JP2007511067A - Electroluminescent device with anthracene derivative host - Google Patents

Abstract

  The OLED device includes an emissive layer containing an anode and a cathode and a host comprising an emissive dopant and an asymmetrically substituted monoanthracene derivative disposed between the anode and the cathode.

Description

  The present invention relates to an organic electroluminescent (EL) device comprising a light-emitting layer containing a host and a dopant, the host comprising a monoanthracene compound having very good operational stability at room temperature and 70 ° C.

  Although organic electroluminescent (EL) devices have been known for over two decades, the performance limitations in these devices have been a barrier to many desirable applications. In its simplest form, the organic EL device consists of an anode for hole injection, a cathode for electron injection, and an organic medium sandwiched between these electrodes to support charge recombination resulting in light emission. Composed. These elements are generally called organic light emitting diodes or OLEDs. Representative of the early organic EL elements are U.S. Pat. No. 3,172,862 to Gurnee et al. Issued on March 9, 1965; U.S. Pat. No. 3, Gurnee issued on March 9, 1965. No. 3,173,050; “Double Injection Electroluminescence in Anthracene” by Dresner, RCA Review, Vol. 30, pp. 322-334, 1969; and Dresner, U.S. Pat. No. 3,710,167, issued Jan. 9, 1973. The organic layer in these devices was usually composed of polycyclic aromatic hydrocarbons and was very thick (much thicker than 1 μm). As a result, the operating voltage was very high, often> 100V.

  More recent organic EL devices include organic EL elements consisting of a very thin layer (eg <1.0 μm) between the anode and cathode. As used herein, the term “organic EL element” encompasses these layers between the anode and cathode electrodes. By reducing the thickness, the resistance of the organic layer was reduced, making it possible to operate these devices at much lower voltages. In the basic two-layer EL device structure first disclosed in US Pat. No. 4,356,429, one organic layer of the EL device on the side adjacent to the anode is specifically selected to transport holes, so that the positive It is referred to as the hole transport layer, and the other organic layer is specifically selected to transport electrons and is therefore referred to as the electron transport layer. The recombination of injected holes and electrons in the organic EL element provides efficient electroluminescence.

  Also, Tang et al. [J. Applied Physics, Vol. 65, 3610-3616, 1989], and the like, three-layer organic EL devices including an organic light emitting layer (LEL) between the hole transport layer and the electron transport layer have also been proposed. . This light emitting layer is generally made of a host material doped with a guest material. Still further, in US Pat. No. 4,769,292, a four-layer EL device including a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (LEL) and an electron transport / injection layer (ETL) is also proposed. Has been. These structures provide improved device efficiency.

  Hosts based on anthracene are often used. A useful group of 9,10-di- (2-naphthyl) anthracene hosts is disclosed in US 5,935,721. Various bis-anthracene compounds used in luminescent layers with improved device half-life are disclosed in US 6,534,199 and US 2002 / 136,922. An electroluminescent device with improved luminance using an anthracene compound is disclosed in US Pat. No. 6,582,837. Anthracene is also used in HTL, as disclosed in US Pat. No. 6,465,115. In addition to these, there are also other disclosures regarding the use of anthracene materials in OLED devices, such as US 5,972,247, JP2001-097897, JP2000-273056, US2002 / 0048687, WO03 / 060956, WO02 / 088274, EP 0429821, WO03 / 007658, JP2000-053677 and JP2001-335516.

  Despite these advances, there remains a need for a host that has better operational stability and can be conveniently manufactured. The improved operational stability of OLED elements will allow the use of these elements in more products.

  The present invention relates to a luminescent dopant or guest material having a defined feature and disposed between the anode and cathode, and between the anode and cathode, and a monoanthracene of formula (I) as described in more detail below. Provided is an OLED device comprising a light emitting layer containing a host containing a derivative.

  The present invention provides an OLED device with improved operational stability and further with other advantages as described below. The present invention also provides a display and a lighting device using such an OLED element.

で定義される。 The present invention has been summarized generally above. A specific example of a host is the general formula (I):

Defined by

R ₁ -R ₈ is H.

R ₉ is a naphthyl group that does not contain a condensed ring with an aliphatic carbon ring member, provided that R ₉ and R ₁₀ are not the same and do not contain amine and sulfur compounds; Suitably R ₉ is a substituted naphthyl group which forms a fused aromatic ring system such as phenanthryl, pyrenyl, fluoranthene, perylene, or a fluorine, cyano group, hydroxy, alkyl, alkoxy, aryloxy, aryl, heterotricycle A naphthyl group substituted with one or more substituents such as a formula oxy group, carboxy, trimethylsilyl group or the like, or an unsubstituted naphthyl group; Conveniently, R ₉ is 2-naphthyl (Inv-1, Inv-3), 1-naphthyl substituted or unsubstituted at the para position (Inv-18, Inv-19).

R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member. Suitably R ₁₀ is a substituted biphenyl group that forms a fused aromatic ring system including but not limited to phenanthryl, perylene, or fluorine, cyano group, hydroxy, alkyl, alkoxy, aryloxy, aryl A biphenyl group substituted with one or more substituents such as a heterotricyclic oxy group, carboxy, trimethylsilyl group and the like. Conveniently, R ₁₀ is 4-biphenyl (Inv-1), unsubstituted 3-biphenyl (Inv-9), or 3-biphenyl (Inv substituted with another phenyl ring to form a terphenyl ring system. -5), 2-biphenyl (Inv-3).

  Unless explicitly stated otherwise, use of the term “substituted” or “substituent” means any group or atom other than hydrogen. Unless explicitly stated otherwise, use of the term “aromatic ring system” refers to a ring system in which the entire ring system is aromatic or more than one ring system fused together. means. Unless explicitly stated otherwise, the use of the term “substituted phenyl ring” is substituted to form one substituted or unsubstituted fused aromatic ring system or more than one substitution. Alternatively, it refers to a phenyl ring that may be substituted to form an unsubstituted fused aromatic ring system. Also, when referring to a group containing a substitutable hydrogen (including a compound or complex), unless otherwise specified, this group is not only in its unsubstituted form, but also in these substituents. Is intended to encompass further substituted forms with any one or more of the substituents set forth herein, including the fused rings, so long as they do not destroy the properties necessary for utility. Suitably the substituent may be halogen or may be bonded to the remainder of the molecule by one atom of carbon, silicon, oxygen or phosphorus.

  If desired, these substituents themselves may be further substituted one or more times with the substituents described herein. The particular substituents used may be selected by those skilled in the art to obtain the desired desirable properties for a particular application and can include, for example, electron withdrawing groups, electron donating groups, and conformational groups.

  Certain asymmetric anthracene has been found to be very useful in OLED devices that exhibit high efficiency. These compounds are useful in OLED devices that produce white light, as well as full color OLED devices and motion imaging devices.

を含む。 Useful compounds of the present invention include

including.

  The compounds of the present invention are typically used in a light emitting layer with a specific thickness, with a dopant as defined below. Examples of useful luminescent materials include anthracene, fluorene, periflanthene, indenoperylene derivatives, bis (azinyl) amine boron compounds. Suitably, the dopant comprises quinacridone such as L7, or perylene such as L2, coumarin such as L30, bis (azinyl) methane or amine boron complexes such as L50, L51 and L52, aminostyryl derivatives such as L47. Conveniently, the dopant comprises a blue or blue-green dopant such as L2 and L50, and L47, or a green dopant such as quinacridone L7.

  The host of the present invention is useful for white device structures in combination with blue-green dopants.

  The host of the present invention can be used in combination with other blue or green co-hosts to improve stability in certain applications. The co-host can be a small molecule or a polymeric material. Useful co-hosts include, but are not limited to, polyfluorene, polyvinylarylene, metal complexes of 8-hydroxyquinoline, benzazole derivatives, distyrylarylene, carbazole. Suitably the co-host is tris (8-quinolinolato) aluminum (III) (Alq).

  One advantage of the hosts of the present invention is that these hosts do not contain sulfur and amines. The process of preparing these materials, as well as the process of purification, is simple and efficient and environmentally friendly, thus making these compounds conveniently manufacturable.

を含め、テトラセン、キサンテン、ペリレン、ルブレン、クマリン、ローダミンおよびキナクリドンの誘導体、ジシアノメチレンピラン化合物、チオピラン化合物、ポリメチン化合物、ピリリウムおよびチアピリリウム化合物、フルオレン誘導体、ペリフランテン誘導体、インデノペリレン誘導体、ビス（アジニル）アミンホウ素化合物、ならびにビス（アジニル）メタンホウ素からなる群から選択されるメンバーを含み、本ＯＬＥＤ素子が一つまたはそれ以上のエミッターの使用を通じて緑色もしくは赤色光、または白色光を放出する。
−これらの素子はアミノスチリル誘導体、着色フィルター、高分子材料またはＡｌｑなどのオキシノイド化合物などの共同ホストを含んでいてよい。共同ホストは、例えばポリフルオレン、ポリビニルアリーレン、８−ヒドロキシキノリンの金属錯体、ベンザゾール誘導体、ジスチリルアリーレンおよびカルバゾールからなる群から選択されるメンバーを含んでいてよい。
−本素子は、式（Ａ）：
Ｑ₁−Ｇ−Ｑ₂ （Ａ）
［式中、
Ｑ₁およびＱ₂は独立して選択される芳香族第三級アミン部分であり、Ｇはアリール連結基であり、Ｑ₁およびＱ₂のうちの少なくとも一つは、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ−１−ナフチル−４，４’−ジアミノビフェニル、
Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ−２−ナフチル−４，４’−ジアミノビフェニル、
４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビフェニル、
４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−（２−ナフチル）アミノ］ビフェニル、
４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ｐ−テルフェニル、または
４，４’−ビス［Ｎ−（２−ナフチル）−Ｎ−フェニルアミノ］ビフェニル
などの多環式縮合環構造を含む］
の第三級アミン化合物を含む正孔輸送層を含んでいてよい。
本ＯＬＥＤ素子は正孔遮断層を含んでいてよく、多数の発光層を用いた積層型ＯＬＥＤであってよく、薄膜トランジスターを有するアクティブマトリックス型基体を含んでいてよい。
−本ＯＬＥＤ素子は、望ましくは、乾燥剤の存在下において不活性雰囲気中に密封されており、またはバリヤー層を用いてカプセル化されている。本ＯＬＥＤ素子は誘電体ミラー構造、光吸収電極、反射防止膜、偏光媒体、着色フィルター、中性濃度フィルターまたは色変換フィルターを含んでいてよい。
−本ＯＬＥＤ素子は、発光層がドナーシートからの空間的に定められた感熱色素転写法を用いてパターン堆積されるようにして製造されてよい。
−特に望ましい化合物は、以下のもの：

を含む。 Embodiments of the Invention Embodiments of the invention include the following aspects.
The naphthyl group is substituted with at least one substituent selected from fluorine, hydroxy, cyano, alkoxy, aryloxy, carboxy, trimethylsilyl and heterocyclic oxy groups; or biphenyl is fluorine, hydroxy, cyano and alkyl , Substituted with at least one substituent selected from alkoxy, aryloxy, carboxy, trimethylsilyl and heterocyclic oxy groups.
The one or more guest luminescent materials are:

Tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone derivatives, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium and thiapyrylium compounds, fluorene derivatives, perifanthene derivatives, indenoperylene derivatives, bis (azinyl) The OLED device emits green or red light, or white light through the use of one or more emitters, including an amine boron compound and a member selected from the group consisting of bis (azinyl) methane boron.
-These devices may contain co-hosts such as aminostyryl derivatives, colored filters, polymeric materials or oxinoid compounds such as Alq. The co-host may comprise a member selected from the group consisting of, for example, polyfluorene, polyvinylarylene, metal complexes of 8-hydroxyquinoline, benzazole derivatives, distyrylarylene, and carbazole.
-This element is represented by formula (A)
Q ₁ -GQ ₂ (A)
[Where:
Q ₁ and Q ₂ are independently selected aromatic tertiary amine moieties, G is an aryl linking group, and at least one of Q ₁ and Q ₂ is N, N, N ′, N′-tetra-1-naphthyl-4,4′-diaminobiphenyl,
N, N, N ′, N′-tetra-2-naphthyl-4,4′-diaminobiphenyl,
4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl,
4,4′-bis [N- (1-naphthyl) -N- (2-naphthyl) amino] biphenyl,
4,4′-bis [N- (1-naphthyl) -N-phenylamino] p-terphenyl or 4,4′-bis [N- (2-naphthyl) -N-phenylamino] biphenyl Including cyclic fused ring structures]
A hole transport layer containing a tertiary amine compound may be included.
The present OLED element may include a hole blocking layer, may be a stacked OLED using a large number of light emitting layers, and may include an active matrix substrate having a thin film transistor.
The OLED device is preferably sealed in an inert atmosphere in the presence of a desiccant or encapsulated with a barrier layer. The OLED element may include a dielectric mirror structure, a light absorbing electrode, an antireflection film, a polarizing medium, a colored filter, a neutral density filter, or a color conversion filter.
The OLED device may be manufactured such that the light emitting layer is pattern deposited using a spatially defined thermal dye transfer method from a donor sheet.
-Particularly desirable compounds are:

including.

General Device Structure The present invention can be used in most OLED device configurations. These OLED device configurations vary from a very simple structure including a single anode and cathode to a passive matrix display including a plurality of anodes and cathodes arranged orthogonally to form a pixel, and, for example, a thin film As with transistors (TFTs), it includes even more complex devices such as active matrix displays where each pixel is controlled independently.

  There are many forms of organic layers that can successfully practice the present invention. The essential conditions for an OLED are an anode, a cathode, and an organic light emitting layer disposed between the anode and the cathode. Additional layers can also be used, as described in more detail below.

Anode When the desired electroluminescent emission (EL) is observed through the anode side, the anode should be transparent to the emitted light of interest or should be substantially transparent. Common transparent anode materials used in the present invention are indium tin oxide, (ITO), indium zinc oxide (IZO), and tin oxide, but are not limited to other metal oxides, such as However, metal oxides including aluminum- or indium-doped zinc oxide, magnesium indium oxide, nickel tungsten oxide, and the like can also be used. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and metal sulfides such as zinc sulfide can also be used as the anode. For applications where EL emission light is observed only through the cathode side, the light transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective can be used. Exemplary conductors for this application include, but are not limited to, gold, iridium, molybdenum, palladium, and platinum. Typical anode materials are light transmissive or otherwise have a work function of 4.1 eV or higher. Desired anode materials are generally deposited by any suitable means such as evaporation, sputtering, chemical vapor deposition or electrochemical means. The anode may be patterned using a well-known photolithography process. In some cases, the anode may be polished to reduce surface roughness for the purpose of minimizing short circuits or increasing reflectivity before applying other layers.

If the cathode emission light is observed only from the anode side, the cathode used in the present invention can be composed of almost any conductive material. Desirable materials have good film-forming properties to ensure good contact with the underlying organic layer, promote electron injection at low voltages, and maintain good stability. Yes. Useful cathode materials often include low work function metals (<4.0 eV) or alloys. One useful cathode material is composed of an Mg: Ag alloy, where the silver percentage ranges from 1% to 20% as described in US Pat. No. 4,885,221. It is. Another suitable class of cathode materials is a cathode and a thin electron injection layer (EIL) in contact with an organic layer (eg, an electron transport layer (ETL)) capped with a thicker layer of conductive metal. Including a two-layer structure. Here, the EIL preferably comprises a low work function metal or metal salt, in which case the thick capping layer described above need not have a low work function. One such cathode is composed of a thin layer of LiF followed by a thicker layer of Al, as described in US Pat. No. 5,677,572. Other useful cathode material groups include, but are not limited to, those disclosed in US Pat. Nos. 5,059,861; 5,059862 and 6,140,763. Including.

  If the emitted light is observed from the cathode side, the cathode must be transparent or almost transparent. For such applications, the metal must be thin or a transparent conductive oxide or combination of these materials must be used. For optically transparent cathodes, US 4,885,211, US 5,247,190, JP 3,234,963, US 5,703,436, US 5,608,287, US 5,837,391 US 5,677,572, US 5,776,622, US 5,776,623, US 5,714,838, US 5,969,474, US 5,739,545, US 5,981,306, This is described in more detail in US 6,137,223, US 6,140,763, US 6,172,459, EP 1 076 368, US 6,278,236 and US 6,284,3936. The cathode material is typically deposited by any suitable method such as evaporation, sputtering or chemical vapor deposition. If necessary, patterning may be, but is not limited to, mask-through deposition, integral shadow masking as described in US Pat. No. 5,276,380 and EP 0 732 868, laser cutting. Can be accomplished by a number of well-known methods, including selective chemical vapor deposition.

Light emitting layer (LEL )
The present invention is mainly directed to a light emitting layer (LEL). As described in more detail in U.S. Pat. Nos. 4,769,292 and 5,935,721, the light-emitting layer (LEL) of organic EL devices is responsible for electron-hole pair recombination in this region. A luminescent, fluorescent or phosphorescent material is included where electroluminescence results. The light-emitting layer can also be composed of a single material, but more commonly, it is composed of a host material doped with one or more guest light-emitting materials, in which case the emitted light mainly consists of these It comes from luminescent materials and can make any color. These host materials in the emissive layer may be electron transport materials as defined below, hole transport materials as defined above, or another material or material that supports hole-electron recombination. It may be a combination of Luminescent materials are usually highly fluorescent dyes and phosphorescent compounds such as transition metals as described in WO 98/55561, WO 00/18851, WO 00/57676 and WO 00/70655. Selected from complexes. The luminescent material is typically incorporated in an amount from 0.01% to 10% of the host material by weight.

  The host material and luminescent material may be non-polymeric small molecules or polymeric materials such as polyfluorene and polyvinylarylene (eg, poly (p-phenylene vinylene), PPV). In the case of polymers, small molecule luminescent materials can be molecularly dispersed in a polymeric host, or these luminescent materials can be added by copolymerizing minor constituents into the host polymer.

  An important relationship in choosing a luminescent material is a comparison of the band gap potential, defined as the energy difference between the highest and lowest unoccupied molecular orbitals of this molecule. A necessary condition for efficient energy transfer from the host to the luminescent material is that the band gap of the dopant is smaller than the band gap of the host material. For phosphorescent emitters, it is also important that the host triplet energy level of the host is high enough to allow energy transfer from the host to the luminescent material.

  Host materials and luminescent materials known to be useful include, but are not limited to, US 4,768,292, US 5,141,671, US 5,150,006, US 5,151, 629, US 5,405,709, US 5,484,922, US 5,593,788, US 5,645,948, US 5,683,823, US 5,755,999, US 5,928,802 No. 5,935,720, US 5,935,721 and US 6,020,078.

［式中、
Ｍは金属を表し；
ｎは１から４までの整数であり；そして
Ｚは、各々独立して、少なくとも二つの縮合芳香環を有する核を完成させる原子を表す。］ Metal complexes of 8-hydroxyquinoline and similar derivatives (formula E) constitute one class of useful host compounds that can support electroluminescence, in particular light of wavelengths longer than 500 nm, such as green, Suitable for emitting yellow, orange and red light.

[Where:
M represents a metal;
n is an integer from 1 to 4; and Z each independently represents an atom that completes a nucleus having at least two fused aromatic rings. ]

  From the foregoing description it is clear that the metal can be a monovalent, divalent, trivalent or tetravalent metal. The metal may be, for example, an alkali metal such as lithium, sodium or potassium; an alkaline earth metal such as magnesium or calcium; an earth metal such as aluminum or gallium; or a transition metal such as zinc or zirconium. In general, any monovalent, divalent, trivalent or tetravalent metal known to be a useful chelating metal can be used.

  Z completes a heterocyclic nucleus containing at least two fused aromatic rings, at least one of which is an azole or azine ring. If necessary, additional rings, including both aliphatic and aromatic rings, can be fused with these two required rings. In order to avoid the addition of molecular bulk without improved function, the number of ring atoms is usually kept at 18 or less.

Illustrative useful chelating oxinoid compounds are the following compounds:
CO-1: Aluminum trisoxin [also known as tris (8-quinolinolato) aluminum (III)]
CO-2: Magnesium bisoxin [also known as bis (8-quinolinolato) magnesium (II)]
CO-3: Bis [benzo {f} -8-quinolinolato] zinc (II)
CO-4: Bis (2-methyl-8-quinolinolato) aluminum (III) -μ-oxo-bis (2-methyl-8-quinolinolato) aluminum (III)
CO-5: Indium trisoxin [also known as tris (8-quinolinolato) indium]
CO-6: Aluminum tris (5-methyloxine) [Also known as tris (5-methyl-8-quinolinolato) aluminum (III)]
CO-7: Lithium oxine [also known as (8-quinolinolato) lithium (I)]
CO-8: gallium oxine [also known as tris (8-quinolinolato) gallium (III)]
CO-9: zirconium oxine [also known as tetra (8-quinolinolato) zirconium (IV)]

［式中：Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は各環における一つまたはそれ以上の置換基を表し、各置換基は以下のグループから個別的に選択される。
グループ１：水素、または１個から２４個までの炭素原子のアルキル；
グループ２：５個から２０個までの炭素原子のアリールまたは置換アリール；
グループ３：アントラセニル；ピレニルまたはペリレニルの縮合芳香環を完成させるのに必要な４個から２４個までの炭素原子；
グループ４：フリル、チエニル、ピリジル、キノリニルの縮合ヘテロ芳香環または他のヘテロ環系を完成させるのに必要な５個から２４個までの炭素原子のヘテロアリールまたは置換へテロアリール；
グループ５：１個から２４個までの炭素原子のアルコキシルアミノ、アルキルアミノまたはアリールアミノ；および
グループ６：フッ素、塩素、臭素またはシアノ。］ Derivatives of 9,10-di- (2-naphthyl) anthracene (formula F) constitute one class of useful host materials that can support electroluminescence, in particular light with wavelengths longer than 400 nm, For example, suitable for emitting blue, green, yellow, orange or red light.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent one or more substituents in each ring, and each substituent is individually selected from the following group: .
Group 1: hydrogen or alkyl of 1 to 24 carbon atoms;
Group 2: aryl or substituted aryl of 5 to 20 carbon atoms;
Group 3: anthracenyl; 4 to 24 carbon atoms necessary to complete a fused aromatic ring of pyrenyl or perylenyl;
Group 4: furyl, thienyl, pyridyl, quinolinyl fused heteroaromatic rings or other heteroaryls of from 5 to 24 carbon atoms necessary to complete other heterocyclic ring systems;
Group 5: alkoxylamino, alkylamino or arylamino of 1 to 24 carbon atoms; and Group 6: fluorine, chlorine, bromine or cyano. ]

  Illustrative examples include 9,10-di- (2-naphthyl) anthracene and 2-t-butyl-9,10-di- (2-naphthyl) anthracene. Other anthracene derivatives, including 9,10-bis [4- (2,2-diphenylethenyl) phenyl] anthracene, may also be useful as hosts in the present LEL.

Benzazole derivatives (formula G) constitute another class of useful host materials that can support electroluminescence, in particular light of wavelengths longer than 400 nm, such as blue, green, yellow, orange or red Suitable for emitting light.

In the formula:
n is an integer from 3 to 8;
Z is O, NR or S; and R and R ′ are independently hydrogen; alkyl of 1 to 24 carbon atoms, such as propyl, t-butyl, heptyl, etc .; 5 to 20 Aryl or heteroatom substituted aryls up to carbon atoms such as phenyl and naphthyl, furyl, thienyl, pyridyl, quinolinyl, and other heterocyclic ring systems; or halo such as chloro, fluoro; or necessary to complete a fused aromatic ring An atom;
L is a chain unit composed of alkyl, aryl, substituted alkyl, or substituted aryl, which binds a large number of benzazoles conjugated or non-conjugated together. One example of a useful benzazole is 2,2 ′, 2 ″-(1,3,5-phenylene) tris [1-phenyl-1H-benzimidazole].

  Distyrylarylene derivatives are also useful hosts as described in US 5,121,029. Carbazole derivatives are particularly useful hosts for phosphorescent emitters.

Useful fluorescent materials include, but are not limited to, anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone derivatives, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium and thiapyrylium compounds. , Fluorene derivatives, perifanthene derivatives, indenoperylene derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyril compounds. Illustrative examples of useful materials include, but are not limited to, the following materials:

A typical device structure, particularly a typical structure useful for small molecule devices, is shown in FIG. 1, which includes a substrate 101, an anode 103, a hole injection layer 105, a hole transport layer 107, a light emitting layer 109. The electron transport layer 111 and the cathode 113 are included. These layers are described in detail below. It should be noted that the substrate may alternatively be positioned adjacent to the cathode, or the substrate may actually constitute the anode or cathode. These organic layers between the anode and the cathode are called organic EL elements for convenience. The total thickness of these organic layers combined is preferably less than 500 nm.

  The anode and cathode of the OLED are connected to a power source 250 through an electrical conductor 260. OLEDs are operated by applying a potential between the anode and cathode so that the anode is at a more positive potential than the cathode. Holes are injected into the organic EL element from the anode, and electrons are injected into the organic EL element at the anode. Increased device stability can sometimes be achieved when the OLED is operated in AC mode (potential bias is reversed and no current flows for a period of time in this cycle). One example of an AC driven OLED is described in US 5,552,678.

Substrate The OLED device of the present invention is typically provided on a support substrate 101, where either the cathode or the anode can be in contact with the substrate. The electrode in contact with the substrate is referred to as the bottom electrode for convenience. Usually, the bottom electrode is an anode, but the invention is not limited to this arrangement. The substrate may be light transmissive or opaque depending on the intended direction of the emitted light. When observing EL emission light through a substrate, it is desirable to have light transmission characteristics. In such cases, transparent glass or plastic is generally used. The substrate may be a complex structure that includes multiple layers of material. Typically, this case corresponds to an active matrix type substrate in which the TFT is provided under the OLED layer. It is further necessary that the substrate is composed of a highly transparent material, such as glass or polymer, at least in the pixil structure region that emits light. For applications where EL emission light is observed through the top electrode, the light transmission characteristics of the bottom support are not critical and may therefore be light transmissive, light absorbing or light reflective. Substrates for use in this case include, but are not limited to, glass, plastic, semiconductor materials, silicon, ceramics, and circuit board materials. Again, the substrate may be a complex structure that includes multiple layers of materials, as found in active matrix TFT designs. Of course, in these element configuration arrangements, it is necessary to provide an optically transparent upper electrode.

Hole injection layer (HIL)
Although not always necessary, it is often useful that the hole injection layer 105 is provided between the anode 103 and the hole transport layer 107. This hole injection material functions to improve film formation characteristics of the subsequent organic layer and promote injection of holes into the hole transport layer. Suitable materials for use in the hole injection layer include, but are not limited to, porphyrinic compounds such as those described in US Pat. No. 4,720,432, described in US Pat. No. 6,208,075. Plasma-deposited fluorocarbon polymers, and several aromatic amines such as m-MTDATA (4,4 ′, 4 ″ -tris [(3-methylphenyl) phenylamino] triphenylamine). Alternative hole injection materials reported to be useful in organic EL devices are described in EP 0 891 121 A1 and EP 1 029 909 A1.

Hole transport layer (HTL)
The hole transport layer 107 of the present organic EL device contains at least one hole transport compound such as an aromatic tertiary amine, where the aromatic tertiary amine is bonded only to a carbon atom. It is understood that the compound contains at least one trivalent nitrogen atom and at least one of the carbon atoms is a member of an aromatic ring. In one form, the aromatic tertiary amine may be an arylamine such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine. An exemplary monomeric triarylamine is shown in US Pat. No. 3,180,730 by Klupfel et al. Other suitable triarylamines substituted with one or more vinyl radicals and / or other suitable triarylamines containing at least one active hydrogen-containing group are described by Brantley et al. US Pat. No. 3,567,450 and US3. , 658, 520.

［式中のＱ₁およびＱ₂は独立して選択される芳香族第三級アミン部分であり、Ｇは、炭素−炭素結合のアリーレン、シクロアルキレンまたはアルキレン基などの連結基である］により表される化合物を含む。一つの実施形態においては、Ｑ₁またはＱ₂のうちの少なくとも一つが多環式の縮合環構造、例えばナフタレンを含む。Ｇがアリール基であるときには、それは、都合よくは、フェニレン、ビフェニレンまたはナフタレン部分である。 A more preferred class of aromatic tertiary amines are those containing at least two aromatic tertiary amine moieties, as described in US 4,720,432 and US 5,061,569. Such compounds have the structural formula (A):

Wherein Q ₁ and Q ₂ are independently selected aromatic tertiary amine moieties, and G is a linking group such as an arylene, cycloalkylene or alkylene group of a carbon-carbon bond. Containing compounds. In one embodiment, at least one of Q ₁ or Q ₂ comprises a polycyclic fused ring structure, such as naphthalene. When G is an aryl group, it is conveniently a phenylene, biphenylene or naphthalene moiety.

により表され、
式中、
Ｒ₁およびＲ₂はそれぞれ独立して水素原子、アリール基もしくはアルキル基を表し、またはＲ₁およびＲ₂が共にシクロアルキル基を完成させる原子を表し；そして
Ｒ₃およびＲ₄はそれぞれ独立してアリール基を表し、このアリール基は、更に、構造式（Ｃ）：

により指示されているように、ジアリール置換アミノ基で置換され、式中のＲ₅およびＲ₆は独立して選択されるアリール基である。一つの実施形態においては、Ｒ₅またはＲ₆のうちの少なくとも一つが多環式の縮合環構造、例えばナフタレンを含む。 One useful class of triarylamines satisfying structural formula (A) and containing two triarylamine moieties is structural formula (B):

Represented by
Where
R ₁ and R ₂ each independently represent a hydrogen atom, an aryl group or an alkyl group, or R ₁ and R ₂ together represent an atom that completes a cycloalkyl group; and R ₃ and R ₄ each independently Represents an aryl group, and the aryl group further has the structural formula (C):

Is substituted with a diaryl-substituted amino group, wherein R ₅ and R ₆ are independently selected aryl groups. In one embodiment, at least one of R ₅ or R ₆ comprises a polycyclic fused ring structure such as naphthalene.

［式中、
各Ａｒｅは、フェニレンまたはアントラセン部分などの独立して選択されるアリーレン基であり、
ｎは１から４までの整数であり、そして
Ａｒ、Ｒ₇、Ｒ₈およびＲ₉は独立して選択されるアリール基である］により表されるものを含む。一つの典型的な実施形態においては、Ａｒ、Ｒ₇、Ｒ₈およびＲ₉のうちの少なくとも一つが多環式の縮合環構造、例えばナフタレンである。 Another class of aromatic tertiary amines are tetraaryldiamines. Desirable tetraaryldiamines contain two diarylamino groups, such as those indicated by formula (C), linked through an arylene group. Useful tetraaryldiamines have the formula (D):

[Where:
Each Are is an independently selected arylene group such as a phenylene or anthracene moiety;
n is an integer from 1 to 4 and Ar, R ₇ , R ₈ and R ₉ are independently selected aryl groups]. In one exemplary embodiment, at least one of Ar, R ₇ , R ₈ and R ₉ is a polycyclic fused ring structure, such as naphthalene.

  Each of the various alkyl, alkylene, aryl, and arylene moieties of the foregoing structural formulas (A), (B), (C), (D) may be further substituted. Typical substituents include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and halogens such as fluorine, chlorine and bromine. The various alkyl and alkylene moieties typically contain from about 1 to 6 carbon atoms. Cycloalkyl moieties can contain from 3 to about 10 carbon atoms, but typically contain 5, 6 or 7 ring carbon atoms, such as cyclopentyl, cyclohexyl and cycloheptyl ring structures. . The aryl and arylene moieties are usually phenyl and phenylene moieties.

The hole transport layer may be formed from a single aromatic tertiary amine compound or may be formed from a mixture of aromatic tertiary amine compounds. Specifically, triarylamines such as triarylamines that satisfy formula (B) can be used in combination with tetraaryldiamines such as those indicated by formula (D). When triarylamine is used in combination with tetraaryldiamine, the latter is arranged as a layer sandwiched between the triarylamine and the electron injection and transport layer. Illustrative useful aromatic tertiary amines are:
1,1-bis (4-di-p-tolylaminophenyl) cyclohexane 1,1-bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane 4,4'-bis (diphenylamino) quadriphenyl Bis (4-dimethylamino-2-methylphenyl) -phenylmethane N, N, N-tri (p-tolyl) amine 4- (di-p-tolylamino) -4 ′-[4 (di-p-tolylamino) -Styryl] stilbene N, N, N ', N'-tetra-p-tolyl-4-4'-diaminobiphenyl N, N, N', N'-tetraphenyl-4,4'-diaminobiphenyl N, N , N ′, N′-tetra-1-naphthyl-4,4′-diaminobiphenyl N, N, N ′, N′-tetra-2-naphthyl-4,4′-diaminobiphenyl N-phenylcarbazole 4,4 '− [N- (1-naphthyl) -N-phenylamino] biphenyl 4,4′-bis [N- (1-naphthyl) -N- (2-naphthyl) amino] biphenyl 4,4 ″ -bis [N -(1-Naphthyl) -N-phenylamino] p-terphenyl 4,4'-bis [N- (2-naphthyl) -N-phenylamino] biphenyl 4,4'-bis [N- (3-acenaphthenyl) ) -N-phenylamino] biphenyl 1,5-bis [N- (1-naphthyl) -N-phenylamino] naphthalene 4,4′-bis [N- (9-anthryl) -N-phenylamino] biphenyl 4 , 4 ″ -bis [N- (1-anthryl) -N-phenylamino] -p-terphenyl 4,4′-bis [N- (2-phenanthryl) -N-phenylamino] biphenyl 4,4 ′ -Bis [N- (8-fluoro Nthenyl) -N-phenylamino] biphenyl 4,4′-bis [N- (2-pyrenyl) -N-phenylamino] biphenyl 4,4′-bis [N- (2-naphthacenyl) -N-phenylamino] Biphenyl 4,4′-bis [N- (2-perylenyl) -N-phenylamino] biphenyl 4,4′-bis [N- (1-coronenyl) -N-phenylamino] biphenyl 2,6-bis (di -P-tolylamino) naphthalene 2,6-bis [di- (1-naphthyl) amino] naphthalene 2,6-bis [N- (1-naphthyl) -N- (2-naphthyl) amino] naphthalene N, N, N ′, N′-tetra (2-naphthyl) -4,4 ″ -diamino-p-terphenyl 4,4′-bis {N-phenyl-N- [4- (1-naphthyl) -phenyl] amino } Biphenyl 4,4'- [N-phenyl-N- (2-pyrenyl) amino] biphenyl 2,6-bis [N, N-di (2-naphthyl) amine] fluorene 1,5-bis [N- (1-naphthyl) -N -Phenylamino] naphthalene 4,4 ', 4''-tris [(3-methylphenyl) phenylamino] triphenylamine.

  Another class of useful hole transport materials includes polycyclic aromatic compounds as described in EP 1 009 041. Tertiary aromatic amines with more than two amine groups, including oligomeric materials, can be used. In addition, polymer hole transport materials such as poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline, and poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfone), also called PEDOT / PSS. Copolymers such as natto) can also be used.

Electron transport layer (ETL )
Preferred thin film forming materials for use in forming the electron transport layer 111 of the organic EL device of the present invention include chelates of oxine itself (commonly also referred to as 8-quinolinol or 8-hydroxyquinoline), It is a metal chelate oxinoid compound. Such compounds are useful for electron injection and transport, not only exhibit high levels of performance, but can also be easily fabricated in the form of thin films. A typical example of the assumed oxinoid compound is a compound that satisfies the structural formula (E) described above.

  Other electron transport materials include various butadiene derivatives as disclosed in US 4,356,429, and various heterocyclic optical brighteners as described in US 4,539,507. Including. Benzazole that satisfies the structural formula (G) is also a useful electron transporting material. Triazine is also known to be useful as an electron transport material.

Other Useful Organic Layers and Device Structures In some examples, layers 109 and 111 can optionally be combined into a single layer that functions to support both light emission and electron transport. It is also known in the art that luminescent materials can be included in hole transport layers that can act as hosts. For example, to create a white light emitting OLED by combining blue- and yellow-light emitting materials, indigo- and red-light-emitting materials, or red-, green- and blue-light-emitting materials, one or more of a number of materials Can be added to the layer. White-light emitting elements are, for example, EP 1 187 235, US 20020025419, EP 1 182 244, US 5,683,823, US 5,503,910, US 5,405,709 and US 5,283,182. And may be provided with a suitable filter arrangement to provide color emission light.

  Additional layers such as electron or hole-blocking layers as taught in the art can be used in the devices of the present invention. Hole blocking layers are generally used to improve the efficiency of phosphorescent emitter elements, as in, for example, US20020015859.

  The present invention may be used in so-called stacked device structures, as taught, for example, in US 5,703,436 and US 6,337,492.

Organic layer deposition The organic material is conveniently deposited by sublimation, but can also be deposited by other means, such as by deposition from a solvent optionally with a binder to improve film formation. When this material is a polymer, solvent deposition is usually preferred. The material to be deposited by sublimation can be vaporized from a sublimator “boat”, often composed of a tantalum material, for example as described in US Pat. No. 6,237,529, or initially on the donor sheet It can also be applied to the substrate and then sublimated onto the substrate at a closer position closer to it. Layers with mixtures of various materials can utilize separate sublimator boats, or these materials can be premixed and coated from a single boat or donor sheet. Patterned deposition is performed with shadow masks, integral shadow masks (US 5,294,870), spatially defined thermal dye transfer from donor sheets (US 5,688,551, US 5,851,709 and US Pat. No. 6,066,357), as well as ink jet methods (US Pat. No. 6,066,357).

Encapsulated Most OLED devices are sensitive to moisture and / or oxygen, and therefore these devices are typically alumina, bauxite, calcium sulfate, clay, silica gel, zeolite, alkali metal oxide, alkali Sealed in an inert atmosphere such as nitrogen or argon with desiccants such as earth metal oxides, sulfates, or metal halides and perchlorates. Methods for encapsulation and drying include, but are not limited to, those described in US Pat. No. 6,226,890. In addition, barrier layers such as SiOx, Teflon and alternating inorganic / polymer layers are known in the art as means for encapsulation.

Optical Optimization The OLED device of the present invention can use a variety of well-known optical effects to enhance its properties, if desired. This optimizes the layer thickness to provide maximum light transmission, provides a dielectric mirror structure, replaces the reflective electrode with a light absorbing electrode, prevents glare or antireflection on the display Providing a film, providing a polarizing medium on the display, or providing a colored filter, ND filter or color conversion filter on the display. The filter, polarizer, and anti-glare or anti-reflection film may be specifically provided on the cover or may be provided as part of the cover.

  The entire contents of the patents and other publications mentioned in this specification are hereby incorporated by reference.

  The following specific examples further illustrate the invention and the advantages of the invention. These embodiments of the present invention can also reveal thermal stability.

Example 1 Preparation of Inv-1 a) Preparation of 9- (2-naphthyl) anthracene. 9-Bromoanthracene (12 g, 46 mmol, 1 eq) and 2-naphthaleneboronic acid (8.0 g, 46 mmol, 1 eq) were combined in 100 ml of toluene and the resulting mixture was sonicated for about 15 minutes. I was degassed. Bis (triphenylphosphine) palladium dichloride (0.110 g, 0.095 mmol, 0.2%) is added and the resulting mixture is thoroughly added under nitrogen while adding 100 ml of 2M Na ₂ CO _3. Stir and heat the mixture to reflux through a heating mantle. The reaction was left to reflux overnight. The reaction was cooled to room temperature when a solid began to precipitate. The organic solid was isolated by filtration, washed with water, and then air dried to give a yield of 11.4 g (80%). Additional extraction of this organic layer with methylene chloride, followed by drying and concentration over MgSO ₄ gave an additional 2 g of product, for a total yield of 94%.
b) Preparation of 9-bromo, 10- (2-naphthyl) anthracene. 9- (2-naphthyl) anthracene (14 g, 48 mmol, 1 eq) and N-bromosuccinimide (8.9 g, 50 mmol, 1.05 eq) together with 140 ml CH ₂ Cl ₂ in a 500 ml round bottom flask. Combined. By stirring the mixture at room temperature under nitrogen in the presence of light coming from a 100 W lamp, the mixture immediately became homogeneous. _{TLC (P950: CH 2 Cl 2} /9: 1) as indicated by the reaction was complete after 3 hours. Approximately half of the solvent volume was removed by the time the solids just started to precipitate. A sufficient amount of acetonitrile was then added while heating to dissolve the solids. After this, further CH ₂ Cl ₂ was removed to a point where the solids just started to precipitate again. The solution was cooled and allowed to recrystallize. The resulting solid was isolated by filtration, washed with a small amount of acetonitrile and dried to give a yield of 17 g (92%).
c) Preparation of 9-biphenyl, 10- (2-naphthyl) anthracene. 9-bromo, 10- (2-naphthyl) anthracene (8.9 g, 23 mmol, 1 eq), 4-biphenylboronic acid (4.8 g, 24 mmol, 1.05 eq) were added to (PPh ₃ ) ₂ PdCl ₂ (0 .16 g, 0.7 eq%) in a 500 ml round bottom flask were combined in 200 mL toluene and the resulting suspension was sonicated for 30 minutes. The solution was then homogenized after 15 minutes of reflux by quickly bringing the mixture to reflux. After 2 hours, the solid began to precipitate while the mixture remained light yellow (indicating that the catalyst was active). The mixture was left to reflux overnight. The mixture was filtered hot through glass fiber filter paper to remove the precipitated solids. The solid was redissolved in about 1 L of hot toluene and the solution was filtered through glass fiber filter paper to remove palladium impurities. Concentration of the filtrate gave 9.2 g off-white solid. The toluene layer is isolated from this initial filtrate containing the aqueous layer, washed with H ₂ O, dried over saturated brine, dried over MgSO ₄ , concentrated and recrystallized to give 1.3 g solids. Got. By combining both solids batches, 10.4 g of clean product (98%) was obtained. Sublimation of this material at 260 ° C. gave a very pure fraction (8.26 g, assay value 99.8%) and a pure fraction (1.45 g, assay value 99.3%).

Examples 2, 3, 5, 6, 8, 9, 10: Invention EL device An EL device satisfying the requirements of the present invention was constructed in the following manner:
A glass substrate is coated with a 42 nm layer of indium tin oxide (ITO) as the anode, which is then sonicated in a commercial detergent, rinsed in deionized water, degreased in toluene vapor, and subjected to oxygen plasma. Exposed for about 1 minute.
a) A 1 nm fluorocarbon hole injection layer (CFx) was deposited on ITO by plasma assisted deposition of CHF ₃ .
b) Thereafter, the hole transport layer of N, N′-di-1-naphthalenyl-N, N′-diphenyl-4,4′-diaminobiphenyl (NPB) having a thickness of 75 nm was evaporated from the tantalum boat. .
c) Next, a 20-40 nm emissive layer of Inv1 doped with various amounts of dopant depending on the dopant used was deposited on the hole transport layer. These materials were co-evaporated from tantalum boats. Here, the doping ratio is reported based on the volume / volume ratio. Individual dopants, proportions and host thicknesses are shown in Tables 1 and 2.
d) A 30 nm electron transport layer of tris (8-quinolinolato) aluminum (III) (Alq) was then deposited on the light emitting layer. This material was also evaporated from the tantalum boat.
e) A 220 nm cathode formed from a 10: 1 volume ratio of Mg and Ag was deposited on the Alq layer.

  The EL device was deposited by the sequence described above. Thereafter, the element was hermetically packaged in a dry glove box in order to protect it from the surrounding environment.

Examples 4, 7, 11, 12, 13, 14, 15 EL elements for comparison The EL element of the comparative example uses another anthracene derivative that does not form part of the present invention as a host instead of Inv1. Except for Example 2, it was produced in the same manner.

The cells of Examples 2-15 thus formed were tested for efficiency in the form of luminance yield (cd / A) measured at 20 mA / cm ² . CIE chromaticity xy coordinates were determined. In the case of blue elements, it is desirable to have a luminance yield of at least about 2.2 cd / A, preferably greater than about 3 cd / A. Luminance loss makes these cells a constant current density of 20 mA / cm ² at 70 ° C. or 40 mA at RT (room temperature) for various lengths of time specified for each individual cell / example. It was measured by subjecting the cell to a constant current density of / cm ² . Extrapolated values are estimated based on actual data at 20 mA / cm ² and 70 ° C. or actual data at 40 mA / cm ² and RT. Useful stability for use in display elements is desirably less than about 40% loss after about 300 hours of these accelerated aging conditions. All these test data are shown in Table 1b.

Table 1a: Device structures of Examples 2-7

Table 1b: Significant benefits regarding stability of Inv-1 (Examples 2-7)

The data in Table 1b show that when Inv-1 is used as a host, it provides a significant improvement in stability while maintaining a high efficiency and at least the same efficiency as the control (Comp-1). Show. Examples 2 and 3 and Examples 5 and 6 show a clear 2-2.5 fold improvement in stability compared to the control. Comp-1 was always used as a reference for each device set for better comparison; Comp-1 formulation (host thickness and dopant level) was the best for good stability and high efficiency. This is the optimal state for obtaining a combination of The devices in Table 1b were fading at 40 mA / cm ² at RT.

Table 2a: Device structures of Examples 8-11

Table 2b: Improved stability of Inv-3 and Inv-4 in comparison to reference Comp-1 (Examples 8-11)

Compound Inv-3 also provides stability advantages over the control Comp-1. The devices in Table 2b were fading at 70 ° C. and 40 mA / cm ² , a more accelerated test method. In the case of Inv-3, the stability improvement is not as pronounced at 70 ° C. and is only in the range of 40% to 60%, but the efficiency of the host remains high.

Table 3a: Device structures of Examples 15-18

Table 3b: Comparative examples of symmetrical analogues (Examples 12-15)

^* Example 14 shows the failure of Comp-4 in one device. Since this device deteriorates quickly under a 9V battery, the operational stability could not be measured. Devices deposited with this material and produced twice yielded the same results. It is considered that the high crystallinity of the solid in the bulk state makes the vitreous formation tendency in the device very low. The fact that this element has a grainy appearance appears to support the above hypothesis. Comp-2 is also symmetrical with a high tendency to crystallize; however, Comp-2 appears to perform as well or better than the t-butyl analog Comp-1 (see Example 12 vs. In Example 4, the element using Comp-1 often fails due to crystallization.

  The data obtained from Examples 2-15 shows a significant improvement on the stability of asymmetric monoanthracene with two different blue dopants, L2 and L47. Comparing the data in Table 1b and Table 3b, there is a clear correlation between the structural characteristics (symmetry / asymmetry) and performance of the device. For example, Inv-1 (Example 2) showing the best performance is a hybrid of Comp-2 and Comp-4 (Examples 12 and 14), but its performance is better than either of these two cases.

Example 16: Comparative EL device example 16 was fabricated in the same manner as example 2 except c). A 37 nm light emitting layer made of Alq was doped with a green dopant. These materials were co-evaporated from tantalum boats. Here, the doping ratio is reported based on the deposition / volume ratio. The individual dopants, proportions and host thicknesses are shown in Table 4.

Examples 17-21: Inventive EL device Examples 17-21 were fabricated in the same manner as Example 16 (two hosts and dopants) except that Alq was co-evaporated with the host portion of the present invention in various amounts. The total thickness was 37.5 nm). The individual dopants, proportions and host thicknesses are shown in Table 4.

Table 4: Significant advantages regarding the stability of green dopant L53 when using a co-host of the present invention (Examples 16-21)

  The data in Table 4 shows that a significant improvement in the stability of L53 was obtained when the inventive co-host was used in combination with Alq. The advantage of incorporating Inv-1 as a co-host in Alq is particularly evident in Examples 18-20 at Inv-1 concentrations between 40-80% and at least a 3-fold improvement over the control (Example 16) Has been observed.

  While the invention has been described with particular reference to certain preferred embodiments of the invention, it will be understood that various modifications and changes may be made within the spirit and scope of the invention.

FIG. 2 shows a cross-sectional view of a typical OLED device in which the present invention can be used.

Explanation of symbols

101 substrate 103 anode 105 hole injection layer (HIL)
107 Hole Transport Layer (HTL)
109 Light emitting layer (LEL)
111 Electron Transport Layer (ETL)
113 cathode 250 power supply 260 electric conductor

Claims (26)

An OLED device having an anode and a cathode, and a light emitting layer disposed between the anode and the cathode, wherein the light emitting layer comprises:
a) Formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
And b) tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone derivatives, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium and thiapyrylium compounds, fluorene derivatives, perifanthene derivatives, One or more guest luminescent materials comprising a member selected from the group consisting of an indenoperylene derivative, a bis (azinyl) amine boron compound, and bis (azinyl) methane boron;
OLED element containing. The guest luminescent material is

The OLED device according to claim 1, comprising:   The OLED device according to claim 2, wherein the guest light-emitting material includes N, N′-diphenylquinacridone. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED element emits green light;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED element emits red light;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED device comprises one or more light-emitting layers with a compound sufficient to emit white light;
OLED element.   The OLED device according to claim 6, wherein at least one light emitting layer contains an aminostyryl derivative.   The OLED device according to claim 6, further comprising a coloring filter. An OLED device having an anode and a cathode, and a light emitting layer disposed between the anode and the cathode, wherein the light emitting layer comprises:
a) Formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A host containing a monoanthracene derivative of
b) a co-host; and c) a light-emitting dopant;
OLED element containing.   The OLED device of claim 9, wherein the co-host is a polymer.   The OLED device according to claim 9, wherein the co-host is an oxinoid compound.   The OLED element according to claim 11, wherein the oxinoid is Alq.   The OLED device according to claim 9, wherein the co-host comprises a member selected from the group consisting of polyfluorene, polyvinylarylene, a metal complex of 8-hydroxyquinoline, a benzazole derivative, distyrylarylene, and carbazole. The luminescent dopant is

Or the OLED element of Claim 9 which is N, N'- diphenylquinacridone. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED element has the formula (A):
Q ₁ -GQ ₂ (A)
[Where:
Q ₁ and Q ₂ are independently selected aromatic tertiary amine moieties, G is an aryl linking group, and at least one of Q ₁ and Q ₂ comprises a polycyclic fused ring structure ]
A hole transport layer comprising a tertiary amine compound of
OLED element. The tertiary amine compound is N, N, N ′, N′-tetra-1-naphthyl-4,4′-diaminobiphenyl;
N, N, N ′, N′-tetra-2-naphthyl-4,4′-diaminobiphenyl,
4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl,
4,4′-bis [N- (1-naphthyl) -N- (2-naphthyl) amino] biphenyl,
4,4′-bis [N- (1-naphthyl) -N-phenylamino] p-terphenyl, or 4,4′-bis [N- (2-naphthyl) -N-phenylamino] biphenyl, The OLED element according to claim 15. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED element comprises a hole blocking layer;
OLED element. A light-emitting device comprising a plurality of stacked organic light-emitting devices, wherein at least one light-emitting layer contains a light-emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
Light emitting element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED element comprises an active matrix substrate having a thin film transistor;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED element is sealed in an inert atmosphere in the presence of a desiccant;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED element is encapsulated with a barrier layer;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The OLED element includes a dielectric mirror structure, a light absorbing electrode, an antireflection film, a polarizing medium, a colored filter, a neutral density filter, or a color conversion filter;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The emissive layer was pattern deposited using a spatially defined thermal dye transfer method from a donor sheet;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
The naphthyl group is substituted with at least one substituent selected from fluorine, hydroxy, cyano, alkoxy, aryloxy, carboxy, trimethylsilyl and heterocyclicoxy;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, wherein the host has the formula (I):

[Where:
R ₁ -R ₈ is H;
R ₉ is not the same as R ₁₀ ;
Provided that R ₉ and R ₁₀ do not contain amine and sulfur compounds;
R ₉ is a naphthyl group having no fused ring with an aliphatic carbon ring member; and
R ₁₀ is a biphenyl group having no fused ring with an aliphatic carbon ring member]
A monoanthracene derivative of
Said biphenyl is substituted with at least one substituent selected from fluorine, hydroxy, cyano, and alkyl, alkoxy, aryloxy, carboxy, trimethylsilyl and heterocyclic oxy groups;
OLED element. An OLED device comprising an anode and a cathode, and a light emitting layer disposed between the anode and cathode, wherein the light emitting layer contains a light emitting dopant and a host, the host comprising:

Selected from the group consisting of:
OLED element.

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