CN102083883B - 基于供体/受体交替共聚物的高性能可溶液加工半导体聚合物 - Google Patents
基于供体/受体交替共聚物的高性能可溶液加工半导体聚合物 Download PDFInfo
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- CN102083883B CN102083883B CN200980125975.4A CN200980125975A CN102083883B CN 102083883 B CN102083883 B CN 102083883B CN 200980125975 A CN200980125975 A CN 200980125975A CN 102083883 B CN102083883 B CN 102083883B
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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Abstract
公开了一种包含式(I)的基团作为重复单元并且具有30-70kg/mol的数均分子量Mn的苯并噻二唑-环戊二烯并二噻吩共聚物,其中R为正十六烷基或3,7-二甲基辛基。本发明还涉及该共聚物作为半导体或电荷传输材料的用途,作为薄膜晶体管(TFT)的用途,或在有机发光二极管(OLED)用半导体组件中的用途,用于光伏组件或在传感器中的用途,在电池中作为电极材料的用途,作为光波导的用途或用于电子照相应用的用途。
Description
本发明涉及苯并噻二唑-环戊二烯并二噻吩共聚物、其制备方法及其作为半导体或电荷传输材料的用途。
在二十世纪下半叶开发(微)电子器件的惊人结构单元是基于无机电极、绝缘体和半导体的场效应晶体管(FET)。已经证明这些材料可靠、高效且具有根据众所周知的Moore定律周期性地提高的性能。不与常规硅技术竞争,基于分子材料和聚合物材料的有机FET(OFET)可大规模应用于低性能存储元件以及集成光电子器件,如有源阵列有机发光二极管显示器、RFID标签、智能ID标签和传感器中的像素驱动器(pixeldrive)和开关元件。
作为开发几种导电性或半导体性有机聚合物的结果,它们在有机薄膜晶体管(OTFT)中作为有源层并因而作为半导体的应用赢得越来越多的关注。
在OTFT中使用有机半导体相比于迄今为止所使用的无机半导体具有一些优点。它们能以从纤维到薄膜的任何形式加工,具有高机械柔韧性,能以低成本生产且重量轻。然而,显著的优点是可通过在大气压力下例如通过印刷技术在聚合物基底上由溶液沉积各层而生产整个半导体组件,从而得到可廉价生产的FET。
电子器件的性能主要取决于载流子在半导体材料中的迁移率以及开启状态和关闭状态之间的电流比(开/关比)。因此,理想的半导体在关闭状态下具有最小导电性且在开启状态下具有最大载流子迁移率(迁移率大于10-3cm2V-1s-1,开/关比大于102)。此外,半导体材料必须对氧化相对稳定,即必须具有足够高的电离电位,因为其氧化降解降低组件性能。
EP1510535A1描述了迁移率为3×10-3或1.7×10-2cm2V-1s-1且开/关比为约106的聚噻吩并(2,3-b)噻吩。WO2006/094645A1描述了具有一个或多个硒吩-2,5-二基和一个或多个噻吩-2,5-二基的聚合物,而WO2006/131185公开了聚噻吩并(3,4-d)噻唑且US2005/0082525A1公开了苯并(1,2-b,4,5-b’)二噻吩。
US2007/0014939公开了被C1-C20烷基取代的环戊二烯并二噻吩和苯并噻二唑的共聚物作为半导体材料。在实施例中制备了分别被正己基和乙基己基二取代的环戊二烯并二噻吩的共聚物。这些材料仅具有中等载流子迁移率(在10-3cm2/Vs范围内)。
Z.Zhu等,Macromolecules2007,40(6),1981-1986公开了分别被正己基和2-乙基己基取代基二取代的环戊二烯并二噻吩和苯并噻二唑的共聚物。对于由该材料制造的场效应晶体管,报道的空穴迁移率为0.015cm2/Vs。
Zhang等,J.Am.Chem.Soc.2007,129(12),3472-3473公开了分别被正十六烷基或3,7-二甲基辛基取代基二取代的环戊二烯并二噻吩和苯并噻二唑的共聚物,其数均分子量为10.2kg/mol且在FET中呈现0.17cm2/Vs的载流子迁移率。
本发明的目的是提供用作有机半导体材料的新型化合物,其易于合成,具有高迁移率和良好的氧化稳定性并且可容易地加工。
该目的由一种包含式(I)的基团作为重复单元并且具有30-70kg/mol的数均分子量Mn的苯并噻二唑-环戊二烯并二噻吩共聚物实现:
其中R为正十六烷基或3,7-二甲基辛基。
本发明苯并噻二唑-环戊二烯并二噻吩共聚物的优点是在场效应晶体管中的载流子迁移率由于改进的更高分子量和材料高纯度的组合而显著提高。
数均分子量Mn优选为40-60kg/mol。在一个特殊实施方案中,Mn为65-70kg/mol。
R为正十六烷基或3,7-二甲基辛基。
“迁移率”指由外部刺激如电场诱发的载流子如在p型半导体材料情况下的空穴(或正电荷单元)和在n型半导体材料情况下的电子在电场的影响下移动通过该材料的速度的度量。
本发明进一步提供了本发明共聚物作为半导体或电荷传输材料的用途,尤其是在光学、电光或电子组件中,作为薄膜晶体管的用途,尤其是在平面视频显示单元中,或用于射频识别标签(RFID标签)或在用于有机发光二极管(OLED)如电致发光显示器或液晶显示器背光的半导体组件中的用途,用于光伏组件或在传感器中的用途,在电池中作为电极材料的用途,作为光波导的用途,用于电子照相应用如电子照相记录的用途。
本发明进一步提供了包含本发明聚合物的光学、电光或电子组件。该类组件例如可为FET、集成电路(IC)、TFT、OLED或对准层(alignmentlayer)。
本发明聚合物特别适合作为半导体,因为它们具有该目的所要求的高迁移率。
该聚合物可被现有技术已知的几种基团封端。优选的端基是H、取代或未取代的苯基或取代或未取代的噻吩,但不限于此。
本发明共聚物可通过已知方法制备。优选的合成路径如下所述。
本发明共聚物可优选由2,1,3-苯并噻二唑-4,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼杂戊环-2-基)(BTZ)和2,6-二溴-4,4-二(十六烷基)-4H-环戊二烯并[2,1-b:3,4-b′]二噻吩(CDT)制备。
单体2,6-二溴-4,4-二(十六烷基)-4H-环戊二烯并[2,1-b:3,4-b′]二噻吩(CDT)可通过P.Coppo等,Macromolecules2003,36,2705-2711中所述方法使用下列反应方案制备:
在该方案中,R为正十六烷基或3,7-二甲基辛基。
共聚单体2,1,3-苯并噻二唑-4,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼杂戊环-2-基)(BTZ)可以如Zhang等,J.Am.Chem.Soc.2007,129(12),3472-3473所述由4,7-二溴-2,1,3-苯并噻二唑制备。
该BTZ/CDT共聚物可经由交叉偶联聚合反应如Stille或Suzuki反应合成,其中使芳基二卤化物与有机锡化合物或硼酸二酯/酸在碱和少量金属催化剂如四(三苯基膦基)钯(0)存在下反应。该反应通常在溶剂或溶剂混合物中在20-130℃的反应温度下进行。
对合成高分子量聚合物必要的是利用Suzuki交叉偶联反应以及纯度>99%的高纯度单体,因此对所用单体需要合适的提纯方法。
将前述以粉红色固体得到(Zhang等,J.Am.Chem.Soc.2007,129(12),3472-3473)的该BTZ单体进行多重再结晶,得到由GC测定的纯度为>99%的无色晶体。
为了以>99%的所需纯度得到CDT,可使用再循环GPC。
分子量可通过调节1∶1单体混合物的浓度而再现性地得到。为了得到50-60kg/mol的数均分子量,单体在反应溶液中的最佳总浓度为约60重量%。
本发明包括本发明聚合物的氧化形式和还原形式二者。电子的缺乏或过量导致形成具有高导电性的离域离子。这可通过用常规掺杂剂掺杂而实现。掺杂剂和掺杂方法是公知常识且例如由EP-A0528662、US5198153或WO96/21659已知。合适的掺杂方法例如包括用掺杂气体掺杂,在包含掺杂剂的溶液中电化学掺杂,通过热扩散以及通过将掺杂剂离子注入半导体材料中。
在使用电子作为载流子的情况下,优选使用卤素(例如I2、Cl2、Br2、ICl、ICl3、IBr和IF),路易斯酸(例如PF5、AsF5、SbF5、BF3、BCl3、SbCl5、BBr3和SO3),无机酸(例如HF、HCl、HNO3、H2SO4、HClO4、FSO3H和ClSO3H),有机酸或氨基酸,过渡金属化合物(例如FeCl3、FeOCl、Fe(ClO4)3、Fe(4-CH3C6H4SO3)3、TiCl4、ZrCl4、HfCl4、NbF5、NbCl5、TaCl5、MoF5、MoCl5、WF5、WCl6、UF6和LnCl3(其中Ln为镧系元素),阴离子(例如Cl-、Br-、I-、I3 -、HSO4 -、SO4 2-、NO3 -、ClO4 -、BF4 -、PF6 -、AsF6 -、SbF6 -、FeCl4 -、Fe(CN)6 3-,以及不同磺酸的阴离子如芳基-SO3 -。在使用空穴作为载流子的情况下,作为掺杂剂的例如是阳离子(例如H+、Li+、Na+、K+、Rb+和Cs+),碱金属(例如Li、Na、K、Rb和Cs),碱土金属(例如Ca、Sr和Ba),O2,XeOF4,(NO2 +)(SbF6 -),(NO2 +)(SbCl6 -),(NO2 +)(BF4 -),AgClO4,H2IrCl6,La(NO3)3,FSO2OOSO2F,Eu,乙酰胆碱,R4N+,R4P+,R6As+和R3S+,其中R为烷基。
本发明共聚物的导电形式可以用作有机导体,例如有机发光二极管(OLED)中的电荷注入层和ITO平面化层,平面屏和触摸屏,抗静电膜,印刷电路和电容器,但不限于此。
本发明共聚物可以用于生产光学、电子和半导体材料,尤其是作为场效应晶体管(FET)中的电荷传输材料,例如作为集成电路(IC)、ID标签或TFT的组件。或者它们可用于电致发光显示器中的有机发光二极管(OLED)中或用作背光,例如液晶显示器(LCD),用于光伏应用或传感器,用于电子照相记录和其他半导体应用。
由于本发明共聚物具有良好的溶解性,它们可作为溶液施涂于基底上。因此可以用廉价方法,例如旋涂施或印刷施涂各层。
合适的溶剂或溶剂混合物例如包括醚、芳烃和尤其是氯代溶剂。
包含半导体材料的FET和其他组件如二极管可以有利地用于ID标签或安全标记中以显示有价值物品如钞票、信用卡、身份文件如ID卡或驾驶执照或具有金钱利益的其他文件如橡皮图章、邮票或票券等的真实性和防止伪造。
或者,本发明聚合物可用于有机发光二极管(OLED)中,例如用于显示器中或用作液晶显示器(LCD)用背光。通常而言,OLED具有多层结构。发光层通常嵌入一个或多个电子-和/或空穴传输层之间。当施加电压时,电子或空穴可在发射层的方向迁移,其中它们在发射层中复合而激发并且发光化合物随后发光。该聚合物、材料和层可根据其电学和光学性能用于一个或多个传输层和/或发射层。当该化合物、材料或层为电致发光的或具有电致发光基团或化合物时,它们特别适合发射层。
类似于用于OLED中的合适聚合物的加工,选择属于公知常识且例如描述于SyntheticMaterials,111-112(2000),31-34或J.Appl.Phys.,88(2000)7124-7128中。
本文所引用的所有文献作为参考引入本专利申请中。所有定量数据(百分数、ppm等)基于重量、基于混合物的总重量,除非另有指明。
实施例
按照下列公开程序(Zhang等,J.Am.Chem.Soc.2007,129(12),3472-3473;P.Coppo等,Macromolecules2003,36,2705-2711)制备单体2,1,3-苯并噻二唑-4,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼杂戊环-2-基)(BTZ)和2,6-二溴-4,4-二(十六烷基)-4H-环戊二烯并[2,1-b:3,4-b′]二噻吩(CDT)。
实施例1
合成二硼酸酯BTZ
将4,7-二溴-2,1,3-苯并噻二唑(1g,3.41mmol)、二(频哪醇根合)二硼(2g,7.8mmol)、PdCl2(dppf)(500mg,0.6mmol)和KOAc(2g,20mmol)在脱气1,4-二烷(10ml)中的溶液于80℃下搅拌过夜。通过加入水猝灭反应并将所得混合物用乙酸乙酯洗涤(30ml×3)。有机层用盐水洗涤,在Na2SO4上干燥并真空浓缩,得到深红色固体。将该固体通过使用在己烷中的3%乙酸乙酯的硅胶层析提纯,以粉红色固体得到所需化合物。将粗产物由乙醇重结晶4次,得到无色晶体,为300mgBTZ。
FD-MS:m/z=388.0(计算值为388.1)。1HNMR(250MHz,CD2Cl2):δ8.10(s,2H),1.41(s,24H)。13CNMR(62.9MHz,CD2Cl2):δ157.55,138.11,84.91,25.3。
实施例2
合成4,4-二正十六烷基环戊二烯并[2,1-b:3,4-b’]二噻吩/4,4-二(3,7-二甲基辛基)环戊二烯并[2,1-b:3,4-b’]二噻吩
将4H-环戊二烯并[2,1-b:3,4-b’]二噻吩(2.0g,11.2mmol)溶解于50mL二甲亚砜中。分别加入正十六烷基溴或2,7-二甲基辛基溴(22.4mmol),然后加入碘化钾(50mg)。将该混合物用氮气吹扫并在冰浴中冷却,最后分批加入磨碎的氢氧化钾(2.0g)。将所得绿色混合物在室温下剧烈搅拌过夜。然后将反应容器在冰浴中冷却并加入水(50mL)。将有机相用乙醚萃取2次,用水、盐水和氯化铵溶液洗涤并用硫酸镁干燥。蒸发溶剂得到黄色油状标题化合物。通过在二氧化硅/己烷上层析提纯而除去痕量单烷基化产物和未反应的烷基溴。以透明油状物得到标题化合物。产率:85%。
实施例3
合成2,6-二溴-4,4-二正十六烷基环戊二烯并[2,1-b:3,4-b’]二噻吩/2,6-二溴-4,4-二(3,7-二甲基辛基)环戊二烯并[2,1-b:3,4-b’]二噻吩
在氮气下于黑暗中将4,4-二正十六烷基环戊二烯并[2,1-b:3,4-b’]二噻吩/4,4-二(3,7-二甲基辛基)环戊二烯并[2,1-b:3,4-b’]二噻吩(4.97mmol)溶解于50mL蒸馏的DMF中。分批加入NBS(1.8g,9.94mmol)。将所得黄色溶液在室温和氮气下搅拌过夜。然后加入水(50mL),并将有机相用乙醚(100mL)萃取2次,用水和1%HCl溶液洗涤并用硫酸镁干燥。减压除去溶剂,以黄色油状物得到标题化合物。通过在二氧化硅/己烷上柱层析和再循环GPC(4-5次)除去杂质。以无色油状物得到标题化合物(产率68%)。
实施例4
合成和提纯聚合物:
经由Suzuki偶联反应合成该BTZ/正十六烷基-CDT共聚物。在装有回流冷凝器的50mLSchlenk烧瓶中将正十六烷基-CDT(300mg,0.382mmol)和BTZ(148mg,0.382mmol)、K2CO3(2mL,2M)和3滴Aliquat336溶入XmL甲苯中。然后使用冷冻/泵/吹扫方法将该溶液脱气3次并加入四(三苯基膦基)钯。然后再将该溶液冷冻/泵/吹扫3次并加热到100℃保持3天。然后加入0.1mL硼酸苯基酯的1M甲苯溶液并额外搅拌12小时,此时加入0.1mL溴苯的1M甲苯溶液以对反应性链端封端。
将所得混合物倾入甲醇和浓盐酸(2∶1)的混合物中并搅拌过夜。过滤固体并溶入热氯苯中,然后由甲醇沉淀并用丙酮进行索式提取。然后将聚合物由己烷、丙酮和乙酸乙酯沉淀3次,然后用己烷进行索式提取,得到190mg(43%)。GPC分析:Mn=5k(X=10mL);14k(X=8mL);51k(X=4mL),D=2.6-4.0。
使用X=4mL甲苯类似地得到该BTZ/3,7-二甲基辛基-CDT,数均分子量为38k,D=4.5。
聚合物的分子量通过凝胶渗透色谱法(GPC)测定,以聚苯乙烯为标样并使用三氯苯作为洗脱剂。使样品通过3根柱,第一根的孔隙率为106,第二根为104且最后一根为500。
实施例5
FET器件制备和测量
将具有150nmSiO2层的高度n++掺杂Si晶片用作晶体管基底。该SiO2介电材料用苯基三乙基硅烷处理。然后将整个基底浸入含有1mg/ml共聚物(溶于氯苯中)的溶液中。通过以1μm/s的速率缓慢取出样品,经由该浸涂方法“定向生长”聚合物膜。或者可通过以50nm的厚度旋涂在氯苯中的0.5重量%溶液而涂敷该半导体层。在氮气气氛下于200℃加热该聚合物层1小时并通过在该层顶部蒸发50nm金触点而提供晶体管。
载流子迁移率由饱和传输曲线推导出。
FET特性:
在场效应晶体管中测定的载流子迁移率清楚地显示出对分子量的依赖性,分子量越高越有利(表1)。
表1:通过旋涂得到的BTZ/正十六烷基-CDT共聚物的
晶体管性能对分子量的依赖性:
分子量Mn(g/mol) | 迁移率(cm2/Vs) | I开/I关 |
5K | 0.06 | 103 |
14K | 0.17 | 105 |
51K | 0.57 | 103 |
对于旋涂Mn为51k的聚合物而言,当在氮气中测量时,FET显示的空穴迁移率为0.65cm2/Vs且电流开/关比为I开/I关=103。
对于聚合物的浸涂而言,当在氮气中测量时,FET显示的空穴迁移率为1.4cm2/Vs且电流开/关比为I开/I关=105。在各种栅电压VG下典型的输出曲线示于图1中。
当在氮气中测量时,该BTZ/3,7-二甲基辛基-CDT共聚物显示的载流子迁移率为0.45cm2/Vs且电流开/关比为I开/I关=105。
实施例6
在装有回流冷凝器的25mLSchlenk烧瓶中将BTZ(148mg,0.382mmol)、正十六烷基-CDT(300mg,0.382mmol)、K2CO3(12eq,4.584mmol,2M溶液)和3滴Aliquat336溶入4mL甲苯中。然后使用冷冻/泵/吹扫方法将该溶液脱气3次并在氩气下加入四(三苯基膦基)钯(0.0191mmol)。然后再将该溶液冷冻/泵/吹扫3次并在氩气下加热到100℃保持24小时。然后将反应冷却到室温并再加入4mL甲苯。然后使用冷冻/泵/吹扫方法将该混合物脱气3次并再加入四(三苯基膦基)钯(0.0191mmol),然后进行3个冷冻/泵/吹扫循环。将反应加热到100℃保持48小时,然后加入硼酸苯基酯(0.1M)在甲苯中的溶液并再搅拌12小时,此时加入溴苯(0.1M)在甲苯中的溶液。将所得混合物倾入甲醇和浓盐酸的混合物(2∶1)中并搅拌4小时。将固体过滤并溶入热1,2,4-三氯苯中,然后由甲醇沉淀并用丙酮进行索式提取。然后将聚合物由己烷、丙酮和乙酸乙酯沉淀3次,然后用己烷进行索式提取,得到200mg(45%)。
GPC分析:由于溶解度有限,不能直接比较该样品的分子量。然而,当与测得Mn为5.1×104的样品比较时,在单一柱中用130℃的三氯苯作为洗脱剂的GPC分析显示增大~35%,外推值为Mn=6.9×104。
FET器件制备和测量
将样品由2mg/mL邻二氯苯溶液在保持于100℃且具有用HMDS官能化的200nmSiO2的底接触FET基底上液滴流延(drop-cast)。沟道长度和宽度分别为20μm和1.4mm。测得4个晶体管具有最低饱和空穴迁移率μ饱和=2.5cm2/Vs和最高饱和空穴迁移率μ饱和=3.3cm2/Vs。平均迁移率μ饱和=2.95cm2/VS。开/关比为106(图4)。在氮气气氛下进行加工。
图1示出了旋涂BTZ/正十六烷基-CDT共聚物(Mn=51K)的典型输出特性。
图2a和b示出了旋涂BTZ/3,7-二甲基辛基-CDT共聚物(Mn=38K)的典型传输(a)和输出(b)特性。
图3示出了浸涂BTZ/正十六烷基-CDT共聚物(Mn=51K)的典型传输特性。
图4a和b示出了正十六烷基-CDT共聚物(Mn=69K)的典型传输(a)和输出(b)特性。
Claims (10)
1.一种包含式(I)的基团作为重复单元并且通过以聚苯乙烯为标样并使用三氯苯为洗脱剂的凝胶渗透色谱法测定具有30-70kg/mol的数均分子量Mn的苯并噻二唑-环戊二烯并二噻吩共聚物:
其中R为正十六烷基。
2.根据权利要求1的共聚物作为半导体或电荷传输材料的用途,作为薄膜晶体管(TFT)的用途,或在有机发光二极管(OLED)用半导体组件中的用途,用于光伏组件或在传感器中的用途,在电池中作为电极材料的用途,作为光波导的用途或用于电子照相应用的用途。
3.一种组合物,包含溶于或分散于液体介质中的一种或多种权利要求1的聚合物。
4.一种薄膜半导体,包含一种或多种权利要求1的共聚物。
5.一种组合件,包含基底和沉积在所述基底上的权利要求4的薄膜半导体。
6.一种制备包含基底和包含一种或多种权利要求1的共聚物的薄膜半导体的组合件的方法,包括将权利要求1的共聚物溶于液体介质中以形成溶液,将所述溶液沉积在基底上并除去溶剂而在基底上形成薄膜半导体。
7.根据权利要求6的方法,其中所述溶液通过旋涂、浸涂或印刷沉积。
8.一种场效应晶体管器件,包含权利要求4的薄膜半导体或权利要求5的组合件。
9.一种光伏器件,包含权利要求4的薄膜半导体或权利要求5的组合件。
10.一种有机发光二极管器件,包含权利要求4的薄膜半导体或权利要求5的组合件。
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