except that the ligand was changed from dpt to dppr, the same procedure as in Synthesis Example 1 was performed to synthesize an organometallic complex Pt (dppr) C1. The yield is 14%. [Example 1] A thin film of 2 wt% of Ct doped with Pt (dpt) Cl synthesized in Synthesis Example 1 was prepared by co-evaporation on a quartz glass substrate. The thickness is 50 nm. In addition, a separate film of Alq having a known f-light quantum yield was fabricated by using 30 1245586 ~ Hing as a reference. Furthermore, the phosphorescent quantum yield of the phosphorescent light-emitting solid (thin film) of the present invention was determined by taking the fluorescence quantum yield of the reference Alq film as 22%. The measurement system was performed as follows. 5 That is, in the device of FIG. 19, the constant light 191 of 365 nm is used as the laser, and the photodiode 192 (Hamamatsu Mizuchi only-ph〇 ト 〇sens〇r 719) is used to monitor the mirror 194,195 The laser light transmittance and reflection of the sample 196 were measured by a spectroradiometer 193 (cs-1000, manufactured by Wuxixixi Co., Ltd.); the luminescent spectrum of this film. The luminous intensity of the laser absorption per grass position and

化口物（Alq)之薄膜之值比較，藉此算出磷光量子獲率。 10結果顯示於表工。 [實施例2] 以Pt (dqt) C1取代發光材料，除此之外，以與實施例工 凡王相同之條件測定磷光發光之量子獲率。結果顯示於表1。 [實施例3] X Pt (dppr) C1取代發光材料，除此之外，以與實施例工 凡王相同之條件測定磷光發光之量子獲率。結果顯示於表1。 表1The value of the Alq film was compared to calculate the phosphorescent quantum yield. 10 results are shown for watchmaker. [Example 2] Except that Pt (dqt) C1 was used instead of the light-emitting material, the quantum yield of phosphorescent emission was measured under the same conditions as those of the example worker. The results are shown in Table 1. [Example 3] Except that X Pt (dppr) C1 replaced the light-emitting material, the quantum yield of phosphorescence emission was measured under the same conditions as those of the example worker. The results are shown in Table 1. Table 1

從表1可清楚得知，本發明之磷光發光薄膜具有非常高的 ^ S 光里子獲率。藉 j A.G.Williams 等在 inorg chem.(第 42 卷P.8609-8611,2003年）中報告之pt (dpt) α錯合物，在溶 31 20 1245586 液狀悲下有68%之填光量子獲率，意外的是，在固體狀態下， 可大幅改善磷光量子獲率達98%。 表1中所顯示之比較例1〜3 (ref_l5ref.2，ref3)，係顯示出 特開2002-363552號公報中所記载之具有三個N，N、C型配位子 5之有機金屬錯合物，在二氯甲烧溶液狀態下之麟光量子獲率。 該等具有三個]ST>TC型配位子之有機金屬錯合物之分子構造 顯示於第20圖。從這個比較可理解出，本發明之利用具有 N CTN型配位子之有機金屬錯合物之磷光發光固體（薄膜）顯 示出非常高的磷光量子獲率。 10 [實施例4] 如下所述地將Pt ( dpt) C1錯合物用於發光層製作積層型 有機EL元件。藉水、丙酮、異丙醇洗淨附IT〇電極之玻璃基 板，利用真空蒸鍍裝置（（IxlO'a)，基板溫度為室溫），於該 附ιτο電極之玻璃基板上以下述膜厚蒸鍍下述各層：4〇nm之 15 2-TNATA (4,4’，4”一三（2—萘基苯基胺基）三苯胺）作為電洞 注入層、lOnm之α—NPD作為電洞輸送層、於其上蒸鍍將pt (dPt)C1於CBP摻雜2重量％之層3〇nm作為發光層、於其上 蒸錢2〇nm之BCP作為電洞阻擔層、於其上蒸錢2〇⑽之峋 乍為電子輸送層、更於其上蒸鍵Q 5nm之LiF作為電子注入層， 20最後蒸錄紹100nm’在氮環境下封止。於該元件以ιτ〇為陽極、 結電極為陰極來外加電壓，則*電壓4V以上觀測到綠色發光。 表2中，顯示出在實施例4〜9及比較例中，當元件為…施加 寺之叙光尚峰波長、電流效率、電力效率'外部量子效率。又， 所謂外部電子效率係表示碟光輸出對輸入之能量之比率。電流 32 1245586 效率、電力效率、外部量子效率係顯示輪入電流為O.lmA/cm2 時之值。 [實施例5] 以Pt (dqt) C1取代發光材料’除此之外，以與實施例4 5 完全相同之條件製作有機EL元件。以1丁〇為陽極、鋁電極為 陰極來外加電壓，則在電麈4V以上觀測到撥色發光。 [實施例6] 以Pt ( dppr) C1取代發光材料，除此之外，以與實施例4 完全相同之條件製作有機EL元件。以ΓΓΟ為陽極、鋁電極為 10陰極來外加電壓，則在電壓4V以上觀測到青綠色發光。 [實施例7] 如下所述地將Pt (dpt) C1錯合物用於發光層製作高分子 有機EL το件。藉水、丙酮、異丙醇洗淨附汀〇電極之玻璃基 板。藉旋轉塗膜法，製作PED〇T:pss (聚（乙烯二羥噻吩）： 15聚（笨乙烯磺酸醋））薄膜（5〇nm厚）作為電洞注入層，在200 C加熱乾燥2小時。於其上藉旋轉塗膜製作在ρνκ (聚（、乙It is clear from Table 1 that the phosphorescent light-emitting film of the present invention has a very high photon neutron yield. Using the pt (dpt) alpha complex reported by j AGWilliams and others in inorg chem. (Vol. 42 P.8609-8611, 2003), 68% of the light-filled quantum is obtained under the condition of solution 31 20 1245586. Surprisingly, in the solid state, the phosphorescence quantum yield can be greatly improved by up to 98%. Comparative Examples 1 to 3 (ref_l5ref.2, ref3) shown in Table 1 are organic metals having three N, N, and C type ligands 5 described in JP-A-2002-363552. Quantum yield of the complex in the dichloromethane solution. The molecular structures of these organometallic complexes with three] ST > TC type ligands are shown in FIG. It can be understood from this comparison that the phosphorescent light-emitting solid (thin film) using an organometallic complex having N CTN type ligands of the present invention shows a very high quantum yield of phosphorescence. [Example 4] A laminated organic EL device was fabricated using a Pt (dpt) C1 complex as a light emitting layer as described below. The glass substrate with the IT0 electrode was washed with water, acetone, and isopropanol, and a vacuum evaporation device ((IxlO'a), substrate temperature was room temperature) was used. The glass substrate with the electrode was coated with the following film thickness: The following layers were vapor-deposited: 15 2-TNATA (4,4 ', 4 "-tris (2-naphthylphenylamino) triphenylamine) as a hole injection layer and 15 nm of α-NPD as an electrode A hole transport layer, a layer 30 nm of pt (dPt) C1 doped with 2% by weight of CBP as a light emitting layer, and a layer of BCP vaporized by 20 nm as a hole resisting layer, The top of the steamed coin is a electron transport layer, and the LiF on which the bond Q is 5 nm is used as the electron injection layer. 20 Finally, it is vaporized to 100 nm 'and sealed in a nitrogen environment. The component is ιτ〇 as The anode and the junction electrode are applied with a voltage from the cathode, and green light emission is observed when the voltage exceeds 4 V. Table 2 shows that in Examples 4 to 9 and Comparative Examples, when the element is ... Current efficiency, power efficiency, 'external quantum efficiency. Also, the so-called external electronic efficiency refers to the ratio of the optical output of the disc to the energy input. Current 32 1245586 Efficiency, power efficiency, and external quantum efficiency are shown when the wheel-in current is O.lmA / cm2. [Example 5] Pt (dqt) C1 is used instead of the light-emitting material. An organic EL element was fabricated under exactly the same conditions. When a voltage was applied with 1 to 0 as an anode and an aluminum electrode as a cathode, a color-emission emission was observed above 4V. [Example 6] Pt (dppr) C1 was used instead of the light-emitting material. Except that, an organic EL device was fabricated under exactly the same conditions as in Example 4. When ΓΓΟ was used as the anode and the aluminum electrode was applied to the 10 cathode to apply a voltage, cyan light emission was observed at a voltage of 4V or more. [Example 7] Use the Pt (dpt) C1 complex for the light-emitting layer to make a high-molecular organic EL το as described below. The glass substrate with Ting electrode was washed with water, acetone, and isopropanol. Fabricated by the spin coating method PEDOT: pss (poly (ethylene dihydroxythiophene): 15 poly (benzyl ethylene sulfonate)) film (50 nm thick) as a hole injection layer, heated and dried at 200 C for 2 hours. Spin on it The coating is made in ρνκ (poly (, B

C1錯合物之發光層 [實施例gj 2小時。將基板移到真空蒸鍍裝置 至溫），在發光層上蒸錢20nm之BCP 篆鍍20nm之Alq作為電子輸送層、 LiF作為電子注入層，最後蒸鍍鋁 於該元件以ITO為陽極、鋁電極為 i 4V以上觀測到綠色發光。 1245586 以Pt (dqt) Cl取代發光材料，除此之外，以與實施例7 完全相同之條件製作有機EL元件。以ITO為陽極、鋁電極為 陰極來外加電壓，則在電壓4V以上觀測到橙色發光。 [實施例9] 5 以Pt (dppr) C1取代發光材料，除此之外，以與實施例7 完全相同之條件製作有機EL元件。以ITO為陽極、鋁電極為 陰極來外加電壓，則在電壓4V以上觀測到青綠色發光。 表2 發光材料 發光波長 (nm) 電流效率 (cd/A ) 電力效率 (lm/W) 外部量子效 率（％) 實施例4 Pt (dpt) Cl 509 45.1 28.0 13.1 實施例5 Pt (dqt) Cl 610 21.0 13.4 10.5 實施例6 Pt (dppr) Cl 479 18.3 10.3 7.3 實施例7 Pt (dpt) Cl 511 25.2 12.2 7.3 實施例8 Pt (dqt) Cl 613 11.2 5.5 5.6 實施例9 Pt (dppr) Cl 479 9.5 3.8 3.8 比較例4 ref. 1 582 4.2 比較例5 ref.2 600 2.4 比較例6 ref.3 616 1.4 從表2可理解，本發明之有機EL元件（實施例4〜9)全都 10 顯示出非常高的EL效率。特別是實施例4之利用Pt (dpt) C1 之元件，其外部量子效率高達13.1% (最大值為5.6V13.4%)。 表2之比較例4〜6中，顯示出與表1之情況相同之特開 2002-363552號公報中所記載之有機EL元件之電流效率。唯， 比較例之發光波長為在二氯曱烷溶液狀態下測定之值，電流效 15 率係顯示在25〜30mA/cm2之效率。從與這些比較，也可得知， 利用有關本發明之磷光發光固體之有機EL元件顯示出非常高 的發光效率。利用Pt( dpt) C1之元件其原本發光效率即很高， 標繪出其EL光譜、電流密度及外部量子效率之關係之結果顯 示於第21;22圖。 34 1245586 產業上可利用性 藉本發明，可提供發光效率高之有機EL元件或高性能之 有機EL裝置。 I：圖式簡翠說明3 5 第1圖是例示以式（4)表示之構造部分之圖。 第2圖是顯示Ar1及Ar3之例之圖。 第3圖是顯示Ar2之例之圖。 第4圖是例示低分子系主體材料之圖。Light emitting layer of C1 complex [Example gj 2 hours. Move the substrate to a vacuum evaporation device, and then vaporize BCP with a thickness of 20nm on the light-emitting layer. Alq with a thickness of 20nm as an electron transport layer and LiF as an electron injection layer. Finally, vapor-deposit aluminum on the element with ITO as the anode and aluminum. The electrode emits green light when i 4V or more. 1245586 An organic EL device was fabricated under the same conditions as in Example 7 except that the light-emitting material was replaced with Pt (dqt) Cl. When an external voltage was applied using ITO as the anode and aluminum electrode as the cathode, orange light emission was observed at a voltage of 4V or more. [Example 9] 5 An organic EL device was fabricated under the same conditions as in Example 7 except that the light-emitting material was replaced with Pt (dppr) C1. When ITO was used as the anode, and the aluminum electrode was used as the cathode, a blue-green light emission was observed when the voltage was above 4V. Table 2 Luminescence wavelength of light-emitting materials (nm) Current efficiency (cd / A) Power efficiency (lm / W) External quantum efficiency (%) Example 4 Pt (dpt) Cl 509 45.1 28.0 13.1 Example 5 Pt (dqt) Cl 610 21.0 13.4 10.5 Example 6 Pt (dppr) Cl 479 18.3 10.3 7.3 Example 7 Pt (dpt) Cl 511 25.2 12.2 7.3 Example 8 Pt (dqt) Cl 613 11.2 5.5 5.6 Example 9 Pt (dppr) Cl 479 9.5 3.8 3.8 Comparative Example 4 ref. 1 582 4.2 Comparative Example 5 ref. 2 600 2.4 Comparative Example 6 ref. 3 616 1.4 As can be understood from Table 2, all the organic EL elements (Examples 4 to 9) of the present invention showed a very high 10 EL efficiency. In particular, the element using Pt (dpt) C1 in Example 4 has an external quantum efficiency as high as 13.1% (the maximum value is 5.6V 13.4%). In Comparative Examples 4 to 6 of Table 2, the current efficiency of the organic EL element described in Japanese Patent Application Laid-Open No. 2002-363552 is the same as that in Table 1. However, the light emission wavelength of the comparative example is a value measured in a dichloromethane solution state, and the current efficiency 15 is an efficiency of 25 to 30 mA / cm2. From comparison with these, it can also be seen that the organic EL element using the phosphorescent light-emitting solid according to the present invention exhibits very high luminous efficiency. The original luminous efficiency of the element using Pt (dpt) C1 is very high. The results of plotting the relationship between its EL spectrum, current density, and external quantum efficiency are shown in Figure 21; 22. 34 1245586 Industrial applicability According to the present invention, it is possible to provide an organic EL device with high luminous efficiency or an organic EL device with high performance. I: Brief description of the drawing 3 5 The first drawing is a diagram illustrating a structural part represented by the formula (4). Fig. 2 is a diagram showing examples of Ar1 and Ar3. Fig. 3 is a diagram showing an example of Ar2. FIG. 4 is a diagram illustrating a low-molecular-based host material.

第5圖是例示咔唑化合物之圖。 10 第6圖是例示第5圖中之Ar之圖。 第7圖是例示第6圖中之連結基R。 第8圖是顯示CBP之構造之圖。 第9圖是例示高分子系主體材料之圖。 第10圖是顯示星狀放射胺（starburstamine)之構造之圖。 15 第11圖是顯示TPD之構造之圖。Fig. 5 is a diagram illustrating a carbazole compound. 10 FIG. 6 is a diagram illustrating Ar in FIG. 5. FIG. 7 illustrates the linking group R in FIG. 6. Fig. 8 is a diagram showing the structure of CBP. Fig. 9 is a view illustrating a polymer-based host material. Fig. 10 is a diagram showing the structure of starburstamine. 15 Figure 11 is a diagram showing the structure of a TPD.

第12圖是顯示Alq之構造之圖。 第13圖是例示光吸收端較有關本發明之磷光發光固體更 為短波長之材料之圖。 第14圖是顯示DCJTB之構造之圖。 20 第15圖是有機EL元件之模式側截面圖。 第16圖是有機EL元件之其他模式側截面圖。 第17圖是顯示dpt之合成路徑之圖。 第18圖是顯示Pt (dpt) C1之合成路徑之圖。 第19圖是顯示磷光量子獲率之測定法之圖。 35 1245586 第20圖是顯示比較例中所使用之有機金屬錯合物之分子 構造之圖。 第21圖是表示有機EL元件之EL光譜之圖。 第22圖是標示有機EL元件之電流密度與外部量子效率之 5 關係之圖表。 第23圖是顯示將關於本發明之有機EL元件使用於被動矩 陣顯示器時之模式立體圖。 第24圖是顯示將關於本發明之有機EL元件使用於動態矩 陣顯示器時之模式立體圖。 10 【圖式之主要元件代表符號表】 1···玻璃製基板 2···陽極 3···電洞輸送層 4…發光層 5···電子輸送層 6…陰極 7···紅色發光 8…綠色發光 9…藍色發光 21…驅動電路 22…TFT電路 161···色變換層 19卜··定常光 192···光電二極體 193···分光放射輝度計 194，195···鏡子 196…樣本 36Fig. 12 is a diagram showing the structure of Alq. Fig. 13 is a diagram illustrating a material having a light absorption end having a shorter wavelength than the phosphorescent light-emitting solid of the present invention. Fig. 14 is a diagram showing the structure of DCJTB. 20 FIG. 15 is a schematic side sectional view of an organic EL element. Fig. 16 is a sectional side view of another mode of the organic EL element. Fig. 17 is a diagram showing a synthetic path of dpt. Fig. 18 is a diagram showing a synthetic path of Pt (dpt) C1. Fig. 19 is a diagram showing a method for measuring the quantum yield of phosphorescence. 35 1245586 Figure 20 is a diagram showing the molecular structure of the organometallic complex used in the comparative example. Fig. 21 is a diagram showing an EL spectrum of an organic EL element. Fig. 22 is a graph showing the relationship between the current density of an organic EL element and the external quantum efficiency. Fig. 23 is a perspective view showing a mode when the organic EL element of the present invention is used in a passive matrix display. Fig. 24 is a perspective view showing a mode when the organic EL element of the present invention is used in a dynamic matrix display. 10 [Representative symbols for main elements of the drawing] 1 ··· Glass substrate 2 ··· Anode 3 ·· hole transport layer 4… light-emitting layer 5 ·· electron transport layer 6… cathode 7 ·· red Light emission 8 ... Green light emission 9 ... Blue light emission 21 ... Drive circuit 22 ... TFT circuit 161 ... Color conversion layer 19 Bu ... Constant light 192 ... Photodiode 193 ... Spectrophotometer 194, 195 ··· Mirror 196 ... Sample 36

Claims (1)

1245586 拾、申請專利範圍： 5 2. 一種磷光發光固體，含有分別配位一個以上之三座配位子 與鹵素原子而形成之有機金屬錯合物，且該三座配位子係 以兩個氮原子、與位於該兩個氮原子間且透過鍵與該兩個 氮原子鍵結之一個碳原子來配位鍵結於中心金屬原子。 如申請專利範圍第1項之磷光發光固體，其中前述有機金屬 錯合物具有以下式（1 )表示之構造：1245586 The scope of patent application: 5 2. A phosphorescent light-emitting solid containing an organometallic complex formed by coordination of one or more three ligands and a halogen atom, and the three ligands are formed by two A nitrogen atom and a carbon atom located between the two nitrogen atoms and bonded to the two nitrogen atoms through a bond are coordinated and bonded to the central metal atom. For example, the phosphorescent light-emitting solid of the first scope of the patent application, wherein the aforementioned organometallic complex has a structure represented by the following formula (1): 10 15 3. (式（1 )中，Μ表示金屬原子，X表示鹵素原子，Ar1，Ar2， Ar3各自獨立地表示可具有取代基之環狀構造，Ar1 — Ar2及 Ar2 — Ar3之鍵可為單鍵或雙鍵，Μ與Ar1及Μ與Ar3具有Μ — N 之配位鍵，Μ與Ar2具有Μ— C之直接鍵，Ar]，Ar2，Ar3之 取代基可分別在Ar1，Ar2，Ar3上互相鍵結形成環狀構造， 以及分別在Ar1與Ar2相互間、及Ar2與Ar3相互間互相鍵結形 成環狀構造）。 如申請專利範圍第1項之磷光發光固體，其中前述有機金屬 錯合物係分別配位一個以上之三座配位子與_素原子而形 成者，且該三座配位子係以兩個氮原子與一個碳原子配位 鍵結於中心金屬原子，又，該兩個氮原子、一個碳原子及 中心金屬原子具有兩個5員環縮合之形狀之構造部分，且該 兩個5員環共用該碳原子與中心金屬原子之鍵。 37 1245586 4·如申請專利範圍第1項之磷光發光固體，其中前述有機金屬 錯合物具有以下式（2)表示之構造部分：10 15 3. (In the formula (1), M represents a metal atom, X represents a halogen atom, Ar1, Ar2, and Ar3 each independently represents a cyclic structure which may have a substituent. The bond of Ar1 — Ar2 and Ar2 — Ar3 may be Single bond or double bond, M and Ar1 and M and Ar3 have M—N coordination bonds, M and Ar2 have M—C direct bonds, and the substituents of Ar], Ar2, and Ar3 can be in Ar1, Ar2, and Ar3, respectively. The two are bonded to each other to form a ring structure, and the two are respectively bonded to each other to form a ring structure between Ar1 and Ar2, and Ar2 and Ar3. For example, the phosphorescent light-emitting solid of item 1 of the patent application scope, wherein the organometallic complex is formed by coordinating one or more three ligands and a prime atom, and the three ligands are formed by two A nitrogen atom and a carbon atom are coordinated and bonded to a central metal atom, and the two nitrogen atoms, one carbon atom, and the central metal atom have two 5-membered ring-condensed structural parts, and the two 5-membered rings The bond between the carbon atom and the central metal atom is shared. 37 1245586 4. If the phosphorescent light-emitting solid according to item 1 of the patent application scope, wherein the aforementioned organometallic complex has a structural portion represented by the following formula (2): (式（2)中，Μ與X同式⑴，γ為相互獨立地表示碳 原子或氮原子，Ν—Υ鍵結部分構成前述式（1)中之A〆或 Ar3之一部份，苯核可具有取代基，且配位子與中心金屬原 子之鍵以外之鍵可為單鍵亦可為雙鍵）。 5.如申請專職圍第i項之麟光發光固體，其中前述有機金屬 錯合物具有以下式（3)表示之構造部分··(In formula (2), M and X are of the same formula ⑴, γ represents a carbon atom or a nitrogen atom independently of each other, and the N-Υ bonding portion constitutes a part of A〆 or Ar3 in the aforementioned formula (1), benzene The core may have a substituent, and the bond other than the bond between the ligand and the central metal atom may be a single bond or a double bond). 5. If you apply for a full-time radiant light-emitting solid in item i, wherein the aforementioned organometallic complex has a structural portion represented by the following formula (3) ... (式（3)中，Μ與X同式（1)，笨核可相互獨立地具有取 代基，且取代基可在同一環上或鄰接之環之間相互鍵結）。 6·如申請專利範圍第2項之填光發光固體，其中前述有機金屬 錯合物具有以下式（3)表示之構造部分：(In formula (3), M and X are the same as in formula (1), and the stupid core may have a substituent independently of each other, and the substituents may be bonded to each other on the same ring or adjacent rings). 6. The light-filled luminescent solid according to item 2 of the scope of patent application, wherein the aforementioned organometallic complex has a structural portion represented by the following formula (3): (式（3)中’Μ與X同式⑴，笨核可相互獨立地具有取 38 1245586 代基，取代基可在同一環上或鄰接之環之間相互鍵結）。 7·如申請專利範圍第丨項之磷光發光固體，其中前述與A, 相互獨立地含有單環或多環之芳香環。 8·如申請專利範圍第〗項之磷光發光固體，其中前述八^與^3 5 相同。 9. 如申請專利範圍第丨項之磷光發光固體，其中前述有機金屬 錯合物係由一個三座配位子、一個鹵素原子與一個中心金 屬原子形成。(In formula (3), 'M and X are of the same type, and the stupid nucleus may have a substituent of 38 1245586, and the substituents may be bonded to each other on the same ring or adjacent rings). 7. The phosphorescent light-emitting solid according to item 丨 of the application, wherein the foregoing and A, independently of each other, contain a monocyclic or polycyclic aromatic ring. 8. The phosphorescent light-emitting solid according to the item of the scope of the patent application, wherein the aforementioned ^^ and ^ 3 5 are the same. 9. The phosphorescent light-emitting solid according to item 丨 of the patent application, wherein the aforementioned organometallic complex is formed by a three-segment ligand, a halogen atom and a central metal atom. 10. 如申請專利範圍第2項之磷光發光固體，其中前述有機金屬 10 錯合物係由一個三座配位子、一個鹵素原子與一個中心金 屬原子形成。 如申請專利範圍第5項之麟光發光固體，其中前述有機金屬 錯合物係由一個三座配位子、一個齒素原子與一個中心金 屬原子形成。 15 12·如中請專利範圍第6項之填光發光固體，其中前述有機金屬10. The phosphorescent light-emitting solid according to item 2 of the patent application, wherein the organometallic 10 complex is formed by a three-segment ligand, a halogen atom, and a central metal atom. For example, the light-emitting luminescent solid of item 5 of the patent application range, wherein the aforementioned organometallic complex is formed by a three-segment ligand, a halogen atom, and a central metal atom. 15 12 · The light-filled light-emitting solid of item 6 of the patent, wherein the aforementioned organometal 錯合物係由一個三座配位子、一個鹵素原子與一個中心金 屬原子形成。 13·如申請專利範圍第1項之填光發光固體，其中前述有機金屬 錯合物在固體狀態下為電中性。 2〇 14·如申請專利範圍第1項之鱗光發光固體，其中前述有機金屬 錯合物可藉真空蒸鍍形成膜。 15·如申請專利範圍第2項之石粦光發光固體，其中前述有機金屬 錯合物可藉真空蒸鍍形成膜。 如申請專利範圍第5項之磷光發光固體，其中 τ月』述有機金屬 39 1245586 錯合物可藉真空蒸鍍形成膜。 Π.如申請專利範圍第6項之鱗光發光固體，其中前述有機金屬 錯合物可藉真空蒸鍍形成膜。 18. 如申請專利範圍第9項之鱗光發光固體，其中前述有機金屬 5 錯合物可藉真空蒸鍍形成膜。 19. 如申請專利範圍第1G項之鱗紐光固體，其中前述有機金 屬錯合物可藉真空蒸鍍形成膜。 2〇·如申請專利範圍第n項之碟光發光固體，其中前述有機金 屬錯合物可藉真空蒸鍍形成膜。 10 2丨.如巾請專利制第12項之料發光㈣，其μ述有機金 屬錯合物可藉真空蒸鍍形成膜。 22.如申請專利範圍第i項之填光發光固體，係使用純度重 量％以上之前述有機金屬錯合物而形成者。 23·如申請專利範圍第1項之磷光發光固體，其中前述中心金屬 原子為翻。 w 24.如申請專利範圍第2項之磷光發光固體，其中前述中心金屬 原子為翻。 25·如申請專利範圍第5項之填光發光固體，其中前述中心金屬 原子為翻。 2〇 此*申請專利範圍第6項之麟光發光固體，其中前迷中心金屬 原子為鉑。 27_如ΐ請專利範圍第9項之填光發光固體，其中前述中心金屬 原子為鉑。 28·如申請專利範圍第1()項之填光發光固體，其中前述中心金 40 1245586 屬原子為翻。 29. 如申請專利範圍第11項之磷光發光固體，其中前述中心金 屬原子為始。 30. 如申請專利範圍第12項之磷光發光固體，其中前述中心金 5 屬原子為翻。 31. 如申請專利範圍第15項之磷光發光固體，其中前述中心金 屬原子為翻。 32. 如申請專利範圍第1項之磷光發光固體，其中至少含有各一 個之前述有機金屬錯合物、與具有高於前述有機金屬錯合 10 物之第一激光三重態激光能量之有機材料。 33. 如申請專利範圍第1項之磷光發光固體，其中前述有機材料 含有可具有取代基之咔唑或其衍生物。 34. 如申請專利範圍第2項之磷光發光固體，其中前述有機材料 含有可具有取代基之味σ坐或其衍生物。 15 35.如申請專利範圍第5項之磷光發光固體，其中前述有機材料 含有可具有取代基之咔唑或其衍生物。 36. 如申請專利範圍第6項之磷光發光固體，其中前述有機材料 含有可具有取代基之咔唑或其衍生物。 37. 如申請專利範圍第9項之磷光發光固體，其中前述有機材料 20 含有可具有取代基之咔唑或其衍生物。 38. 如申請專利範圍第15項之磷光發光固體，其中前述有機材 料含有可具有取代基之咔唑或其衍生物。 39. —種有機電致發光元件，係使用申請專利範圍第1〜38項任 一項之磷光發光固體而形成者。 41 1245586 40, 如申請專利範圍第39項之有機電致發光元件，係包含一發 光層，且該發光層内含有前述磷光發光固體。 41. 如申請專利範圍第40項之有機電致發光元件，其中前述磷 “ 光發光固體係作為主體或客體產生機能。 ： 5 42.如申請專利範圍第41項之有機電致發光元件，係於前述發 光層中含有前述磷光發光固體與低分子主體材料。 43. 如申請專利範圍第41項之有機電致發光元件，係於前述發 光層中含有前述磷光發光固體與高分子主體材料。 · 44. 如申請專利範圍第39項之有機電致發光元件，係含有一色 10 變換層，且該色變換層内含有前述磷光發光固體。 45. —種有機電致發光裝置，係使用申請專利範圍第40〜44項任 一項之有機電致發光元件而形成者。 46. —種有機電致發光顯示器，係使用申請專利範圍第40〜44項 任一項之有機電致發光元件而形成者。 15 47. —種有機電致發光照明裝置，係使用申請專利範圍第40〜44 項任一項之有機電致發光元件而形成者。 φ 42The complex is formed by a three-seat ligand, a halogen atom, and a central metal atom. 13. The light-filled luminescent solid according to item 1 of the application, wherein the aforementioned organometallic complex is electrically neutral in a solid state. 2014. The scale-emitting luminescent solid according to item 1 of the application, wherein the aforementioned organometallic complex can be formed into a film by vacuum evaporation. 15. The light-emitting solid of amarine according to item 2 of the application, wherein the organic metal complex can be formed into a film by vacuum evaporation. For example, the phosphorescent light-emitting solid under the scope of the patent application No. 5 in which the organometallic 39 1245586 complex described in τmonth can be formed into a film by vacuum evaporation. Π. The scale-emitting luminescent solid according to item 6 of the application, wherein the aforementioned organometallic complex can be formed into a film by vacuum evaporation. 18. For example, the scale-like light-emitting solid according to item 9 of the application, wherein the aforementioned organometallic 5 complex can be formed into a film by vacuum evaporation. 19. For example, a scale-like solid in the scope of application for item 1G, wherein the organic metal complex can be formed into a film by vacuum evaporation. 20. If the disc light-emitting solid of item n in the scope of the application is filed, wherein the aforementioned organic metal complex can be formed into a film by vacuum evaporation. 10 2 丨. If the material of the patented item No. 12 of the patent is luminous, the organic metal complex compound can be formed by vacuum evaporation. 22. The light-filled luminescent solid according to item i of the scope of patent application is formed by using the aforementioned organometallic complex compound with a purity of more than% by weight. 23. The phosphorescent light-emitting solid according to item 1 of the patent application, wherein the aforementioned central metal atom is a flip. w 24. The phosphorescent light-emitting solid according to item 2 of the patent application, wherein the aforementioned central metal atom is a flip. 25. The light-filled light-emitting solid according to item 5 of the patent application, wherein the aforementioned central metal atom is a flip. 20 This lin light-emitting solid according to item 6 of this patent application, wherein the central metal atom of the front fan is platinum. 27_ If the light-filled luminescent solid of item 9 of the patent is requested, the aforementioned central metal atom is platinum. 28. If the light-filled light-emitting solid according to item 1 () of the patent application scope, wherein the aforementioned central gold 40 1245586 is an atom, it is a tumbling. 29. For the phosphorescent light-emitting solid according to item 11 of the application, wherein the aforementioned central metal atom is the starting point. 30. For example, the phosphorescent light-emitting solid according to item 12 of the patent application, wherein the aforementioned central metal 5 atom is a transfection. 31. For example, the phosphorescent light-emitting solid according to item 15 of the patent application, wherein the aforementioned central metal atom is a flip atom. 32. The phosphorescent light-emitting solid according to item 1 of the application, which contains at least one of the aforementioned organic metal complexes and an organic material having a first laser triplet laser energy higher than the aforementioned organic metal complexes. 33. The phosphorescent light-emitting solid according to item 1 of the application, wherein the aforementioned organic material contains a carbazole or a derivative thereof which may have a substituent. 34. The phosphorescent light-emitting solid according to item 2 of the patent application, wherein the aforementioned organic material contains a sigma or a derivative thereof which may have a substituent. 15 35. The phosphorescent light-emitting solid according to item 5 of the application, wherein the aforementioned organic material contains a carbazole or a derivative thereof which may have a substituent. 36. The phosphorescent light-emitting solid according to item 6 of the application, wherein the aforementioned organic material contains a carbazole or a derivative thereof which may have a substituent. 37. The phosphorescent light-emitting solid according to item 9 of the application, wherein the aforementioned organic material 20 contains a carbazole or a derivative thereof which may have a substituent. 38. The phosphorescent light-emitting solid according to item 15 of the application, wherein the aforementioned organic material contains a carbazole or a derivative thereof which may have a substituent. 39. An organic electroluminescence element formed by using a phosphorescent light-emitting solid according to any one of claims 1 to 38 in the scope of patent application. 41 1245586 40. The organic electroluminescence element according to item 39 of the patent application range includes a light-emitting layer, and the light-emitting layer contains the aforementioned phosphorescent light-emitting solid. 41. For example, the organic electroluminescence element of the scope of application for the patent No. 40, wherein the aforementioned phosphorous "light-emitting solid is used as the host or the object to generate the function .: 5 42. If the organic electroluminescence element of the scope of the application for the patent, No. 41, is The aforementioned light-emitting layer contains the aforementioned phosphorescent light-emitting solid and low-molecular host material. 43. For example, the organic electroluminescence element of the scope of application for patent No. 41 includes the aforementioned phosphorescent light-emitting solid and polymer host material in the aforementioned light-emitting layer. 44. If the organic electroluminescence element of item 39 of the scope of patent application contains a color 10 conversion layer, and the color conversion layer contains the aforementioned phosphorescent light-emitting solid. 45.-An organic electroluminescence device, which uses the scope of patent application Formed by an organic electroluminescence element according to any one of items 40 to 44. 46. An organic electroluminescence display formed by using an organic electroluminescence element according to any one of claims 40 to 44 15 47. — An organic electroluminescence lighting device formed by using an organic electroluminescence element according to any one of the scope of application patents Nos. 40 to 44. φ 42
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