CN102186800B - 用于光电子器件的2,5-连接的聚芴 - Google Patents
用于光电子器件的2,5-连接的聚芴 Download PDFInfo
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- CN102186800B CN102186800B CN200980141362.XA CN200980141362A CN102186800B CN 102186800 B CN102186800 B CN 102186800B CN 200980141362 A CN200980141362 A CN 200980141362A CN 102186800 B CN102186800 B CN 102186800B
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- 230000005693 optoelectronics Effects 0.000 title claims description 7
- 229920002098 polyfluorene Polymers 0.000 title abstract description 16
- 239000000126 substance Substances 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- -1 aryl compound Chemical class 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
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- 125000000732 arylene group Chemical group 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000005259 triarylamine group Chemical group 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
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- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract description 34
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- 239000000203 mixture Substances 0.000 description 23
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 5
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- VDULMXJUOWIPGE-UHFFFAOYSA-N 1-phenylisoquinoline quinoline Chemical class N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)C1=NC=CC2=CC=CC=C12 VDULMXJUOWIPGE-UHFFFAOYSA-N 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
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- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/42—Halogenated derivatives containing six-membered aromatic rings and other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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Abstract
具有相当量(10-100%)的芴的聚芴聚合物和共聚物在其中需要三线态能量>2.10eV的OLED器件中可用作活性层,所述相当量(10-100%)的芴连接在芴的2位和5位。
Description
关于联邦资助的研究和开发的声明
本发明根据美国能源部授予的合同号DE-FC26-05NT42343在政府支持下完成。政府可拥有本发明的某些权利。
背景
本发明主要涉及2,5-二取代的芴单体、由其衍生的低聚物和聚合物以及含所述低聚物和聚合物的光电子器件。
聚芴均聚物和共聚物作为用于聚合物有机发光器件中的活性层的优选的物质出现。术语“聚芴”一般指通过在分子的2位和7位连接芴单体单元生成的聚合物。此连接方式通过芳基提供线性共轭,产生具有可得到带隙、优良电荷输送性质和极佳成膜性质的聚合物。另外,由于这些位置朝向亲电子试剂最具反应性,在2和7位芴的官能化很容易完成。2,7-二官能芴与适合二官能亚芳基单体共聚提供具有可调谐带隙的共聚物,所述带隙取决于所用的共聚单体结构。
从芳基偶联反应衍生的2,7-连接芴链段的连续积累产生具有单线态(S1)能量和三线态(T1)能量的共轭亚芳基链,所述能量随低聚物长度最高达约7个芴单元改变(表1)。2,5-和2,7-笏物质的三线态能量数据部分根据“Comparison of the chain length dependence of the singlet-and triplet-excited states of oligofluorenes”(低聚芴的单线激发态和三线激发态的链长依赖性比较),Chemical Physics Letters,Vol.411,pg.273,2005年7月1号。可以看到,对于芴基物质,单线态和三线态的相对能量相关,因此,显示较高单线态能量的物质也显示较高三线态能量。
表1.2,7-连接芴作为芴链段数函数的单线态(S1)能量和三线态(T1)能量
芴链段# | S1(eV) | T1(eV) |
1 | 2.85 | |
2 | 3.35 | 2.30 |
3 | 3.19 | 2.25 |
5 | 3.05 | 2.18 |
7 | 3.02 | 2.16 |
聚合物 | 2.97 | 2.11 |
在OLED器件中,从阴极和阳极注入的电子和空穴分别在发射层中组合,产生能够衰减的单线态和三线态激子,从而辐射产生光或非辐射产生热。对于聚芴和其他轭合聚合物,来自三线态的发光为自旋禁戒过程,此过程与衰减非辐射模式不完全竞争,因此,三线态激子不具有很大发射性。在基于这些物质的器件中,从活性层中产生的三线态激子提取光非常合乎需要,因为每个单线态激子在统计上产生三个这样的激子。由于自旋轨道耦合,过渡金属络合物可以与非辐射途径竞争的效率辐射衰减。在这些络合物结合到聚合物OLED器件时,可能达到近100%内量子效率,因为在器件中产生的单线态激子和三线态激子两者均可发光。
2,7-连接的聚芴物质的相对低三线态能量(表1)使能够在这些器件中加入的过渡金属络合物限于从三线态发红光或橙光的那些。为了在扩展可与这些物质一起使用的磷光发射体的颜色范围的同时,利用聚芴聚合物和共聚物在OLED器件中作为层的合乎需要的特征,需要具有较高三线态能量的2,7-连接的聚芴类似物。
发明概述
一方面,本发明涉及式I的化合物
其中R1和R2在每次出现时独立为H、C1-20烃基、含一个或多个S、N、O、P或Si原子的C1-20烃基、C4-16烃基羰基氧基、C4-16芳基(三烷基甲硅烷氧基),或者R1和R2与其间的(intervening)碳原子结合在一起形成C5-20烃基环或含至少一个S、N或O杂原子的C4-20烃基环;
R3和R4在每次出现时独立为C1-20烃基、C1-20烃基氧基、C1-20硫醚、C1-20烃基羰基氧基或氰基;
X在每次出现时独立为卤素、三氟甲磺酸酯基、-B(OH)2、-B(OR)2、-BO2R或其组合;
R为烷基或亚烷基;并且
a和b独立为0或1。
另一方面,本发明涉及包含至少一个结构单元的低聚物和聚合物,所述结构单元由至少一种式I的化合物衍生。还另一方面,本发明涉及光电子器件,所述光电子器件具有包含所述低聚物和/或聚合物的发射层。
发明详述
式I的化合物在2-和5-位具有可聚合取代基。这些可以为卤素,更特别是溴;或硼酸或酯,如-B(OH)2、-B(OR)2或-BO2R,其中R为经取代或未取代的亚烷基;或卤素和硼酸酯的组合。单体可在2-和5-位不对称取代,以促进头-尾类型聚合。在本发明上下文中,头-尾是指在聚合期间,各单体在第一单体的2-位和第二单体的5-位之间连接。不对称取代的单体为式II的化合物
其中X和Y之一为卤素或三氟甲磺酸酯基,X和Y的另一个为-B(OH)2、-B(OR)2或-BO2R。在一些实施方案中,X为卤素,Y为-B(OH)2、-B(OR)2或-BO2R,在其他实施方案中,X为-B(OH)2、-B(OR)2或-BO2R,Y为卤素。特别是,X和Y之一为溴,X和Y的另一个为-BO2R。
式I和式II的化合物也在9-/9,9-位单或二取代。R1和R2这些取代基相同或不同,并且可以为烷基、经取代烷基、芳基、经取代芳基、杂芳基或经取代杂芳基。特别是,R1和R2可以为烷氧基苯基或烷基。
2,5,9,9-取代的芴单体可另外在1-、3-、4-、6-、7-或8-位取代,或者在这些位可未取代。在后一种情况下,R3和R4为H。
在具体实施方案中,式I的化合物为下式的化合物:
,式II的化合物为:
式I和II的化合物的实例包括:
在升高温度(40-60℃),通过在酸性介质中用N-溴琥珀酰亚胺溴化芴或芴酮衍生物,可制备式I和II的化合物。直接溴化得到大量的2,5-二溴芴(15-25%)。此异构体或由其衍生的产物可与2,7-异构体分离,并转化成适用于聚合的单体,特别是9-和9,9-取代的化合物。或者,含2,5-和2,7-二溴化芴衍生物的混合物可直接用于制备共聚物。或者,可通过芴衍生物的合理合成路线而不是直接溴化得到2,5-二溴取代的衍生物。
可通过制备聚芴领域已知的方法制备本发明的聚合物和低聚物,包括适合二卤化物和二硼酸酯/二硼酸的Suzuki偶联和Yamamoto偶联。例如,Dow Global Technologies的US 5,708,130、US 5,777,070、US 6,169,163、US 6,255,449、US 6,512,083、US 6593,450和US 6,900285描述含芴亚单元的聚合物的合成,这些专利的全部内容通过引用结合到本文中。
本发明的聚合物和低聚物包含至少一个结构单元,所述结构单元衍生自式I和/或II的至少一种化合物。在本发明上下文中,低聚物与聚合物的区别在于其较低分子量,由小于约20个单体单元组成,包括式I和II的化合物和适合共聚单体和端单元,特别是小于约7个单体单元,更特别是小于约3个单体单元。在一个实施方案中,本发明的低聚物为三聚物,三聚物为由三个单元(即,两个端单元和一个中心单元)组成的低聚物。在一些实施方案中,式I和式II的化合物在头-尾结构中组合成本发明的聚合物和低聚物。
本发明的聚合物和低聚物可另外包括式III的化合物,即,已知的2,7-取代芴单体中的任何化合物
其中R1、R2、R3、R4和X同式I和II化合物的定义。然而,结合到聚芴物质的显著量(10-100%)的2,5-单体单元可生成非完全轭合聚合物和低聚物,导致显著高于仅仅或主要由2,7-单体单元衍生的物质的所得低聚物和聚合物的单线态能量和三线态能量。因此,在很多实施方案中,本发明的聚合物和低聚物包含大于约50%重量的衍生自式I和II化合物的结构单元,特别是大于约90%重量的所述结构单元。
式I和II的化合物与式III的2,7-二取代芴化合物和/或适用于芳基-芳基偶联的其他单体的共聚可类似的产生共聚物,此类共聚物具有高于由2,7-二取代芴单体制成的相应聚合物的S1和T1能量。因此,本发明的聚合物和低聚物可另外包含衍生自轭合化合物的结构单元,包括亚芳基单体(特别是芳基化合物)、杂芳基化合物或三芳基胺。适合的芳基胺描述于Dow Global Technologies的US 5,728,801、US5,929,194、US 5,948,552、US 6,309,763、US 6,605,373、US 6,900,285、WO 2004/060970、WO 2005/049546和WO 2005/052027,这些专利的全部内容通过引用结合到本文中。其他适合亚芳基单体的实例包括1,4-亚苯基或经取代亚苯基、1,3-亚苯基或经取代亚苯基、2,6-亚萘基、9,10-亚蒽基和下式的化合物
本发明的低聚物可另外包含下式的端单元
其中R1、R2、R3、R4和X同式I和II化合物的定义。本发明的低聚物的实例包括
光电子器件,例如OLED,一般在最简单的情况下包括阳极层和相应的阴极层,并且有机电致发光层置于所述阳极和所述阴极之间。在跨电极施加偏压时,电子通过阴极注入电致发光层,同时电子从阳极的电致发光层去除(或者“空穴”“注入”阳极的电致发光层)。在空穴与电子在电致发光层内组合形成单线态或三线态激子时发光,在单线态和/或三线态激子通过辐射衰减衰减到其基态时发光。
除了阳极、阴极和发光物质外,可在OLED中存在的其他部分包括空穴注入层、电子注入层和电子传输层。电子传输层不必与阴极直接接触,并且通常电子传输层也作为空穴阻挡层防止空穴向阴极迁移。可在有机发光器件中存在的另外部分包括空穴传输层、空穴传输发射(发射)层和电子传输发射(发射)层。
OLED器件可以为包含单线态发射体的荧光器件,或磷光器件,该磷光器件包含至少一种三线态发射体或至少一种单线态发射体和至少一种三线态发射体的组合。所述器件可包含蓝色、黄色、橙色、红色磷光染料中的一种或多种、任何染料或其组合,包括但不限于过渡金属(如Ir、Os和Pt)的络合物。可使用适合的电磷光和电荧光金属络合物,包括American Dye Source,Inc.,Quebec,Canada提供的那些。
有机电致发光层,即发射层,为有机发光器件内的层,此层在操作时含显著浓度的电子和空穴两者,并且提供用于激子形成和发光的部位。空穴注入层为与阳极接触的层,此层促进空穴从阳极注入OLED的内层,而电子注入层为与阴极接触的层,此层促进电子从阴极注入OLED,电子传输层则是促进电子从阴极和/或电子注入层传到电荷重组部位的层。在含电子传输层的有机发光器件操作期间,在电子传输层中存在的大部分载流子(即,空穴和电子)为电子,并且可通过发射层中存在的空穴和电子重组发光。空穴传输层是在OLED操作时促进空穴从阳极和/或空穴注入层传到电荷重组部位并且不必与阳极直接接触的层。空穴传输发射层是其中在OLED工作时促进空穴传到电荷重组部位的层,其中大部分载流子为空穴,并且其中发射不仅通过与残余电子重组,而且也通过从器件中别处的电荷重组区域转移能量。电子传输发射层是其中在OLED工作时促进电子传到电荷重组部位的层,其中大部分载流子为电子,并且其中发射不仅通过与残余空穴重组,而且也通过从器件中别处的电荷重组区域转移能量。
适合用作阳极的物质包括但不限于具有通过四点探针技术测定小于约1000欧姆/平方的体电阻率的物质。氧化锡铟(ITO)通常用作阳极,因为它基本上对光透射透明,并因此促进从电活性有机层发射的光逸出。可用作阳极层的其他物质包括氧化锡、氧化铟、氧化锌、氧化锌铟、氧化锡铟锌、氧化锑及其混合物。
适合用作阴极的物质包括可将负载流子(电子)注入OLED一个或多个内层的一般电导体,包括但不限于金属和金属氧化物,如ITO。适合用作阴极的金属包括K、Li、Na、Cs、Mg、Ca、Sr、Ba、Al、Ag、Au、In、Sn、Zn、Zr、Sc、Y、镧系元素、其合金及其混合物。用作阴极层的适合合金物质包括Ag-Mg、Al-Li、In-Mg、Al-Ca和Al-Au合金。分层非合金结构也可用于阴极,如由较厚层金属(如铝或银)覆盖的金属(如钙)或金属氟化物(如LiF)的薄层。特别是,阴极可由单一金属(尤其是铝金属)组成。
适合用于电子传输层的物质包括但不限于聚(9,9-单或二取代的芴)、三(8-羟基喹啉根)合铝(Alq3)、2,9-二甲基-4,7-二苯基-1,1-菲咯啉、4,7-二苯基-1,10-菲咯啉、2-(4-联苯基)-5-(4-叔丁基苯基)-1,3,4-二唑、3-(4-联苯基)-4-苯基-5-(4-叔丁基苯基)-1,2,4-三唑、含1,3,4-二唑的聚合物、含1,3,4-三唑的聚合物、含喹喔啉的聚合物和氰基-PPV。
适用于空穴传输层的物质包括但不限于1,1-双((二-4-甲苯基氨基)苯基)环己烷、N,N′-双(4-甲基苯基)-N,N′-双(4-乙基苯基)-(1,1′-(3,3′-二甲基)联苯基)-4,4′-二胺、四-(3-甲基苯基)-N,N,N′,N′-2,5-苯二胺、苯基-4-N,N-二苯基氨基苯乙烯、对-(二乙基氨基)苯甲醛二苯腙、三苯胺、1-苯基-3-(对-(二乙基氨基)苯乙烯基)-5-(对-(二乙基氨基)苯基)吡唑啉、1,2-反-双(9H-咔唑-9-基)环丁烷、N,N,N′,N′-四(4-甲基苯基)-(1,1′-联苯)-4,4′-二胺、铜酞菁、聚乙烯基咔唑、(苯基甲基)聚硅烷;聚(3,4-亚乙二氧基噻吩)(PEDOT)、聚苯胺、聚乙烯基咔唑、三芳基二胺、四苯基二胺、芳族叔胺、腙衍生物、咔唑衍生物、三唑衍生物、咪唑衍生物、具有氨基的二唑衍生物和聚噻吩,如美国专利号6,023,371所公开。
适用于发光层的物质包括但不限于电致发光聚合物,如聚芴,优选聚(9,9-二辛基芴)及其共聚物,如9,9′-二辛基芴-双-N,N′-(4-丁基苯基)二苯基胺共聚物(F8-TFB);聚(乙烯基咔唑)和聚对苯乙炔及其衍生物。另外,发光层可包括蓝色、黄色、橙色、绿色或红色磷光染料或金属络合物或其组合。适合用作磷光染料的物质包括但不限于三(1-苯基异喹啉)合铱(III)(红色染料)、三(2-苯基吡啶)合铱(绿色染料)和双(2-(4,6-二氟(fluore)苯基)吡啶-N,C2)合铱(III)(蓝色染料)。也可使用购自ADS(American Dyes Source,Inc.)的市售电荧光和电磷光金属络合物。ADS绿色染料包括ADS060GE、ADS061GE、ADS063GE和ADS066GE、ADS078GE及ADS090GE。ADS蓝色染料包括ADS064BE、ADS065BE和ADS070BE。ADS红色染料包括ADS067RE、ADS068RE、ADS069RE、ADS075RE、ADS076RE、ADS067RE和ADS077RE。
本发明的低聚物和聚合物可用于空穴传输层、电子传输层和发射层。例如,由2,5-双-亚乙基二氧杂硼烷基-9,9-双-(4-甲氧基苯基)-芴和二溴三芳基胺反应生成的50/50共聚物适用于空穴传输层。或者,由主要部分的式I和II化合物与较少部分的发射性三芳基胺反应生成的共聚物适用于发射层。或者,发射性聚合物可通过式I和II的化合物与含发射单元的单体(例如,通过芴9-位连接的电荧光和电磷光金属络合物)的反应生成。适合可聚合金属络合物的实例描述于Showa Denko的WO 2003/001616、Dow Global Technologies的WO 20050016945和General Electric Company的WO 2008/014037,其全部内容通过引用结合到本文中。另外,2,5-芴均聚物适合作为电子传输层和深蓝色发射层两者。例如,可使2,5-芴均聚物与发光染料混合成适合用作发射层的掺混物质。发光染料可以为荧光(从主要单线态发射)或磷光(从非主要单线态发射)。另外,本发明的低聚物和聚合物也可作为基质(host)用于具有特定空穴传输、电子传输或发射功能的物质,例如,通过与上列空穴和电子传输物质掺混,以便得到一些所需的电荷传输能力。
定义
在本发明上下文中,除非另外说明,烃基指只含氢和碳的任何有机部分,并且可包括芳族、脂族、脂环族及含两个或更多个脂族、脂环族和芳族部分的部分,包括但不限于烷基、烷基芳基、芳基、芳基烷基及其经取代类似物。含一个或多个S、N、O、P或Si原子的烃基包括但不限于烷氧基、酰基、杂芳基、杂芳基-烷基、氧杂烷基、卤代烷基和甲硅烷基及其经取代类似物。
烷基将包括直链、支链或环状烃结构及其组合,包括低级烷基和高级烷基。优选的烷基为C20或以下的那些。低级烷基是指1至6个碳原子,优选1至4个碳原子的烷基,包括甲基、乙基、正丙基、异丙基、正丁基、仲丁基和叔丁基。高级烷基是指具有7或更多个碳原子,优选7至20个碳原子的烷基,包括正、仲和叔庚基、辛基和十二烷基。环烷基为烷基的一个子集,包括3至8个碳原子的环烃基。环烷基的实例包括环丙基、环丁基、环戊基和降冰片基。烯基和炔基是指其中两个或更多个氢原子分别由双键或三键置换的烷基。
芳基和杂芳基是指含0至3个选自氮、氧或硫的杂原子的5元或6元芳族或杂芳族环;含0至3个选自氮、氧或硫的杂原子的双环9元或10元芳族或杂芳族环系统;或含0至3个选自氮、氧或硫的杂原子的三环13元或14元芳族或杂芳族环系统。芳族6至14元碳环包括例如苯、萘、茚满、萘满和芴,5至10元芳族杂环包括例如咪唑、吡啶、吲哚、噻吩、苯并吡喃酮、噻唑、呋喃、苯并咪唑、喹啉、异喹啉、喹喔啉、嘧啶、吡嗪、四唑和吡唑。
芳基烷基是指连接到芳基环的烷基残基。实例为苄基和苯乙基。杂芳基烷基是指连接到杂芳基环的烷基残基。实例包括吡啶基甲基和嘧啶基乙基。烷基芳基是指具有一个或多个与其连接的烷基的芳基残基。实例为甲苯基和1,3,5-三甲基苯基。
烷氧基或烷氧基是指通过氧连接到母体结构的直链、支链、环状结构及其组合的1至8个碳原子的基团。实例包括甲氧基、乙氧基、丙氧基、异丙氧基、环丙基氧基和环己基氧基。低级烷氧基是指含1至4个碳的基团。
酰基是指通过羰基官能团连接到母体结构的直链、支链、环状结构、饱和、不饱和和芳族及其组合的1至8个碳原子的基团。酰基残基中的一个或多个碳可由氮、氧或硫代替,只要与母体连接的点保持在羰基。实例包括乙酰基、苯甲酰基、丙酰基、异丁酰基、叔丁氧基羰基和苄基氧基羰基。低级酰基是指含1至4个碳的基团。
杂环是指其中一个或两个碳由杂原子(如氧、氮或硫)代替的环烷基或芳基残基。落在本发明范围内的杂环的实例包括吡咯烷、吡唑、吡咯、吲哚、喹啉、异喹啉、四氢异喹啉、苯并呋喃、苯并二氧杂环己烷、苯并二氧杂环戊二烯(在作为取代基出现时,一般称为亚甲二氧基苯基)、四唑、吗啉、噻唑、吡啶、哒嗪、嘧啶、噻吩、呋喃、唑、唑啉、异唑、二烷和四氢呋喃。
取代的是指残基,包括但不限于烷基、烷基芳基、芳基、芳基烷基和杂芳基,其中残基的最多3个H原子用低级烷基、经取代烷基、烯基、经取代烯基、芳基、经取代芳基、卤代烷基、烷氧基、羰基、羧基、羰基烷氧基(carboxalkoxy)、甲酰胺基、酰基氧基、脒基、硝基、卤素、羟基、OCH(COOH)2、氰基、伯氨基、仲氨基、酰基氨基、烷硫基、亚砜、砜、苯基、苄基、苯氧基、苄基氧基、杂芳基或杂芳基氧基置换。
卤代烷基是指其中一个或多个H原子由卤素原子代替的烷基残基,术语卤代烷基包括全卤代烷基。落在本发明范围内的卤代烷基的实例包括CH2F、CHF2和CF3。
氧杂烷基是指其中一个或多个碳由氧代替的烷基残基。它通过烷基残基连接到母体结构。实例包括甲氧基丙氧基、3,6,9-三氧杂癸基等。术语氧杂烷基按本领域理解的那样理解[参见Naming and Indexing ofChemical Substances for Chemical Abstracts,American Chemical Society出版,196,但没有127(a)的限制],即,指其中氧通过单键连接到其相邻原子(形成醚键)的化合物,它不表示在羰基中发现的双键氧。类似地,硫杂烷基和氮杂烷基是指其中一个或多个碳已分别由硫或氮代替的烷基残基。实例包括乙基氨基乙基和甲基硫基丙基。
甲硅烷基是指其中一至三个碳由四价硅代替,并且通过硅原子连接到母体结构的烷基残基。甲硅烷氧基为其中两个碳由四价硅代替,并且通过氧原子连接到母体结构的烷氧基残基,所述四价硅用烷基残基、芳基残基或环烷基残基封端。
实施例
通用
从2,5-二溴-9,9-双(4-己基氧基苯基)芴1制备9,9-双(4-己基氧基)苯基-2,7-二基-交替聚合(alt)-9,9-双(4-己基氧基)苯基-2,5-二基聚合物2描述于流程1中。分别从2,7-二溴和2,5-二溴异构体的~80/20混合物分离2,5-二溴-9,9-双(4-羟基苯基)芴。用聚合物结合的硫醇作为助催化剂,通过2,7-二溴和2,5-二溴芴酮的混合物与过量苯酚在甲磺酸中反应得到异构体混合物。在~50℃,通过在乙酸/甲磺酸混合物中用N-溴琥珀酰亚胺溴化芴酮,得到二溴芴酮异构体混合物。通过选择性萃取,随后重复层析,完成纯双酚的分离。
流程1.制备9,9-双(4-己基氧基)苯基-2,7-二基-交替聚合-9,9-双(4-己基氧基)苯基-2,5-二基聚合物
实施例1:制备2,5-二溴-双(4-己基氧基苯基)芴,1
将2.54g(5.0mmol)2,5-二溴-9,9-双(4-羟基苯基)芴和2.06g(12.5mmol)正己基溴在甲苯(10ml)和1.0ml(~5mmol)50%(aq)NaOH和Adogen 464(~100mg)的磁力搅拌混合物加热回流约16小时。将经冷却的混合物用甲苯(15ml)和水(20ml)稀释,然后转移到分液漏斗,并弃去含水相。有机相用水(3×25ml)和盐水(1×25ml)洗涤,然后通过Drierite锥体。溶剂蒸发得到3.4g无色油,无色油在硅胶(120g)上层析,用己烷-乙酸乙酯梯度(0-10%EtOAc)洗脱。将产物分离为无色粘胶。该物质用乙醇在-20℃结晶,但晶体低于室温熔融。
实施例2:制备9,9-双(4-己基氧基苯基)芴-2,7-二基-交替聚合-9,9-双(4-己基氧基苯基)芴-2,5-二基聚合物,2
用氩气使279mg(0.413mmol)1、272mg(0.414mmol)2,7-双-亚乙基二氧杂硼烷基-9,9-双-(4-己基氧基苯基)芴和17.8mg(0.043mmol)2-(2,6-二甲氧基苯基)苯基-二环己基膦在甲苯(25ml)中的溶液脱气10分钟,并加入2.8mg(0.0124mmol)乙酸钯。在单独的烧瓶中,使3.04g(2.07mmol)10%氢氧化四乙基铵溶液脱气15分钟,然后加入到甲苯溶液。将烧瓶浸入70℃油浴中,并在正N2压力下搅拌20小时。用甲苯和水稀释经冷却混合物,然后通过硅藻土过滤。弃去含水相,有机相用水(3×50ml)和盐水(1×50ml)洗涤,然后通过用硅藻土、胺官能硅胶和Drierite成层的锥体。使滤液在真空下浓缩至约5ml体积,并通过沉淀进入甲醇(~75ml)分离聚合物。2的数均分子量为~13K(相对于聚苯乙烯标准品)。
实施例3:制备聚9,9-双(4-己基氧基苯基)芴-2,7二基,3
以类似于制备聚合物2所述方法的方式,用2,7-双-亚乙基-二氧杂硼烷基-9,9-双-(4-己基氧基苯基)芴与2,7-二溴-双-(4-己基氧基-苯基)芴的Pd(0)催化偶联得到聚合物3。3的数均分子量为~182K(相对于聚苯乙烯标准品)。
实施例4:制备9,9-双(4-己基氧基苯基)2,7-双-(9,9-二辛基芴-2-基)芴,4
用氩气使100mg(0.153mmol)1、161mg(0.321mmol)2-(2,2-二甲基)亚丙二氧基硼烷基-9,9-二辛基芴和10.0mg(0.025mmol)2-(2,6-二甲氧基苯基)苯基-二环己基膦在甲苯(5ml)中的溶液脱气10分钟,并加入1.5mg(0.007mmol)乙酸钯。在单独的烧瓶中,使1.2g(0.822mmol)10%氢氧化四乙基铵溶液脱气15分钟,然后加入到甲苯溶液。将烧瓶浸入70℃油浴中,并在正N2压力下搅拌20小时。用甲苯和水稀释经冷却混合物,然后通过硅藻土过滤。弃去含水相,有机相用水(3×50ml)和盐水(1×50ml)洗涤,然后通过用硅藻土、胺官能硅胶和Drierite成层的锥体。滤液在真空下浓缩至干,得到残余物,残余物在硅胶上层析(12g-0-10%EtOAc/己烷),得到150mg(76%)4,为无色油。
实施例5:制备芴三聚物5
以类似方式,通过2-(2,2-二甲基)亚丙二氧基硼烷基-9,9-二辛基芴与2,7-二溴-9,9-双(4-己基氧基苯基)芴缩合制备芴三聚物5。聚合物2和相应2,7-连接的聚芴3的单线态(S1)能量和三线态(T1)能量显示于表2中。用2,5-连接的芴代替50%2,7-连接的芴导致所有芴聚合物的三线态能量增加0.1-0.2eV。
表2:单线态(S1)能量和三线态(T1)能量
聚合物 | S1(eV) | T1(eV) |
2 | 3.14 | 2.2-2.3 |
3 | 2.99 | 2.14 |
4 | 3.34 | |
5 | 3.14 |
实施例6:制备9,9-双(4-甲氧基苯基)芴-2,5-双-新戊二醇硼酸酯
向装配有磁力搅拌棒、橡胶塞和氮气插管的干燥250mL烧瓶加入无水四氢呋喃(100ml)中2.841g(5.30mmol)9,9-双-(4-甲氧基苯基)-2,5-二溴-芴的溶液。使烧瓶和内容物冷却到-78℃,并经2-3分钟加入己烷中丁基锂的溶液(2.06M,6.5ml,13.25mmol)。将浅黄色溶液在-78℃搅拌5.5小时,然后加入3.2ml(18.55mmol)硼酸三乙酯。使混合物升温至室温,并搅拌过夜,然后通过加入饱和氯化铵(25ml)和0.1NHCl(5ml)猝灭反应。将此混合物转移到分液漏斗,并用乙醚(50ml)萃取含水相。合并的有机相用水(1×100ml)和盐水(1×100ml)洗涤,然后通过无水CaSO4锥体过滤。蒸发溶剂得到2.82g白色固体。固体用氯仿(50ml)和新戊二醇(1.20g,11.5mmol)的混合物回流。在1小时后,将经冷却混合物转移到分液漏斗,并用盐水洗涤有机相,然后浓缩,得到约4.5g固体物质,固体物质在120g硅胶上层析,用己烷中的5-60%乙酸乙酯洗脱。在硅胶上层析后,产物分离为2.36g(74%)无色泡沫,用乙醚/己烷重结晶,得到无色晶体。1H NMR(CDCl3)δ8.30(d,1,芴基-4-H),7.80(m,1,芴基-H),7.75(s,1,芴基-H)δ,7.69(m,1,芴基-H),7.40(m,1,芴基-H),7.28(t,1,芴基-7H),7.12和6.79(双峰的双峰(9-芳基-H),3.94(s,4,硼酸酯-CH2的),3.77(s,10,ArOCH3和硼酸酯CH2的),1.17(s,6,成对(geminal)CH3)和1.04ppm(s,6,成对CH3).
实施例7:制备9,9-双(4-甲氧基苯基)-2,5-芴基-交替聚合-N-4-丁基苯基-4,4’-二苯基胺-二基聚合物
用氩气使12mL甲苯中327mg(0.543mmol)9,9-双(4-甲氧基苯基)芴-2,5-双-新戊二醇硼酸酯、249mg(0.543mmol)N-4-丁基苯基-N,N-双-4-溴苯基三苯基胺和16mg(0.0385mmol)二环己基-2-(2,6-二甲氧基苯基)-苯基膦的溶液脱气15分钟,然后加入2.4mg(0.011mmol)乙酸钯。加入3.8g氢氧化四乙基铵的10%脱气溶液,并将混合物浸入70℃油浴,在氮气下在此温度搅拌19小时。用水(10ml)和甲苯(20ml)稀释经冷却混合物,然后通过硅藻土过滤。将滤液转移到分液漏斗,弃去含水相,有机相用水(3×25ml)和盐水(2×25ml)洗涤,然后通过无水CaSO4锥体。将滤液与250mg胺官能硅胶一起搅拌过夜,然后过滤。将滤液浓缩,至约10ml体积。剧烈搅拌浓缩物,同时分部分加入75ml甲醇。过滤收集沉淀,并在真空烘箱中在40℃干燥过夜。收率为362mg(98%)。1H NMR(CDCl3)δ7.75-6.75(m,26,ArH),3.80(m,6,arOCH3),2.65(m,2,NCH2R),1.60(m,2,NCH2CH 2CH2CH3),1.45(m,2,NCH2CH2CH 2CH3)和1.0ppm(m,3,NCH2CH2CH2CH 3).UV图谱(CH2Cl2)λmax=359nm;ε=30,563)
实施例8A:制备9,9-二辛基-2-(9,9-双-4-(2-吗啉代乙氧基苯基)-2,7-二基)-9,9-二辛基芴-2-基三芴
原料:在Adogen 464作为相转移催化剂存在下,通过用盐酸2-氯乙基吗啉与50%NaOH/甲苯使9,9-双-4-羟基苯基-2,7-二溴芴烷基化,制备9,9-双-4-(2-吗啉代乙氧基)苯基-2,7-二溴芴;通过9,9-二辛基芴锂化(BuLi,Et2O/-78℃),随后硼烷化(三乙氧基硼酸酯),水解,并用新戊二醇再酯化,制备9,9-二辛基-2-新戊二醇硼酸酯。
制备三聚物:使甲苯(30ml)中1.101g(1.5mmol)9,9-双-4-(2-吗啉代乙氧基)苯基-2,7-二溴芴、1.544g(3.075mmol)9,9-二辛基-2-新戊二醇硼酸酯和0.054g(0.131mmol)二环己基-2-(2,6-二甲氧基苯基)苯基膦的溶液脱气15分钟,然后加入0.084g(0.0375mmol)Pd(OAc)2和11g经单独脱气的10%氢氧化四乙铵水溶液。将搅拌的混合物浸入70℃油浴中,并在氮气下搅拌18小时。过滤经冷却的混合物,并转移到分液漏斗。弃去含水相,有机相用水(3×50ml)和盐水(1×50ml)洗涤,然后通过无水CaSO4锥体。去除溶剂得到白色泡沫,在80g氧化铝(中性)上层析纯化,产量1.23g(60%)。1H NMR(CDCl3)δ8.0-7.4(m,20,芴基-H),7.3和6.8(AB双峰,8,9-芳基H),4.1(t,4,arOCH2),3.7(t,8,吗啉OCH2),2.75(t,4,arOCH2CH 2N),2.5(t,8,吗啉-NCH2),2.08(t,8,9-CH2R),1.3-1.0(m,40,9-CH2(CH 2)5CH2CH3),0.8(t,12,9-CH2(CH2)5CH2CH 3)和0.7ppm(m,8,9-CH2(CH2)5CH 2CH3)
实施例8B:制备9,9-二辛基-2-(9,9-双-4-(2-吗啉代乙氧基苯基)-2,5-双-9,9-二辛基芴-2-基
原料:在Adogen 464作为相转移催化剂存在下,通过用盐酸2-氯乙基吗啉与50%NaOH/甲苯使9,9-双-4-羟基苯基-2,5-二溴芴烷基化,制备9,9-双-4-(2-吗啉代乙氧基)苯基-2,5-二溴芴;通过9,9-二辛基芴锂化(BuLi,Et2O/-78℃),随后硼烷化(三乙氧基硼酸酯),水解,并用新戊二醇再酯化,制备9,9-二辛基-2-新戊二醇硼酸酯。
制备三聚物:使甲苯(30ml)中1.101g(1.5mmol)9,9-双-4-(2-吗啉代乙氧基)苯基-2,5-二溴芴、1.544g(3.075mmol)9,9-二辛基-2-新戊二醇硼酸酯和0.054g(0.131mmol)二环己基-2-(2,6-二甲氧基苯基)苯基膦的溶液脱气15分钟,然后加入0.084g(0.0375mmol)Pd(OAc)2和11g经单独脱气的10%氢氧化四乙铵水溶液。将搅拌的混合物浸入70℃油浴中,并在氮气下搅拌18小时。过滤经冷却的混合物,并转移到分液漏斗。弃去含水相,有机相用水(3×50ml)和盐水(1×50ml)洗涤,然后通过无水CaSO4锥体。去除溶剂得到白色泡沫,在80g氧化铝(中性)上层析纯化。
器件制造
以下实施例描述器件的制造和评价,所述器件用聚合物2或市售聚-2,7-芴(ADS-131)作为发射层制造。用聚合物2作为发光层制造的试验OLED器件的表现可与用市售聚-2,7-芴(ADS-131)作为发光层制造的类似器件相当。
实施例9:利用2,5-芴聚合物的OLED
通过在洁净UV臭氧处理的2.5cm×2.5cm ITO图案化玻璃基片上旋涂,沉积具有约60nm厚度的PEDOT/PSS层(Baytron P VP 8000,聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸酯),作为溶液购自HC Starck,Inc.)。然后将经涂覆的基片在热板上在空气中在160℃烘烤30分钟。在F8-TFB层顶上由溶液沉积电致发光聚合物2层。此层具有通过表面光度测定法测量约40-50nm的厚度。
沉积双层(NaF,Al)阴极。然后将经涂覆的基片放入钟罩式蒸发器,泵抽系统,直至达到约1×10-6托压力。然后,通过物理蒸气沉积,在经涂覆基片的最终层的顶上沉积约3nm厚氟化钠层(通过校准的石英晶体微量天平测量)。随后,通过蒸气沉积,在真空下在氟化钠层的顶上沉积约130nm厚铝金属层,以形成OLED的阴极部分。
实施例10:利用2,5-芴聚合物和TFB中间层的OLED
通过在洁净UV臭氧处理的2.5cm×2.5cm ITO图案化玻璃基片上旋涂,沉积具有约60nm厚度的PEDOT/PSS层(Baytron P VP 8000,聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸酯),作为溶液购自HC Starck,Inc.)。然后将经涂覆的基片在热板上在空气中在160℃烘烤30分钟。然后在PEDOT/PSS涂覆的基片顶上旋涂具有约10-20nm厚度的F8-TFB(辛基芴-三芳基胺共聚物,得自Sumation,Inc.)空穴传输层的层。然后将F8-TFB-PEDOT/PSS涂覆的基片在热板上在氩气中在170℃烘烤30分钟。在F8-TFB层顶上由溶液沉积电致发光聚合物2的最终层。此层具有约40-50nm的厚度。
沉积双层(NaF,Al)阴极。然后将经涂覆的基片放入钟罩式蒸发器,泵抽系统,直至达到约1×10-6托压力。然后,通过物理蒸气沉积,在经涂覆基片的最终层的顶上沉积约3nm厚氟化钠层(通过校准的石英晶体微量天平测量)。随后,通过蒸气沉积,在真空下在氟化钠层的顶上沉积约130nm厚铝金属层,以形成OLED的阴极部分。
实施例11:利用2,5-芴聚合物/TFB掺混物、TFB中间层的OLED
通过在洁净UV臭氧处理的2.5cm×2.5cm ITO图案化玻璃基片上旋涂,沉积具有约60nm厚度的PEDOT/PSS层(Baytron P VP 8000,聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸酯),作为溶液购自HC Starck,Inc.)。然后将经涂覆的基片在热板上在空气中在160℃烘烤30分钟。然后在PEDOT/PSS涂覆的基片顶上旋涂具有约10-20nm厚度的F8-TFB(辛基芴-三芳基胺共聚物,得自Sumation,Inc.)空穴传输层的层。然后将F8-TFB-PEDOT/PSS涂覆的基片在热板上在氩气中在170℃烘烤30分钟。在F8-TFB层顶上由溶液沉积由电致发光聚合物(JC392-147)与F8-TFB(90∶10比)的掺混物组成的最终层。此层具有约40-50nm的厚度。
沉积双层(NaF,Al)阴极。然后将经涂覆的基片放入钟罩式蒸发器,泵抽系统,直至达到约1×10-6托压力。然后,通过物理蒸气沉积,在经涂覆基片的最终层的顶上沉积约3nm厚氟化钠层(通过校准的石英晶体微量天平测量)。随后,通过蒸气沉积,在真空下在氟化钠层的顶上沉积约130hm厚铝金属层,以形成OLED的阴极部分。
比较实施例:利用2,7-芴和TFB中间层的OLED
通过在洁净UV臭氧处理的2.5cm×2.5cm ITO图案化玻璃基片上旋涂,沉积具有约60nm厚度的PEDOT/PSS层(Baytron P VP 8000,聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸酯),作为溶液购自HC Starck,Inc.)。然后将经涂覆的基片在热板上在空气中在160℃烘烤30分钟。然后在PEDOT/PSS涂覆的基片顶上旋涂具有约10-20nm厚度的F8-TFB(辛基芴-三芳基胺共聚物,得自Sumation,Inc.)空穴传输层的层。然后将F8-TFB-PEDOT/PSS涂覆的基片在热板上在氩气中在170℃烘烤30分钟。在F8-TFB层顶上由溶液沉积得到的电致发光聚合物ADS131(聚芴,得自American Dye Source)的最终层。此层具有约40-50nm的厚度。
沉积双层(NaF,Al)阴极。然后将经涂覆的基片放入钟罩式蒸发器,泵抽系统,直至达到约1×10-6托压力。然后,通过物理蒸气沉积,在经涂覆基片的最终层的顶上沉积约3nm厚氟化钠层(通过校准的石英晶体微量天平测量)。随后,通过蒸气沉积,在真空下在氟化钠层的顶上沉积约130nm厚铝金属层,以形成OLED的阴极部分。
检测实施例中所述各OLED的流明/瓦(LPW)、外量子效率(EQE)和电流-电压(IV)及光谱特征。为了检测各器件的IV特征,施加电压,并用Keithley 237 Source检测装置测定得到的电流响应。使用相对于Minolta LS 100亮度计校准的硅二极管,同时检测发光输出(坎德拉/米2)。为了从在亮度计上检测的cd/m2转化成流明,假定Lambertian发射模式,并使用以下方程。流明=(cd/m2)×(器件面积)×(π)。用固定在1/4米Acton研究光谱仪的CCD照相机,检测实施例中所述各OLED的光谱。用校准的白炽灯校准CCD/光谱仪组合的相对光谱响应。光谱检测确定CIEx和CIEy点,并允许LPW数据转化成EQE数据。在10ma/cm2电流密度检测的器件特性汇总显示于表3中。以下器件数据显示,由本发明所述物质制成的这些OLED器件显示与对照2-7聚芴物质相当的EQE性能。这表明作为用于多种电致发光物质的基本结构模块,它们具有宽的适用性。
表3
虽然本文只举例说明和描述了本发明的某些特征,但本领域的技术人员会想到很多修改和变化。因此,应理解,所附权利要求将覆盖落在本发明真实精神内的所有这些修改和变化。
Claims (1)
1.一种式I的化合物
其中R1和R2在每次出现时独立为C1-20烃基、含一个或多个S、N、O、P或Si原子的C1-20烃基、C4-16烃基羰基氧基、C4-16芳基(三烷基甲硅烷氧基),或者R1和R2与其间的碳原子结合在一起形成C5-20烃基环或含至少一个S、N或O杂原子的C4-20烃基环;
R3和R4在每次出现时独立为H、C1-20烃基、C1-20烃基氧基、C1-20硫醚、C1-20烃基羰基氧基或氰基;
X在每次出现时独立为卤素、三氟甲磺酸酯基、-B(OH)2、-B(OR)2、-BO2R或其组合;
R为烷基或亚烷基;并且
a和b独立为0或1。
2. 权利要求1的化合物,其中X为卤素。
3. 权利要求2的化合物,其中X为溴。
4. 权利要求1的化合物,其中X为-B(OH)2、-B(OR)2或-BO2R。
5. 权利要求1的化合物,其中R3和R4为H。
6. 权利要求1的化合物,其中R1和R2为烷基、经取代烷基、芳基、经取代芳基、杂芳基或经取代杂芳基。
7. 权利要求6的化合物,其中R1和R2为烷氧基苯基或烷基。
8. 权利要求1的化合物,所述化合物具有式II
其中X和Y之一为卤素或三氟甲磺酸酯基,X和Y的另一个为-B(OH)2、-B(OR)2或-BO2R。
9. 一种以头-尾结构组合的低聚物,所述低聚物包含至少一个结构单元,所述结构单元由权利要求1-8中任一项的至少一种化合物通过聚合形成,且包含所述结构单元少于约10个。
10. 权利要求9的低聚物,所述低聚物还包含下式的端单元
。
11. 权利要求9的低聚物,所述低聚物还包含由式III化合物通过聚合形成的结构单元
。
12. 一种聚合物,所述聚合物包含结构单元,所述结构单元由权利要求1-8中任一项的至少一种化合物通过聚合形成。
13. 权利要求12的聚合物,所述聚合物还包含由式III化合物通过聚合形成的结构单元
。
14. 权利要求12的聚合物,所述聚合物还包含由至少一种亚芳基单体通过聚合形成的结构单元。
15. 权利要求14的聚合物,其中所述亚芳基单体为芳基化合物,杂芳基化合物或三芳基胺。
16. 权利要求15的聚合物,其中所述亚芳基单体为三芳基胺。
17. 权利要求12的聚合物,所述聚合物包含大于约50%重量的所述结构单元。
18. 权利要求17的聚合物,所述聚合物包含大于约90%重量的所述结构单元。
19. 一种具有发射层的光电子器件,所述发射层包含权利要求12的聚合物,任选还包含至少一种磷光染料。
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KR101737131B1 (ko) | 2017-05-17 |
WO2010044940A3 (en) | 2010-06-10 |
US7635792B1 (en) | 2009-12-22 |
JP2012505831A (ja) | 2012-03-08 |
JP5562967B2 (ja) | 2014-07-30 |
WO2010044940A2 (en) | 2010-04-22 |
KR20110073566A (ko) | 2011-06-29 |
EP2349965B1 (en) | 2017-01-25 |
EP2349965A2 (en) | 2011-08-03 |
CN102186800A (zh) | 2011-09-14 |
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