TW202440819A - Formulation of an organic functional material - Google Patents

Abstract

The present invention relates to a formulation containing at least one organic functional material and at least one organic solvent, preferably at least two different organic solvents, characterized in that at least one organic solvent is a deuterated solvent having a degree of deuteration of at least 25%, preferably at least 50%, more preferably at least 75% and most preferably 90%, to a process for the preparation of an electroluminescent device using the formulation of the present invention as well as to an electroluminescent device prepared by using the formulation of the present invention.

Description

Translated fromChinese

有機功能性材料之調配物Organic functional material formulation

本發明係關於一種調配物，其含有至少一種有機功能性材料及至少一種有機溶劑A，較佳地至少兩種不同的有機溶劑A及B，其特徵在於至少一種有機溶劑係氘化度為至少25%、較佳地至少50%、更佳地至少75%且最佳地至少90%的氘化溶劑，關於一種用於製備電子裝置、較佳地電致發光裝置之方法，以及關於一種電子裝置、較佳地電致發光裝置，該電子裝置係藉由使用本發明之調配物製備的。The present invention relates to a formulation containing at least one organic functional material and at least one organic solvent A, preferably at least two different organic solvents A and B, characterized in that at least one organic solvent is a deuterated solvent with a degree of deuteration of at least 25%, preferably at least 50%, more preferably at least 75% and most preferably at least 90%, to a method for preparing an electronic device, preferably an electroluminescent device, and to an electronic device, preferably an electroluminescent device, prepared by using the formulation of the present invention.

有機發光裝置(OLED)長期以來一直藉由真空沉積方法製造。其他技術（諸如噴墨印刷）最近因其等之諸如節省成本及規模放大的可能性之優點已得到了徹底研究。多層印刷的主要挑戰之一係識別相關參數以在基板上獲得均勻的墨水沉積。為了觸發這些參數，諸如表面張力、黏度或沸點，可將一些添加劑添加至調配物中。Organic light-emitting devices (OLEDs) have long been manufactured by vacuum deposition methods. Other technologies, such as inkjet printing, have recently been thoroughly investigated for their advantages, such as cost savings and the possibility of scale-up. One of the main challenges of multi-layer printing is to identify the relevant parameters to obtain a uniform ink deposition on the substrate. In order to trigger these parameters, such as surface tension, viscosity or boiling point, some additives can be added to the formulation.

本發明之技術問題及目的Technical Problem and Purpose of the Invention

已提出有機電子裝置中用於噴墨印刷的許多溶劑。然而，在沉積及乾燥方法期間發揮作用的重要參數之數目使得溶劑的選擇非常具有挑戰性。因此，用於藉由噴墨印刷而沉積之含有有機半導體之調配物仍需要改進。本發明之一個目的係提供一種有機功能性材料、較佳地有機半導體之調配物，其允許受控的沉積以形成具有良好的層性質及有效的性能之有機功能性材料層、較佳地有機半導體層。本發明之其他目的係提供有機功能性材料、較佳地有機半導體之調配物，當使用例如噴墨印刷方法沉積在基板上並乾燥時，允許優異的膜均一性，從而給出良好的層性質及有效的性能。Many solvents have been proposed for inkjet printing in organic electronic devices. However, the number of important parameters that play a role during the deposition and drying process makes the choice of solvent very challenging. Therefore, there is still a need for improvement in formulations containing organic semiconductors for deposition by inkjet printing. One object of the present invention is to provide a formulation of an organic functional material, preferably an organic semiconductor, which allows controlled deposition to form an organic functional material layer, preferably an organic semiconductor layer, with good layer properties and effective performance. A further object of the present invention is to provide formulations of organic functional materials, preferably organic semiconductors, which when deposited on a substrate using, for example, an inkjet printing method and dried, allow excellent film uniformity, thereby giving good layer properties and effective performance.

在JP 2015/191792 A2中揭示一種溶質，其由溶解在第一及第二溶劑中的功能層之構成材料或其前驅物所組成，其中第一溶劑具有第一溶解度參數及第一沸點，且第二溶劑具有比第一溶解度參數小的第二溶解度參數及比第一沸點低的第二沸點，第一沸點係≥250℃且第二沸點係≥170℃，第二沸點與第二沸點之間的差值係≥40℃且第二溶解度參數係9.0(cal/cm³)^1/2或更小。JP 2015/191792 A2 discloses a solute composed of constituent materials of a functional layer or precursors thereof dissolved in first and second solvents, wherein the first solvent has a first solubility parameter and a first boiling point, and the second solvent has a second solubility parameter smaller than the first solubility parameter and a second boiling point lower than the first boiling point, the first boiling point is ≥250°C and the second boiling point is ≥170°C, the difference between the first boiling point and the second boiling point is ≥40°C, and the second solubility parameter is 9.0 (cal/cm³ )^1/2 or less.

在EP 2924083 A1中揭示一種用於形成功能層的墨水，其包含為溶質的第一組分；沸點在280至350℃之範圍內的第二組分，其對於第一組分係好的溶劑且係選自由包括至少二個芳族環之芳族烴、芳族二醇醚、脂族二醇醚、脂族乙酸酯、及脂族酯所組成之群組中之至少一種類型；以及沸點在200℃至300℃之範圍內的第三組分，其對於第一組分係好的溶劑且係選自由芳族烴、芳族醚、及脂族醚所組成之群組中之至少一種類型，其中第二組分在包括第二組分及第三組分的混合溶劑中的比例係10 wt%或更大。EP 2924083 A1 discloses an ink for forming a functional layer, which comprises a first component as a solute; a second component having a boiling point in the range of 280 to 350°C, which is a good solvent for the first component and is selected from at least one type in the group consisting of aromatic hydrocarbons including at least two aromatic rings, aromatic glycol ethers, aliphatic glycol ethers, aliphatic acetates, and aliphatic esters; and a third component having a boiling point in the range of 200°C to 300°C, which is a good solvent for the first component and is selected from at least one type in the group consisting of aromatic hydrocarbons, aromatic ethers, and aliphatic ethers, wherein the proportion of the second component in the mixed solvent comprising the second component and the third component is 10 wt% or more.

在US 2013/256636 A1中揭示一種藉由液體塗佈法形成功能層之功能層墨水，其中功能層材料含有巨分子或低分子量材料、及含有0.1重量%或更多的溶劑A及溶劑B的混合溶劑，溶劑A的黏度在0.01至0.05 Pa･s之範圍內，且溶劑B的黏度小於0.01 Pa･s且沸點比溶劑A低，混合溶劑的黏度小於0.02 Pa･s且沸點在200至350℃之範圍內。US 2013/256636 A1 discloses a functional layer ink for forming a functional layer by a liquid coating method, wherein the functional layer material contains macromolecules or low molecular weight materials, and a mixed solvent containing 0.1 wt % or more of solvent A and solvent B, the viscosity of solvent A is in the range of 0.01 to 0.05 Pa･s, the viscosity of solvent B is less than 0.01 Pa･s and the boiling point is lower than that of solvent A, and the viscosity of the mixed solvent is less than 0.02 Pa･s and the boiling point is in the range of 200 to 350°C.

在WO 2005/083814 A1中揭示至少一種有機半導體之溶液，該溶液在至少三種不同溶劑A、B及C之溶劑混合物中含有至少一種高分子量成分。溶劑A及B對於有機半導體係好的溶劑，溶劑C對於有機半導體係差的溶劑。WO 2005/083814 A1 discloses a solution of at least one organic semiconductor, which contains at least one high molecular weight component in a solvent mixture of at least three different solvents A, B and C. Solvents A and B are good solvents for the organic semiconductor, while solvent C is a poor solvent for the organic semiconductor.

在WO 2005/112145 A1中揭示單相液體組成物(溶液)，其包含至少一種有機半導體、至少一種有機溶劑A、及至少一種有機溶劑B，該有機半導體包含至少一種高分子量組分，該有機溶劑A對於有機半導體係好的溶劑，該有機溶劑B對於有機半導體係差的溶劑，其特徵在於下列適用於溶劑A及B的沸點(b.p.)：b.p.(A)＞b.p.(B)。 解決問題之手段WO 2005/112145 A1 discloses a single-phase liquid composition (solution) comprising at least one organic semiconductor, at least one organic solvent A, and at least one organic solvent B, wherein the organic semiconductor comprises at least one high molecular weight component, the organic solvent A is a good solvent for the organic semiconductor, and the organic solvent B is a poor solvent for the organic semiconductor, and is characterized in that the following boiling points (b.p.) apply to solvents A and B: b.p.(A)＞b.p.(B).Means for solving the problem

本發明之上述目的係藉由下列方式來解決：提供一種調配物，其含有至少一種有機功能性材料及至少一種有機溶劑A，較佳地至少兩種不同的有機溶劑A及B，其特徵在於至少一種有機溶劑係氘化度為至少25%、較佳地至少50%、更佳地至少75%且最佳地至少90%的氘化溶劑。 發明之有利功效The above-mentioned object of the present invention is solved by the following method: providing a formulation containing at least one organic functional material and at least one organic solvent A, preferably at least two different organic solvents A and B, characterized in that at least one organic solvent is a deuterated solvent with a deuteration degree of at least 25%, preferably at least 50%, more preferably at least 75% and most preferably at least 90%.Beneficial effects of the invention

本發明人已驚訝地發現，使用本發明之調配物允許有效的墨水沉積以形成具有良好的層性質及性能之功能性材料的均一且界限分明的有機層。The inventors have surprisingly found that the use of the formulations of the invention allows efficient ink deposition to form uniform and well-defined organic layers of functional materials with good layer properties and performance.

本發明係關於一種調配物，其含有至少一種有機功能性材料及至少一種有機溶劑A，較佳地至少兩種不同的有機溶劑A及B，其特徵在於至少一種有機溶劑係氘化度為至少25%、較佳地至少50%、更佳地至少75%且最佳地至少90%的氘化溶劑。The present invention relates to a formulation containing at least one organic functional material and at least one organic solvent A, preferably at least two different organic solvents A and B, characterized in that at least one organic solvent is a deuterated solvent having a deuteration degree of at least 25%, preferably at least 50%, more preferably at least 75% and most preferably at least 90%.

根據本發明，氘化度(degree of deuteration)對應於化合物中的氘原子數目佔該化合物中的氘原子及氕原子總數目，以%計，如下： 氘化度(%)=(N_D* 100) / (N_P+ N_D) 其中： N_D係化合物中氘原子的數目； N_P係化合物中氘及氕原子的數目。According to the present invention, the degree of deuteration corresponds to the number of deuterium atoms in a compound relative to the total number of deuterium atoms and hydrogen atoms in the compound, expressed as %, as follows: Degree of deuteration (%) = (N_D * 100) / (N_P + N_D ) Where: N_D is the number of deuterium atoms in the compound; N_P is the number of deuterium and hydrogen atoms in the compound.

除非另有說明，否則本發明中之用語氫係指氫的氕同位素，其佔海洋中天然存在的氫多於99.98%。Unless otherwise specified, the term hydrogen used in this invention refers to the protium isotope of hydrogen, which accounts for more than 99.98% of the hydrogen naturally occurring in the ocean.

用語「氘化化合物」對應於一種化合物，其中至少一個氫原子經氘原子置換且在化合物之各氘化位置處之氘的豐度高於氘的天然豐度，其係約為0.015%。要成為「氘化化合物」，化合物/前驅物必須經過氘富集或氘化方法。The term "deuterated compound" corresponds to a compound in which at least one hydrogen atom is replaced by a deuterium atom and the abundance of deuterium at each deuterated position of the compound is higher than the natural abundance of deuterium, which is about 0.015%. To become a "deuterated compound", the compound/precursor must have been subjected to a deuterium enrichment or deuteration process.

氘化度可例如經由NMR或LC-MS判定。 較佳實施例The degree of deuteration can be determined, for example, by NMR or LC-MS.Preferred embodiments

在一較佳實施例中，調配物的特徵在於其含有至少兩種不同的有機溶劑，第一有機溶劑A及第二有機溶劑B，其中第一有機溶劑A及/或第二有機溶劑B係氘化溶劑。In a preferred embodiment, the formulation is characterized in that it contains at least two different organic solvents, a first organic solvent A and a second organic solvent B, wherein the first organic solvent A and/or the second organic solvent B is a deuterated solvent.

第一有機溶劑A及第二有機溶劑B各自的沸點較佳地在100至400℃之範圍內。The boiling points of the first organic solvent A and the second organic solvent B are preferably in the range of 100 to 400°C.

第一有機溶劑A及第二有機溶劑B各自的黏度較佳地在1至60 mPas之範圍內，更佳地在2至50 mPas之範圍內。The viscosity of each of the first organic solvent A and the second organic solvent B is preferably in the range of 1 to 60 mPas, more preferably in the range of 2 to 50 mPas.

在本發明之第一實施例中，第一有機溶劑A係氘化溶劑。In the first embodiment of the present invention, the first organic solvent A is a deuterated solvent.

在本發明之第二實施例中，第二有機溶劑B係氘化溶劑。In the second embodiment of the present invention, the second organic solvent B is a deuterated solvent.

在本發明之第三實施例中，第一有機溶劑A及第二有機溶劑B係氘化溶劑。In the third embodiment of the present invention, the first organic solvent A and the second organic solvent B are deuterated solvents.

合適的第一有機溶劑A較佳地係有機溶劑，其特別包括酮、醚、酯、醯胺(諸如二-C_1-2-烷基甲醯胺)、硫化合物、硝基化合物、烴、鹵化烴(例如氯化烴)、芳族或雜芳族烴(例如萘衍生物)及鹵化芳族或雜芳族烴。Suitable first organic solvent A is preferably an organic solvent, which includes in particular ketones, ethers, esters, amides (such as di-C_1-2 -alkylformamide), sulfur compounds, nitro compounds, alkalis, halogenated alkalis (such as chlorinated alkalis), aromatic or heteroaromatic hydrocarbons (such as naphthalene derivatives) and halogenated aromatic or heteroaromatic hydrocarbons.

較佳地，第一有機溶劑A可選自由下列群組中之一者：經取代及未經取代之芳族或直鏈醚，諸如3-苯氧基甲苯或苯甲醚；經取代或未經取代之芳烴衍生物，諸如環己基苯；經取代或未經取代之茚烷，諸如六甲基茚烷；經取代及未經取代之芳族或直鏈酮，諸如二環己基甲酮；經取代及未經取代之雜環，諸如吡咯啶酮、吡啶、吡；其它氟化或氯化芳族烴、經取代或未經取代之萘，諸如經烷基取代之萘，諸如1-乙基萘。Preferably, the first organic solvent A can be selected from one of the following groups: substituted and unsubstituted aromatic or linear ethers, such as 3-phenoxytoluene or anisole; substituted or unsubstituted aromatic derivatives, such as cyclohexylbenzene; substituted or unsubstituted indanes, such as hexamethylindane; substituted and unsubstituted aromatic or linear ketones, such as dicyclohexyl ketone; substituted and unsubstituted heterocyclics, such as pyrrolidone, pyridine, ... ; other fluorinated or chlorinated aromatic hydrocarbons, substituted or unsubstituted naphthalenes, such as alkyl-substituted naphthalenes, such as 1-ethylnaphthalene.

特佳的第一有機溶劑A係例如1-乙基-萘、2-乙基萘、2-丙基萘、2-(1-甲基乙基)-萘、1-(1-甲基乙基)-萘、2-丁基萘、1,6-二甲基萘、2,2'-二甲基聯苯、3,3'-二甲基聯苯、1-乙醯基萘、1,2,3,4-四甲基苯、1,2,3,5-四甲基-苯、1,2,4,5-四甲基苯、1,2,4-三氯苯、1,2-二氫萘、1,2-二甲基萘、1,3-苯并二㗁呃(benzodioxole)、1,3-二異丙基苯、1,3-二甲基萘、1,4-苯并二㗁烷、1,4-二異丙基苯、1,4-二甲基萘、1,5-二甲基四氫萘、1-苯并噻吩、噻萘(thianaphthalene)、1‑溴萘、1-氯甲基萘、1-甲氧基萘、1-甲基萘、2-溴-3-溴甲基萘、2-溴甲基-萘、2-溴萘、2‑乙氧基萘、2-異丙基-苯甲醚、3,5-二甲基-苯甲醚、5-甲氧基茚烷、5-甲氧基吲哚、5-三級丁基-間二甲苯、6-甲基喹啉、8-甲基喹啉、苯乙酮、苯并噻唑、乙酸苄酯、丁基苯基醚、環己基苯、十氫萘酚、二甲基甲苯、3-苯氧基甲苯、二苯醚、苯丙酮、己基苯、六甲基茚烷、異色滿(isochromane)、乙酸苯酯、苯丙酮、藜蘆素(veratrol)、吡咯啶酮、N,N-二丁基苯胺、己酸環己酯、異戊酸酯(menthyl isovalerate)、二環己基甲酮、月桂酸乙酯、癸酸乙酯。Particularly preferred first organic solvents A are 1-ethyl-naphthalene, 2-ethyl-naphthalene, 2-propyl-naphthalene, 2-(1-methylethyl)-naphthalene, 1-(1-methylethyl)-naphthalene, 2-butyl-naphthalene, 1,6-dimethyl-naphthalene, 2,2'-dimethyl-biphenyl, 3,3'-dimethyl-biphenyl, 1-acetyl-naphthalene, 1,2,3,4-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1, 2,4,5-Tetramethylbenzene, 1,2,4-Trichlorobenzene, 1,2-Dihydronaphthalene, 1,2-Dimethylnaphthalene, 1,3-Benzodioxole, 1,3-Diisopropylbenzene, 1,3-Dimethylnaphthalene, 1,4-Benzodioxane, 1,4-Diisopropylbenzene, 1,4-Dimethylnaphthalene, 1,5-Dimethyltetrahydronaphthalene, 1-Benzothiophene, Thionaphthalene ( thianaphthalene), 1-bromonaphthalene, 1-chloromethylnaphthalene, 1-methoxynaphthalene, 1-methylnaphthalene, 2-bromo-3-bromomethylnaphthalene, 2-bromomethyl-naphthalene, 2-bromonaphthalene, 2-ethoxynaphthalene, 2-isopropyl-anisole, 3,5-dimethyl-anisole, 5-methoxyindole, 5-tert-butyl-m-xylene, 6-methylquinoline, 8-methylquinoline, acetophenone, benzothiazole, benzyl acetate, butylphenyl ether, cyclohexylbenzene, decahydronaphthol, dimethyltoluene, 3-phenoxytoluene, diphenyl ether, propiophenone, hexylbenzene, hexamethylindane, isochromane, phenyl acetate, propiophenone, veratrol, pyrrolidone, N,N-dibutylaniline, cyclohexyl hexanoate, isovaleric acid Ethyl isovalerate, dicyclohexyl ketone, ethyl laurate, ethyl caprate.

第一有機溶劑A的沸點較佳地在200至350℃之範圍內，更佳地在225至325℃之範圍內且最佳地在250至300℃之範圍內。The boiling point of the first organic solvent A is preferably in the range of 200 to 350°C, more preferably in the range of 225 to 325°C and most preferably in the range of 250 to 300°C.

第一有機溶劑A的含量較佳地在50至99.9 vol.-%之範圍內，更佳地在75至99.9 vol.-%之範圍內，且最佳地在90至99.9 vol.-%之範圍內，以調配物中有機溶劑之總量計。The content of the first organic solvent A is preferably in the range of 50 to 99.9 vol.-%, more preferably in the range of 75 to 99.9 vol.-%, and most preferably in the range of 90 to 99.9 vol.-%, based on the total amount of organic solvents in the formulation.

第一有機溶劑A的黏度較佳地在1至30 mPas之範圍內，更佳地在1至20 mPas之範圍內，且最佳地在2至15 mPas之範圍內。The viscosity of the first organic solvent A is preferably in the range of 1 to 30 mPas, more preferably in the range of 1 to 20 mPas, and most preferably in the range of 2 to 15 mPas.

至少一種有機功能性材料在第一有機溶劑A中的溶解度較佳地係≥5 g/l且更佳地≥10 g/l。The solubility of the at least one organic functional material in the first organic solvent A is preferably ≥5 g/l and more preferably ≥10 g/l.

如果第一有機溶劑A係氘化溶劑，則其氘化度為至少25%、較佳地至少50%、更佳地至少75%且最佳地至少90%。If the first organic solvent A is a deuterated solvent, its degree of deuteration is at least 25%, preferably at least 50%, more preferably at least 75% and most preferably at least 90%.

如上所述，第一有機溶劑A之各者可用作氘化溶劑。As described above, each of the first organic solvents A can be used as a deuterated solvent.

如果第一有機溶劑A係以其氘化形式使用，則其較佳地係以其完全氘化形式使用，意指其氘化度為至少90%。If the first organic solvent A is used in its deuterated form, it is preferably used in its fully deuterated form, meaning that its degree of deuteration is at least 90%.

第一有機溶劑A之各者可具有特定的氘化度，其取決於例如用於製備有機溶劑之氘化方法以及反應物。不同的氘化方法亦可導致溶劑分子之特定原子的H原子較佳地交換成D原子。Each of the first organic solvents A may have a specific degree of deuteration, which depends, for example, on the deuteration method and reactants used to prepare the organic solvent. Different deuteration methods may also result in a preferred exchange of H atoms for D atoms at specific atoms of the solvent molecule.

對於表1之一些較佳第一有機溶劑A，未氘化以及不同的氘化結構顯示於下表2中。For some preferred first organic solvents A in Table 1, the undeuterated and different deuterated structures are shown in Table 2 below.

在本發明之一較佳實施例中，本發明之調配物除了至少一種第一有機溶劑A之外還包含至少一不同於第一有機溶劑A之第二有機溶劑B。第二有機溶劑B係與第一個有機溶劑A一起使用。In a preferred embodiment of the present invention, the formulation of the present invention comprises, in addition to at least one first organic solvent A, at least one second organic solvent B different from the first organic solvent A. The second organic solvent B is used together with the first organic solvent A.

第二有機溶劑B的沸點較佳地在250至350℃之範圍內，更佳地在260至340℃之範圍內且最佳地在270至330℃之範圍內。The boiling point of the second organic solvent B is preferably in the range of 250 to 350°C, more preferably in the range of 260 to 340°C and most preferably in the range of 270 to 330°C.

較佳地，第二有機溶劑B具有比第一有機溶劑A更高的沸點，且第二有機溶劑B的沸點較佳地比第一有機溶劑A的沸點高至少10℃、且更佳地至少20℃。Preferably, the second organic solvent B has a higher boiling point than the first organic solvent A, and the boiling point of the second organic solvent B is preferably higher than the boiling point of the first organic solvent A by at least 10°C, and more preferably at least 20°C.

第二有機溶劑B的熔點較佳地低於25℃，意指第二有機溶劑B在室溫下係液體。The melting point of the second organic solvent B is preferably lower than 25°C, which means that the second organic solvent B is liquid at room temperature.

第二有機溶劑B的含量較佳地係0.1至50 vol.-%、更佳地0.1至≤25 vol.-%、最佳地0.5至10 vol.-%且特佳地0.5至8 vol.-%，以調配物中有機溶劑之總量計。The content of the second organic solvent B is preferably 0.1 to 50 vol.-%, more preferably 0.1 to ≤25 vol.-%, most preferably 0.5 to 10 vol.-% and particularly preferably 0.5 to 8 vol.-%, based on the total amount of organic solvents in the formulation.

第二有機溶劑B的黏度較佳地係＞15 mPas、更佳地＞20 mPas、且最佳地＞25 mPas。The viscosity of the second organic solvent B is preferably >15 mPas, more preferably >20 mPas, and most preferably >25 mPas.

較佳地，第二有機溶劑B比第一有機溶劑A具有更高的黏度，且第二有機溶劑B的黏度比第一有機溶劑A的黏度高至少5 mPas、較佳地至少10 mPas。Preferably, the second organic solvent B has a higher viscosity than the first organic solvent A, and the viscosity of the second organic solvent B is higher than the viscosity of the first organic solvent A by at least 5 mPas, preferably at least 10 mPas.

至少一種有機功能性材料在第二有機溶劑B中的溶解度較佳地係≥5 g/l。The solubility of the at least one organic functional material in the second organic solvent B is preferably ≥ 5 g/l.

在本發明之一較佳實施例中，第二有機溶劑B係選自萘衍生物、部分氫化萘衍生物(例如四氫萘衍生物)、全氫化萘衍生物(例如十氫萘衍生物)、茚烷衍生物及全氫化蒽衍生物。In a preferred embodiment of the present invention, the second organic solvent B is selected from naphthalene derivatives, partially hydrogenated naphthalene derivatives (such as tetrahydronaphthalene derivatives), fully hydrogenated naphthalene derivatives (such as decahydronaphthalene derivatives), indane derivatives and fully hydrogenated anthracene derivatives.

本申請案上下文中所使用的表述「衍生物」意指環結構(core structure)(例如萘環(naphthalene core)或部分/完全氫化萘環)至少經取代基R單取單或多取代。The term "derivative" as used in the context of the present application means that the core structure (eg, naphthalene core or partially/completely hydrogenated naphthalene core) is at least mono- or poly-substituted by substituents R.

R  在每次出現時相同或不同地為 -具有1至12個碳原子之直鏈烷基或具有3至12個碳原子之支鏈或環狀烷基，其中一或多個非相鄰的CH₂基團可經-O-、-S-、-NR¹-、-CO-O-、-C=O-、-CH=CH-或-C≡C-置換，且其中一或多個氫原子可經F或具有4至14個碳原子且可經一或多個非芳族R¹基團取代之芳基或雜芳基置換，並且在同一環上或在二個不同環上之複數個取代基R¹可轉而一起形成單環或多環脂族、芳族或雜芳族環系統，其可經複數個取代基R¹取代，或者二個R可轉而一起形成具有4至14個碳原子之單環或多環脂族、芳族或雜芳族環系統，其可經複數個取代基R¹取代，或 -具有4至14個碳原子且可經一或多個非芳族R¹基團取代之芳基或雜芳基，並且在同一環上或在二個不同環上之複數個取代基R¹可轉而一起形成單環或多環脂族、芳族或雜芳族環系統，其可經複數個取代基R¹取代，或者二個R可轉而一起形成具有4至14個碳原子之單環或多環脂族、芳族或雜芳族環系統，其可經複數個取代基R¹取代。 R¹在各情況下係相同或不同，且係具有1至12個碳原子之直鏈烷基或烷氧基或具有3至20個碳原子之支鏈或環狀烷基或烷氧基，其中一或多個非相鄰的CH₂基團可經 -O-、-S-、-CO-O-、-C=O-、-CH=CH-或-C≡C-置換。R is identically or differently at each occurrence - a linear alkyl group having 1 to 12 carbon atoms or a branched or cyclic alkyl group having 3 to 12 carbon atoms, wherein one or more non-adjacent CH₂ groups may be replaced by -O-, -S-, -NR¹ -, -CO-O-, -C=O-, -CH=CH- or -C≡C-, and wherein one or more hydrogen atoms may be replaced by F or an aryl or heteroaryl group having 4 to 14 carbon atoms and which may be substituted by one or more non-aromatic R¹ groups, and a plurality of substituents R¹ on the same ring or on two different rings may in turn form together a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by a plurality of substituents R¹ , or two R may in turn form together a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system having 4 to 14 carbon atoms, which may be substituted by a plurality of substituents R¹ , or - an aryl or heteroaryl group having 4 to 14 carbon atoms and which may be substituted by one or more non-aromatic R¹ groups, and a plurality of substituents R¹ on the same ring or on two different rings may in turn form together a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by a plurality of substituents R¹ , or two R may in turn form together a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system having 4 to 14 carbon atoms, which may be substituted by a plurality of substituents R¹ .^R1 is identical or different in each case and is a linear alkyl or alkoxy group having 1 to 12 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein one or more non-adjacent_CH2 groups may be replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C-.

在本發明之一更佳實施例中，第二有機溶劑B係選自萘衍生物、四氫萘衍生物及十氫萘衍生物。In a more preferred embodiment of the present invention, the second organic solvent B is selected from naphthalene derivatives, tetrahydronaphthalene derivatives and decahydronaphthalene derivatives.

如果第二有機溶劑B係萘衍生物，則其較佳地係根據通式(I)之溶劑：其中R可具有如上文所給的含義。If the second organic solvent B is a naphthalene derivative, it is preferably a solvent according to the general formula (I): wherein R may have the meaning given above.

較佳地，R係具有6至10個碳原子之環狀烷基，其中一或多個非相鄰的CH₂基團可經-O-、-S-、-NR¹-、-CO-O-、-C=O-、-CH=CH-或-C≡C-置換；或具有6至10個碳原子且可經一或多個取代基R¹取代之芳基或雜芳基，並且在同一環上或在二個不同環上之複數個取代基R¹可轉而一起形成單環或多環脂族、芳族或雜芳族環系統，其可經複數個取代基R¹取代。Preferably, R is a cyclic alkyl group having 6 to 10 carbon atoms, wherein one or more non-adjacent CH₂ groups may be replaced by -O-, -S-, -NR¹ -, -CO-O-, -C=O-, -CH=CH- or -C≡C-; or an aryl or heteroaryl group having 6 to 10 carbon atoms and which may be substituted by one or more substituents R¹ , and a plurality of substituents R¹ on the same ring or on two different rings may in turn form together a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by a plurality of substituents R¹ .

在第一最佳實施例中，萘衍生物係1-環己基萘或1-苯基萘。In a first preferred embodiment, the naphthalene derivative is 1-cyclohexylnaphthalene or 1-phenylnaphthalene.

如果第二有機溶劑B係四氫萘衍生物，則其較佳地係根據通式(II)或(III)之溶劑：其中R可具有如上文所給的含義。If the second organic solvent B is a tetrahydronaphthalene derivative, it is preferably a solvent according to the general formula (II) or (III): wherein R may have the meaning given above.

在第二最佳實施例中，四氫萘衍生物係1-苯基-1,2,3,4-四氫萘。In a second preferred embodiment, the tetrahydronaphthalene derivative is 1-phenyl-1,2,3,4-tetrahydronaphthalene.

如果第二有機溶劑B係十氫萘衍生物，則其較佳地係根據通式(IV)之溶劑其中R可具有如上文所給的含義。If the second organic solvent B is a decahydronaphthalene derivative, it is preferably a solvent according to the general formula (IV): wherein R may have the meaning given above.

在第三最佳實施例中，十氫萘衍生物係1-環己基十氫萘或1-苯基十氫萘。In a third preferred embodiment, the decahydronaphthalene derivative is 1-cyclohexyldecahydronaphthalene or 1-phenyldecahydronaphthalene.

較佳的第二溶劑B之實例及其沸點(BP)及熔點(MP)顯示於以下表3中。Examples of preferred second solvents B and their boiling points (BP) and melting points (MP) are shown in Table 3 below.

如果第二有機溶劑B係氘化溶劑，則其氘化度為至少25%、較佳地至少50%、更佳地至少75%且最佳地至少90%。If the second organic solvent B is a deuterated solvent, its degree of deuteration is at least 25%, preferably at least 50%, more preferably at least 75% and most preferably at least 90%.

如果第二有機溶劑B係以其氘化形式使用，則其較佳地係以其完全氘化形式使用，意指其氘化度為至少90%。If the second organic solvent B is used in its deuterated form, it is preferably used in its fully deuterated form, meaning that its degree of deuteration is at least 90%.

如上所述，第二有機溶劑B之各者可用作氘化溶劑。As described above, each of the second organic solvents B can be used as a deuterated solvent.

第二有機溶劑B之各者可具有特定的氘化度，其取決於例如用於製備有機溶劑之氘化方法以及析出物(educt)。Each of the second organic solvents B may have a specific degree of deuteration, which depends, for example, on the deuteration method used to prepare the organic solvent and the educt.

對於表3之二種較佳第二有機溶劑B，未氘化以及不同的氘化結構顯示於下表4中。For two preferred second organic solvents B in Table 3, the undeuterated and different deuterated structures are shown in Table 4 below.

根據本發明之一較佳實施例，如上文所詳述，本發明之調配物包含至少一種有機功能性材料及至少二種不同的有機溶劑A及B。According to a preferred embodiment of the present invention, as described above in detail, the formulation of the present invention comprises at least one organic functional material and at least two different organic solvents A and B.

至少一種溶劑A意指調配物包含一或多於一種、較佳地一或二種有機溶劑A。萬一調配物包含多於一種有機溶劑A，則這些溶劑是不同的。At least one solvent A means that the formulation contains one or more than one, preferably one or two, organic solvents A. In case the formulation contains more than one organic solvent A, these solvents are different.

至少一種溶劑B意指調配物包含一或多於一種、較佳地一或二種有機溶劑B。萬一調配物包含多於一種有機溶劑B，則這些溶劑是不同的。At least one solvent B means that the formulation comprises one or more than one, preferably one or two, organic solvents B. In case the formulation comprises more than one organic solvent B, these solvents are different.

因此，在本發明之一個實施例中，調配物包含一或多於一種、較佳地一或二種有機溶劑A及/或一或多種、較佳地一或二種有機溶劑B。Therefore, in one embodiment of the present invention, the formulation comprises one or more than one, preferably one or two, organic solvents A and/or one or more, preferably one or two, organic solvents B.

此外可能的是，本發明之調配物除了至少一種有機溶劑A及至少一種有機溶劑B之外還包含至少一種其他有機溶劑C，其不同於至少一種有機溶劑A及至少一種有機溶劑B。第三有機溶劑C係與第一有機溶劑A及第二有機溶劑B一起使用。It is also possible that the formulation of the present invention contains, in addition to at least one organic solvent A and at least one organic solvent B, at least one other organic solvent C which is different from at least one organic solvent A and at least one organic solvent B. The third organic solvent C is used together with the first organic solvent A and the second organic solvent B.

較佳地，第三有機溶劑C的沸點在100至300℃之範圍內，更佳地在125至275℃之範圍內，且最佳地在150至250℃之範圍內。此外，第三有機溶劑C的沸點比第一有機溶劑A的沸點低至少10℃，較佳地低至少20℃，更佳地低至少30℃。Preferably, the boiling point of the third organic solvent C is in the range of 100 to 300° C., more preferably in the range of 125 to 275° C., and most preferably in the range of 150 to 250° C. In addition, the boiling point of the third organic solvent C is at least 10° C. lower than the boiling point of the first organic solvent A, preferably at least 20° C. lower, and more preferably at least 30° C. lower.

第三有機溶劑C的含量較佳地在1至30 vol.‑%之範圍內，更佳地在3至25 vol.-%之範圍內，且最佳地在5至20 vol.-%之範圍內，以調配物中有機溶劑之總量計。The content of the third organic solvent C is preferably in the range of 1 to 30 vol.-%, more preferably in the range of 3 to 25 vol.-%, and most preferably in the range of 5 to 20 vol.-%, based on the total amount of organic solvents in the formulation.

作為第三有機溶劑C，可使用所屬技術領域中具有通常知識者已知的任何滿足上述要求、任何適合有機功能性材料印刷的溶劑。較佳的有機溶劑列示於以下表5中。As the third organic solvent C, any solvent known to a person skilled in the art that meets the above requirements and is suitable for printing an organic functional material can be used. Preferred organic solvents are listed in Table 5 below.

第三有機溶劑可係未氘化的或氘化的。如果第三有機溶劑C係氘化的，則其氘化度為至少25%、較佳地至少50%、更佳地至少75%且最佳地至少90%。The third organic solvent may be undeuterated or deuterated. If the third organic solvent C is deuterated, its degree of deuteration is at least 25%, preferably at least 50%, more preferably at least 75% and most preferably at least 90%.

如果第三有機溶劑C係以其氘化形式使用，則其較佳地係以其完全氘化形式使用，意指其氘化度為至少90%。If the third organic solvent C is used in its deuterated form, it is preferably used in its fully deuterated form, meaning that its degree of deuteration is at least 90%.

如上所述，第三有機溶劑C之各者可以其氘化形式使用。As described above, each of the third organic solvents C may be used in its deuterated form.

調配物中之至少一種有機功能性材料的含量係在0.001至20重量%之範圍內，較佳地在0.01至10重量%之範圍內，更佳地在0.1至5重量%之範圍內且最佳地在0.3至5重量%之範圍內，以調配物之總重量計。The content of at least one organic functional material in the formulation is in the range of 0.001 to 20 wt %, preferably in the range of 0.01 to 10 wt %, more preferably in the range of 0.1 to 5 wt % and most preferably in the range of 0.3 to 5 wt %, based on the total weight of the formulation.

此外，本發明之調配物的黏度較佳地在0.8至50 mPa･s之範圍內，更佳地在1至40 mPa･s之範圍內，且最佳地在2至15 mPa･s之範圍內。Furthermore, the viscosity of the formulation of the present invention is preferably in the range of 0.8 to 50 mPa•s, more preferably in the range of 1 to 40 mPa•s, and most preferably in the range of 2 to 15 mPa•s.

根據本發明之調配物及溶劑的黏度係用Discovery AR3型(Thermo Scientific)之1°錐板旋轉流變儀來測量。設備允許精確控制溫度及剪切速率。黏度測量係在25.0℃(+/- 0.2℃)之溫度及500 s^-1之剪切速率下進行。各樣本測量3次，並將所得測量值平均。The viscosity of the formulations and solvents according to the invention was measured using a 1° cone plate rotational rheometer, Discovery AR3 model (Thermo Scientific). The equipment allows precise control of temperature and shear rate. Viscosity measurements were performed at a temperature of 25.0°C (+/- 0.2°C) and a shear rate of 500 s^-1 . Each sample was measured 3 times and the measured values were averaged.

本發明之調配物的表面張力較佳地在15至70 mN/m之範圍內，更佳地在10至50 mN/m之範圍內，且最佳地在20至40 mN/m之範圍內。The surface tension of the formulation of the present invention is preferably in the range of 15 to 70 mN/m, more preferably in the range of 10 to 50 mN/m, and most preferably in the range of 20 to 40 mN/m.

較佳地，有機溶劑摻合物的表面張力在15至70 mN/m之範圍內，更佳地在10至50 mN/m之範圍內，且最佳地在20至40 mN/m之範圍內。Preferably, the surface tension of the organic solvent admixture is in the range of 15 to 70 mN/m, more preferably in the range of 10 to 50 mN/m, and most preferably in the range of 20 to 40 mN/m.

表面張力可使用FTA(First Ten Angstrom) 1000接觸角測角計在20℃下測量。該方法的細節可獲自First Ten Angstrom，由Roger P. Woodward, Ph.D.所發表之「Surface Tension Measurements Using the Drop Shape Method」。較佳地，可使用懸滴法來判定表面張力。此測量技術為從針頭分配一液滴於大量液相或氣相中。液滴的形狀係由表面張力、重力及密度差之間的關係導致的。使用懸滴法，可使用http://www.kruss.de/services/education-theory/glossary/drop-shape-analysis由懸滴的陰影影像來計算表面張力。使用常用的市售高精確度液滴形狀分析工具(亦即來自First Ten Ångstrom的FTA1000)來進行所有表面張力測量。表面張力係藉由軟體FTA1000判定。所有測量皆在20℃至25℃之範圍內的室溫下進行。標準操作程序包括使用新的拋棄式液滴分配系統(注射器及針頭)判定各調配物的表面張力。各液滴係在一分鐘的持續時間內進行六十次測量，之後將該等測量值平均。各調配物測量三滴。最終值係所述測量值的平均值。工具定期與具有眾所周知的表面張力之各種液體進行交叉檢查。Surface tension can be measured using a FTA (First Ten Angstrom) 1000 contact angle goniometer at 20°C. Details of the method can be obtained from "Surface Tension Measurements Using the Drop Shape Method" by Roger P. Woodward, Ph.D., First Ten Angstrom. Preferably, the hanging drop method can be used to determine surface tension. This measurement technique involves dispensing a drop of liquid from a needle into a bulk liquid or gas phase. The shape of the drop is caused by the relationship between surface tension, gravity, and density differences. Using the hanging drop method, the surface tension can be calculated from the shadow image of the drop using http://www.kruss.de/services/education-theory/glossary/drop-shape-analysis. All surface tension measurements were performed using a commonly used commercially available high-precision drop shape analysis tool, namely the FTA1000 from First Ten Ångstrom. The surface tension was determined by means of the software FTA1000. All measurements were performed at room temperature in the range of 20°C to 25°C. The standard operating procedure consists in determining the surface tension of each formulation using a new disposable droplet dispensing system (syringe and needle). Sixty measurements were taken for each droplet over a duration of one minute, after which the measurements were averaged. Three drops were measured for each formulation. The final value is the average of the measurements. The tool was regularly cross-checked with various liquids of known surface tension.

根據本發明之調配物包含至少一種可用於生產電子裝置之功能層的有機功能性材料。功能性材料通常係引入在電子裝置的陽極與陰極之間的有機材料。The formulation according to the invention comprises at least one organic functional material which can be used to produce a functional layer of an electronic device. The functional material is usually an organic material introduced between the anode and cathode of the electronic device.

用語有機功能性材料尤其表示有機導體、有機半導體、有機螢光化合物、有機磷光化合物、有機光吸收化合物、有機光敏化合物、有機光敏化劑及其他有機光活性化合物。用語有機功能性材料另外涵蓋過渡金屬、稀土元素、鑭系元素及錒系元素之有機金屬錯合物。The term organic functional materials refers in particular to organic conductors, organic semiconductors, organic fluorescent compounds, organic phosphorescent compounds, organic light-absorbing compounds, organic photosensitizers and other organic photoactive compounds. The term organic functional materials also covers organic metal complexes of transition metals, rare earth elements, lanthanides and lanthanides.

有機功能性材料係選自由下列所組成之群組：螢光發射體、磷光發射體、主體材料、基質材料、激子阻擋材料、電子傳輸材料、電子注入材料、電洞導體材料、電洞注入材料、n-摻雜劑、p-摻雜劑、寬帶隙材料、電子阻擋材料及電洞阻擋材料。The organic functional material is selected from the group consisting of: fluorescent emitters, phosphorescent emitters, host materials, matrix materials, exciton blocking materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, n-doping agents, p-doping agents, wide bandgap materials, electron blocking materials and hole blocking materials.

有機功能性材料之較佳實施例詳細揭示於WO 2011/076314 A1中，其中該文獻藉由引用方式併入本申請案中。Preferred embodiments of the organic functional material are disclosed in detail in WO 2011/076314 A1, which is incorporated into the present application by reference.

在一較佳實施例中，有機功能性材料係選自由下列所組成之群組的有機半導體：電洞注入材料、電洞傳輸材料、發光材料、電子傳輸材料及電子注入材料。In a preferred embodiment, the organic functional material is an organic semiconductor selected from the group consisting of: hole injection materials, hole transport materials, light emitting materials, electron transport materials and electron injection materials.

有機功能性材料可係分子量低的化合物、聚合物、寡聚物或樹枝狀聚合物，其中有機功能性材料亦可呈混合物的形式。因此，根據本發明之調配物可包含二或更多種不同的具有低分子量之化合物、一種具有低分子量之化合物及一種聚合物或兩種聚合物(摻合物)。The organic functional material can be a low molecular weight compound, polymer, oligomer or dendrimer, wherein the organic functional material can also be in the form of a mixture. Therefore, the formulation according to the present invention can include two or more different low molecular weight compounds, a low molecular weight compound and a polymer or two polymers (blends).

有機功能性材料通常經由前沿軌域的性質來描述，將在下文中更詳細地描述。分子軌域，特別亦是最高佔據分子軌域(HOMO)及最低未佔據分子軌域(LUMO)，彼等的能階及材料的最低三重態T₁或最低激發單重態S₁的能量可基於量子化學計算來估計。為了計算沒有金屬的有機物質的這些性質，首先使用「基態/半經驗/預設自旋/AM1/電荷0/自旋單重態」方法進行幾何最佳化。隨後基於最佳化的幾何進行能量計算。在此使用「TD-SCF/DFT/預設自旋/B3PW91」方法與「6-31G(d)」基底函數組(base set)(電荷0，自旋單重態)。對於含金屬化合物，經由「基態/哈崔-福克(Hartree-Fock)/預設自旋/LanL2MB/電荷0/自旋單重態」方法將幾何最佳化。與上述類似於用於有機物質的方法進行能量計算，差異在於金屬原子使用「LanL2DZ」基底函數組，而配位基使用「6-31G(d)」基底函數組。能量計算給出HOMO能階HEh或LUMO能階LEh，以哈崔單位計。參考循環伏安法測量值校準的以電子伏特計之HOMO及LUMO能階由此判定如下： HOMO(eV)=((HEh*27.212)-0.9899)/1.1206 LUMO(eV)=((LEh*27.212)-2.0041)/1.385Organic functional materials are usually described by the properties of frontier orbitals, which will be described in more detail below. The energy levels of molecular orbitals, especially the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), and the energy of the lowest triplet state T₁ or the lowest excited singlet state S₁ of the material can be estimated based on quantum chemical calculations. In order to calculate these properties of organic substances without metal, the geometry is first optimized using the "ground state/semi-empirical/preset spin/AM1/charge 0/spin singlet" method. Energy calculations are then performed based on the optimized geometry. The "TD-SCF/DFT/preset spin/B3PW91" method and the "6-31G(d)" basis function set (charge 0, spin singlet) are used here. For metal-containing compounds, the geometry is optimized by the "Ground State/Hartree-Fock/Default Spin/LanL2MB/Charge 0/Spin Singlet" method. Energy calculations are performed similarly to the method described above for organics, with the difference that the "LanL2DZ" basis set is used for metal atoms and the "6-31G(d)" basis set is used for ligands. Energy calculations give the HOMO energy level HEh or the LUMO energy level LEh in Hartree units. The HOMO and LUMO energy levels of the electron voltmeter calibrated with reference to the cyclic voltammetry values are determined as follows: HOMO (eV) = ((HEh*27.212) - 0.9899) / 1.1206 LUMO (eV) = ((LEh*27.212) - 2.0041) / 1.385

為了本申請案之目的，這些值將分別被視為材料的HOMO及LUMO能階。For the purposes of this application, these values will be considered to be the HOMO and LUMO energy levels, respectively, of the material.

最低三重態T₁係定義為由所述量子化學計算產生之具有最低能量之三重態的能量。The lowest triplet state_T1 is defined as the energy of the triplet state with the lowest energy produced by the quantum chemical calculation.

最低激發單重態S₁係定義為由所述量子化學計算產生之具有最低能量之激發單重態的能量。The lowest excited singlet state_S1 is defined as the energy of the excited singlet state with the lowest energy generated by the quantum chemical calculation.

本文所述之方法獨立於所使用之套裝軟體且總是給出相同結果。用於此目的之常用程式之實例係「"Gaussian09W」(Gaussian Inc.)及Q-Chem 4.1(Q-Chem, Inc.)。The method described here is independent of the software package used and always gives the same results. Examples of commonly used programs for this purpose are "Gaussian09W" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

根據本發明，調配物包含至少一種可用於生產電子裝置之功能層的有機功能性材料。在一較佳實施例中，本發明之調配物中含有的至少一種有機功能性材料係氘化有機功能性材料。作為氘化有機功能性材料，可使用上文及下文所述之任何有機功能性材料。According to the present invention, the formulation comprises at least one organic functional material that can be used to produce a functional layer of an electronic device. In a preferred embodiment, at least one organic functional material contained in the formulation of the present invention is a deuterated organic functional material. As the deuterated organic functional material, any organic functional material described above and below can be used.

根據本發明之氘化有機功能性材料意指有機功能性材料的氘化度較佳為至少25%、更佳為至少50%、最佳為至少75%且特佳為至少90%。The deuterated organic functional material according to the present invention means that the degree of deuteration of the organic functional material is preferably at least 25%, more preferably at least 50%, most preferably at least 75% and particularly preferably at least 90%.

氘化有機功能性材料的氘化度如上文關於氘化溶劑所述來定義。The degree of deuteration of the deuterated organic functional material is defined as described above with respect to the deuterated solvent.

具有電洞注入性質之化合物，在本文中亦稱為電洞注入材料，簡化或促進電洞(亦即正電荷)從陽極轉移至有機層。通常，電洞注入材料的HOMO能階係在陽極能階的區域內或高於陽極能階，亦即通常係至少-5.3 eV。Compounds with hole injection properties, also referred to herein as hole injection materials, simplify or promote the transfer of holes (i.e., positive charges) from the anode to the organic layer. Typically, the HOMO energy level of the hole injection material is in the region of or above the anode energy level, i.e., typically at least -5.3 eV.

具有電洞傳輸性質之化合物，在本文中亦稱為電洞傳輸材料，能夠傳輸電洞(亦即正電荷)，其通常從陽極或相鄰層(例如電洞注入層)注入。電洞傳輸材料通常具有較佳地至少-5.4 eV的高HOMO能階。根據電子裝置的結構，亦可使用電洞傳輸材料作為電洞注入材料。Compounds with hole transport properties, also referred to herein as hole transport materials, are capable of transporting holes (i.e., positive charges), which are usually injected from the anode or an adjacent layer (e.g., a hole injection layer). Hole transport materials usually have a high HOMO energy level, preferably at least -5.4 eV. Depending on the structure of the electronic device, hole transport materials can also be used as hole injection materials.

具有電洞注入及/或電洞傳輸性質之較佳化合物包括例如三芳基胺、聯苯胺、四芳基對苯二胺、三芳基膦、啡噻、啡㗁、二氫啡、噻嗯、二苯并對戴奧辛、啡㗁噻、咔唑、薁、噻吩、吡咯及呋喃及其衍生物以及其他具有高HOMO(HOMO=最高佔據分子軌域)之含O、S或N之雜環。Preferred compounds having hole injection and/or hole transport properties include, for example, triarylamines, benzidine, tetraaryl-p-phenylenediamine, triarylphosphines, phenanthridines, , coffee , dihydrophenoxyacetyl , thionine, dibenzo-p-dioxin, phenthiophene, carbazole, azulene, thiophene, pyrrole and furan and their derivatives, as well as other heterocyclic rings containing O, S or N with high HOMO (HOMO = highest occupied molecular orbital).

作為具有電洞注入及/或電洞傳輸性質之化合物，可特別提及者係苯二胺衍生物(US 3615404)、芳基胺衍生物(US 3567450)、經胺基取代之查耳酮衍生物(US 3526501)、苯乙烯基蒽衍生物(JP-A-56-46234)、多環芳族化合物(EP 1009041)、聚芳烷衍生物(US 3615402)、茀酮衍生物(JP-A-54-110837)、腙衍生物(US 3717462)、醯腙、二苯乙烯衍生物(JP-A-61-210363)、矽氮烷衍生物(US 4950950)、聚矽烷(JP-A-2-204996)、苯胺共聚物(JP-A-2-282263)、噻吩寡聚物(JP Heisei 1(1989)211399)、聚噻吩、聚(N-乙烯基咔唑)(PVK)、聚吡咯、聚苯胺及其他導電巨分子、卟啉(porphyrin)化合物(JP-A-63-2956965、US 4720432)、芳族二亞甲基型化合物、咔唑化合物(諸如例如CDBP、CBP、mCP、芳族三級胺及苯乙烯基胺化合物(US 4127412)(諸如例如聯苯胺型之三苯胺、苯乙烯基胺型之三苯胺及二胺型之三苯胺。亦可使用芳基胺樹枝狀聚合物(JP Heisei 8(1996) 193191)、單體三芳基胺(US 3180730)、含有一或多個乙烯基及/或至少一個含有活性氫之官能基的三芳基胺(US 3567450及US 3658520) 、或四芳基二胺(二個三級胺單元係經由芳基連接)。分子中亦可存在更多三芳基胺基。酞菁衍生物、萘酞菁衍生物、丁二烯衍生物及喹啉衍生物，諸如例如二吡并[2,3-f:2',3'-h]喹㗁啉六甲腈亦係合適的。As compounds having hole injection and/or hole transport properties, there may be mentioned in particular phenylenediamine derivatives (US 3615404), arylamine derivatives (US 3567450), amino-substituted chalcone derivatives (US 3526501), styrylanthracene derivatives (JP-A-56-46234), polycyclic aromatic compounds (EP 1009041), polyarylalkane derivatives (US 3615402), fluorenone derivatives (JP-A-54-110837), hydrazone derivatives (US 3717462), acylhydrazone, stilbene derivatives (JP-A-61-210363), silazane derivatives (US 4950950), polysilane (JP-A-2-204996), aniline copolymers (JP-A-2-282263), thiophene oligomers (JP-A-54-110837 ... polycyclic aromatic compounds (EP 1 Heisei 1 (1989) 211399), polythiophene, poly(N-vinylcarbazole) (PVK), polypyrrole, polyaniline and other conductive macromolecules, porphyrin compounds (JP-A-63-2956965, US 4720432), aromatic dimethylene compounds, carbazole compounds (such as CDBP, CBP, mCP, aromatic tertiary amines and styrylamine compounds (US 4127412) (such as benzidine type triphenylamine, styrylamine type triphenylamine and diamine type triphenylamine. Aromatic amine dendrimers (JP Heisei 8 (1996) 193191), monomeric triarylamines (US 3180730), triarylamines containing one or more vinyl groups and/or at least one functional group containing active hydrogen (US 3567450 and US 3658520), or tetraaryl diamine (two tertiary amine units are linked via an aryl group). More triaryl amine groups may also be present in the molecule. Phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives and quinoline derivatives, such as dipyridinium Also suitable is [2,3-f:2',3'-h]quinolinehexacarbonitrile.

較佳者係含有至少二個三級胺單元之芳族三級胺(US 2008/0102311 A1、US 4720432及US 5061569)，諸如例如，NPD(α-NPD=4,4'-雙[N-(1-萘基)-N-苯基胺基]聯苯)(US 5061569)、TPD 232(=N,N'-雙-(N,N'-二苯基-4-胺基苯基)-N,N-二苯基-4,4'-二胺基-1,1'-聯苯)或MTDATA(MTDATA或m-MTDATA=4,4',4"-參[3-甲基苯基)苯基胺基]三苯胺)(JP-A-4-308688)、TBDB(=N,N,N',N'-四(4-聯苯)二胺基聯苯)、TAPC(=1,1-雙(4-二-對甲苯基胺基苯基)環己烷)、TAPPP(=1,1-雙(4-二-甲苯基胺基苯基)-3-苯基丙烷)、BDTAPVB(=1,4-雙[2-[4- [N,N-二(對甲苯基)胺基]苯基]乙烯基]苯)、TTB(=N,N,N',N'-四-對甲苯基-4,4'-二胺基聯苯)、TPD(=4,4'-雙[N-3-甲基苯基]-N-苯基胺基)聯苯)、N,N,N',N'-四苯基-4,4"'-二胺基-1,1',4',1",4",1"'-聯四苯，同樣含有咔唑單元之三級胺，諸如例如，TCTA(=4-(9H-咔唑-9-基)-N,N-雙[4-(9H-咔唑-9-基)苯基]苯胺)。同樣較佳者係根據US 2007/0092755 A1之六氮雜聯伸三苯化合物及酞菁衍生物(例如H₂Pc、CuPc(=銅酞青)、CoPc、NiPc、ZnPc、PdPc、FePc、MnPc、ClAlPc、ClGaPc、ClInPc、ClSnPc、Cl₂SiPc、(HO)AlPc、(HO)GaPc、VOPc、TiOPc、MoOPc、GaPc-O-GaPc)。Preferred are aromatic tertiary amines containing at least two tertiary amine units (US 2008/0102311 A1, US 4720432 and US 5061569), such as NPD (α-NPD = 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl) (US 5061569), TPD 232 (=N,N'-bis-(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl-4,4'-diamino-1,1'-biphenyl) or MTDATA (MTDATA or m-MTDATA=4,4',4"-tris[3-methylphenyl)phenylamino]triphenylamine) (JP-A-4-308688), TBDB (=N,N,N',N'-tetrakis(4-biphenyl)diaminobiphenyl), TAPC (=1,1-bis(4-di-p-tolylaminophenyl)cyclohexane), TAPPP (=1,1-bis(4-di-tolylaminophenyl)-3-phenylpropane), BDTAPVB (=1,4-bis[2-[4- [N,N-di(p-tolyl)amino]phenyl]vinyl]benzene), TTB (=N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl), TPD (=4,4'-bis[N-3-methylphenyl]-N-phenylamino)biphenyl), N,N,N',N'-tetraphenyl-4,4"'-diamino-1,1',4',1",4",1"'-tetraphenyl, and tertiary amines containing carbazole units, such as, for example, TCTA (=4-(9H-carbazole-9-yl)-N,N-bis[4-(9H-carbazole-9-yl)phenyl]aniline). Also preferred are hexaazatriphenyl compounds according to US 2007/0092755 A1 and phthalocyanine derivatives (such as H₂ Pc, CuPc (= copper phthalocyanine), CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl₂ SiPc, (HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc).

特佳者係下列式(TA-1)至(TA-12)之三芳基胺化合物，其等揭示於EP 1162193 B1、EP 650 955 B1、Synth.Metals1997, 91(1-3), 209、DE 19646119 A1、WO 2006/122630 A1、EP 1 860 097 A1、EP 1834945 A1、JP 08053397 A、US 6251531 B1、US 2005/0221124、JP 08292586 A、US 7399537 B2、US 2006/0061265 A1、EP 1 661 888及WO 2009/041635中。所述式(TA-1)至(TA-12)之化合物亦可經取代：Particularly preferred are triarylamine compounds of the following formulae (TA-1) to (TA-12), which are disclosed in EP 1162193 B1, EP 650 955 B1,Synth. Metals1997 , 91(1-3), 209, DE 19646119 A1, WO 2006/122630 A1, EP 1 860 097 A1, EP 1834945 A1, JP 08053397 A, US 6251531 B1, US 2005/0221124, JP 08292586 A, US 7399537 B2, US 2006/0061265 A1, EP 1 661 888 and WO 2009/041635. The compounds of formula (TA-1) to (TA-12) may also be substituted:

可用作電洞注入材料的其他化合物描述於EP 0891121 A1及EP 1029909 A1中，注入層通常描述於US 2004/0174116 A1中。Other compounds useful as hole injection materials are described in EP 0891121 A1 and EP 1029909 A1, injection layers are generally described in US 2004/0174116 A1.

通常用作電洞注入及/或電洞傳輸材料的這些芳基胺及雜環較佳地導致聚合物中的HOMO大於-5.8 eV(相對於真空水平)，特佳地大於-5.5 eV。These aromatic amines and heterocycles, which are generally used as hole injection and/or hole transport materials, preferably result in a HOMO in the polymer greater than -5.8 eV (relative to the vacuum level), particularly preferably greater than -5.5 eV.

具有電子注入及/或電子傳輸性質的化合物係例如吡啶、嘧啶、嗒、吡、㗁二唑、喹啉、喹㗁啉、蒽、苯并蒽、芘、苝、苯并咪唑、三、酮、氧化膦及啡及其衍生物，而且還係三芳基硼烷及其他具有低LUMO(LUMO＝最低未佔據分子軌域)之含O、S或N之雜環。Compounds having electron injection and/or electron transport properties are, for example, pyridine, pyrimidine, , pyridine , oxadiazole, quinoline, quinoline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, tris(III) , ketones, phosphine oxides and phenanthracene and their derivatives, but also triarylboranes and other heterocyclic rings containing O, S or N with a low LUMO (LUMO = lowest unoccupied molecular orbital).

特別適合用於電子傳輸層及電子注入層之化合物係8‑羥基喹啉之金屬螯合物(例如LiQ、AlQ₃、GaQ₃、MgQ₂、ZnQ₂、InQ₃、ZrQ₄)、BAlQ、Ga類奧辛(oxinoid)錯合物、4‑氮雜菲-5-醇-Be錯合物(US 5529853 A，參見式ET-1)、丁二烯衍生物(US 4356429)、雜環光學增白劑(optical brightener)(US 4539507)、苯并咪唑衍生物(US 2007/0273272 A1)(諸如例如TPBI(US 5766779，參見式ET-2))、1,3,5-三(例如螺聯茀基三衍生物(例如根據DE 102008064200者)、芘、蒽、稠四苯、茀、螺茀、樹枝狀聚合物、稠四苯(例如紅螢烯衍生物)、1,10-菲啉衍生物(JP 2003-115387、JP 2004-311184、JP 2001-267080、WO 02/043449)、矽雜環戊二烯衍生物(EP 1480280、EP 1478032、EP 1469533)、硼烷衍生物[諸如例如含矽之三芳基硼烷衍生物(US 2007/0087219 A1，參見式ET-3)、吡啶衍生物(JP 2004-200162)、啡啉(尤其是1,10-啡啉衍生物，諸如例如BCP及Bphen)，亦有一些經由聯苯或其他芳族基團連接的啡啉(US-2007-0252517 A1)或連接至蒽之啡啉(US 2007-0122656 A1，參見式ET-4及ET-5)。Compounds particularly suitable for use in the electron transport layer and the electron injection layer are metal chelates of 8-hydroxyquinoline (e.g., LiQ, AlQ₃ , GaQ₃ , MgQ₂ , ZnQ₂ , InQ₃ , ZrQ₄ ), BAlQ, Ga-oxinoid complexes, 4-nitrophenanthren-5-ol-Be complexes (US 5529853 A, see formula ET-1), butadiene derivatives (US 4356429), heterocyclic optical brighteners (US 4539507), benzimidazole derivatives (US 2007/0273272 A1) (e.g., TPBI (US 5766779, see formula ET-2)), 1,3,5-triazine, and the like. (e.g. spirofluorenyl tris( derivatives (e.g. according to DE 102008064200), pyrene, anthracene, fused tetraphenyl, fluorene, spirofluorene, dendrimers, fused tetraphenyl (e.g. erythrene derivatives), 1,10-phenanthroline derivatives (JP 2003-115387, JP 2004-311184, JP 2001-267080, WO 02/043449), silylcyclopentadiene derivatives (EP 1480280, EP 1478032, EP 1469533), borane derivatives [such as, for example, silicon-containing triarylborane derivatives (US 2007/0087219 A1, see formula ET-3), pyridine derivatives (JP 2004-200162), phenanthenes (especially 1,10-phenanthene derivatives, such as BCP and Bphen), and some phenanthenes linked via biphenyl or other aromatic groups (US-2007-0252517 A1) or phenanthenes linked to anthracenes (US 2007-0122656 A1, see formula ET-4 and ET-5).

同樣合適的係雜環有機化合物，諸如例如二氧化噻喃、㗁唑、三唑、咪唑或㗁二唑。使用含有N的五員環之實例，諸如例如㗁唑，較佳地1,3,4-㗁二唑，例如式ET-6、ET-7、ET-8及ET-9之化合物，尤其是在US 2007/0273272 A1中所揭示者；尤其是噻唑類、㗁二唑類、噻二唑類、三唑類，參見US 2008/0102311 A1及Y.A. Levin, M.S. Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967(2), 339-341，較佳地式ET-10之化合物，矽雜環戊二烯衍生物。較佳的化合物係下列式(ET-6)至(ET-10)之化合物：Also suitable are heterocyclic organic compounds such as, for example, thiopyran, oxadiazole, triazole, imidazole or oxadiazole. Examples of N-containing five-membered rings include, for example, oxadiazoles, preferably 1,3,4-oxadiazoles, such as compounds of the formula ET-6, ET-7, ET-8 and ET-9, in particular those disclosed in US 2007/0273272 A1, in particular thiazoles, oxadiazoles, thiadiazoles, triazoles, see US 2008/0102311 A1 and YA Levin, MS Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967 (2), 339-341, preferably compounds of the formula ET-10, silacyclopentadiene derivatives. Preferred compounds are the following compounds of formula (ET-6) to (ET-10):

亦可使用有機化合物，諸如茀酮、亞茀基甲烷、苝四碳酸、蒽醌二甲烷、聯苯醌(diphenoquinone)、蒽酮及蒽醌二乙二胺(anthraquinonediethylenediamine)及其衍生物。Organic compounds such as fluorenone, fluorenyl methane, perylene tetracarbonic acid, anthraquinone dimethane, diphenoquinone, anthrone and anthraquinone diethylenediamine and their derivatives may also be used.

較佳者係2,9,10-經取代之蒽(用1-或2-萘基及4-或3-聯苯基取代)或含有二個蒽單元之分子(US 2008/ 0193796 A1，參見式ET-11)。此外，非常有利的是9,10-經取代之蒽單元與苯并咪唑衍生物之連接(US 2006/147747 A及EP 1551206 A1，參見式ET-12及ET‑13)。Preferred are 2,9,10-substituted anthracenes (substituted with 1- or 2-naphthyl and 4- or 3-biphenyl) or molecules containing two anthracene units (US 2008/0193796 A1, see formula ET-11). In addition, very advantageous are the linkages of 9,10-substituted anthracene units with benzimidazole derivatives (US 2006/147747 A and EP 1551206 A1, see formulas ET-12 and ET-13).

能夠產生電子注入及/或電子傳輸性質之化合物較佳造成小於-2.5 eV(相對於真空能階)、特佳小於‑2.7 eV的LUMO。The compound capable of producing electron injection and/or electron transport properties preferably has a LUMO of less than -2.5 eV (relative to the vacuum level), and more preferably less than -2.7 eV.

本發明調配物可包含發射體。用語發射體表示在可藉由任何類型之能量的轉移而發生激發之後允許輻射躍遷至基態並發射光的材料。通常，有兩類發射體係已知的，稱為螢光發射體及磷光發射體。用語螢光發射體表示在其中發生從激發的單重態輻射躍遷至基態的材料或化合物。用語磷光發射體較佳地表示含有過渡金屬的發光材料或化合物。The formulations of the invention may comprise an emitter. The term emitter refers to a material that, after excitation which may occur by transfer of energy of any type, allows a radiative transition to the ground state and emits light. Generally, two classes of emitters are known, called fluorescent emitters and phosphorescent emitters. The term fluorescent emitter refers to a material or compound in which a radiative transition from an excited singlet state to the ground state occurs. The term phosphorescent emitter preferably refers to a luminescent material or compound containing a transition metal.

如果摻雜劑在系統中引起上述性質，則發射體通常亦稱為摻雜劑。包含基質材料及摻雜劑的系統中之摻雜劑係用來意指混合物中比例較小的組分。對應地，包含基質材料及摻雜劑的系統中之基質材料係用來意指混合物中比例較大的組分。因此，用語磷光發射體亦可被視為意指例如磷光摻雜劑。If the dopant causes the above-mentioned properties in the system, the emitter is often also called a dopant. The dopant in a system comprising a matrix material and a dopant is used to refer to the component with a smaller proportion in the mixture. Correspondingly, the matrix material in a system comprising a matrix material and a dopant is used to refer to the component with a larger proportion in the mixture. Thus, the term phosphorescent emitter can also be considered to mean, for example, a phosphorescent dopant.

能夠發光之化合物尤其包括螢光發射體及磷光發射體。這些尤其包括含有二苯乙烯(stilbene)、二苯乙烯胺、苯乙烯基胺、香豆素、紅螢烯、玫瑰紅(rhodamine)、噻唑、噻二唑、花青、噻吩、對伸苯基(paraphenylene)、苝、酞菁、卟啉(porphyrin)、酮、喹啉、亞胺、蒽及/或芘結構之化合物。特佳者係即使在室溫下也能夠以高效率從三重態發光之化合物，亦即展現出電致磷光而非電致螢光，其通常引起能量效率增加。適合此目的者首先係含有原子序大於36的重原子之化合物。較佳者係含有滿足上述條件之d‑或f‑過渡金屬之化合物。特佳者在此係含有第8至10族元素(Ru、Os、Rh、Ir、Pd、Pt)之對應的化合物。合適的功能性化合物在此係例如各種錯合物，如例如於WO 02/068435 A1、WO 02/081488 A1、EP 1239526 A2及WO 2004/026886 A2中所述。Compounds capable of emitting light include in particular fluorescent and phosphorescent emitters. These include in particular compounds containing stilbene, distyrylamine, styrylamine, coumarin, rubrene, rhodamine, thiazole, thiadiazole, cyanine, thiophene, paraphenylene, perylene, phthalocyanine, porphyrin, ketone, quinoline, imine, anthracene and/or pyrene structures. Particularly preferred are compounds that can emit light from the triplet state with high efficiency even at room temperature, i.e., exhibit electrophosphorescence instead of electrofluorescence, which generally leads to an increase in energy efficiency. Suitable for this purpose are firstly compounds containing heavy atoms with an atomic number greater than 36. Preferred are compounds containing d- or f-transition metals that meet the above conditions. Particularly preferred are corresponding compounds containing elements of Groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt). Suitable functional compounds are, for example, various complexes, as described, for example, in WO 02/068435 A1, WO 02/081488 A1, EP 1239526 A2 and WO 2004/026886 A2.

可當作螢光發射體之較佳化合物藉由舉實例之方式描述於下文中。較佳的螢光發射體係選自單苯乙烯基胺、二苯乙烯基胺、三苯乙烯基胺、四苯乙烯基胺、苯乙烯膦、苯乙烯醚及芳基胺。Preferred compounds that can be used as fluorescent emitters are described below by way of example. Preferred fluorescent emitters are selected from monostyrylamine, distyrylamine, tristyrylamine, tetrastyrylamine, styrylphosphine, styrylether and arylamine.

單苯乙烯基胺係用來意指含有一個經取代或未經取代之苯乙烯基及至少一種胺、較佳地芳族胺之化合物。二苯乙烯基胺係用來意指含有二個經取代或未經取代之苯乙烯基及至少一種胺、較佳地芳族胺之化合物。三苯乙烯基胺係用來意指含有三個經取代或未經取代之苯乙烯基及至少一種胺、較佳地芳族胺之化合物。四苯乙烯基胺係用來意指含有四個經取代或未經取代之苯乙烯基及至少一種胺、較佳地芳族胺之化合物。苯乙烯基基團特佳地係二苯乙烯，其亦可進一步經取代。對應的膦及醚與胺類似地定義。在本發明的意義上，芳基胺或芳族胺係用來意指含有三個直接鍵結至氮之經取代或未經取代之芳族或雜芳族環系統之化合物。這些芳族或雜芳族環系統中之至少一者較佳係縮合環系統，較佳地具有至少14個芳族環原子。其較佳實例係芳族蒽胺、芳族蒽二胺、芳族芘胺、芳族芘二胺、胺或二胺。芳族蒽胺係用來意指一個二芳基胺基直接鍵結至蒽基團、較佳地在9‑位之化合物。芳族蒽二胺係用來意指二個二芳基胺基直接鍵結至蒽基團、較佳地在2,6-或9,10-位之化合物。芳族芘胺、芘二胺、胺及二胺與此類似地定義，其中二芳基胺基較佳地在1‑位或在1,6-位鍵結至芘。Monostyrylamines are taken to mean compounds which contain one substituted or unsubstituted styryl group and at least one amine, preferably an aromatic amine. Distyrylamines are taken to mean compounds which contain two substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. Tristyrylamines are taken to mean compounds which contain three substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. Tetrastyrylamines are taken to mean compounds which contain four substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. The styryl groups are particularly preferably diphenylethylene, which may also be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. In the sense of the present invention, arylamines or aromatic amines are taken to mean compounds which contain three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a condensed ring system, preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyreneamine, aromatic pyrenediamine, Amine or Diamines. Aromatic anthraceneamines are used to refer to compounds in which one diarylamine group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracenediamines are used to refer to compounds in which two diarylamine groups are directly bonded to an anthracene group, preferably at the 2, 6- or 9, 10-positions. Aromatic pyreneamines, pyrenediamines, Amine and Diamines are defined analogously, wherein the diarylamine group is preferably bonded to the pyrene in the 1-position or in the 1,6-position.

其他較佳的螢光發射體係選自茚并茀胺或茚并茀二胺，其特別描述於WO 2006/122630中；苯并茚并茀胺或苯并茚并茀二胺，其特別描述於WO 2008/006449中；及二苯并茚并茀胺或二苯并茚并茀二胺，其特別描述於WO 2007/140847中。Other preferred fluorescent emitters are selected from indenofluorenamine or indenofluorenediamine, which are described in particular in WO 2006/122630; benzoindenofluorenamine or benzoindenofluorenediamine, which are described in particular in WO 2008/006449; and dibenzoindenofluorenamine or dibenzoindenofluorenediamine, which are described in particular in WO 2007/140847.

來自可用作螢光發射體的苯乙烯基胺類化合物之實例係經取代或未經取代之三苯乙烯基胺或摻雜劑，描述於WO 2006/000388、WO 2006/058737、WO 2006/000389、WO 2007/065549及WO 2007/115610中。二苯乙烯苯及二苯乙烯聯苯衍生物係描述於US 5121029中。其他苯乙烯基胺可在US 2007/0122656 A1中找到。Examples of compounds from the class of styrylamines useful as fluorescent emitters are substituted or unsubstituted tristyrylamines or dopants, as described in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 and WO 2007/115610. Distyrylbenzene and distyrylbiphenyl derivatives are described in US 5121029. Other styrylamines can be found in US 2007/0122656 A1.

特佳的苯乙烯基胺化合物係描述於US 7250532 B2中之式EM-1之化合物及描述於DE 10 2005 058557 A1中之式EM-2之化合物：Particularly preferred styrylamine compounds are the compounds of formula EM-1 described in US 7250532 B2 and the compounds of formula EM-2 described in DE 10 2005 058557 A1:

特佳的三芳基胺化合物係式EM-3至EM-15之化合物，其揭示於CN 1583691 A、JP 08/053397 A及US 6251531 B1、EP 1957606 A1、US 2008/0113101 A1、US 2006/210830 A、WO 2008/006449及DE 102008035413及其衍生物：Particularly preferred triarylamine compounds are compounds of formula EM-3 to EM-15, which are disclosed in CN 1583691 A, JP 08/053397 A and US 6251531 B1, EP 1957606 A1, US 2008/0113101 A1, US 2006/210830 A, WO 2008/006449 and DE 102008035413 and their derivatives:

可作為螢光發射體之其他較佳的化合物係選自下列者的衍生物：萘、蒽、稠四苯、苯并蒽、苯并菲(DE 10 2009 005746)、茀、丙二烯合茀(fluoranthene)、二茚并苝(periflanthene)、茚并苝、菲、苝(US 2007/0252517 A1)、芘、、十環烯、蔻、四苯基環戊二烯、五苯基環戊二烯、茀、螺茀、紅螢烯、香豆素(US 4769292, US 6020078, US 2007/0252517 A1)、哌喃、㗁唑、苯并㗁唑、苯并噻唑、苯并咪唑、吡、肉桂酸酯、二酮吡咯并吡咯、吖啶酮及喹吖啶酮(US 2007/0252517 A1)。Other preferred compounds that can be used as fluorescent emitters are derivatives selected from the following: naphthalene, anthracene, tetraphenylene, benzanthracene, triphenylene (DE 10 2009 005746), fluorene, fluoranthene, periflanthene, indenoperylene, phenanthrene, perylene (US 2007/0252517 A1), pyrene, , decacyclopentene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, erythrofluorene, coumarin (US 4769292, US 6020078, US 2007/0252517 A1), pyran, oxadiazole, benzoxazole, benzothiazole, benzimidazole, pyridine , cinnamate, diketopyrrolopyrrole, acridones and quinacridones (US 2007/0252517 A1).

在蒽化合物中，特佳者係9,10-經取代之蒽，諸如例如9,10-二苯基蒽及9,10-雙(苯基乙炔基)蒽。1,4-雙(9'-乙炔基蒽基)苯亦係較佳的摻雜劑。Among the anthracene compounds, 9,10-substituted anthracenes are particularly preferred, such as 9,10-diphenylanthracene and 9,10-bis(phenylethynyl)anthracene. 1,4-bis(9'-ethynylanthryl)benzene is also a preferred dopant.

同樣較佳者係紅螢烯、香豆素、玫瑰紅、喹吖啶酮的衍生物，諸如例如DMQA(=N,N'-二甲基喹吖啶酮)、二氰基亞甲基哌喃，諸如例如DCM(=4-(二氰基亞乙基)-6-(4-二甲基胺基苯乙烯基-2-甲基)-4H-哌喃)、噻喃、聚次甲基(polymethine)、哌喃鎓鹽及噻喃鎓鹽、二茚并苝及茚并苝。Also preferred are rubrene, coumarin, rose bengal, derivatives of quinacridone, such as, for example, DMQA (=N,N'-dimethylquinacridone), dicyanomethylenepyrans, such as, for example, DCM (=4-(dicyanoethylidene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyran), thiopyrans, polymethines, pyrylium and thiopyranium salts, diindenoperylene and indenoperylene.

藍色螢光發射體較佳地係聚芳族化合物，諸如例如9,10-二(2-萘基蒽)及其他蒽衍生物；稠四苯、𠮿、苝的衍生物，諸如例如2,5,8,11-四-三級丁基苝、伸苯基，例如4,4'-雙(9-乙基-3-咔唑伸乙烯基)-1,1'-聯苯、茀、丙二烯合茀、芳基芘(US 2006/0222886 A1)、伸芳基伸乙烯基(US 5121029、US 5130603)、雙(吖基)亞胺-硼化合物(US 2007/0092753 A1)、雙(吖基)亞甲基化合物及喹諾酮化合物。The blue fluorescent emitter is preferably a polyaromatic compound, such as, for example, 9,10-di(2-naphthylanthracene) and other anthracene derivatives; fused tetraphenyl, chrysene , perylene derivatives, such as, for example, 2,5,8,11-tetra-tert-butylperylene, phenylene, such as 4,4'-bis(9-ethyl-3-carbazolylvinylene)-1,1'-biphenyl, fluorene, allylfluorene, arylpyrene (US 2006/0222886 A1), arylvinylene (US 5121029, US 5130603), bis(acrylamide ... Imido-boron compounds (US 2007/0092753 A1), bis(acrylamide) 1-(4-(2-nitrophenyl)-2-nitropropene) methylene compounds and quinolone compounds.

其他較佳的藍色螢光發射體描述於C.H. Chen et al.: “Recent developments in organic electroluminescent materials” Macromol. Symp. 125,(1997) 1-48及“Recent progress of molecular organic electroluminescent materials and devices” Mat. Sci. and Eng. R, 39(2002), 143-222中。Other preferred blue fluorescent emitters are described in C.H. Chen et al.: "Recent developments in organic electroluminescent materials" Macromol. Symp. 125, (1997) 1-48 and "Recent progress of molecular organic electroluminescent materials and devices" Mat. Sci. and Eng. R, 39 (2002), 143-222.

其他較佳的藍色螢光發射體係如WO 2010/ 012328 A1中所揭示之下式(1)之烴。其中下列適用於所使用的符號及標號： Ar¹、Ar²、Ar³在每次出現時相同或不同地係具有5至30個芳族環原子之芳基或雜芳基，其可經一或多個基團R¹取代，先決條件為Ar²不代表蒽、稠四苯或稠五苯； X        在每次出現時相同或不同地係選自下列之基團：BR²、C(R²)₂、Si(R²)₂、C=O、C=NR²、C=C(R²)₂、O、S、S=O、SO₂、NR²、PR²、P(=O)R²及P(=S)R²； R¹、R²在每次出現時相同或不同地係H；D；F；Cl；Br；I；N(Ar⁴)₂；C(=O)Ar⁴；P(=O)(Ar⁴)₂；S(=O)Ar⁴；S(=O)₂Ar⁴；CR²=CR²Ar⁴；CHO；CR³=C(R³)₂；CN；NO₂；Si(R³)₃；B(OR³)₂；B(R³)₂；B(N(R³)₂)₂；OSO₂R³；具有1至40個C原子之直鏈烷基、烷氧基或硫代烷氧基(thioalkoxy)或具有2至40個C原子之直鏈烯基或炔基或具有3至40個C原子之支鏈或環狀烷基、烯基、炔基、烷氧基或硫代烷氧基，其各者可經一或多個基團R³取代，其中在各情況下一或多個非相鄰的CH₂基團可經R³C=CR³、C≡C、Si(R³)₂、Ge(R³)₂、Sn(R³)₂、C=O、C=S、C=Se、C=NR³、P(=O)R³、SO、SO₂、NR³、O、S或CONR³置換，且其中一或多個H原子可經F、Cl、Br、I、CN或NO₂置換；或具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R³取代；或這些系統的組合；二或更多個取代基R¹或R²在此亦可彼此形成單環或多環脂族或芳族環系統； R³在每次出現時相同或不同地係H、D或具有1至20個C原子之脂族或芳族烴基； Ar⁴在每次出現時相同或不同地係具有5至30個芳族環原子之芳族或雜芳族環系統，其可經一或多個非芳族基團R¹取代；相同的氮或磷原子上之二個基團Ar在此亦可藉由單鍵或橋X彼此連接； m、n    係0或1，其先決條件為m + n=1； p         係1、2、3、4、5或6； Ar¹、Ar²及X在此一起形成五員環或六員環，且Ar²、Ar³及X一起形成五員環或六員環，其先決條件為不是式(1)之化合物中的所有符號X皆鍵結在五員環中，就是式(1)之化合物中的所有符號X鍵結在六員環中； 其特徵在於，如果p=1，則基團Ar¹、Ar²及Ar³中所有π電子的總和係至少28；如果p=2，則係至少34；如果p=3，則係至少40；如果p=4，則係至少46；如果p=5，則係至少52；且如果p=6，則係至少58； n=0或m=0在此意指對應的基團X不存在，反而是氫或取代基R¹鍵結至Ar²及Ar³的對應位置。Other preferred blue fluorescent emitters are hydrocarbons of formula (1) as disclosed in WO 2010/012328 A1. wherein the following applies to the symbols and reference numerals used: Ar¹ , Ar² , Ar³ are, at each occurrence, identical or different, an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R¹ , provided that Ar² does not represent anthracene, fused tetraphenyl or fused pentphenyl; X is, at each occurrence, identical or different, a radical selected from the group consisting of BR² , C(R² )₂ , Si(R² )₂ , C═O, C═NR² , C═C(R² )₂ , O, S, S═O, SO₂ , NR² , PR² , P(═O)R² and P(═S)R² ; R¹ , R² are, at each occurrence, identical or different, H; D; F; Cl; Br; I; N(Ar⁴ )₂ ; C(═O)Ar⁴ ; P(═O)(Ar⁴ )₂ ; S(═O)Ar⁴ ; S(═O)₂ Ar⁴ ; CR² ═CR² Ar⁴ ; CHO; CR³ ═C(R³ )₂ ; CN; NO₂ ; Si(R³ )₃ ; B(OR³ )₂ ; B(R³ )₂ ; B(N(R³ )₂ )₂ ; OSO₂ R³ ; a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted with one or more radicals R³ , wherein in each case one or more non-adjacent CH₂ groups may be replaced by R³ C═CR³ , C≡C, Si(R³ )₂ , Ge(R³ )₂ , Sn(R³ )₂ , C═O, C═S, C═Se, C═NR³ , P(═O)R³ , SO, SO₂ , NR³ , O, S or CONR³ , and wherein one or more H atoms may be replaced by F, Cl, Br, I, CN or NO₂ ; or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R³ in each case; or a combination of these systems; two or more substituents R¹ or R 3² here can also form a monocyclic or polycyclic aliphatic or aromatic ring system with each other; R³ is H, D or an aliphatic or aromatic alkyl radical having 1 to 20 C atoms at each occurrence, identically or differently; Ar⁴ is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms at each occurrence, identically or differently, which may be substituted by one or more non-aromatic radicals R¹ ; two radicals Ar on the same nitrogen or phosphorus atom can also be linked to each other via a single bond or a bridge X; m, n are 0 or 1, with the prerequisite that m + n = 1; p is 1, 2, 3, 4, 5 or 6; Ar 1, Ar² and X together form a five-membered ring or a six-membered ring, and Ar² , Ar³ and X are substituted by one or more non-aromatic radicals R 1.³ and X together form a five-membered ring or a six-membered ring, the prerequisite being that either all symbols X in the compound of formula (1) are bonded to a five-membered ring or all symbols X in the compound of formula (1) are bonded to a six-membered ring; the characteristic being that if p=1, the sum of all π electrons in the groups Ar¹ , Ar² and Ar³ is at least 28; if p=2, it is at least 34; if p=3, it is at least 40; if p=4, it is at least 46; if p=5, it is at least 52; and if p=6, it is at least 58; n=0 or m=0 here means that the corresponding group X does not exist, but instead hydrogen or a substituent R¹ is bonded to the corresponding position of Ar² and Ar³ .

其他較佳的藍色螢光發射體係如WO 2014/111269 A2中所揭示之下式(2)之烴。其中： Ar¹在每次出現時相同或不同地係具有6至18個芳族環原子之芳基或雜芳基，其可經一或多個基團R¹取代； Ar²在每次出現時相同或不同地係具有6個芳族環原子之芳基或雜芳基，其可經一或多個基團R²取代； X¹在每次出現時相同或不同地係BR³、C(R³)₂、-C(R³)₂-C(R³)₂-、-C(R³)₂-O-、-C(R³)₂-S-、 -R³C=CR³-、-R³C=N-、Si(R³)₂、-Si(R³)₂-Si(R³)₂-、C=O、O、S、S=O、SO₂、NR³、PR³或P(=O)R³； R¹、R²、R³在每次出現時相同或不同地係H；D；F；Cl；Br；I；C(=O)R⁴；CN；Si(R⁴)₃；N(R⁴)₂；P(=O)(R⁴)₂；OR⁴；S(=O)R⁴；S(=O)₂R⁴；具有1至20個C原子之直鏈烷基或烷氧基或具有3至20個C原子之支鏈或環狀烷基或烷氧基或具有2至20個C原子之烯基或炔基，其中上述基團可各自經一或多個基團R⁴取代，並且其中上述基團中之一或多個CH₂基團可經-R⁴C=CR⁴-、-C≡C-、Si(R⁴)₂、C=O、C=NR⁴、-C(=O)O-、-C(=O)NR⁴-、NR⁴、P(=O)(R⁴)、-O-、-S-、SO或SO₂置換；或具有5至30個芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R⁴取代，其中二或更多個基團R³可彼此連接且可形成環； R⁴在每次出現時相同或不同地係H；D；F；Cl；Br；I；C(=O)R⁵；CN；Si(R⁵)₃；N(R⁵)₂；P(=O)(R⁵)₂；OR⁵；S(=O)R⁵；S(=O)₂R⁵；具有1至20個C原子之直鏈烷基或烷氧基或具有3至20個C原子之支鏈或環狀烷基或烷氧基或具有2至20個C原子之烯基或炔基，其中上述基團可各自經一或多個基團R⁵取代，並且其中上述基團中之一或多個CH₂基團可經-R⁵C=CR⁵-、-C≡C-、Si(R⁵)₂、C=O、C=NR⁵、-C(=O)O-、-C(=O)NR⁵-、NR⁵、P(=O)(R⁵)、-O-、-S-、SO或SO₂置換；或具有5至30個芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R⁵取代，其中二或更多個基團R⁴可彼此連接且可形成環； R⁵在每次出現時相同或不同地係H、D、F或具有1至20個C原子之脂族、芳族或雜芳族有機基團，此外，其中一或多個H原子可經D或F置換；二或更多個取代基R⁵在此可彼此連接且可以形成環； 其中二個基團Ar¹中之至少一者必須含有10或更多個芳族環原子；及 其中，如果二個基團Ar¹中之一者係苯基，則二個基團Ar¹中之另一者必須不含有多於14個芳族環原子。Other preferred blue fluorescent emitters are hydrocarbons of formula (2) as disclosed in WO 2014/111269 A2. wherein: Ar¹ is, at each occurrence, identical or different, an aryl or heteroaryl group having 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R¹ ; Ar² is, at each occurrence, identical or different, an aryl or heteroaryl group having 6 aromatic ring atoms, which may be substituted by one or more radicals R² ; X¹ is, at each occurrence, identical or different, BR³ , C(R³ )₂ , -C(R³ )₂ -C(R³ )₂ -, -C(R³ )₂ -O-, -C(R³ )₂ -S-, -R³ C═CR³ -, -R³ C═N-, Si(R³ )₂ , -Si(R³ )₂ -Si(R³ )₂ -, C═O, O, S, S═O, SO₂ , NR³ , PR³ or P(═O)R³ ; R¹ , R² , R³ are, at each occurrence, identically or differently, H; D; F; Cl; Br; I; C(═O)R⁴ ; CN; Si(R⁴ )₃ ; N(R⁴ )₂ ; P(═O)(R⁴ )₂ ; OR⁴ ; S(═O)R⁴ ; S(═O)₂ R⁴ ; a linear alkyl or alkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, or an alkenyl or alkynyl group having 2 to 20 C atoms, wherein the above groups may each be substituted by one or more groups R⁴ , and wherein one or more CH₂ groups in the above groups may be substituted by -R⁴ C═CR⁴ -, -C≡C-, Si(R⁴ )₂ , C=O, C=NR⁴ , -C(=O)O-, -C(=O)NR⁴ -, NR⁴ , P(=O)(R⁴ ), -O-, -S-, SO or SO₂ ; or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which in each case may be substituted by one or more radicals R⁴ , wherein two or more radicals R³ may be linked to one another and may form a ring; R⁴ is, identically or differently on each occurrence, H; D; F; Cl; Br; I; C(=O)R⁵ ; CN; Si(R⁵ )₃ ; N(R⁵ )₂ ; P(=O)(R⁵ )₂ ; OR⁵ ; S(=O)R⁵ ; S(=O)₂ R⁵ ; linear alkyl or alkoxy having 1 to 20 C atoms or branched or cyclic alkyl or alkoxy having 3 to 20 C atoms or alkenyl or alkynyl having 2 to 20 C atoms, wherein the aforementioned radicals may each be substituted by one or more radicals R⁵ and wherein one or more CH₂ radicals in the aforementioned radicals may be replaced by -R⁵ C═CR⁵ -, -C≡C-, Si(R⁵ )₂ , C═O, C═NR⁵ , -C(═O)O-, -C(═O)NR⁵ -, NR⁵ , P(═O)(R⁵ ), -O-, -S-, SO or SO₂ ; or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which in each case may be substituted by one or more radicals R⁵ , wherein two or more radicals R 5⁴ can be linked to each other and can form a ring; R⁵ is H, D, F or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 C atoms, the same or different at each occurrence, and one or more H atoms can be replaced by D or F; two or more substituents R⁵ here can be linked to each other and can form a ring; at least one of the two groups Ar¹ must contain 10 or more aromatic ring atoms; and if one of the two groups Ar¹ is phenyl, the other of the two groups Ar¹ must not contain more than 14 aromatic ring atoms.

其他較佳的藍色螢光發射體係如PCT/ EP2017/066712中所揭示之下式(3)之烴。其中下列適用於所使用的符號及標號： Ar¹在每次出現時相同或不同地代表具有6至18個芳族環原子之芳基或雜芳基，其在各情況下可經一或多個基團R¹取代，其中式(1)中之基團Ar¹中之至少一者具有10或更多個芳族環原子； Ar²在每次出現時相同或不同地代表具有6個芳族環原子之芳基或雜芳基，其在各情況下可經一或多個基團R¹取代； Ar³、Ar⁴在每次出現時相同或不同地代表具有5至25個芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R¹取代； E在每次出現時相同或不同地選自-BR⁰-、-C(R⁰)₂-、 -C(R⁰)₂-C(R⁰)₂-、-C(R⁰)₂-O-、-C(R⁰)₂-S-、-R⁰C=CR⁰-、 -R⁰C=N-、Si(R⁰)₂、-Si(R⁰)₂-Si(R⁰)₂-、-C(=O)-、 -C(=NR⁰)-、-C(=C(R⁰)₂)-、-O-、-S-、-S(=O)-、-SO₂-、 -N(R⁰)-、-P(R⁰)-及-P((=O)R⁰)-，且二個基團E相對於彼此可呈順式或反式位置； R⁰、R¹在每次出現時相同或不同地代表H；D；F；Cl；Br；I；CHO；CN；N(Ar⁵)₂；C(=O)Ar⁵；P(=O)(Ar⁵)₂；S(=O)Ar⁵；S(=O)₂Ar⁵；NO₂；Si(R²)₃；B(OR²)₂；OSO₂R²；具有1至40個C原子之直鏈烷基、烷氧基或硫代烷氧基(thioalkyl)或具有3至40個C原子的支鏈或環狀烷基、烷氧基或硫代烷氧基，其各者可經一或多個基團R²取代，其中在各情況下一或多個非相鄰的CH₂基團可經R²C=CR²、C≡C、Si(R²)₂、Ge(R²)₂、Sn(R²)₂、C=O、C=S、C=Se、P(=O)(R²)、SO、SO₂、O、S或CONR²置換，且其中一或多個H原子可經D、F、Cl、Br、I、CN或NO₂置換；具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R²取代；或具有5至40個芳族環原子之芳氧基，其可經一或多個基團R²取代，其中二個相鄰的取代基R⁰及/或二個相鄰的取代基R¹可形成單環或多環脂族環系統或芳族環系統，其可經一或多個基團R²取代； R²在每次出現時相同或不同地代表H；D；F；Cl；Br；I；CHO；CN；N(Ar⁵)₂；C(=O)Ar⁵；P(=O)(Ar⁵)₂；S(=O)Ar⁵；S(=O)₂Ar⁵；NO₂；Si(R³)₃；B(OR³)₂；OSO₂R³；具有1至40個C原子之直鏈烷基、烷氧基或硫代烷氧基或具有3至40個C原子之支鏈或環狀烷基、烷氧基或硫代烷氧基，其各者可經一或多個基團R³取代，其中在各情況下一或多個非相鄰的CH₂基團可經R³C=CR³、C≡C、Si(R³)₂、Ge(R³)₂、Sn(R³)₂、C=O、C=S、C=Se、P(=O)(R³)、SO、SO₂、O、S或CONR³置換，且其中一或多個H原子可經D、F、Cl、Br、I、CN或NO₂置換；具有5至60個芳族環原子之芳族或雜芳族環系統，其在各情況下可經一或多個基團R³取代；或具有5至60個芳族環原子之芳氧基，其可經一或多個基團R³取代，其中二個相鄰的取代基R²可形成單環或多環脂族環系統或芳族環系統，其可經一或多個基團R³取代； R³在每次出現時相同或不同地代表H；D；F；Cl；Br；I；CN；具有1至20個C原子之直鏈烷基、烷氧基或硫代烷氧基或具有3至20個C原子之支鏈或環狀烷基、烷氧基或硫代烷氧基，其中在各情況下一或多個非相鄰的CH₂基團可經SO、SO₂、O、S置換，且其中一或多個H原子可經D、F、Cl、Br或I置換；或具有5至24個C原子之芳族或雜芳族環系統； Ar⁵係具有5至24個芳族環原子、較佳係5至18個芳族環原子之芳族或雜芳族環系統，且在各情況下亦可經一或多個基團R³取代； n係1至20之整數； 其中如果n等於1且基團Ar³或Ar⁴中之至少一者代表苯基，則式(1)之化合物帶有至少一個基團R⁰或R¹，其代表具有2至40個C原子之直鏈烷基或具有3至40個C原子之支鏈或環狀烷基，其各者可經一或多個基團R²取代。Other preferred blue fluorescent emitters are hydrocarbons of formula (3) as disclosed in PCT/EP2017/066712. wherein the following applies to the symbols and indices used: Ar¹ represents, at each occurrence, identically or differently, an aryl or heteroaryl group having 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R¹ , wherein at least one of the radicals Ar¹ in formula (1) has 10 or more aromatic ring atoms; Ar² represents, at each occurrence, identically or differently, an aryl or heteroaryl group having 6 aromatic ring atoms, which may in each case be substituted by one or more radicals R¹ ; Ar³ and Ar⁴ represent, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, which may in each case be substituted by one or more radicals R¹ ; E is, at each occurrence, identically or differently, selected from -BR⁰ -, -C(R⁰ )₂ -, -C(R⁰ )₂ -C(R⁰ )₂ -、-C(R⁰ )₂ -O-、-C(R⁰ )₂ -S-、-R⁰ C=CR⁰ -、 -R⁰ C=N-、Si(R⁰ )₂ 、-Si(R⁰ )₂ -Si(R⁰ )₂ -、-C(=O)-、 -C(=NR⁰ )-、-C(=C(R⁰ )₂ )-、-O-、-S-、-S(=O)-、-SO₂ -、 -N(R⁰ )-、-P(R⁰ )-and -P((=O)R⁰ )-, and the two groups E may be in the cis or trans position relative to each other; R⁰ , R¹ represents, identically or differently on each occurrence, H; D; F; Cl; Br; I; CHO; CN; N(Ar⁵ )₂ ; C(═O)Ar⁵ ; P(═O)(Ar⁵ )₂ ; S(═O)Ar⁵ ; S(═O)₂ Ar⁵ ; NO₂ ; Si(R² )₃ ; B(OR² )₂ ; OSO₂ R² ; linear alkyl, alkoxy or thioalkoxy radicals having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkoxy radicals having 3 to 40 C atoms, each of which may be substituted by one or more radicals R² , wherein in each case one or more non-adjacent CH₂ radicals may be substituted by R² C═CR² , C≡C, Si(R² )₂ , Ge(R² )₂ , Sn(R² )₂ , C═O, C═S, C═Se, P(═O)(R² ), SO, SO₂ , O, S or CONR² , and one or more H atoms thereof may be replaced by D, F, Cl, Br, I, CN or NO₂ ; an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted in each case by one or more radicals R² ; or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R² , wherein two adjacent substituents R⁰ and/or two adjacent substituents R¹ may form a monocyclic or polycyclic aliphatic ring system or an aromatic ring system, which may be substituted by one or more radicals R² ; R² represents, identically or differently on each occurrence, H; D; F; Cl; Br; I; CHO; CN; N(Ar⁵ )₂ ; C(═O)Ar⁵ ; P(═O)(Ar⁵ )₂ ; S(═O)Ar⁵ ; S(═O)₂ Ar⁵ ; NO₂ ; Si(R³ )₃ ; B(OR³ )₂ ; OSO₂ R³ ; a linear alkyl, alkoxy or thioalkoxy radical having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 40 C atoms, each of which may be substituted by one or more radicals R³ , wherein in each case one or more non-adjacent CH₂ radicals may be substituted by R³ C═CR³ , C≡C, Si(R³ )₂ , Ge(R³ )₂ , Sn(R³ )₂ , C═O, C═S, C═Se, P(═O)(R³ ), SO, SO₂ , O, S or CONR³ substituted, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂ ; an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R³ in each case; or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R³ , wherein two adjacent substituents R² may form a monocyclic or polycyclic aliphatic ring system or an aromatic ring system, which may be substituted by one or more radicals R³ ; R³ represents, identically or differently on each occurrence, H; D; F; Cl; Br; I; CN; a linear alkyl, alkoxy or thioalkoxy radical having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 20 C atoms, wherein in each case one or more non-adjacent CH₂ radicals may be replaced by SO, SO₂ , O, S and wherein one or more H atoms may be replaced by D, F, Cl, Br or I; or an aromatic or heteroaromatic ring system having 5 to 24 C atoms; Ar⁵ is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, preferably 5 to 18 aromatic ring atoms, and in each case may also be substituted by one or more radicals R³ ; n is an integer from 1 to 20; Wherein if n is equal to 1 and at least one of the groups Ar³ or Ar⁴ represents a phenyl group, the compound of formula (1) carries at least one group R⁰ or R¹ representing a linear alkyl group having 2 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which may be substituted by one or more groups R² .

其他較佳的螢光發射體係如揭示於以下之含硼-氮結構，例如WO 2015/102118、CN108409769、CN107266484、WO2017195669、US2018069182，以及WO 2020/208051、WO2021/058406、及WO 2021/094269。這些結構之實例描繪於下表中：Other preferred fluorescent emitters are boron-nitrogen containing structures as disclosed in WO 2015/102118, CN108409769, CN107266484, WO2017195669, US2018069182, and WO 2020/208051, WO2021/058406, and WO 2021/094269. Examples of these structures are described in the following table:

可當作磷光發射體之較佳化合物藉由舉實例之方式描述於下文中。Preferred compounds that can serve as phosphorescent emitters are described below by way of example.

磷光發射體之實例由以下所揭示：WO 00/70655、WO 01/41512、WO 02/02714、WO 02/15645、EP 1191613、EP 1191612、EP 1191614及WO 2005/033244。通常，根據先前技術用於磷光OLED且為有機電致發光所屬技術領域中具有通常知識者已知的所有磷光錯合物皆適合，且所屬技術領域中具有通常知識者將能夠在無進步性的情況下使用其他磷光錯合物。Examples of phosphorescent emitters are disclosed by WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP 1191613, EP 1191612, EP 1191614 and WO 2005/033244. Generally, all phosphorescent complexes which are used in phosphorescent OLEDs according to the prior art and are known to the person skilled in the art for organic electroluminescence are suitable, and the person skilled in the art will be able to use other phosphorescent complexes without further development.

磷光金屬錯合物較佳地含有Ir、Ru、Pd、Pt、Os或Re，更佳地Ir。The phosphorescent metal complex preferably contains Ir, Ru, Pd, Pt, Os or Re, more preferably Ir.

較佳的配位基係2‑苯基吡啶衍生物、7,8-苯并喹啉衍生物、2-(2-噻吩基)吡啶衍生物、2-(1-萘基)吡啶衍生物、1-苯基異喹啉衍生物、3-苯基異喹啉衍生物或2-苯基喹啉衍生物。所有這些化合物皆可經例如經氟、氰基及/或三氟甲基取代基取代而用於藍光。輔助配位基較佳地係乙醯丙酮或吡啶甲酸。Preferred ligands are 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2-(2-thienyl)pyridine derivatives, 2-(1-naphthyl)pyridine derivatives, 1-phenylisoquinoline derivatives, 3-phenylisoquinoline derivatives or 2-phenylquinoline derivatives. All of these compounds can be substituted, for example, with fluorine, cyano and/or trifluoromethyl substituents for use in blue light. The auxiliary ligand is preferably acetylacetone or picolinic acid.

特別地，Pt或Pd與式EM-16之四牙配位基的錯合物係合適的。In particular, complexes of Pt or Pd with a tetradentate ligand of formula EM-16 are suitable.

式EM-16之化合物更詳細地描述於US 2007/0087219 A1中，其中，為了解釋上式中的取代基及標號，出於揭露目的本說明書引用之。此外，具有擴大的環系統之Pt-卟啉錯合物(US 2009/0061681 A1)及Ir錯合物，例如2,3,7,8,12,13,17,18-八乙基-21H, 23H-卟啉-Pt(II)、四苯基-Pt(II)四苯并卟啉(US 2009/0061681 A1)、順式-雙(2-苯基吡啶基-N,C²')Pt(II)、順式-雙(2-(2'-噻吩基)吡啶基-N,C³')Pt(II)、順式-雙(2-(2'-噻吩基)喹啉基-N,C⁵')Pt(II)、(2-(4,6-二氟苯基)吡啶基-N,C²')Pt(II)(乙醯丙酮)、或參(2-苯基吡啶基-N,C²')Ir(III)(=Ir(ppy)₃，綠色)、雙(2-苯基吡啶基-N,C²)Ir(III)(乙醯丙酮)(=Ir(ppy)₂乙醯丙酮，綠色，US 2001/0053462 A1，Baldo, Thompson et al.Nature403,(2000), 750-753)、雙(1-苯基異喹啉基-N,C²')(2-苯基吡啶基-N,C²')銥(III)、雙(2-苯基吡啶基-N,C²')(1-苯基異喹啉基-N,C²')銥(III)、雙(2-(2'-苯并噻吩基)吡啶基-N,C³')銥(III)(乙醯丙酮)、雙(2-(4',6'-)二氟苯基)吡啶基-N,C²')銥(III)(吡啶甲酸)(FIrpic，藍色)、雙(2-(4',6'-二氟苯基)吡啶基-N,C²')Ir(III)(肆(1-吡唑基)硼酸酯)、參(2-(聯苯-3-基)-4-三級丁基吡啶)銥(III)、(ppz)₂Ir(5phdpym)(US 2009/ 0061681 A1)、(45ooppz)₂Ir(5phdpym)(US 2009/0061681 A1)、2‑苯基吡啶-Ir錯合物的衍生物，諸如例如PQIr(=雙(2-苯基喹啉基-N,C²')乙醯丙酮銥(III))、參(2-苯基異喹啉基) -N,C)Ir(III)(紅色)、雙(2-(2'-苯并[4,5-a]噻吩基)吡啶基-N,C³)Ir(乙醯丙酮)([Btp₂Ir(acac)]，紅色，Adachi et al.Appl. Phys. Lett. 78(2001), 1622-1624)。The compound of formula EM-16 is described in more detail in US 2007/0087219 A1, wherein the substituents and numbers in the above formula are cited in this specification for disclosure purposes. In addition, Pt-porphyrin complexes with expanded ring systems (US 2009/0061681 A1) and Ir complexes, such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin-Pt(II), tetraphenyl-Pt(II)tetrabenzoporphyrin (US 2009/0061681 A1), cis-bis(2-phenylpyridinyl-N,C² ′)Pt(II), cis-bis(2-(2′-thienyl)pyridinyl-N,C³ ′)Pt(II), cis-bis(2-(2′-thienyl)quinolyl-N,C⁵ ′)Pt(II), (2-(4,6-difluorophenyl)pyridinyl-N,C² ')Pt(II)(acetylacetone), or tris(2-phenylpyridinyl-N,C² ')Ir(III)(=Ir(ppy)₃ , green), bis(2-phenylpyridinyl-N,C² )Ir(III)(acetylacetone)(=Ir(ppy)_{2acetylacetone} , green, US 2001/0053462 A1, Baldo, Thompson et al.Nature 403, (2000), 750-753), bis(1-phenylisoquinolyl-N,C² ')(2-phenylpyridinyl-N,C² ')irium(III), bis(2-phenylpyridinyl-N,C² ')(1-phenylisoquinolyl-N,C² ') iridium (III), bis (2-(2'-benzothienyl) pyridinyl-N, C³ ') iridium (III) (acetylacetone), bis (2-(4',6'-) difluorophenyl) pyridinyl-N, C² ') iridium (III) (picolinic acid) (FIrpic, blue), bis (2-(4',6'-difluorophenyl) pyridinyl-N, C² ') Ir (III) (tetrakis (1-pyrazolyl) borate), tris (2-(biphenyl-3-yl)-4-tert-butylpyridinium) iridium (III), (ppz)₂ Ir (5phdpym) (US 2009/ 0061681 A1), (45ooppz)₂ Ir (5phdpym) (US 2009/0061681 A1), derivatives of 2-phenylpyridine-Ir complexes, such as, for example, PQIr (=bis(2-phenylquinolyl-N,C² ')acetylacetonitrile(III)), tris(2-phenylisoquinolyl)-N,C)Ir(III) (red), bis(2-(2'-benzo[4,5-a]thienyl)pyridinyl-N,C³ )Ir(acetylacetonate) ([Btp₂ Ir(acac)], red, Adachi et al.Appl. Phys. Lett . 78(2001), 1622-1624).

同樣合適的係三價鑭系元素的錯合物，諸如例如Tb³⁺及Eu³⁺(J. Kido et al.Appl. Phys. Lett. 65(1994), 2124、Kido et al. Chem. Lett. 657, 1990、US 2007/0252517 A1)、或Pt(II)、Ir(I)、Rh(I)與馬來腈二硫根(maleonitrile dithiolate)之磷光錯合物(Johnson et al.,JACS105, 1983, 1795)、Re(I)三羰基-二亞胺錯合物(尤其是Wrighton,JACS96, 1974, 998)、具有氰基配位基及聯吡啶或啡啉配位基的Os(II)錯合物(Ma et al.,Synth.Metals94, 1998, 245)。Also suitable are complexes of trivalent iodine elements, such as, for example, Tb³⁺ and Eu³⁺ (J. Kido et al.Appl. Phys. Lett . 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1), or phosphorescent complexes of Pt(II), Ir(I), Rh(I) and maleonitrile dithiolate (Johnson et al.,JACS 105, 1983, 1795), Re(I) tricarbonyl-diimine complexes (especially Wrighton,JACS 96, 1974, 998), Os(II) complexes with cyano ligands and bipyridine or phenanthroline ligands (Ma et al.,Synth. Metals 94, 1998, 245).

具有三牙配位基之其他磷光發射體描述於US 6824895及US 10/729238中。發紅光的磷光錯合物發現於US 6835469及US 6830828中。Other phosphorescent emitters with tridentate ligands are described in US 6824895 and US 10/729238. Red-emitting phosphorescent complexes were found in US 6835469 and US 6830828.

用作磷光摻雜劑之特佳的化合物尤其是式EM-17之化合物，尤其描述於US 2001/0053462 A1及Inorg. Chem.2001, 40(7), 1704-1711, JACS 2001, 123(18), 4304-4312中，及其衍生物。Particularly preferred compounds for use as phosphorescent dopants are compounds of the formula EM-17, described inter alia in US 2001/0053462 A1 andInorg. Chem. 2001, 40(7), 1704-1711, JACS 2001, 123(18), 4304-4312, and derivatives thereof.

衍生物描述於US 7378162 B2、US 6835469 B2及JP 2003/253145 A中。Derivatives are described in US 7378162 B2, US 6835469 B2 and JP 2003/253145 A.

此外，描述於US 7238437 B2、US 2009/008607 A1及EP 1348711中之式EM-18至EM-21之化合物、及其衍生物可用作發射體。Furthermore, compounds of formulae EM-18 to EM-21 described in US 7238437 B2, US 2009/008607 A1 and EP 1348711, and derivatives thereof can be used as emitters.

可用作磷光發射體之較佳化合物顯示於下表中：Preferred compounds that can be used as phosphorescent emitters are shown in the following table:

量子點同樣可用作發射體，這些材料詳細揭示於WO 2011/076314 A1中。Quantum dots can also be used as emitters, and these materials are disclosed in detail in WO 2011/076314 A1.

用作主體材料之化合物，特別是與發光化合物一起使用的化合物，包括來自各種類別的物質之材料。Compounds used as host materials, especially compounds used with light-emitting compounds, include materials from various classes of matter.

主體材料通常比所使用的發射體材料具有更大的HOMO與LUMO之間的帶隙。此外，較佳的主體材料展現出電洞傳輸材料或電子傳輸材料的性質。此外，主體材料可同時具有電子傳輸性質及電洞傳輸性質。The host material generally has a larger band gap between the HOMO and LUMO than the emitter material used. In addition, preferred host materials exhibit properties of hole transport materials or electron transport materials. In addition, the host material can have both electron transport properties and hole transport properties.

主體材料在某些情況下亦稱為基質材料，特別係如果主體材料與OLED中之磷光發射體組合使用時。The host material is also referred to as a matrix material in some cases, especially if the host material is used in combination with a phosphorescent emitter in an OLED.

較佳的主體材料或共主體材料，特別是與螢光摻雜劑一起使用，係選自以下類別：寡聚伸芳基類(例如根據EP 676461之2,2',7,7'-四苯基螺聯茀或二萘基蒽)，特別是含有縮合芳族基團之寡聚伸芳基，諸如例如蒽、苯并蒽、苯并菲(DE 10 2009 005746、WO 2009/069566)、菲、稠四苯、蔻(coronene)、、茀、螺聯茀、苝、酞苝(phthaloperylene)、萘并苝(naphthaloperylene)、十環烯、紅螢烯；寡聚伸芳基伸乙烯基類(例如根據EP 676461之DPVBi=4,4'-雙(2,2-二苯基乙烯基)-1,1'-聯苯或螺-DPVBi)；多足金屬錯合物類(例如根據WO 04/081017)，特別是8-羥基喹啉之金屬錯合物，例如AlQ₃(=參(8-羥基喹啉基)鋁(III))或雙(2-甲基-8-羥基喹啉基)-4-(苯基苯酚基)鋁，亦與下列者一起使用：咪唑螯合物(US 2007/0092753 A1)及喹啉-金屬錯合物；胺基喹啉-金屬錯合物；苯并喹啉-金屬錯合物；電洞傳導化合物(例如根據WO 2004/058911)；電子傳導化合物，特別是酮、氧化膦、亞碸等(例如根據WO 2005/084081及WO 2005/084082)；阻轉異構體(例如根據WO 2006/048268)；有機硼酸衍生物(例如根據WO 2006/117052)或苯并蒽(例如根據WO 2008/ 145239)。Preferred host materials or co-host materials, in particular for use with fluorescent dopants, are selected from the following classes: oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobiphenylfluorene or dinaphthylanthracene according to EP 676461), in particular oligoarylenes containing condensed aromatic groups, such as anthracene, benzanthracene, triphenylene (DE 10 2009 005746, WO 2009/069566), phenanthrene, tetraphenylene, coronene, , fluorene, spirobifluorene, perylene, phthaloperylene, naphthaloperylene, decacyclic fluorene; oligoarylene vinylenes (e.g. DPVBi=4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl according to EP 676461 or spiro-DPVBi); polypodal metal complexes (e.g. according to WO 04/081017), in particular metal complexes of 8-hydroxyquinoline, such as AlQ₃ (=tris(8-hydroxyquinolyl)aluminum(III)) or bis(2-methyl-8-hydroxyquinolyl)-4-(phenylphenolyl)aluminum, also with the following: imidazole chelates (US 2007/0092753 A1) and quinoline-metal complexes; aminoquinoline-metal complexes; benzoquinoline-metal complexes; hole-conducting compounds (for example according to WO 2004/058911); electron-conducting compounds, in particular ketones, phosphine oxides, sulfones, etc. (for example according to WO 2005/084081 and WO 2005/084082); atropisomers (for example according to WO 2006/048268); organic boronic acid derivatives (for example according to WO 2006/117052) or benzanthracene (for example according to WO 2008/145239).

可當作主體材料或共主體材料之特佳的化合物係選自寡聚伸芳基類，包含蒽、苯并蒽及/或芘，或這些化合物的阻轉異構物。在本發明的意義上，寡聚伸芳基旨在用來意指至少三個芳基或伸芳基基團彼此鍵結之化合物。Particularly preferred compounds that can be used as host materials or co-host materials are selected from oligoarylene groups, including anthracene, benzanthracene and/or pyrene, or atropisomers of these compounds. In the sense of the present invention, oligoarylene is intended to mean a compound having at least three aryl or arylene groups bonded to each other.

較佳的主體材料係特別選自式(H-1)之化合物其中Ar⁴、Ar⁵、Ar⁶在每次出現時相同或不同地係具有5至30個芳族環原子之芳基或雜芳基，其可隨意地經取代，並且p表示在1至5之範圍內的整數；如果p=1，Ar⁴、Ar⁵及Ar⁶中的π電子總和係至少30；如果p=2，則係至少36；且如果p=3，則係至少42。The preferred host material is a compound of formula (H-1): wherein Ar⁴ , Ar⁵ , Ar⁶ are identically or differently each time present an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which may be optionally substituted, and p represents an integer in the range of 1 to 5; if p=1, the sum of the π electrons in Ar⁴ , Ar⁵ and Ar⁶ is at least 30; if p=2, it is at least 36; and if p=3, it is at least 42.

在式(H-1)之化合物中，基團Ar⁵特佳地代表蒽，且基團Ar⁴及Ar⁶在9-位及10-位鍵結，其中這些基團可隨意地經取代。非常特佳地，基團Ar⁴及/或Ar⁶中之至少一者係選自下列者之縮合芳基：1-或2-萘基；2-、3-或9-菲基；或2-、3-、4-、5-、6-或7-苯并蒽基。蒽系化合物係描述於US 2007/0092753 A1及US 2007/0252517 A1中，例如2-(4-甲基苯基)-9,10-二-(2-萘基)蒽、9-(2-萘基)-10-(1,1'-聯苯)蒽及9,10-雙[4-(2,2-二苯基乙烯基)苯基]蒽、9,10-二苯基蒽、9,10-雙(苯基乙炔基)蒽及1,4-雙(9'-乙炔基蒽基)苯。亦較佳者係含有二個蒽單元之化合物(US 2008/0193796 A1)，例如10,10'-雙[1,1',4',1"]聯三苯-2-基-9,9'-雙蒽基。In the compound of formula (H-1), the group Ar⁵ particularly preferably represents anthracene, and the groups Ar⁴ and Ar⁶ are bonded at the 9-position and 10-position, wherein these groups may be substituted at will. Very particularly preferably, at least one of the groups Ar⁴ and/or Ar⁶ is a condensed aryl group selected from the following: 1- or 2-naphthyl; 2-, 3- or 9-phenanthrenyl; or 2-, 3-, 4-, 5-, 6- or 7-benzanthryl. Anthracene compounds are described in US 2007/0092753 A1 and US 2007/0252517 A1, such as 2-(4-methylphenyl)-9,10-di-(2-naphthyl)anthracene, 9-(2-naphthyl)-10-(1,1'-biphenyl)anthracene and 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene, 9,10-diphenylanthracene, 9,10-bis(phenylethynyl)anthracene and 1,4-bis(9'-ethynylanthryl)benzene. Also preferred are compounds containing two anthracene units (US 2008/0193796 A1), such as 10,10'-bis[1,1',4',1"]terphenyl-2-yl-9,9'-dianthracene.

其他較佳的化合物係下列者的衍生物：芳基胺、苯乙烯基胺、螢光素、二苯基丁二烯、四苯基丁二烯、環戊二烯、四苯基環戊二烯、五苯基環戊二烯、香豆素、㗁二唑、雙苯并㗁唑啉、㗁唑、吡啶、吡、亞胺、苯并噻唑、苯并㗁唑、苯并咪唑(US 2007/0092753 A1)，例如2,2',2"-(1,3,5-伸苯基)參[1-苯基-1H-苯并咪唑]、醛(aldazine)、二苯乙烯、苯乙烯基伸芳基衍生物，例如9,10-雙[4-(2,2-二苯基乙烯基)苯基]蒽、及二苯乙烯基伸芳基衍生物(US 5121029)、二苯基乙烯、乙烯基蒽、二胺基咔唑、哌喃、噻喃、二酮吡咯并吡咯、聚次甲基、肉桂酸酯及螢光染料。Other preferred compounds are derivatives of arylamines, styrylamines, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarin, oxadiazole, bisbenzoxazolin, oxazole, pyridine, pyridine, , imines, benzothiazoles, benzoxazoles, benzimidazoles (US 2007/0092753 A1), such as 2,2',2"-(1,3,5-phenylene)tris[1-phenyl-1H-benzimidazole], aldehydes (aldazine), distilbenes, styryl arylene derivatives, such as 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene, and distyryl arylene derivatives (US 5121029), diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, diketopyrrolopyrrole, polymethine, cinnamate and fluorescent dyes.

特佳者係芳基胺及苯乙烯基胺的衍生物，例如TNB(=4,4'-雙[N-(1-萘基)-N-(2-萘基)胺基]聯苯)。金屬-類奧辛錯合物，諸如LiQ或AlQ₃，可用作共主體。Particularly preferred are derivatives of arylamines and styrylamines, such as TNB (=4,4'-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl). Metal-oxine complexes, such as LiQ or_AlQ3 , can be used as co-hosts.

具有寡聚伸芳基為基質之較佳的化合物係揭示於US 2003/0027016 A1、US 7326371 B2、US 2006/ 043858 A、WO 2007/114358、WO 2008/145239、JP 3148176 B2、EP 1009044、US 2004/018383、WO 2005/ 061656 A1、EP 0681019B1、WO 2004/013073A1、US 5077142、WO 2007/065678及DE 102009005746中，其中特佳的化合物係由式H-2至H-8所描述。Preferred compounds having oligoarylene groups as the matrix are disclosed in US 2003/0027016 A1, US 7326371 B2, US 2006/043858 A, WO 2007/114358, WO 2008/145239, JP 3148176 B2, EP 1009044, US 2004/018383, WO 2005/061656 A1, EP 0681019B1, WO 2004/013073A1, US 5077142, WO 2007/065678 and DE 102009005746, wherein particularly preferred compounds are described by formula H-2 to H-8.

此外，可用作主體或基質之化合物包括與磷光發射體一起使用的材料。In addition, compounds that can be used as a host or matrix include materials used together with phosphorescent emitters.

這些化合物，其亦可用作聚合物中的結構元件，包括CBP(N,N-雙咔唑基聯苯)、咔唑衍生物(例如根據WO 2005/039246、US 2005/0069729、JP 2004/288381、EP 1205527或WO 2008/086851)、氮雜咔唑(例如根據EP 1617710、EP 1617711、EP 1731584或JP 2005/347160)、酮(例如根據WO 2004/093207或根據DE 102008033943)、氧化膦、亞碸及碸(例如根據WO 2005/003253)、寡聚伸苯基、芳族胺(例如根據US 2005/0069729)、雙極性基質材料(例如根據WO 2007/137725)、矽烷(例如根據WO 2005/111172)、9,9-二芳基茀衍生物(例如根據DE 102008017591)、氮雜硼雜環戊二烯或硼酸酯(例如根據WO 2006/117052)、三衍生物(例如根據DE 102008036982)、吲哚并咔唑衍生物(例如根據WO 2007/063754或WO 2008/ 056746)、茚并咔唑衍生物(例如根據DE 102009023155及DE 102009031021)、二氮磷雜環戊二烯衍生物(例如根據DE 102009022858)、三唑衍生物、㗁唑及㗁唑衍生物、咪唑衍生物、聚芳烷衍生物、吡唑啉衍生物、吡唑酮衍生物、二苯乙烯基吡衍生物、二氧化噻喃衍生物、苯二胺衍生物、三級芳族胺、苯乙烯基胺、經胺基取代之查耳酮衍生物、吲哚、腙衍生物、二苯乙烯衍生物、矽氮烷衍生物、芳族二亞甲基化合物、碳二亞胺衍生物、8-羥基喹啉衍生物之金屬錯合物(諸如例如AlQ₃，其亦可含有三芳基胺基苯酚配位基(US 2007/0134514 A1))、金屬錯合物/聚矽烷化合物、以及噻吩、苯并噻吩及二苯并噻吩衍生物。These compounds, which can also be used as structural elements in polymers, include CBP (N,N-biscarbazolylbiphenyl), carbazole derivatives (for example according to WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851), nitrogen-doped carbazoles (for example according to EP 1617710, EP 1617711, EP 1731584 or JP 2005/347160), ketones (for example according to WO 2004/093207 or according to DE 102008033943), phosphine oxides, sulfones and sulfones (for example according to WO 2005/003253), oligophenylenes, aromatic amines (for example according to US 2005/0069729), bipolar matrix materials (for example according to WO 2007/137725), silanes (for example according to WO 2005/111172), 9,9-diarylfluorene derivatives (for example according to DE 102008017591), nitrogen-doped boron-doped cyclopentadiene or boric acid esters (for example according to WO 2006/117052), tris(III)-dipamides (for example according to WO 2006/117052), derivatives (for example according to DE 102008036982), indolecarbazole derivatives (for example according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (for example according to DE 102009023155 and DE 102009031021), diazophocyclopentadiene derivatives (for example according to DE 102009022858), triazole derivatives, oxazole and oxazole derivatives, imidazole derivatives, polyarane derivatives, pyrazoline derivatives, pyrazolone derivatives, distyrylpyrrolidone derivatives, derivatives, thiopyran derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines, amino-substituted chalcone derivatives, indoles, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylene compounds, carbodiimide derivatives, metal complexes of 8-hydroxyquinoline derivatives (such as AlQ₃ , which may also contain a triarylaminophenol ligand ( US 2007/0134514 A1 )), metal complexes/polysilane compounds, and thiophene, benzothiophene and dibenzothiophene derivatives.

較佳的咔唑衍生物之實例係mCP(=1,3-N,N-二咔唑基苯(=9,9'-(1,3-伸苯基)雙-9H-咔唑))(式H‑9)、CDBP(=9,9'-(2,2'-二甲基[1,1'-聯苯]-4,4'-二基)雙-9H-咔唑)、1,3-雙(N,N'-二咔唑基)苯(=1,3-雙(咔唑-9-基)苯)、PVK(聚乙烯基咔唑)、3,5-二(9H-咔唑-9-基)聯苯及CMTTP(式H-10)。特別提及的化合物揭示於US 2007/ 0128467 A1及US 2005/0249976 A1中(式H-11及H-13)。Examples of preferred carbazole derivatives are mCP (=1,3-N,N-dicarbazolylbenzene (=9,9'-(1,3-phenylene)bis-9H-carbazole)) (Formula H-9), CDBP (=9,9'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-9H-carbazole), 1,3-bis(N,N'-dicarbazolyl)benzene (=1,3-bis(carbazole-9-yl)benzene), PVK (polyvinylcarbazole), 3,5-bis(9H-carbazole-9-yl)biphenyl and CMTTP (Formula H-10). Particularly mentioned compounds are disclosed in US 2007/0128467 A1 and US 2005/0249976 A1 (Formulas H-11 and H-13).

較佳的四芳基-Si化合物揭示於例如US 2004/ 0209115、US 2004/0209116、US 2007/0087219 A1中及於H. Gilman, E.A. Zuech, Chemistry & Industry(London, United Kingdom), 1960, 120中。Preferred tetraaryl-Si compounds are disclosed, for example, in US 2004/0209115, US 2004/0209116, US 2007/0087219 A1 and in H. Gilman, E.A. Zuech, Chemistry & Industry (London, United Kingdom), 1960, 120.

特佳的四芳基-Si化合物係由式H-14至H-21所描述。Particularly preferred tetraaryl-Si compounds are described by formulas H-14 to H-21.

來自第4組用於製備磷光摻雜劑之基質的特佳化合物尤其揭示於DE 102009022858、DE 102009023155、EP 652273 B1、WO 2007/063754及WO 2008/056746中，其中特佳化合物係由式H-22至H-25所描述。Particularly preferred compounds from group 4 for preparing substrates for phosphorescent dopants are disclosed in DE 102009022858, DE 102009023155, EP 652273 B1, WO 2007/063754 and WO 2008/056746, wherein particularly preferred compounds are described by formulae H-22 to H-25.

關於可根據本發明使用且可當作主體材料之功能性化合物，尤佳者係含有至少一個氮原子之物質。這些較佳包括芳族胺、三衍生物及咔唑衍生物。因此，咔唑衍生物特別展現出令人驚訝的高效率。三衍生物使電子裝置具有意想不到的長壽命。With regard to the functional compounds that can be used according to the present invention and can be used as the host material, preferably those containing at least one nitrogen atom. These preferably include aromatic amines, tri Derivatives and carbazole derivatives. Therefore, carbazole derivatives in particular show surprisingly high efficiency. Derivatives give electronic devices an unexpectedly long life.

亦可較佳地以混合物形式使用複數種不同的基質材料，特別是至少一種電子傳導基質材料及至少一種電洞傳導基質材料。同樣較佳者係使用電荷傳輸基質材料及電惰性基質材料的混合物，該電惰性基質材料在顯著程度上不參與電荷傳輸(如果有的話)，如例如於WO 2010/ 108579中所述。It is also preferred to use a plurality of different matrix materials, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material, in the form of a mixture. It is also preferred to use a mixture of a charge-transporting matrix material and an electrically inert matrix material which does not participate in the charge transport to a significant extent, if at all, as described, for example, in WO 2010/108579.

此外，亦可使用改善從單重態至三重態的躍遷之化合物，並且其用於支撐具有發射體性質之功能性化合物，改善這些化合物的磷光性質。適合此目的者特別是咔唑及橋聯咔唑二聚物單元，如例如於WO 2004/070772 A2及WO 2004/113468 A1中所述。亦適合此目的者係酮、氧化膦、亞碸、碸、矽烷衍生物及類似的化合物，如例如於WO 2005/040302 A1中所述。Furthermore, compounds which improve the transition from the singlet state to the triplet state can also be used and which serve to support functional compounds having emitter properties, improving the phosphorescent properties of these compounds. Suitable for this purpose are in particular carbazole and bridged carbazole dimer units, as described, for example, in WO 2004/070772 A2 and WO 2004/113468 A1. Also suitable for this purpose are ketones, phosphine oxides, sulfonyl, sulfonyl, silane derivatives and similar compounds, as described, for example, in WO 2005/040302 A1.

本文中之n-摻雜劑意指還原劑，亦即電子供體。n-摻雜劑之較佳實例係W(hpp)₄及根據WO 2005/ 086251 A2之其他富電子金屬錯合物、P=N化合物(例如WO 2012/175535 A1、WO 2012/175219 A1)、萘碳二亞胺(例如WO 2012/168358 A1)、茀(例如WO 2012/031735 A1)、自由基及雙自由基(例如EP 1837926 A1、WO 2007/107306 A1)、吡啶(例如EP 2452946 A1、EP 2463927 A1)、N-雜環化合物(例如WO 2009/000237 A1)及吖啶以及吩(例如US 2007/145355 A1)。The n-doping agent herein refers to a reducing agent, i.e., an electron donor. Preferred examples of n-dopants are W(hpp)₄ and other electron-rich metal complexes according to WO 2005/086251 A2, P=N compounds (e.g. WO 2012/175535 A1, WO 2012/175219 A1), naphthylcarbodiimide (e.g. WO 2012/168358 A1), fluorene (e.g. WO 2012/031735 A1), free radicals and diradicals (e.g. EP 1837926 A1, WO 2007/107306 A1), pyridine (e.g. EP 2452946 A1, EP 2463927 A1), N-heterocyclic compounds (e.g. WO 2009/000237 A1) and acridine and phenanthracene. (e.g. US 2007/145355 A1).

此外，調配物可包含寬帶隙材料作為功能性材料。寬帶隙材料係用來意指US 7,294,849的揭露內容意義上的材料。這些系統在電致發光裝置中展現出特別有利的性能數據。Furthermore, the formulation may comprise wide bandgap materials as functional materials. Wide bandgap materials are used to mean materials in the sense of the disclosure of US 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

用作寬帶隙材料的化合物可較佳地具有2.5 eV或更多、較佳地3.0 eV或更多、特佳地3.5 eV或更多的帶隙。尤其可藉由最高佔據分子軌域(HOMO)及最低未佔據分子軌域(LUMO)的能階來計算帶隙。The compound used as a wide bandgap material may preferably have a bandgap of 2.5 eV or more, preferably 3.0 eV or more, particularly preferably 3.5 eV or more. The bandgap may be calculated particularly by the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

此外，調配物可包含電洞阻擋材料(HBM)作為功能性材料。電洞阻擋材料表示防止或最小化多層系統中的電洞(正電荷)傳輸之材料，特別係如果該材料以與發射層或電洞傳導層相鄰之層的形式配置。通常，電洞阻擋材料比相鄰層中的電洞傳輸材料具有更低的HOMO能階。在OLED中，電洞阻擋層通常配置在發光層與電子傳輸層之間。Furthermore, the formulation may comprise a hole blocking material (HBM) as functional material. A hole blocking material is a material which prevents or minimizes the transport of holes (positive charges) in a multilayer system, in particular if the material is arranged in the form of a layer adjacent to an emissive layer or a hole transporting layer. Typically, a hole blocking material has a lower HOMO energy level than a hole transporting material in an adjacent layer. In OLEDs, a hole blocking layer is usually arranged between a light-emitting layer and an electron transporting layer.

基本上可使用任何已知的電洞阻擋材料。除了本申請案別處所述之其他電洞阻擋材料之外，有利的電洞阻擋材料係金屬錯合物(US 2003/0068528)，諸如例如雙(2-甲基-8-羥基喹啉基)(4-苯基苯酚基)鋁(III)(bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminium(III)) (BAlQ)。面式-參(1-苯基吡唑基-N,C2)銥(III)(Ir(ppz)₃)同樣用於此目的(US 2003/0175553 A1)。同樣可使用啡啉衍生物，諸如例如BCP；或鄰苯二甲醯亞胺，諸如例如TMPP。Basically any known hole-blocking material can be used. Advantageous hole-blocking materials are metal complexes (US 2003/0068528), such as, for example, bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminium(III) (BAlQ), in addition to other hole-blocking materials described elsewhere in the present application. Fa-tris(1-phenylpyrazolyl-N,C2)iridium(III) (Ir(ppz)₃ ) is likewise used for this purpose (US 2003/0175553 A1). Phenanthroline derivatives, such as, for example, BCP, or phthalimides, such as, for example, TMPP, can also be used.

此外，有利的電洞阻擋材料描述於WO 00/ 70655 A2、WO 01/41512及WO 01/93642 A1中。Furthermore, advantageous hole-blocking materials are described in WO 00/70655 A2, WO 01/41512 and WO 01/93642 A1.

此外，調配物可包含電子阻擋材料(EBM)作為功能性材料。電子阻擋材料表示防止或最小化多層系統中的電子傳輸之材料，特別係如果該材料以與發射層或電子傳導層相鄰之層的形式配置。通常，電子阻擋材料比相鄰層中的電子傳輸材料具有更高的LUMO能階。Furthermore, the formulation may comprise an electron blocking material (EBM) as functional material. An electron blocking material refers to a material that prevents or minimizes electron transport in a multilayer system, in particular if the material is arranged in the form of a layer adjacent to an emissive layer or an electron conducting layer. Typically, an electron blocking material has a higher LUMO energy level than an electron transporting material in the adjacent layer.

基本上可使用任何已知的電子阻擋材料。除了本申請案別處所述之其他電子阻擋材料之外，有利的電子阻擋材料係過渡金屬錯合物，諸如例如Ir(ppz)₃(US 2003/0175553)。Basically any known electron-blocking material can be used. In addition to other electron-blocking materials described elsewhere in this application, advantageous electron-blocking materials are transition metal complexes such as, for example, Ir(ppz)₃ ( US 2003/0175553 ).

電子阻擋材料可較佳地選自胺、三芳基胺及其衍生物。The electron blocking material may be preferably selected from amines, triarylamines and their derivatives.

此外，如果可用作調配物中之有機功能性材料的功能性化合物係低分子量化合物，則其分子量較佳地為≤3,000 g/mol、更佳地≤2,000 g/mol、且最佳地≤1,000 g/mol。Furthermore, if the functional compound useful as the organic functional material in the formulation is a low molecular weight compound, its molecular weight is preferably ≤3,000 g/mol, more preferably ≤2,000 g/mol, and most preferably ≤1,000 g/mol.

此外，特別感興趣的是以高玻璃轉移溫度區分之功能性化合物。在這方面，可在調配物中用作有機功能性材料之特佳的功能性化合物係玻璃轉移溫度為≥70℃、較佳地≥100℃、更佳地≥125℃且最佳地≥150℃之化合物，根據DIN 51005所判定。Furthermore, functional compounds distinguished by a high glass transition temperature are of particular interest. In this respect, particularly preferred functional compounds which can be used as organic functional materials in the formulation are compounds having a glass transition temperature of ≥70°C, preferably ≥100°C, more preferably ≥125°C and most preferably ≥150°C, as determined in accordance with DIN 51005.

調配物亦可包含作為有機功能性材料之聚合物。上述作為有機功能性材料之化合物，其通常具有相對低的分子量，亦可與聚合物混合。同樣可將這些化合物共價併入到聚合物中。這對於經反應性脫離基諸如溴、碘、氯、硼酸或硼酸酯，或經反應性可聚合基團諸如烯烴或氧雜環丁烷取代之化合物係特別可能的。這些可用作製造對應寡聚物、樹枝狀聚合物或聚合物之單體。寡聚合或聚合在此較佳經由鹵素官能性或硼酸官能性或經由可聚合基團進行。此外可能經由此類型的基團交聯聚合物。根據本發明之化合物及聚合物可用作經交聯或未經交聯之層。The formulation may also contain polymers as organic functional materials. The above-mentioned compounds as organic functional materials, which usually have a relatively low molecular weight, can also be mixed with polymers. These compounds can also be covalently incorporated into polymers. This is particularly possible for compounds substituted with reactive ionizable groups such as bromine, iodine, chlorine, boric acid or boric esters, or with reactive polymerizable groups such as olefins or cyclohexane. These can be used as monomers for making corresponding oligomers, dendrimers or polymers. Oligomerization or polymerization is preferably carried out via halogen functionality or boronic acid functionality or via polymerizable groups. In addition, it is possible to crosslink polymers via groups of this type. The compounds and polymers according to the present invention can be used as crosslinked or uncrosslinked layers.

可用作有機功能性材料的聚合物經常含有已在上述化合物的上下文中描述的單元或結構元件，尤其是在WO 02/077060 A1、WO 2005/014689 A2及WO 2011/ 076314 A1中揭示及廣泛列出者。這些係藉由引用方式併入本申請案中。功能性材料可源自例如以下類別： 第1組：能夠產生電洞注入及/或電洞傳輸性質的結構元件； 第2組：能夠產生電子注入及/或電子傳輸性質的結構元件； 第3組：組合關於第1組及第2組中所述之性質的結構元件； 第4組：具有發光性質的結構元件，特別是磷光基團； 第5組：改善從所謂的單重態至三重態的躍遷之結構元件； 第6組：影響所得聚合物的形態或發射顏色之結構元件； 第7組：通常用作骨架之結構元件。Polymers useful as organic functional materials often contain the units or structural elements that have been described in the context of the above compounds, in particular those disclosed and extensively listed in WO 02/077060 A1, WO 2005/014689 A2 and WO 2011/076314 A1. These are incorporated into the present application by reference. Functional materials can be derived, for example, from the following categories:Group 1: structural elements capable of producing hole injection and/or hole transport properties;Group 2: structural elements capable of producing electron injection and/or electron transport properties;Group 3: structural elements combining the properties described in relation to groups 1 and 2;Group 4: structural elements with luminescent properties, in particular phosphorescent groups;Group 5: structural elements that improve the transition from the so-called singlet state to the triplet state;Group 6: structural elements that influence the morphology or emission color of the resulting polymer;Group 7: structural elements that are generally used as a backbone.

此處的結構元件亦可具有各種功能，因此明確的分配不一定是有利的。例如，第1組之結構元件可同樣當作骨架。Here, the structural elements can also have various functions, so a clear allocation is not necessarily advantageous. For example, the structural elements of the first group can also be used as a skeleton.

用作有機功能性材料之具有電洞傳輸或電洞注入性質且含有第1組結構元件的聚合物可較佳地含有對應於上述電洞傳輸或電洞注入材料之單元。The polymer having hole transport or hole injection properties and containing the first group of structural elements used as an organic functional material may preferably contain units corresponding to the above-mentioned hole transport or hole injection materials.

第1組之其他較佳的結構元件係例如三芳基胺、聯苯胺、四芳基對苯二胺、咔唑、薁、噻吩、吡咯及呋喃及其衍生物以及其他具有高HOMO之含O、S或N之雜環 。這些芳基胺及雜環較佳地具有高於-5.8 eV(相對於真空能階)的HOMO，特佳地高於-5.5 eV。Other preferred structural elements of the first group are triarylamines, benzidine, tetraaryl-p-phenylenediamines, carbazole, azulene, thiophene, pyrrole and furan and their derivatives and other heterocyclic rings containing O, S or N with high HOMO. These arylamines and heterocyclic rings preferably have a HOMO higher than -5.8 eV (relative to the vacuum energy level), particularly preferably higher than -5.5 eV.

較佳者尤其係具有電洞傳輸或電洞注入性質之聚合物，其含有至少一種以下式HTP-1的重複單元：其中符號具有下列含義： Ar¹在各情況下對於不同的重複單元相同或不同地係單鍵或單環或多環芳基，其可隨意地經取代； Ar²在各情況下對於不同的重複單元相同或不同地係單環或多環芳基，其可隨意地經取代； Ar³在各情況下對於不同的重複單元相同或不同地係單環或多環芳基，其可隨意地經取代； m      係1、2或3。Preferred are polymers having hole transport or hole injection properties which contain at least one repeating unit of the following formula HTP-1: wherein the symbols have the following meanings: Ar¹ is, in each case identically or differently for different repeating units, a single bond or a monocyclic or polycyclic aromatic group, which may be optionally substituted; Ar² is, in each case identically or differently for different repeating units, a monocyclic or polycyclic aromatic group, which may be optionally substituted; Ar³ is, in each case identically or differently for different repeating units, a monocyclic or polycyclic aromatic group, which may be optionally substituted; m is 1, 2 or 3.

特佳者係式HTP-1的重複單元，其係選自由式HTP-1A至HTP-1C之單元所組成之群組：其中符號具有下列含義： R^a在每次出現時相同或不同地係H、經取代或未經取代之芳族或雜芳族基團、烷基、環烷基、烷氧基、芳烷基、芳氧基、芳硫基、烷氧基羰基、矽基或羧基、鹵素原子、氰基、硝基或羥基； r       係0、1、2、3或 4，及 s       係0、1、2、3、4或5。Particularly preferred are repeated units of type HTP-1 selected from the group consisting of units of types HTP-1A to HTP-1C: wherein the symbols have the following meanings:^Ra , identically or differently on each occurrence, is H, a substituted or unsubstituted aromatic or heteroaromatic group, an alkyl group, a cycloalkyl group, an alkoxy group, an aralkyl group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a silyl group or a carboxyl group, a halogen atom, a cyano group, a nitro group or a hydroxyl group; r is 0, 1, 2, 3 or 4, and s is 0, 1, 2, 3, 4 or 5.

較佳者尤其係具有電洞傳輸或電洞注入性質之聚合物，其含有至少一種以下式HTP-2的重複單元：其中符號具有下列含義： T¹及T²係獨立地選自噻吩、硒吩、噻吩并[2,3-b]噻吩、噻吩并[3,2-b]噻吩、二噻吩并噻吩、吡咯及苯胺，其中這些基團可經一或多個基團R^b取代； R^b在每次出現時獨立地選自鹵素、-CN、-NC、-NCO、-NCS、-OCN、-SCN、-C(=O)NR⁰R⁰⁰、-C(=O)X、-C(=O)R⁰、-NH₂、-NR⁰R⁰⁰、-SH、-SR⁰、-SO₃H、-SO₂R⁰、-OH、 -NO₂、-CF₃、-SF₅、隨意地經取代之具有1至40個碳原子之矽基、碳基或烴基，其可隨意地經取代且可隨意地含有一或多個雜原子； R⁰及R⁰⁰各自獨立地係H或隨意地經取代之具有1至40個碳原子之碳基或烴基，其可隨意地經取代且可隨意地含有一或多個雜原子； Ar⁷及Ar⁸彼此獨立地表示單環或多環芳基或雜芳基，其可隨意地經取代且可隨意地鍵結至一或二個相鄰的噻吩或硒吩基團的2,3-位； c及e彼此獨立地係0、1、2、3或4，其中1＜c + e≤6； d及f彼此獨立地係0、1、2、3或4。Preferred are polymers having hole transport or hole injection properties which contain at least one repeating unit of the following formula HTP-2: wherein the symbols have the following meanings:^T1 and^T2 are independently selected from thiophene, selenophene, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene, dithienothiophene, pyrrole and aniline, wherein these groups may be substituted by one or more groups^Rb ;^Rb is independently selected at each occurrence from halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN,^{-C(=O)NR0R00,} -C(=O)X, -C(=O)^R0 ,^-NH2 ,_-NR0R00 , -SH,_-SR0,^-SO3H,_-SO2R0 , -OH,^-NO2 ,_-CF3 ,_-SF5 , an optionally substituted silyl, carbonyl or alkyl group having 1 to 40 carbon atoms, which may be optionally substituted and may optionally contain one or more heteroatoms; R⁰ and R⁰⁰ are each independently H or an optionally substituted carbonyl or alkyl group having 1 to 40 carbon atoms, which may be optionally substituted and may optionally contain one or more heteroatoms; Ar⁷ and Ar⁸ independently represent a monocyclic or polycyclic aromatic group or heteroaromatic group, which may be optionally substituted and may optionally be bonded to the 2,3-position of one or two adjacent thiophene or selenophene groups; c and e are independently 0, 1, 2, 3 or 4, wherein 1＜c + e≤6; d and f are independently 0, 1, 2, 3 or 4.

具有電洞傳輸或電洞注入性質之聚合物的較佳實例尤其描述於WO 2007/131582 A1及WO 2008/009343 A1中。Preferred examples of polymers having hole transport or hole injection properties are described in particular in WO 2007/131582 A1 and WO 2008/009343 A1.

用作有機功能性材料之具有電子注入及/或電子傳輸性質且含有第2組結構元件的聚合物可較佳地含有對應於上述電子注入及/或電子傳輸材料之單元。The polymer having electron injection and/or electron transport properties and containing the second set of structural elements used as an organic functional material may preferably contain units corresponding to the above-mentioned electron injection and/or electron transport materials.

具有電子注入及/或電子傳輸性質之第2組之其他較佳的結構元件係衍生自例如吡啶、嘧啶、嗒、吡、㗁二唑、喹啉、喹㗁啉及啡及其衍生物，而且還係三芳基硼烷及其他具有低LUMO能階之含O、S或N之雜環。第2組的這些結構元件較佳地具有低於-2.7 eV(相對於真空能階)的LUMO，特佳地低於-2.8 eV。Other preferred structural elements of the second group having electron injection and/or electron transport properties are derived from, for example, pyridine, pyrimidine, tantalum, , pyridine , oxadiazole, quinoline, quinazoline and phenanthroline and their derivatives, but also triarylboranes and other heterocyclic rings containing O, S or N with low LUMO energy levels. These structural elements of the second group preferably have a LUMO below -2.7 eV (relative to the vacuum energy level), particularly preferably below -2.8 eV.

有機功能性材料可較佳地係含有來自第3組的結構元件之聚合物，其中改善電洞及電子遷移率的結構元件(亦即來自第1組及第2組之結構元件)彼此直接連接。這些結構元件中的一些在此可當作發射體，其中發射顏色可轉換為例如綠色、紅色或黃色。因此，彼等的使用係有利的，例如，對於產生其他發射顏色或藉由最初發射藍色的聚合物進行寬頻發射。The organic functional material can preferably be a polymer containing structural elements from group 3, wherein the structural elements that improve the mobility of holes and electrons (i.e. structural elements from groups 1 and 2) are directly connected to each other. Some of these structural elements can be used as emitters here, wherein the emission color can be converted to, for example, green, red or yellow. Therefore, their use is advantageous, for example, for the generation of other emission colors or for broadband emission by polymers that initially emit blue.

用作有機功能性材料之具有發光性質且含有第4組結構元件的聚合物可較佳地含有對應於上述發射體材料之單元。較佳者在此係含有磷光基團之聚合物，特別是含有對應單元之上述發光金屬錯合物，該等對應單元含有第8至10族元素(Ru、Os、Rh、Ir、Pd、Pt)。The polymer having luminescent properties and containing the fourth group of structural elements used as an organic functional material may preferably contain a unit corresponding to the above-mentioned emitter material. Preferably, it is a polymer containing a phosphorescent group, especially the above-mentioned luminescent metal complex containing a corresponding unit containing elements of Groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt).

用作含有改善從所謂的單重態至三重態的躍遷之第5組單元的有機功能性材料之聚合物可較佳地用於支撐磷光化合物，較佳地含有上述第4組結構元件之聚合物。在此可使用聚合物三重態基質。A polymer used as an organic functional material containing the fifth group of units that improve the transition from the so-called singlet state to the triplet state can be preferably used to support the phosphorescent compound, preferably a polymer containing the fourth group of structural elements mentioned above. A polymer triplet matrix can be used here.

適合此目的者特別是咔唑及連接的咔唑二聚物單元，如例如於DE 10304819 A1及DE 10328627 A1中所述。亦適合此目的者係酮、氧化膦、亞碸、碸及矽烷衍生物以及類似的化合物，如例如於DE 10349033 A1中所述。此外，較佳的結構單元可衍生自上文已描述與磷光化合物一起使用之基質材料有關的化合物。Suitable for this purpose are in particular carbazole and linked carbazole dimer units, as described, for example, in DE 10304819 A1 and DE 10328627 A1. Also suitable for this purpose are ketones, phosphine oxides, sulfonium, sulfonium and silane derivatives and similar compounds, as described, for example, in DE 10349033 A1. Furthermore, preferred structural units can be derived from the compounds already described above in connection with the matrix materials used with the phosphorescent compounds.

其他的有機功能性材料較佳係含有影響聚合物的形態及/或發射顏色之第6組單元的聚合物。除了上述聚合物之外，這些聚合物係具有至少一種不計入上述組的其它芳族或另一種共軛結構之聚合物。因此，這些組對電荷載子遷移率、非有機金屬錯合物或單重態-三重態躍遷僅具有很小的影響或沒有影響。The other organic functional materials are preferably polymers containing group 6 units that affect the polymer morphology and/or emission color. In addition to the above polymers, these polymers are polymers having at least one other aromatic or another conjugated structure not included in the above groups. Therefore, these groups have only a small effect or no effect on charge carrier mobility, non-organic metal complexes or singlet-triplet transitions.

這類型的結構單元能夠影響所得聚合物的形態及/或發射顏色。因此，取決於結構單元，這些聚合物亦可用作發射體。This type of structural unit can influence the morphology and/or the emission color of the resulting polymers. Depending on the structural unit, these polymers can therefore also be used as emitters.

因此，在螢光OLED的情況下，較佳者係具有6至40個C原子之芳族結構元件或亦為二苯乙炔(tolan)、二苯乙烯或雙苯乙烯基伸芳基衍生物單元，其等之各者可經一或多個基團取代。特佳者在此係使用衍生自下列之基團：1,4-伸苯基；1,4-伸萘基；1,4-或9,10-伸蒽基；1,6-、2,7-或4,9-伸芘基；3,9-或3,10-伸苝基；4,4'-聯伸二苯；4,4"-聯伸三苯；4,4'-雙-1,1'-伸萘基；4,4'-伸二苯乙炔基(tolanylene)；4,4'-伸二苯乙烯基(stilbenylene)或4,4"-雙苯乙烯基伸芳基(bisstyrylarylene)衍生物。In the case of fluorescent OLEDs, preference is therefore given to aromatic structural elements having 6 to 40 C atoms or also tolan, stilbene or bisstyrylarylene derivative units, each of which may be substituted by one or more radicals. Particularly preferably, groups derived from the following are used: 1,4-phenylene; 1,4-naphthylene; 1,4- or 9,10-anthrylene; 1,6-, 2,7- or 4,9-pyrenylene; 3,9- or 3,10-perylene; 4,4'-biphenylene; 4,4"-triphenylene; 4,4'-bis-1,1'-naphthylene; 4,4'-tolanylene; 4,4'-stilbenylene or 4,4"-bisstyrylarylene derivatives.

用作有機功能性材料之聚合物較佳地含有第7組之單元，其較佳地含有通常用作骨架之具有6至40個C原子之芳族結構。The polymer used as the organic functional material preferably contains a unit of Group 7, which preferably contains an aromatic structure having 6 to 40 C atoms generally used as a skeleton.

這些尤其包括4,5-二氫芘衍生物、4,5,9,10-四氫芘衍生物、茀衍生物，其揭示於例如US 5962631、WO 2006/052457 A2及WO 2006/118345 A1中；9,9-螺聯茀衍生物，其揭示於例如WO 2003/020790 A1中；9,10-菲衍生物，其揭示於例如WO 2005/104264 A1中；9,10-二氫菲衍生物，其揭示例如於WO 2005/014689 A2中；5,7‑二氫二苯并㗁呯(dihydrodibenzoxepine)衍生物及順式-及反式-茚并茀衍生物，其揭示於例如WO 2004/041901 A1及WO 2004/113412 A2中；以及聯萘衍生物，其揭示於例如WO 2006/063852 A1中，以及其它單元，其揭示於例如WO 2005/ 056633 A1、EP 1344788 A1、WO 2007/043495 A1、WO 2005/033174 A1、WO 2003/099901 A1及DE 102006003710中。These include in particular 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, which are disclosed, for example, in US 5962631, WO 2006/052457 A2 and WO 2006/118345 A1; 9,9-spirofluorene derivatives, which are disclosed, for example, in WO 2003/020790 A1; 9,10-phenanthrene derivatives, which are disclosed, for example, in WO 2005/104264 A1; 9,10-dihydrophenanthrene derivatives, which are disclosed, for example, in WO 2005/014689 A2; 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives, which are disclosed, for example, in WO 2004/041901 A1 and WO 2004/113412 A2; and binaphthyl derivatives, which are disclosed in, for example, WO 2006/063852 A1, and other units, which are disclosed in, for example, WO 2005/056633 A1, EP 1344788 A1, WO 2007/043495 A1, WO 2005/033174 A1, WO 2003/099901 A1 and DE 102006003710.

特佳者係選自下列者之第7組的結構單元：茀衍生物，其揭示於例如US 5,962,631、WO 2006/052457 A2及WO 2006/118345 A1中；螺聯茀衍生物，其揭示於例如WO 2003/020790 A1中；苯并茀；二苯并茀；苯并噻吩及二苯并茀基團及其衍生物，其揭示於例如WO 2005/ 056633 A1、EP 1344788 A1及WO 2007/043495 A1中。Particularly preferred are structural units of Group 7 selected from the following: fluorene derivatives, which are disclosed, for example, in US 5,962,631, WO 2006/052457 A2 and WO 2006/118345 A1; spirofluorene derivatives, which are disclosed, for example, in WO 2003/020790 A1; benzofluorene; dibenzofluorene; benzothiophene and dibenzofluorene groups and their derivatives, which are disclosed, for example, in WO 2005/056633 A1, EP 1344788 A1 and WO 2007/043495 A1.

第7組之尤佳的結構元件係由通式PB-1表示：其中符號及標號具有下列含義： 亦對於不同的重複單元，A、B及B'各自相同或不同地係二價基團，其較佳係選自-CR^cR^d-、-NR^c-、-PR^c-、-O-、-S-、-SO-、-SO₂-、-CO-、-CS-、-CSe-、-P(=O)R^c-、 -P(=S)R^c-及-SiR^cR^d-； R^c及R^d在每次出現時獨立地選自H、鹵素、-CN、 -NC、-NCO、-NCS、-OCN、-SCN、-C(=O)NR⁰R⁰⁰、 -C(=O)X、-C(=O)R⁰、-NH₂、-NR⁰R⁰⁰、-SH、-SR⁰、 -SO₃H、-SO₂R⁰、-OH、-NO₂、-CF₃、-SF₅-、隨意地經取代之具有1至40個碳原子之矽基、碳基(carbyl)或烴基，其可隨意地經取代且可隨意地含有一或多個雜原子，其中基團R^c及R^d可隨意地與彼等所鍵結之茀基團形成螺環； X係鹵素； R⁰及R⁰⁰各自獨立地係H或隨意地經取代之具有1至40個碳原子之碳基或烴基，其可隨意地經取代且可隨意地含有一或多個雜原子； g在各情況下獨立地係0或1，且h在各情況下獨立地係0或1，其中次單元中之g及h的總和較佳係1； m係≥1之整數； Ar¹及Ar²彼此獨立地表示單環或多環芳基或雜芳基，其可隨意地經取代且可隨意地鍵結至茚并茀基團的7,8-位或8,9-位；及 a及b彼此獨立地係0或1。The preferred structural element of the seventh group is represented by the general formula PB-1: wherein the symbols and labels have the following meanings: Also for different repeating units, A, B and B' are each the same or different divalent groups, which are preferably selected from^-CRcRd- ,^-NRc- ,^-PRc- ,^-O- , -S-, -SO-,_-SO2- , -CO-, -CS-, -CSe-, -P(=O)^Rc- , -P(=S)^{Rc-and -SiRcRd-;Rc} and^Rd are independently selected from H, halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)^NR0R00 , -C(=O)^X , -C(=O)^R0 ,_-NH2 ,^-NR0R00 ,_-SH ,^-SR0, -SO3H^,_-SO2R0 , -OH, -NO₂ , -CF₃ , -SF₅ -, an optionally substituted silyl, carbyl or alkyl group having 1 to 40 carbon atoms, which may be optionally substituted and may optionally contain one or more heteroatoms, wherein the groups R^c and R^d may optionally form a spiro ring with the fluorene group to which they are bonded; X is a halogen; R⁰ and R⁰⁰ are each independently H or an optionally substituted carbyl or alkyl group having 1 to 40 carbon atoms, which may be optionally substituted and may optionally contain one or more heteroatoms; g is independently 0 or 1 in each case, and h is independently 0 or 1 in each case, wherein the sum of g and h in the subunit is preferably 1; m is an integer ≥ 1; Ar¹ and Ar² are independently monocyclic or polycyclic aromatic or heteroaryl groups, which may be optionally substituted and may be optionally bonded to the 7,8-position or 8,9-position of the indenofluorene group; and a and b are independently 0 or 1.

如果基團R^c及R^d與這些基團所鍵結的茀基團形成螺基團，則該基團較佳地表示螺聯茀。If the groups R^c and R^d form a spiro group with the fluorene group to which these groups are bonded, the group preferably represents a spirofluorene.

特佳者係式PB-1的重複單元，其係選自由式PB‑1A至PB-1E的單元所組成之群組：其中R^c具有上述式PB-1的含義，r係0、1、2、3或4，且R^e具有與基團R^c相同的含義。 R^e較佳地係-F；-Cl；-Br；-I；-CN；-NO₂；-NCO； -NCS；-OCN；-SCN；‑C(=O)NR⁰R⁰⁰；-C(=O)X； -C(=O)R⁰；-NR⁰R⁰⁰；隨意地經取代之具有4至40個、較佳地6至20個C原子之矽基、芳基或雜芳基；或具有1至20個、較佳地1至12個C原子之直鏈、支鏈或環狀烷基、烷氧基、烷基羰基、烷氧基羰基、烷基羰基氧基或烷氧基羰基氧基，其中一或多個氫原子可隨意地經F或Cl取代，且基團R⁰、R⁰⁰及X具有上文對於式PB-1所述之含義。Particularly preferred are duplicate units of type PB-1, which are selected from a group consisting of units of types PB-1A to PB-1E: wherein R^c has the meaning of the above formula PB-1, r is 0, 1, 2, 3 or 4, and^Re has the same meaning as the group R^c . R^e is preferably -F; -Cl; -Br; -I; -CN; -NO₂ ; -NCO; -NCS; -OCN; -SCN; -C(=O)NR⁰ R⁰⁰ ; -C(=O)X; -C(=O)R⁰ ; -NR⁰ R⁰⁰ ; an optionally substituted silyl, aryl or heteroaryl group having 4 to 40, preferably 6 to 20 C atoms; or a linear, branched or cyclic alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 20, preferably 1 to 12 C atoms, wherein one or more hydrogen atoms may be optionally substituted by F or Cl, and the groups R⁰ , R⁰⁰ and X have the meanings described above for formula PB-1.

特佳者係式PB-1的重複單元，其係選自由式PB-1F至PB-1I的單元所組成之群組：其中符號具有下列含義： L係H、鹵素或隨意地經氟化之具有1至12個C原子之直鏈或支鏈烷基或烷氧基，且較佳地代表H、F、甲基、異丙基、三級丁基、正戊氧基或三氟甲基；及 L'係隨意經氟化之具有1至12個C原子之直鏈或支鏈烷基或烷氧基，且較佳地代表正辛基或正辛氧基。Particularly preferred are repeated units of type PB-1, which are selected from the group consisting of units of types PB-1F to PB-1I: wherein the symbols have the following meanings: L is H, a halogen or an optionally fluorinated straight or branched alkyl or alkoxy group having 1 to 12 C atoms, and preferably represents H, F, methyl, isopropyl, tertiary butyl, n-pentyloxy or trifluoromethyl; and L' is an optionally fluorinated straight or branched alkyl or alkoxy group having 1 to 12 C atoms, and preferably represents n-octyl or n-octyloxy.

為了實施本發明，較佳者係含有上述第1組至第7組的結構元件中多於一者之聚合物。此外可規定，聚合物較佳地含有來自上述一個組別之多於一種結構元件，亦即包含選自一個組別之結構元件的混合物。For the implementation of the present invention, polymers containing more than one of the structural elements of the above-mentioned groups 1 to 7 are preferred. In addition, it can be stipulated that the polymer preferably contains more than one structural element from one of the above-mentioned groups, that is, a mixture containing structural elements selected from one group.

特別地，特佳者係除了至少一種具有發光性質的結構元件(第4組)、較佳地至少一種磷光基團之外，額外含有至少一種如上所述之第1組至第3組、第5組或第6組的其他結構元件之聚合物，其中其等較佳地選自第1組至第3組。In particular, the preferred polymers are polymers that, in addition to at least one structural element with luminescent properties (Group 4), preferably at least one phosphorescent group, additionally contain at least one other structural element from Groups 1 to 3, Group 5 or Group 6 as described above, wherein they are preferably selected from Groups 1 to 3.

如果存在於聚合物中，各類基團的比例可係在寬範圍內，其中這些對於所屬技術領域中具有通常知識者係已知的。如果存在於聚合物中之一個類別(其在各情況下選自上述第1至7組之結構元件)的比例較佳地在各情況下≥5 mol%、特佳地在各情況下≥10 mol%，則可達到令人驚訝的優點。If present in the polymer, the proportions of the individual classes of radicals may be within wide ranges, which are known to those skilled in the art. Surprising advantages are achieved if one class, which is in each case selected from the structural elements of groups 1 to 7 above, is present in the polymer in a proportion of preferably in each case ≥ 5 mol %, particularly preferably in each case ≥ 10 mol %.

發白光共聚物的製備尤其詳細描述於DE 10343606 A1中。The preparation of white-emitting copolymers is described in detail in DE 10343606 A1.

為了提高溶解度，聚合物可含有對應的基團。較佳地，聚合物可含有取代基，使得每重複單元平均存在至少2個非芳族碳原子，特佳地至少4個且尤佳地至少8個非芳族碳原子，其中平均值係關於數目平均值。此處個別碳原子可經例如O或S置換。然而，一定比例、隨意地所有重複單元可不含有包含非芳族碳原子之取代基。此處短鏈取代基係較佳的，因為長鏈取代基可能對使用有機功能性材料可獲得的層有不利影響。取代基較佳地在直鏈中含有至多12個碳原子、較佳地至多8個碳原子且特佳地至多6個碳原子。In order to increase the solubility, the polymer may contain corresponding groups. Preferably, the polymer may contain substituents such that there are on average at least 2 non-aromatic carbon atoms per repeating unit, particularly preferably at least 4 and particularly preferably at least 8 non-aromatic carbon atoms, wherein the average value is about the numerical average. Individual carbon atoms may be replaced by, for example, O or S. However, a certain proportion, optionally all repeating units may not contain substituents comprising non-aromatic carbon atoms. Short-chain substituents are preferred here, because long-chain substituents may have an adverse effect on the layers that can be obtained using organic functional materials. The substituent preferably contains at most 12 carbon atoms, preferably at most 8 carbon atoms and particularly preferably at most 6 carbon atoms in a straight chain.

根據本發明用作有機功能性材料之聚合物可係隨機、交替或位置規則性共聚物、嵌段共聚物或這些共聚物形式的組合。The polymer used as the organic functional material according to the present invention may be a random, alternating or position-regular copolymer, a block copolymer or a combination of these copolymer forms.

在其他實施例中，用作有機功能性材料之聚合物可係具有側鏈的非共軛聚合物，其中該實施例對於基於聚合物之磷光OLED特別重要。通常，磷光聚合物可藉由乙烯基化合物之自由基共聚來獲得，其中這些乙烯基化合物含有至少一種具有磷光發射體的單元及/或至少一種電荷傳輸單元，尤其如在US 7250226 B2中所揭示的。其他磷光聚合物尤其描述於JP 2007/211243 A2、JP 2007/ 197574 A2、US 7250226 B2及JP 2007/059939 A中。In other embodiments, the polymer used as organic functional material may be a non-conjugated polymer with side chains, wherein this embodiment is particularly important for polymer-based phosphorescent OLEDs. Typically, phosphorescent polymers can be obtained by free radical copolymerization of vinyl compounds, wherein these vinyl compounds contain at least one unit with a phosphorescent emitter and/or at least one charge transport unit, as disclosed in US 7250226 B2 in particular. Other phosphorescent polymers are described in particular in JP 2007/211243 A2, JP 2007/197574 A2, US 7250226 B2 and JP 2007/059939 A.

在其他較佳的實施例中，非共軛聚合物含有藉由間隔單元彼此連接之骨架單元。此類基於非共軛聚合物之基於主鏈單元的三重態發射體之實例揭示於例如DE 102009023154中。In other preferred embodiments, the non-conjugated polymer contains backbone units connected to each other via spacer units. Examples of such triplet emitters based on backbone units based on non-conjugated polymers are disclosed in, for example, DE 102009023154.

在其他較佳的實施例中，非共軛聚合物可經設計為螢光發射體。基於具有側鏈的非共軛聚合物之較佳的螢光發射體在側鏈中含有蒽或苯并蒽基團或這些基團的衍生物，其中這些聚合物揭示於例如JP 2005/108556、JP 2005/285661及JP 2003/338375中。In other preferred embodiments, non-conjugated polymers can be designed as fluorescent emitters. Preferred fluorescent emitters based on non-conjugated polymers with side chains contain anthracene or benzanthracene groups or derivatives of these groups in the side chains, wherein these polymers are disclosed in, for example, JP 2005/108556, JP 2005/285661 and JP 2003/338375.

這些聚合物通常可用作電子或電洞傳輸材料，其中這些聚合物較佳地經設計為非共軛聚合物。These polymers are generally useful as electron or hole transport materials, wherein these polymers are preferably designed as non-conjugated polymers.

此外，在聚合化合物的情況下，在配調配物中用作有機功能性材料之功能性化合物的分子量M_w較佳地為≥10,000 g/mol、特佳地≥20,000 g/mol且尤佳地≥40,000 g/mol。Furthermore, in the case of polymeric compounds, the molecular weight_Mw of the functional compound used as the organic functional material in the formulation is preferably ≥10,000 g/mol, particularly preferably ≥20,000 g/mol and even more preferably ≥40,000 g/mol.

聚合物的分子量M_w在此較佳地在10,000至2,000,000 g/mol之範圍內，特佳地在20,000至1,000,000 g/mol之範圍內且非常特佳地在40,000至300,000 g/mol之範圍內。分子量M_w係藉由GPC(=凝膠滲透層析法)相對於聚苯乙烯內標準品來判定。The molecular weight_Mw of the polymer is preferably in the range from 10,000 to 2,000,000 g/mol, particularly preferably in the range from 20,000 to 1,000,000 g/mol and very particularly preferably in the range from 40,000 to 300,000 g/mol. The molecular weight_Mw is determined by GPC (=gel permeation chromatography) relative to a polystyrene internal standard.

出於揭露目的，以上所引用之用於描述功能性化合物的公開案係藉由引用方式併入本申請案中。For disclosure purposes, the above-cited publications describing functional compounds are incorporated into this application by reference.

根據本發明之調配物可包含生產電子裝置的對應功能層所必需的所有有機功能性材料。例如，如果電洞傳輸層、電洞注入層、電子傳輸層或電子注入層精確地由一種功能性化合物建構，則調配物精確地包含該化合物作為有機功能性材料。如果發射層包含例如發射體與基質或主體材料的組合，則調配物精確地包含發射體及基質或主體材料的混合物作為有機功能性材料，如於本申請案中別處所更詳細描述者。The formulation according to the invention may contain all organic functional materials necessary for producing the corresponding functional layer of the electronic device. For example, if the hole transport layer, hole injection layer, electron transport layer or electron injection layer is constructed from exactly one functional compound, the formulation contains exactly this compound as organic functional material. If the emissive layer contains, for example, a combination of an emitter and a matrix or host material, the formulation contains exactly a mixture of an emitter and a matrix or host material as organic functional material, as described in more detail elsewhere in this application.

除了所述組分之外，根據本發明之調配物可包含其他添加劑及加工助劑。這些尤其包括界面活性物質(界面活性劑)、潤滑劑及潤滑脂、修飾黏度的添加劑、增加導電性的添加劑、分散劑、疏水劑、助黏劑、流動改良劑、消泡劑、脫氣劑、稀釋劑(其可係反應性或非反應性的)、填料、助劑、加工助劑、染料、顏料、穩定劑、敏化劑、奈米粒子及抑制劑。In addition to the components mentioned, the formulations according to the invention may contain further additives and processing aids. These include, in particular, surface-active substances (surfactants), lubricants and greases, viscosity-modifying additives, conductivity-increasing additives, dispersants, hydrophobic agents, adhesion promoters, flow improvers, defoamers, deaerators, diluents (which may be reactive or non-reactive), fillers, auxiliary agents, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors.

本發明另外關於製備根據本發明之配調配物之方法，其中可用於生產電子裝置之功能層的至少一種有機功能性材料及至少一種有機溶劑A係混合的。The invention further relates to a method for preparing a formulation according to the invention, wherein at least one organic functional material which can be used to produce a functional layer of an electronic device and at least one organic solvent A are mixed.

根據本發明之調配物可用於生產層或多層結構，其中有機功能性材料以層的形式存在，如生產較佳的電子或光電組件(諸如OLED)所需要的。The formulations according to the invention can be used to produce layer or multilayer structures in which organic functional materials are present in the form of layers, as is required for the production of preferred electronic or optoelectronic components such as OLEDs.

本發明之調配物可較佳地用於在基板或施加至基板的層中之一者上形成功能層。基板可具有或不具有觸排結構(bank structure)。The formulation of the invention can preferably be used to form a functional layer on a substrate or one of the layers applied to a substrate. The substrate may or may not have a bank structure.

本發明同樣係關於一種用於製備電子裝置、較佳地電致發光裝置之方法，其中電子裝置、較佳地電致發光裝置中之至少一個功能層係藉由將本發明之調配物沉積、較佳地印刷、更佳地噴墨印刷在表面上並隨後乾燥來製備。The invention also relates to a method for preparing an electronic device, preferably an electroluminescent device, wherein at least one functional layer in the electronic device, preferably an electroluminescent device, is prepared by depositing, preferably printing, more preferably inkjet printing, a formulation according to the invention onto a surface and subsequently drying it.

本發明另外關於一種電子裝置、較佳地電致發光裝置，其中至少一個功能層係藉由將本發明之調配物沉積、較佳地印刷、更佳地噴墨印刷在表面上並隨後乾燥來製備。The invention further relates to an electronic device, preferably an electroluminescent device, wherein at least one functional layer is produced by depositing, preferably printing, more preferably inkjet printing, a formulation according to the invention onto a surface and subsequently drying it.

功能層可例如藉由溢塗(flood coating)、浸塗、噴塗、旋塗、網版印刷、凸版印刷、凹版印刷、旋轉印刷、輥塗、柔版印刷、平版印刷或噴嘴印刷、較佳地噴墨印刷在基板或施加至基板的層中之一者上來製造。The functional layer can be produced, for example, by flood coating, dip coating, spray coating, spin coating, screen printing, relief printing, gravure printing, rotary printing, roll coating, flexographic printing, lithography or nozzle printing, preferably inkjet printing on the substrate or one of the layers applied to the substrate.

在將根據本發明之調配物施加至基板或已施加的功能層上之後，可進行乾燥步驟以從上述連續相中移除溶劑。乾燥較佳可在相對低的溫度及相對較長的期間內進行，以避免氣泡形成並獲得均一的塗層。乾燥可較佳地在80至300℃、更佳地150至250℃且最佳地160至200℃之範圍內的溫度下進行。乾燥在此可較佳地在10^-6毫巴至2巴之範圍內、更佳地在10^-2毫巴至1巴之範圍內且最佳地在10^-1毫巴至100毫巴之範圍內的壓力下進行。在乾燥方法期間，基板的溫度可自-15℃至250℃變化。乾燥的持續時間取決於欲達成的乾燥程度，其中少量的水可隨意地在相對高的溫度下移除且較佳地與燒結組合來進行。After the formulation according to the invention has been applied to the substrate or to the applied functional layer, a drying step may be carried out to remove the solvent from the continuous phase. Drying may preferably be carried out at a relatively low temperature and for a relatively long period in order to avoid bubble formation and to obtain a uniform coating. Drying may preferably be carried out at a temperature in the range of 80 to 300° C., more preferably 150 to 250° C. and most preferably 160 to 200° C. Drying may preferably be carried out at a pressure in the range of 10^-6 mbar to 2 bar, more preferably in the range of 10^-2 mbar to 1 bar and most preferably in the range of 10^-1 mbar to 100 mbar. During the drying process, the temperature of the substrate may vary from -15° C. to 250° C. The duration of drying depends on the degree of dryness to be achieved, wherein small amounts of water may optionally be removed at relatively high temperatures and preferably in combination with sintering.

此外，重複方法多次可形成不同或相同的功能層。在此可發生所形成的功能層之交聯，以防止其溶解，如例如於EP 0637899 A1中所揭示。Furthermore, the method can be repeated several times to form different or identical functional layers. Crosslinking of the functional layers formed can occur here to prevent their dissolution, as disclosed, for example, in EP 0637899 A1.

本發明亦關於一種可藉由用於生產電子裝置之方法獲得的電子裝置。The invention also relates to an electronic device obtainable by a method for producing an electronic device.

本發明另外關於一種具有至少一個功能層之電子裝置，該功能層包含至少一種可藉由上述用於生產電子裝置之方法獲得的有機功能性材料。The invention further relates to an electronic device having at least one functional layer comprising at least one organic functional material obtainable by the above-described method for producing an electronic device.

電子裝置係用來意指包含陽極、陰極及兩者間之至少一個功能層的裝置，其中該功能層包含至少一種有機或有機金屬化合物。An electronic device is used to refer to a device comprising an anode, a cathode and at least one functional layer therebetween, wherein the functional layer comprises at least one organic or organometallic compound.

有機電子裝置較佳地係有機電致發光裝置(OLED)、聚合物電致發光裝置(PLED)、有機積體電路(O-IC)、有機場效電晶體(O-FET)、有機薄膜電晶體(O-TFT)、有機發光電晶體(O-LET)、有機太陽能電池(O-SC)、有機光伏(OPV)電池、有機光學偵測器、有機感光器、有機場淬滅裝置(O-FQD)、有機電感測器、發光電化學電池(LEC)或有機雷射二極體(O-雷射)，更佳地有機電致發光裝置(OLED)或聚合物電致發光裝置(PLED)。The organic electronic device is preferably an organic electroluminescent device (OLED), a polymer electroluminescent device (PLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic photovoltaic (OPV) cell, an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), an organic inductor, a light emitting electrochemical cell (LEC) or an organic laser diode (O-laser), more preferably an organic electroluminescent device (OLED) or a polymer electroluminescent device (PLED).

活性組分通常是在陽極與陰極之間引入的有機或無機材料，其中該等活性組分會影響、維持及/或改善電子裝置的性質，例如其性能及/或其壽命，例如電荷注入、電荷傳輸或電荷阻擋材料，但特別是發射材料及基質材料。因此，可用於生產電子裝置的功能層之有機功能性材料較佳地包含電子裝置的活性組分。Active components are usually organic or inorganic materials introduced between the anode and the cathode, wherein the active components influence, maintain and/or improve the properties of the electronic device, such as its performance and/or its life, such as charge injection, charge transport or charge blocking materials, but in particular emissive materials and matrix materials. Therefore, the organic functional materials that can be used to produce the functional layers of the electronic device preferably contain active components of the electronic device.

有機電致發光裝置係本發明之較佳實施例。有機電致發光裝置包含陰極、陽極及至少一個發光層。An organic electroluminescent device is a preferred embodiment of the present invention, and comprises a cathode, an anode and at least one luminescent layer.

另外較佳地使用二或更多種三重態發射體與基質一起的混合物。具有較短波發射光譜之三重態發射體在此當作具有較長波發射光譜之三重態發射體的共基質。It is also preferred to use a mixture of two or more triplet emitters together with a matrix. The triplet emitter with a shorter emission spectrum is considered here as a co-matrix for the triplet emitter with a longer emission spectrum.

在這種情況下，發光層中之基質材料的比例對於螢光發光層較佳地在50與99.9體積%之間、更佳地在80與99.5體積%之間且最佳地在92與99.5體積%之間，且對於磷光發光層在85與97體積%之間。In this case, the proportion of the matrix material in the light-emitting layer is preferably between 50 and 99.9 volume %, more preferably between 80 and 99.5 volume % and most preferably between 92 and 99.5 volume % for the fluorescent light-emitting layer, and between 85 and 97 volume % for the phosphorescent light-emitting layer.

對應地，摻雜劑的比例對於螢光發光層較佳地在0.1與50體積%之間、更佳地在0.5與20體積%之間且最佳地在0.5與8體積%之間，且對於磷光發光層在3與15體積%之間。Correspondingly, the proportion of the dopant is preferably between 0.1 and 50 volume %, more preferably between 0.5 and 20 volume % and most preferably between 0.5 and 8 volume % for the fluorescent light-emitting layer, and between 3 and 15 volume % for the phosphorescent light-emitting layer.

有機電致發光裝置之發光層亦可涵蓋包含複數種基質材料(混合基質系統)及/或複數種摻雜劑的系統。同樣在這種情況下，摻雜劑通常是在系統中比例較小的材料，並且基質材料係在系統中比例較大的材料。然而，在個別情況下，系統中個別基質材料的比例可能小於個別摻雜劑的比例。The light-emitting layer of an organic electroluminescent device may also include a system comprising a plurality of matrix materials (mixed matrix system) and/or a plurality of dopants. In this case, the dopant is usually the material with a smaller proportion in the system, and the matrix material is the material with a larger proportion in the system. However, in individual cases, the proportion of an individual matrix material in the system may be smaller than the proportion of an individual dopant.

混合基質系統較佳地包含二或三種不同的基質材料、更佳地二種不同的基質材料。二種材料中之一者在此較佳地係具有電洞傳輸性質的材料，且另一種材料係具有電子傳輸性質的材料。然而，混合基質組分之所欲電子傳輸及電洞傳輸性質亦可主要地或完全地組合在單一混合基質組分中，其中其他混合基質組分滿足其他功能。二種不同的基質材料在此可以1:50至1:1、較佳地1:20至1:1、更佳地1:10至1:1且最佳地1:4至1:1的比例存在。混合基質系統較佳地用於磷光有機電致發光裝置。關於混合基質系統的其他細節可例如在WO 2010/108579中找到。The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. One of the two materials is preferably a material having hole transport properties, and the other material is a material having electron transport properties. However, the desired electron transport and hole transport properties of the mixed matrix components can also be mainly or completely combined in a single mixed matrix component, wherein the other mixed matrix components meet other functions. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1 and most preferably 1:4 to 1:1. The mixed matrix system is preferably used in phosphorescent organic electroluminescent devices. Further details about the mixed matrix system can be found, for example, in WO 2010/108579.

除了這些層之外，有機電致發光裝置亦可包含其他層，例如在各情況下一或多個電洞注入層、電洞傳輸層、電洞阻擋層、電子傳輸層、電子注入層、激子阻擋層、電子阻擋層、電荷產生層(IDMC 2003, Taiwan; Session 21 OLED(5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido,Multiphoton Organic EL Device Having Charge Generation Layer)及/或有機或無機p/n接面。在此，對於一或多個電洞傳輸層可例如用金屬氧化物(諸如MoO₃或WO₃)、或用(全)氟化缺電子芳族化合物進行p-摻雜，及/或對於一或多個電子傳輸層進行n-摻雜。同樣可在二個發光層之間引入具有例如激子阻擋功能及/或控制電致發光裝置中的電荷平衡之中間層。然而，應當指出，這些層中之各者不一定都必須存在。這些層同樣可在使用如上所定義之根據本發明之調配物時存在。In addition to these layers, an organic electroluminescent device may also comprise further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers (IDMC 2003, Taiwan; Session 21 OLED(5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido,Multiphoton Organic EL Device Having Charge Generation Layer ) and/or an organic or inorganic p/n junction. Here, one or more hole transport layers may be p-doped, for example, with metal oxides such as MoO₃ or WO₃ , or with (per)fluorinated electron-deficient aromatic compounds, and/or one or more electron transport layers may be n-doped. It is also possible to introduce an intermediate layer between two luminescent layers which has, for example, an exciton blocking function and/or controls the charge balance in the electroluminescent device. However, it should be pointed out that each of these layers does not necessarily have to be present. These layers may also be present when using the formulations according to the invention as defined above.

在本發明之其他實施例中，裝置包含複數個層。本發明之調配物在此可較佳地用於生產電洞傳輸層、電洞注入層、電子傳輸層、電子注入層及/或發光層。In other embodiments of the invention, the device comprises a plurality of layers. The formulations of the invention can be preferably used to produce hole transport layers, hole injection layers, electron transport layers, electron injection layers and/or light emitting layers.

因此，本發明亦關於一種電子裝置，其包含至少三層，但在一較佳實施例中，所有所述層包括電洞注入層、電洞傳輸層、發射層、電子傳輸層、電子注入層、電荷阻擋層及/或電荷產生層，並且其中至少一層已藉由根據本發明所使用之調配物獲得。層(例如電洞傳輸層及/或電洞注入層)的厚度可較佳地在1至500 nm之範圍內，更佳地在2至200 nm之範圍內。Therefore, the present invention also relates to an electronic device comprising at least three layers, but in a preferred embodiment, all of the layers include a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, an electron injection layer, a charge blocking layer and/or a charge generation layer, and at least one of the layers has been obtained by a formulation used according to the present invention. The thickness of a layer (e.g. a hole transport layer and/or a hole injection layer) may preferably be in the range of 1 to 500 nm, more preferably in the range of 2 to 200 nm.

裝置可進一步包含由未曾藉由使用根據本發明之調配物來施加的其他低分子量化合物或聚合物建構的層。這些亦可藉由在高真空中蒸發低分子量化合物來製造。The device may further comprise layers built up from other low molecular weight compounds or polymers which have not been applied by using the formulations according to the invention. These can also be produced by evaporating low molecular weight compounds in a high vacuum.

額外較佳的是使用不以純物質使用之化合物，而是作為與任何所欲類型之其他聚合、寡聚、樹枝狀或低分子量物質一起之混合物(摻合物)。這些可例如改善電子性質或自身發射。It is particularly preferred to use the compounds not as pure substances but as mixtures (blends) with other polymeric, oligomeric, dendritic or low molecular weight substances of any desired type. These may, for example, improve the electronic properties or the self-emission.

在本發明之一較佳實施例中，根據本發明之調配物包含用作發光層中的主體材料或基質材料之有機功能性材料。除了主體材料或基質材料之外，調配物在此可包含上述發射體。此處的有機電致發光裝置可包含一或多層發光層。如果存在複數個發射層，則這些較佳地具有在380 nm與750 nm之間的複數個發射最大值，整體上得到白色發射，亦即，將能夠發螢光或磷光的各種發光化合物使用於發光層中。非常特佳者係三層系統，其中三個層展現藍色、綠色及橙色或紅色發射(關於基本結構，請參見例如WO 2005/011013)。發白光的裝置適合用作例如LCD顯示器的背光或用於一般照明應用。In a preferred embodiment of the present invention, the formulation according to the present invention comprises an organic functional material used as a host material or matrix material in the luminescent layer. In addition to the host material or matrix material, the formulation may comprise the above-mentioned emitter. The organic electroluminescent device here may comprise one or more luminescent layers. If there are a plurality of luminescent layers, these preferably have a plurality of emission maxima between 380 nm and 750 nm, and white emission is obtained as a whole, that is, various luminescent compounds capable of fluorescing or phosphorescing are used in the luminescent layer. Very particularly preferred are three-layer systems, in which the three layers exhibit blue, green and orange or red emission (for basic structures, see, for example, WO 2005/011013). Devices emitting white light are suitable for use as, for example, backlights for LCD displays or for general lighting applications.

亦可將複數個OLED一者配置在另一者之上，從而能夠進一步提高相對於待達成之光產率的效率。It is also possible to arrange a plurality of OLEDs one above the other, thereby making it possible to further increase the efficiency relative to the light yield to be achieved.

為了改良光的耦合輸出，OLED中的光射出側上的最終有機層亦可例如呈奈米發泡體的形式，從而導致全反射的比例降低。In order to improve the outcoupling of the light, the final organic layer on the light exit side in the OLED can also be in the form of a nanofoam, for example, so that the proportion of total reflection is reduced.

此外較佳者係有機電致發光裝置，其中利用昇華方法施加一或多層，其中藉由蒸氣沈積於真空昇華單元中在低於10^-5毫巴、較佳地低於10^-6毫巴、更佳地低於10^-7毫巴之壓力下施加材料。Also preferred are organic electroluminescent devices in which one or more layers are applied by means of a sublimation method, wherein the material is applied by vapor deposition in a vacuum sublimation cell at a pressure below 10⁻⁵ mbar, preferably below 10⁻⁶ mbar, more preferably below 10⁻⁷ mbar.

此外，根據本發明之電子裝置之一或多層可藉由OVPD(有機蒸氣相沈積)方法或輔以載體-氣體昇華來施加，其中該等材料係在10^-5毫巴與1巴之間的壓力下施加。Furthermore, one or more layers of the electronic device according to the invention may be applied by an OVPD (organic vapor phase deposition) method or with the aid of carrier-gas sublimation, wherein the materials are applied at a pressure between 10⁻⁵ mbar and 1 bar.

此外，根據本發明之電子裝置之一或多層可從溶液中製造，諸如例如藉由旋轉塗佈、或藉由任何所欲印刷方法，諸如例如網版印刷、柔版印刷、平版印刷，但特佳的是LITI(光誘導熱成像、熱轉移印刷)或噴墨印刷。Furthermore, one or more layers of the electronic device according to the invention can be produced from solution, such as, for example, by spin coating, or by any desired printing method, such as, for example, screen printing, flexographic printing, lithographic printing, but particularly preferably LITI (light induced thermal imaging, thermal transfer printing) or inkjet printing.

該裝置通常包含陰極及陽極(電極)。為了本發明之目的，選擇電極(陰極、陽極)，以此方式彼等的帶能量盡可能接近地對應於相鄰有機層的帶能量，以確保高效的電子或電洞注入。The device usually comprises a cathode and an anode (electrodes). For the purposes of the present invention, the electrodes (cathode, anode) are selected in such a way that their band energy corresponds as closely as possible to the band energy of the adjacent organic layer, in order to ensure efficient electron or hole injection.

陰極較佳地包含金屬錯合物、具有低功函的金屬、金屬合金或包含各種金屬的多層結構，諸如例如鹼土金屬、鹼金屬、主族金屬或鑭系元素(例如Ca、Ba、Mg、Al、In、Mg、Yb、Sm等)。在多層結構的情況下，除了所述金屬之外，亦可使用具有相對高功函數之其他金屬，諸如例如Ag及Ag奈米線(Ag NW)，在該情況下，通常使用金屬的組合，諸如例如Ca/Ag或Ba/Ag。亦可較佳地在金屬陰極與有機半導體之間引入具有高介電常數的材料之薄中間層。適合此目的者係例如鹼金屬或鹼土金屬氟化物，而且還係對應的氧化物(例如LiF、Li₂O、BaF₂、MgO、NaF等)。此層的層厚度較佳地在0.1與10 nm之間，更佳地在0.2與8 nm之間，且最佳地在0.5與5 nm之間。The cathode preferably comprises a metal complex, a metal with a low work function, a metal alloy or a multilayer structure comprising various metals, such as, for example, alkali earth metals, alkali metals, main group metals or chalcogenides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). In the case of a multilayer structure, in addition to the metals mentioned above, other metals with relatively high work functions may also be used, such as, for example, Ag and Ag nanowires (Ag NW), in which case a combination of metals is generally used, such as, for example, Ca/Ag or Ba/Ag. It is also preferred to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal or alkaline earth metal fluorides, but also the corresponding oxides (eg LiF, Li₂ O, BaF₂ , MgO, NaF, etc.) The layer thickness of this layer is preferably between 0.1 and 10 nm, more preferably between 0.2 and 8 nm and most preferably between 0.5 and 5 nm.

陽極較佳地包含具有高功函數的材料。陽極較佳具有相對於真空大於4.5 eV的電位。一方面，適合此目的者係具有高氧化還原電位的金屬，諸如例如Ag、Pt或Au。另一方面，金屬/金屬氧化物電極(例如Al/Ni/NiO_x、Al/PtO_x)亦可係較佳的。對於一些應用，電極中之至少一者必須是透明的，以便促進有機材料(O-SC)的照射或光的耦合輸出(OLED/PLED、O-雷射)。較佳的結構使用透明陽極。較佳的陽極材料在此係導電的混合金屬氧化物。特佳者係氧化銦錫(ITO)或氧化銦鋅(IZO)。進一步較佳者係導電的經摻雜有機材料，特別是導電的經摻雜聚合物，諸如例如聚(乙烯二氧基噻吩)(PEDOT)及聚苯胺(PANI)或這些聚合物的衍生物。此外較佳的是將p‑摻雜的電洞傳輸材料作為電洞注入層施加至陽極，其中合適的p-摻雜劑係金屬氧化物，例如MoO₃或WO₃、或(全)氟化缺電子芳族化合物。其他合適的p-摻雜劑係HAT-CN(六氰基六氮雜聯伸三苯)或來自Novaled之化合物NDP9。此類型之層簡化了具有低HOMO(亦即具有大值之HOMO)的材料中之電洞注入。The anode preferably comprises a material with a high work function. The anode preferably has a potential greater than 4.5 eV relative to vacuum. On the one hand, metals with a high redox potential, such as, for example, Ag, Pt or Au, are suitable for this purpose. On the other hand, metal/metal oxide electrodes (e.g., Al/Ni/NiO_x , Al/PtO_x ) may also be preferred. For some applications, at least one of the electrodes must be transparent in order to facilitate the irradiation of organic materials (O-SC) or the coupling-out of light (OLED/PLED, O-laser). The preferred structure uses a transparent anode. The preferred anode material here is a conductive mixed metal oxide. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Further preferred are electrically conductive doped organic materials, in particular electrically conductive doped polymers, such as, for example, poly(ethylenedioxythiophene) (PEDOT) and polyaniline (PANI) or derivatives of these polymers. It is also preferred to apply a p-doped hole transport material as hole injection layer to the anode, suitable p-dopants being metal oxides, such as MoO₃ or WO₃ , or (per)fluorinated electron-deficient aromatic compounds. Other suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NDP9 from Novaled. Layers of this type simplify hole injection in materials with a low HOMO, i.e. with a large HOMO.

通常，用於根據先前技術之層的所有材料皆可用於其他層中，並且所屬技術領域中具有通常知識者將能夠將這些材料中之各者與根據本發明之材料組合於電子裝置中而無需進步性。Generally, all materials used for layers according to the prior art can be used in other layers, and a person having ordinary skill in the art will be able to combine each of these materials with the materials according to the invention in an electronic device without further developments.

該裝置取決於應用，本身以已知的方式對應地結構化，設置有觸點且最終氣密式密封，因為此類裝置的壽命在水及/或空氣的存在下急劇縮短。The device is structured accordingly in a known manner, depending on the application, provided with contacts and ultimately sealed hermetically, since the service life of such devices is drastically shortened in the presence of water and/or air.

根據本發明之調配物及由其獲得的電子裝置，特別是有機電致發光裝置相較於先前技術，具有下列令人驚奇的優點中之一或多者： 1.   相較於使用習知方法所獲得的電子裝置，使用根據本發明之調配物可獲得的電子裝置展現出非常高的穩定性及非常長的壽命。 2.   根據本發明之調配物可使用習知方法處理，藉此亦可實現成本優勢。 3.   根據本發明之調配物中所使用的有機功能性材料不受任何特別限制，使得本發明之方法能夠被廣泛地使用。 4.   使用本發明之調配物可獲得的塗層展現出優異的品質，特別是關於塗層的均勻度。The formulation according to the present invention and the electronic devices obtained therefrom, in particular the organic electroluminescent devices, have one or more of the following surprising advantages compared to the prior art:1.   Compared to the electronic devices obtained using the known methods, the electronic devices obtained using the formulation according to the present invention exhibit very high stability and very long life.2.   The formulation according to the present invention can be processed using known methods, thereby also achieving cost advantages.3.   The organic functional materials used in the formulation according to the present invention are not subject to any special restrictions, so that the method of the present invention can be widely used.4.   The coatings obtainable using the formulations of the present invention exhibit excellent quality, especially with regard to the uniformity of the coating.

上述這些優點不伴隨其他電子性質的損害。These advantages are not accompanied by any loss of other electronic properties.

應當指出，在本發明中描述的實施例之變化均落入本發明之範疇。除非明確排除，否則本發明中所揭示之各特徵皆可由當作相同、等效或類似目的之替代性特徵置換。因此，除非另有說明，否則本發明中所揭示之各特徵皆應被視為上位系列之實例或為等效或類似特徵。It should be noted that variations of the embodiments described in the present invention all fall within the scope of the present invention. Unless explicitly excluded, each feature disclosed in the present invention may be replaced by an alternative feature that serves the same, equivalent or similar purpose. Therefore, unless otherwise stated, each feature disclosed in the present invention should be regarded as an example of a superordinate series or as an equivalent or similar feature.

除非某些特徵及/或步驟係互斥的，否則本發明之所有特徵可以任何方式彼此組合。這特別適用於本發明之較佳特徵。同樣地，非必要組合之特徵可單獨使用(且不組合)。Unless certain features and/or steps are mutually exclusive, all features of the present invention can be combined with each other in any way. This applies in particular to the preferred features of the present invention. Similarly, features that are not necessarily combined can be used alone (and not combined).

亦應指出，許多特徵且特別是本發明之較佳實施例的特徵，其本身具有進步性，而不僅僅被視為是本發明之實施例之一部分。對於這些特徵，可尋求獨立保護來額外或替代目前所請之各發明。It should also be noted that many features, especially those of the preferred embodiments of the present invention, are themselves advanced and are not merely considered to be part of the embodiments of the present invention. For these features, independent protection may be sought in addition to or in place of the various inventions currently claimed.

與本發明一起揭示之技術教示可係抽象的並與其他實例組合。The technical teachings disclosed with the present invention may be abstracted and combined with other examples.

以下參考工作實例更詳細解釋本發明，但不限於此。The following reference working examples explain the present invention in more detail, but are not limited thereto.

所屬技術領域中具有通常知識者將能夠使用說明書來生產根據本發明之其他電子裝置，而不需要採用進步性技能，並且因此可在所請之通篇範圍內實施本發明。工作實例A)合成例：A person having ordinary skill in the art will be able to use the instructions to produce other electronic devices according to the invention without resorting to advanced techniques and thus can implement the invention within the scope of the application.Working ExamplesA)Synthesis Example:

將高沸點溶劑1-苯基萘(PNA)進行氘化以獲得D-PNA。The high boiling point solvent 1-phenylnaphthalene (PNA) was deuterated to obtain D-PNA.

將100 g的PNA與1470 g的D₂O及30 g的5% C上Pt混合。將混合物在密閉容器中在180至190℃下攪拌72小時。 濾掉催化劑並將兩相分離。將D₂O層用300 ml甲基三級丁基醚(MTB醚)萃取三次。將有機相用200 ml飽和NaCl溶液並以Na₂SO₄乾燥。過濾後將MTB醚在真空中蒸發以得到92 g黃色澄清液體。 將粗產物在減壓下蒸餾，以產出68.2 g的主要餾分(在135℃下、在0.65毫巴下沸騰)。 藉由NMR判定氘化度為96%。100 g of PNA were mixed with 1470 g of D₂ O and 30 g of 5% Pt on C. The mixture was stirred in a sealed container at 180 to 190° C. for 72 hours. The catalyst was filtered off and the two phases were separated. The D₂ O layer was extracted three times with 300 ml of methyl tertiary butyl ether (MTB ether). The organic phase was treated with 200 ml of saturated NaCl solution and dried over Na₂ SO_4. After filtration, the MTB ether was evaporated in vacuo to give 92 g of a yellow clear liquid. The crude product was distilled under reduced pressure to yield 68.2 g of the main distillate (boiling at 135° C. at 0.65 mbar). The degree of deuteration was determined to be 96% by NMR.

用Haake-Mars III旋轉黏度計使用錐板幾何形狀(1°錐體，60 mm直徑)測量黏度。 57.9 mPa*s(@25℃, @500 s^-1)。Viscosity was measured with a Haake-Mars III rotational viscometer using a cone-plate geometry (1° cone, 60 mm diameter). 57.9 mPa*s (@25°C, @500 s^-1 ).

用Krüss DSA100以懸滴模式測量表面張力(假設密度與PNA相同，1.088 g/cm³）。 41.23 mN/m(@23.8℃)。B)裝置實例：實例1：a) 膜及裝置之製備Surface tension was measured using Krüss DSA100 in hanging drop mode (assuming the density is the same as PNA, 1.088 g/cm³). 41.23 mN/m (@23.8℃).B)Device examples:Example1: a) Preparation of membrane and device

使用超音波於去離子水中清洗覆蓋有預先結構化的ITO(50 nm)及觸排材料(bank material)的玻璃基板。接下來，使用氣槍乾燥基板，隨後在230℃的加熱板上退火2小時。Glass substrates covered with pre-structured ITO (50 nm) and bank material were cleaned by ultrasound in deionized water. Next, the substrates were dried using an air gun and subsequently annealed on a hot plate at 230°C for 2 hours.

所有以下程序步驟均在黃光下進行。All the following procedure steps were performed under yellow light.

以下層順序顯示於圖1中。The following layer sequence is shown in Figure 1.

將電洞注入層(HIL)噴墨印刷到基板上，厚度為25 nm，並在真空中乾燥。為此，HIL墨水固體濃度為7 g/l。然後將HIL在225℃下退火30分鐘。在空氣中進行HIL的噴墨列印及退火。作為HIL材料，將電洞傳輸之可交聯聚合物及p-摻雜鹽溶解於3-苯氧基甲苯中。這些材料描述於例如WO 2016/107668、WO 2013/081052及EP 2325190中。The hole injection layer (HIL) was inkjet printed onto the substrate with a thickness of 25 nm and dried in vacuum. For this purpose, the HIL ink solid concentration was 7 g/l. The HIL was then annealed at 225° C. for 30 minutes. Inkjet printing and annealing of the HIL were performed in air. As HIL materials, a crosslinkable polymer for hole transport and a p-doped salt were dissolved in 3-phenoxytoluene. These materials are described, for example, in WO 2016/107668, WO 2013/081052 and EP 2325190.

在HIL頂部，在環境條件下噴墨印刷電洞傳輸層，在真空中乾燥並在氮氣氣氛中在230℃下退火30分鐘。電洞傳輸層係表1中所示結構之聚合物(HTM1)，其係根據WO 2013/156130合成的。On top of the HIL, a hole transport layer was inkjet printed under ambient conditions, dried in vacuum and annealed at 230 °C for 30 min in a nitrogen atmosphere. The hole transport layer was a polymer (HTM1) with the structure shown in Table 1, which was synthesized according to WO 2013/156130.

將聚合物溶解於3-苯氧基甲苯中，使得溶液一般具有大約6 g/l的固體含量，若如本文所述，則係藉由噴墨印刷來達到裝置之典型的15 nm之層厚度。The polymer was dissolved in 3-phenoxytoluene to a solution typically having a solids content of about 6 g/l and, as described herein, was inkjet printed to achieve a typical layer thickness of 15 nm for the device.

發射層包含二種基質材料H1及H2以及發射體E1，其結構如下表1中所述。材料係用20% H1、60% H2及20% E1混合的。將發光層之混合物溶解於表2中所示之溶劑組合中。此類溶液的固體含量係約18 mg/ml，若如本文所述，則係藉由噴墨印刷來達到裝置之典型的60 nm之層厚度。綠色發射層(G-EML)亦係噴墨印刷的，然後真空乾燥並在150℃下退火10分鐘。噴墨印刷係在環境氣氛中進行，而退火則係在氮氣氣氛中進行。The emissive layer comprises two base materials H1 and H2 and an emitter E1, the structure of which is described in Table 1 below. The materials are mixed with 20% H1, 60% H2 and 20% E1. The mixture of the luminescent layer is dissolved in the solvent combination shown in Table 2. The solid content of such a solution is about 18 mg/ml, and if as described in this article, it is achieved by inkjet printing to achieve a typical layer thickness of 60 nm for the device. The green emission layer (G-EML) is also inkjet printed, then vacuum dried and annealed at 150°C for 10 minutes. Inkjet printing is carried out in ambient atmosphere, while annealing is carried out in a nitrogen atmosphere.

為了製備根據圖1之用於電光表徵的裝置，接著將樣本轉移到真空沉積室中，其中使用熱蒸發進行二個電子傳輸層(ETL1, ETL2)、一電子注入層(EIL)及一陰極(Al)的沉積。特此，ETL1由ETM1(10 nm膜厚度)組成，而ETL2由ETM1及ETM2(40 nm膜厚度)之1:1體積%混合物組成。電子注入層由ETM2(1 nm)組成，且陰極係鋁(100 nm)。結構顯示於表1中。To prepare the device for electro-optical characterization according to FIG. 1 , the sample was then transferred to a vacuum deposition chamber, where deposition of two electron transport layers (ETL1, ETL2), an electron injection layer (EIL) and a cathode (Al) was performed using thermal evaporation. Hereby, ETL1 consisted of ETM1 (10 nm film thickness) and ETL2 consisted of a 1:1 vol. % mixture of ETM1 and ETM2 (40 nm film thickness). The electron injection layer consisted of ETM2 (1 nm) and the cathode was aluminum (100 nm). The structure is shown in Table 1.

蒸發後，將裝置在氮氣氣氛中之手套箱中封裝。After evaporation, the device was packaged in a glove box under a nitrogen atmosphere.

b) 裝置結果b) Device Results

根據a)部分製備裝置。Ref.1係參考範例，而Ex.1係根據本發明之實例。 為了判定所製造之OLED的裝置性能，藉由標準方法對其進行表徵。為此目的，記錄電致發光光譜、假設朗伯發射特性及(操作)壽命的電流/電壓/發光密度特性曲線(IUL特性曲線)。IUL特性曲線係用於判定特性特徵優質，諸如在某種亮度下之外部量子效率(以%計)。這些裝置在所施加的電壓斜坡之各步均由恆定電壓驅動。裝置壽命係在對應於初始亮度時之給定電流下測量的。然後藉由校準的光電二極體隨時間測量亮度。Devices are prepared according to part a). Ref.1 is a reference example and Ex.1 is an example according to the invention.In order to determine the device performance of the manufactured OLEDs, they are characterized by standard methods. For this purpose, the electroluminescence spectrum, the current/voltage/luminescence density characteristic curve assuming Lambertian emission characteristics and the (operating) lifetime are recorded (IUL characteristic curve). The IUL characteristic curve is used to determine the quality of characteristic features, such as the external quantum efficiency (in %) at a certain brightness. The devices are driven by a constant voltage at each step of the applied voltage ramp. The device lifetime is measured at a given current corresponding to the initial brightness. The brightness is then measured over time by a calibrated photodiode.

在表3中，彙總相對外部量子效率(在1000 cd/m²下之相對EQE)及相對裝置壽命(在1000 cd/m²下之相對LT90)。In Table 3, the relative external quantum efficiency (relative EQE at 1000 cd/m² ) and the relative device lifetime (relative LT90 at 1000 cd/m² ) are summarized.

可看出，藉由使用含有氘化高沸點溶劑之溶劑組合的裝置實例Ex.1比使用非氘化高沸點溶劑的參考實施例Ref.1，達成了更佳的裝置性能及顯著更高的壽命。表示裝置性能的改善主要歸功於溶劑組成。實例2：a) 膜及裝置之製備It can be seen that the device example Ex.1 using the solvent composition containing the deuterated high boiling point solvent achieves better device performance and significantly longer life than the reference example Ref.1 using the non-deuterated high boiling point solvent. This indicates that the improvement in device performance is mainly attributed to the solvent composition.Example2: a) Preparation of membrane and device

使用超音波於去離子水中清洗覆蓋有預先結構化的ITO(50 nm)及觸排材料(bank material)的玻璃基板。接下來，使用氣槍乾燥基板，隨後在230℃的加熱板上退火2小時。Glass substrates covered with pre-structured ITO (50 nm) and bank material were cleaned by ultrasound in deionized water. Next, the substrates were dried using an air gun and subsequently annealed on a hot plate at 230°C for 2 hours.

所有以下程序步驟均在黃光下進行。All the following procedure steps were performed under yellow light.

以下層順序顯示於圖1中。The following layer sequence is shown in Figure 1.

將電洞注入層(HIL)噴墨印刷到基板上，厚度為20 nm，並在真空中乾燥。為此，HIL墨水固體濃度為6 g/l。然後將HIL在225℃下退火30分鐘。在空氣中進行HIL的噴墨列印及退火。作為HIL材料，將電洞傳輸之可交聯聚合物及p-摻雜鹽溶解於3-苯氧基甲苯中。這些材料描述於例如WO 2016/107668、WO 2013/081052及EP 2325190中。The hole injection layer (HIL) was inkjet printed onto the substrate with a thickness of 20 nm and dried in vacuum. For this purpose, the HIL ink solid concentration was 6 g/l. The HIL was then annealed at 225° C. for 30 minutes. Inkjet printing and annealing of the HIL were performed in air. As HIL materials, a hole-transporting crosslinkable polymer and a p-doped salt were dissolved in 3-phenoxytoluene. These materials are described, for example, in WO 2016/107668, WO 2013/081052 and EP 2325190.

在HIL頂部，在環境條件下噴墨印刷電洞傳輸層，在真空中乾燥並在氮氣氣氛中在230℃下退火30分鐘。電洞傳輸層係表4中所示結構之聚合物(HTM2)，其係根據WO 2018/114882 A1合成的(聚合物Po32)。將聚合物溶解於3-苯氧基甲苯中，使得溶液一般具有大約5 g/l的固體含量，若如本文所述，則係藉由噴墨印刷來達到裝置之典型的20 nm之層厚度。On top of the HIL, a hole transport layer was inkjet printed under ambient conditions, dried in vacuum and annealed at 230 °C for 30 min in a nitrogen atmosphere. The hole transport layer was a polymer (HTM2) of the structure shown in Table 4, synthesized according to WO 2018/114882 A1 (polymer Po32). The polymer was dissolved in 3-phenoxytoluene so that the solution generally had a solid content of about 5 g/l and was inkjet printed to achieve a typical layer thickness of 20 nm for the device as described herein.

發射層包含基質材料H3及發射體E2，其結構如下表4中所述。材料係用98% H3及2% E2混合的。將發光層之混合物溶解於表5中所示之溶劑組合中。此類溶液的固體含量係約9 mg/ml，若如本文所述，則係藉由噴墨印刷來達到裝置之典型的35 nm之層厚度。藍色發射層(B-EML)亦係噴墨印刷的，然後真空乾燥並在150℃下退火10分鐘。噴墨印刷係在環境氣氛中進行，而退火則係在氮氣氣氛中進行。The emissive layer comprises a matrix material H3 and an emitter E2, the structure of which is described in Table 4 below. The materials are mixed with 98% H3 and 2% E2. The mixture of the luminescent layer is dissolved in the solvent combination shown in Table 5. The solid content of such a solution is about 9 mg/ml, and if as described herein, a typical layer thickness of 35 nm of the device is achieved by inkjet printing. The blue emissive layer (B-EML) is also inkjet printed, then vacuum dried and annealed at 150°C for 10 minutes. Inkjet printing is performed in ambient atmosphere, while annealing is performed in a nitrogen atmosphere.

為了製備根據圖1之用於電光表徵的裝置，接著將樣本轉移到真空沉積室中，其中使用熱蒸發進行二個電子傳輸層(ETL1, ETL2)、一電子注入層(EIL)及一陰極(Al)的沉積。特此，ETL1由ETM1(10 nm膜厚度)組成，而ETL2由ETM1及ETM2(40 nm膜厚度)之1:1體積%混合物組成。電子注入層由ETM2(1 nm)組成，且陰極係鋁(100 nm)。結構顯示於表4中。To prepare a device according to FIG. 1 for electro-optical characterization, the sample was then transferred to a vacuum deposition chamber, where deposition of two electron transport layers (ETL1, ETL2), an electron injection layer (EIL) and a cathode (Al) was performed using thermal evaporation. Hereby, ETL1 consisted of ETM1 (10 nm film thickness) and ETL2 consisted of a 1:1 vol. % mixture of ETM1 and ETM2 (40 nm film thickness). The electron injection layer consisted of ETM2 (1 nm) and the cathode was aluminum (100 nm). The structure is shown in Table 4.

蒸發後，將裝置在氮氣氣氛中之手套箱中封裝。After evaporation, the device was packaged in a glove box under a nitrogen atmosphere.

b) 裝置結果b) Device Results

根據a)部分製備裝置。Ref.2係參考範例，而Ex.2係根據本發明之實例。 為了判定所製造之OLED的裝置性能，藉由標準方法對其進行表徵。為此目的，記錄電致發光光譜、假設朗伯發射特性及(操作)壽命的電流/電壓/發光密度特性曲線(IUL特性曲線)。IUL特性曲線係用於判定特性特徵優質，諸如在某種亮度下之外部量子效率(以%計)。這些裝置在所施加的電壓斜坡之各步均由恆定電壓驅動。裝置壽命係在對應於初始亮度時之給定電流下測量的。然後藉由校準的光電二極體隨時間測量亮度。Devices are prepared according to part a). Ref.2 is a reference example and Ex.2 is an example according to the invention.In order to determine the device performance of the manufactured OLEDs, they are characterized by standard methods. For this purpose, the electroluminescence spectrum, the current/voltage/luminescence density characteristic curve assuming Lambertian emission characteristics and the (operating) lifetime are recorded (IUL characteristic curve). The IUL characteristic curve is used to determine the quality of characteristic features, such as the external quantum efficiency (in %) at a certain brightness. The devices are driven by a constant voltage at each step of the applied voltage ramp. The device lifetime is measured at a given current corresponding to the initial brightness. The brightness is then measured over time by means of a calibrated photodiode.

在表6中，彙總相對電壓、相對外部量子效率(在1000 cd/m²下之相對EQE)及相對裝置壽命(在1000 cd/m²下之相對LT90)、以及CIE色座標。In Table 6, the relative voltage, relative external quantum efficiency (relative EQE at 1000 cd/m² ) and relative device lifetime (relative LT90 at 1000 cd/m² ) are summarized, as well as the CIE color coordinates.

可看出，使用含有氘化高沸點溶劑之溶劑組合的裝置實例Ex.2比使用非氘化高沸點溶劑的參考實施例Ref.2，達成了更佳的裝置性能及顯著更高的壽命。表示裝置性能的改善主要歸功於溶劑組成。It can be seen that the device example Ex.2 using the solvent combination containing the deuterated high boiling point solvent achieves better device performance and significantly longer life than the reference example Ref.2 using the non-deuterated high boiling point solvent, indicating that the improvement in device performance is mainly attributed to the solvent composition.

[圖1]顯示裝置的典型層結構，其含有基板、ITO陽極、電洞注入層(HIL)、電洞傳輸層(HTL)、綠光發射層(G-EML)、二個電子傳輸層(ETL1及ETL2)、電子注入層E(IL)及鋁陰極。[Figure 1] shows the typical layer structure of the device, which includes a substrate, an ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a green light emitting layer (G-EML), two electron transport layers (ETL1 and ETL2), an electron injection layer E(IL), and an aluminum cathode.

Claims (23)

Translated fromChinese

一種調配物，其含有至少一種有機功能性材料及至少一種有機溶劑A，較佳地至少兩種不同的有機溶劑A及B，其特徵在於至少一種有機溶劑係氘化度為至少25%、較佳地至少50%、更佳地至少75%及最佳地至少90%的氘化溶劑。A formulation containing at least one organic functional material and at least one organic solvent A, preferably at least two different organic solvents A and B, characterized in that at least one organic solvent is a deuterated solvent having a deuteration degree of at least 25%, preferably at least 50%, more preferably at least 75% and most preferably at least 90%.如請求項1之調配物，其中其含有至少兩種不同的有機溶劑，第一有機溶劑A及第二有機溶劑B，其中該第一有機溶劑A及/或該第二有機溶劑B係氘化溶劑。The formulation of claim 1, wherein it contains at least two different organic solvents, a first organic solvent A and a second organic solvent B, wherein the first organic solvent A and/or the second organic solvent B is a deuterated solvent.如請求項2之調配物，其中該第一有機溶劑A及該第二有機溶劑B各自的沸點在100至400℃之範圍內。The formulation of claim 2, wherein the first organic solvent A and the second organic solvent B each have a boiling point in the range of 100 to 400°C.如請求項2或3之調配物，其中在於該第二有機溶劑B具有比該第一有機溶劑A更高的沸點，且該第二有機溶劑B的沸點比該第一有機溶劑A的沸點高至少10℃、較佳地至少20℃。The formulation of claim 2 or 3, wherein the second organic solvent B has a higher boiling point than the first organic solvent A, and the boiling point of the second organic solvent B is higher than the boiling point of the first organic solvent A by at least 10°C, preferably at least 20°C.如請求項2至4中一或多項之調配物，其中該第二有機溶劑的沸點在250至350℃之範圍內。The formulation of one or more of claims 2 to 4, wherein the second organic solvent has a boiling point in the range of 250 to 350°C.如請求項2至5中一或多項之調配物，其中該第一有機溶劑A及該第二有機溶劑B各自的黏度在1至60 mPas之範圍內、較佳地在2至50 mPas之範圍內。The formulation of one or more of claims 2 to 5, wherein the viscosity of each of the first organic solvent A and the second organic solvent B is in the range of 1 to 60 mPas, preferably in the range of 2 to 50 mPas.如請求項2至6中一或多項之調配物，其中該第二有機溶劑B比該第一有機溶劑A具有更高的黏度，且該第二有機溶劑B的黏度比該第一有機溶劑A的黏度高至少5 mPas、較佳地至少10 mPas。The formulation of one or more of claims 2 to 6, wherein the second organic solvent B has a higher viscosity than the first organic solvent A, and the viscosity of the second organic solvent B is higher than the viscosity of the first organic solvent A by at least 5 mPas, preferably at least 10 mPas.如請求項2至7中一或多項之調配物，其中該第二有機溶劑B的黏度為＞15 mPas、較佳地＞20 mPas且更佳地＞25 mPas。The formulation of one or more of claims 2 to 7, wherein the viscosity of the second organic solvent B is >15 mPas, preferably >20 mPas and more preferably >25 mPas.如請求項2至8中一或多項之調配物，其中該第一有機溶劑A係該氘化溶劑。The formulation of one or more of claims 2 to 8, wherein the first organic solvent A is the deuterated solvent.如請求項2至8中一或多項之調配物，其中該第二有機溶劑B係該氘化溶劑。The formulation of one or more of claims 2 to 8, wherein the second organic solvent B is the deuterated solvent.如請求項2至10中一或多項之調配物，其中該第一有機溶劑A的含量在50至99.9體積%之範圍內，以該調配物中溶劑之總量計。The formulation of one or more of claims 2 to 10, wherein the content of the first organic solvent A is in the range of 50 to 99.9 volume %, based on the total amount of solvents in the formulation.如請求項2至11中一或多項之調配物，其中該第二有機溶劑B的含量在0.1至50體積%之範圍內，以該調配物中溶劑之總量計。The formulation of one or more of claims 2 to 11, wherein the content of the second organic solvent B is in the range of 0.1 to 50 volume %, based on the total amount of solvents in the formulation.如請求項2至10中一或多項之調配物，其中該第二有機溶劑B係選自萘衍生物、部分氫化萘衍生物、完全氫化萘衍生物、茚烷衍生物及完全氫化蒽衍生物。The formulation of one or more of claims 2 to 10, wherein the second organic solvent B is selected from naphthalene derivatives, partially hydrogenated naphthalene derivatives, fully hydrogenated naphthalene derivatives, indane derivatives and fully hydrogenated anthracene derivatives.如請求項1至13中一或多項之調配物，其中該調配物的表面張力在15至70 mN/m之範圍內。The formulation of one or more of claims 1 to 13, wherein the surface tension of the formulation is in the range of 15 to 70 mN/m.如請求項1至14中一或多項之調配物，其中該調配物的黏度在0.8至50 mPas之範圍內。The formulation of one or more of claims 1 to 14, wherein the viscosity of the formulation is in the range of 0.8 to 50 mPas.如請求項1至15中一或多項之調配物，其中該調配物中之該至少一種有機功能性材料的含量在0.001至20重量%之範圍內，以該調配物之總重量計。The formulation of one or more of claims 1 to 15, wherein the content of the at least one organic functional material in the formulation is in the range of 0.001 to 20 wt %, based on the total weight of the formulation.如請求項1至16中一或多項之調配物，其中該至少一種有機功能性材料係選自由下列所組成之群組：有機導體、有機半導體、有機螢光化合物、有機磷光化合物、有機光吸收化合物、有機光敏化合物、有機光敏化劑及其他有機光活性化合物，諸如過渡金屬、稀土、鑭系元素及錒系元素之有機金屬錯合物。A formulation as in one or more of claims 1 to 16, wherein the at least one organic functional material is selected from the group consisting of: organic conductors, organic semiconductors, organic fluorescent compounds, organic phosphorescent compounds, organic light absorbing compounds, organic photosensitizers and other organic photoactive compounds, such as organic metal complexes of transition metals, rare earths, ruthenium elements and ruthenium elements.如請求項17之調配物，其中該至少一種有機功能性材料係選自由下列所組成之群組的有機半導體：螢光發射體、磷光發射體、主體材料、基質材料、激子阻擋材料、電子傳輸材料、電子注入材料、電洞導體材料、電洞注入材料、n-摻雜劑、p-摻雜劑、寬帶隙材料、電子阻擋材料及電洞阻擋材料。A formulation as in claim 17, wherein the at least one organic functional material is an organic semiconductor selected from the group consisting of: a fluorescent emitter, a phosphorescent emitter, a host material, a matrix material, an exciton blocking material, an electron transport material, an electron injection material, a hole conductor material, a hole injection material, an n-dopant, a p-dopant, a wide bandgap material, an electron blocking material and a hole blocking material.如請求項18之調配物，其中該至少一種有機功能性材料係選自由下列所組成之群組的有機半導體：電洞注入材料、電洞傳輸材料、發光材料、電子傳輸材料及電子注入材料。The formulation of claim 18, wherein the at least one organic functional material is an organic semiconductor selected from the group consisting of: hole injection materials, hole transport materials, light-emitting materials, electron transport materials and electron injection materials.如請求項1至19中一或多項之調配物，其中該至少一種有機功能性材料係氘化有機功能性材料。The formulation of one or more of claims 1 to 19, wherein the at least one organic functional material is a deuterated organic functional material.一種用於製備如請求項1至20中一或多項之調配物之方法，其特徵在於，將該至少一種有機功能性材料及該至少一種有機溶劑A混合。A method for preparing a formulation as claimed in one or more of claims 1 to 20, characterized in that the at least one organic functional material and the at least one organic solvent A are mixed.一種用於製備電子裝置之方法，其特徵在於該電子裝置之至少一個功能層係藉由將如請求項1至20中之一或多項之調配物沉積、較佳地印刷、更佳地噴墨印刷在表面上並隨後乾燥來製備。A method for producing an electronic device, characterized in that at least one functional layer of the electronic device is produced by depositing, preferably printing, more preferably inkjet printing, a formulation according to one or more of claims 1 to 20 onto a surface and subsequently drying it.一種電子裝置，其特徵在於至少一個功能層係藉由將如請求項1至20中一或多項之調配物沉積、較佳地印刷、更佳地噴墨印刷在表面上並隨後乾燥來製備。An electronic device, characterized in that at least one functional layer is produced by depositing, preferably printing, more preferably inkjet printing, a formulation according to one or more of claims 1 to 20 onto a surface and subsequently drying it.

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