CN102822181B - 一种醌型硅芴类有机半导体材料及其制备方法和应用 - Google Patents
一种醌型硅芴类有机半导体材料及其制备方法和应用 Download PDFInfo
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- CN102822181B CN102822181B CN201080065999.8A CN201080065999A CN102822181B CN 102822181 B CN102822181 B CN 102822181B CN 201080065999 A CN201080065999 A CN 201080065999A CN 102822181 B CN102822181 B CN 102822181B
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Classifications
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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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- 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
- 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
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- H—ELECTRICITY
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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
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/16—End groups
- C08G2261/164—End groups comprising organic end groups
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3244—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing only one kind of heteroatoms other than N, O, S
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
- C08G2261/526—Luminescence used as active layer in lasers
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Abstract
公开了一种如式(Ⅰ)所示的醌型硅芴类有机半导体材料,其中R1、R2、R5和R6选自H或C1-C20的烷基,R3和R4选自C1-C20的烷基,m和n为0-10之间的整数。还公开了上述醌型硅芴类有机半导体材料的制备方法和应用。
Description
技术领域
本发明属于有机化合物合成技术领域,具体的说是涉及一种醌型硅芴类有机半导体材料及其制备方法和应用。
背景技术
当今世界经济主要是建立在以化石能源,如煤炭、石油和天然气等基础之上的经济。然而,这些不可再生的化石能源都在不断的枯竭。进入21世纪以来,全球性的能源问题以及随之而来的环境污染和气候变暖等问题日益凸现和逐渐加剧。由于太阳能具有分布普遍和广阔,资源数量多,无污染,清洁,安全以及获取方便等突出优点,被认为是最有希望的可再生能源之一。太阳能电池直接把太阳光能转化成电能,是利用太阳能切实可行的有效方法。然而,目前商品化的太阳能电池还局限于硅基等无机太阳能电池,但它们的价格过于昂贵,超出了目前人们普遍可以接受的程度,这大大限制了它们的使用范围。为了降低电池成本,拓展应用范围,长期以来,人们一直在寻找新型的太阳能电池材料。
有机太阳能电池是一种新型的太阳能电池,相对于无机半导体材料来源有限,价格昂贵,有毒,制备工艺复杂,成本太高等而言,它具有无机太阳能电池无法比拟的一些优点,如材料来源广泛,结构多样性和可调控性,成本低廉,安全环保,制作工艺简单,产品重量轻,可大面积柔性制备等等,可以广泛应用在建筑、照明和发电等多种领域,具有重要的发展和应用前景。因此,国内外众多的研究机构和企业等都给予了相当的关注和投入。然而,到目前为止,有机太阳能电池的光电转换效率比无机太阳能电池还是要低很多。因此,开发新型的有机半导体材料对于提高有机太阳能电池的效率具有重要意义。
发明内容
本发明的目的在于克服现有技术的上述不足,提供一种醌型硅芴类有机半导体材料,该材料的溶解度、稳定性高,材料的能带隙低,从而扩宽太阳光谱吸收范围,提高光电转化效率。
本发明的另一目的在于提供一种工艺流程简单、产率高,易于操作和控制的醌型硅芴类有机半导体材料的制备方法。
本发明进一步的目的在于提供上述醌型硅芴类有机半导体材料在有机光电材料、聚合物太阳能电池、有机电致发光器件、有机场效应晶体管、有机光存储器件、有机非线性材料或/和有机激光中的应用。
为了实现上述发明目的,本发明的技术方案如下:
一种醌型硅芴类有机半导体材料,其分子结构通式为下述(I):
式中:R1、R2、R5、R6选自H或C1~C20的烷基,R3、R4选自C1~C20的烷基,m、n为0~10之间的整数。
以及,一种醌型硅芴类有机半导体材料制备方法,包括如下步骤:
选取如下结构式表示的化合物A、B、C、D,
其中,R1、R2、R5、R6选自H或C1~C20的烷基,R3、R4选自C1~C20的烷基,m、n为0~10之间的整数;
在碱性环境中和催化剂、有机溶剂存在的条件下,选取化合物A、B、C进行Suzuki偶联反应,得到如下结构式表示的化合物E,
在有机溶剂存在的条件下,将化合物E与N-溴代丁二酰亚胺进行溴化反应,得到化合物E的二溴类化合物;
在催化剂、缩合剂和有机溶剂存在的条件下,将化合物E的二溴类化合物与丙二腈进行缩合反应,得到如下结构通式(I)表示的醌型硅芴类有机半导体材料,此时,式中m、n为1~10之间的整数;
或在催化剂、缩合剂和有机溶剂存在的条件下,将化合物D与丙二腈进行缩合反应,得到如下结构通式(I)表示的所述醌型硅芴类有机半导体材料,式中m=n=0,
进一步的,本发明醌型硅芴类有机半导体材料在有机光电材料、聚合物太阳能电池、有机电致发光器件、有机场效应晶体管、有机光存储器件、有机非线性材料或/和有机激光中的应用。
本发明与现有技术相比至少具备以下优点:
1.在醌型硅芴类有机半导体材料分子中易于引入烷基,提高了该材料的溶解性;
2.含有的二氰基乙烯基(=C(CN)2)是一种很强的吸电子基团,通过在共轭性很强的醌型结构中引入这种基团,一方面提高了材料的稳定性,另一方面有利于降低材料的能带隙,从而扩宽太阳光谱吸收范围,提高光电转化效率;
3.醌型硅芴类有机半导体材料制备方法简单,产率高,反应条件温和,易于操作和控制,适合于工业化生产。
附图说明
图1是本发明实施例的醌型硅芴类有机半导体材料分子结构通式的示意图;
图2是以实施例1制备的醌型硅芴类有机半导体材料为活性层的有机太阳能电池器件的结构示意图;
图3是以实施例1制备的醌型硅芴类有机半导体材料为发光层的有机电致发光器件的结构示意图;
图4是以实施例1制备的醌型硅芴类有机半导体材料为有机半导体层的有机场效应晶体管器件的结构示意图。
具体实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
请参阅图1,显示本发明实施例的一种醌型硅芴类有机半导体材料,其分子结构通式为下述(I):
式中:R1、R2、R5、R6选自-H或C1~C20的烷基,R3、R4选自C1~C20的烷基,m、n为0~10之间的整数。其中,所述R1、R2、R5、R6优选为-C6H13或-C6H13的烷基,R3、R4优选为-CH3、-C6H13或-C20H41的烷基。
在上述本发明实施例醌型硅芴类有机半导体材料分子中易于引入烷基,当烷基的引入,有效改善了该分子的原有刚性,因此,在相同的溶剂中,与没有引入烷基的该分子材料相比,本发明实施例醌型硅芴类有机半导体材料溶解性有效的得以提高,同时,该醌型硅芴类有机半导体材料分子中还含有二氰基乙烯基(=C(CN)2),该二氰基乙烯基是一种很强的吸电子基团,通过在共轭性很强的醌型结构中引入这种基团,一方面提高了材料的稳定性,另一方面有利于降低材料的能带隙,从而扩宽太阳光谱吸收范围,提高光电转化效率。芴基团的存在,有效增大了该半导体材料骨架电子云的密度,使得本实施例半导体材料的带隙变窄,提高了其在有机半导体材料方面的潜在应用价值。
以及,本发明实施例还提供了该醌型硅芴类有机半导体材料制备方法,包括如下步骤:
(1)分别选取如下结构式表示的化合物A、B、C、D,
其中,R1、R2、R5、R6选自H或/和C1~C20的烷基,R3、R4选自C1~C20的烷基,m、n为0~10之间的整数;
(2)在碱性环境中和催化剂、有机溶剂存在的条件下,选取化合物A、B、C进行Suzuki偶联反应,得到化合物E,该步骤的化学反应式如下,
(3)在有机溶剂存在的条件下,将化合物E与N-溴代丁二酰亚胺进行溴化反应,得到化合物E的二溴类化合物F,该步骤的化学反应式如下,
(4)在催化剂、缩合剂和有机溶剂存在的条件下,将化合物E的二溴类化合物F与丙二腈进行缩合反应,得到所述醌型硅芴类有机半导体材料,其结构式为下述(I)式,其中,(I)式中m、n为1~10之间的整数,该步骤的化学反应式如下,
或在催化剂、缩合剂和有机溶剂存在的条件下,将化合物D与丙二腈进行缩合反应,得到如下结构通式(I’)表示的所述醌型硅芴类有机半导体材料,该步骤的化学反应式如下,
上述通式(I’)是通式(I)中m、n均为0的特例。
上述步骤(1)中化合物B、C可市购或者按本技术领域常用的制备方法制备,化合物A的制备方法,包括如下工艺步骤:
a)在有机溶剂存在的条件下,将4,4’-二溴-2,2’-二碘联苯、锂的烷基衍生物、二烷基二氯硅烷进行反应,得到2,7-二溴-9,9-二烷基硅芴类化合物,该步骤的化学反应式如下,
b)在有机溶剂存在的条件下,将2,7-二溴-9,9-二烷基硅芴类化合物、锂的烷基衍生物、2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷进行反应,得到化合物A,该步骤的化学反应式如下,
上述a)步骤中所述4,4’-二溴-2,2’-二碘联苯、锂的烷基衍生物、二烷基二氯硅烷三反应物的摩尔比优选为1.0∶2.0~4.0∶2.0~4.0;所述有机溶剂优选为四氢呋喃、乙醚、二氯甲烷、三氯甲烷、乙酸乙酯中至少一种;该反应步骤中反应温度优选为-100~-25℃,时间优选为24~48小时。
上述b)步骤中所述2,7-二溴-9,9-二烷基硅芴化合物、锂的烷基衍生物、2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷三反应物的摩尔比优选为1.0∶2.0~4.0∶2.0~4.0;所述有机溶剂优选为四氢呋喃、乙醚、二氯甲烷、三氯甲烷、乙酸乙酯中至少一种;该反应步骤中反应温度优选为-100℃~-25℃,时间优选为24~48小时。
上述的a)步骤和/或b)步骤可在有氧环境或者在无氧环境中进行反应。优选在无氧环境中进行,无氧环境可以采用真空或充满惰性气体来实现,优选充满惰性气体来实现无氧环境,该惰性气体是本技术领域常用的惰性气体,例如氮气、氩气等,优选氮气。这是因为在无氧环境中进行可提高各反应步骤中产物的得率,因为氧气是个很活泼的成分,能与反应物反应,干扰了反应的顺利进行,从而降低了产物得率。a)步骤和/或b)步骤中所述锂的烷基衍生物优选为正丁基锂、叔丁基锂、甲基锂、苯基锂中的一种或几种。
上述步骤(2)所述Suzuki偶联反应所得的得到化合物E结构式中,当m=n=0时,步骤(1)就只选取化合物D直接与丙二腈进行缩合反应,得到m=n=0的结构式为上述(I)的醌型硅芴类有机半导体材料,其中,化合物D可市购获得;当m=0、0<n≤10时,步骤(1)就只选取化合物A和化合物C进行步骤(2)的偶联反应,得到m=0、0<n≤10的结构式为上述(I)的醌型硅芴类有机半导体材料;当n=0、0<m≤10时,步骤(1)就只选取化合物A和化合物B进行步骤(2)的偶联反应,得到n=0、0<m≤10的结构式为上述(I)的醌型硅芴类有机半导体材料;当0<m≤10、0<n≤10时,步骤(1)就选取化合物A、B、C进行步骤(2)的偶联反应,得到0<m≤10、0<n≤10的结构式为上述(I)的醌型硅芴类有机半导体材料,当0<m≤10、0<n≤10时,化合物A、B、C三反应物的摩尔比优选为1.0∶1.0~1.5∶1.0~1.5,其中,化合物B、C反应物的摩尔比优选为1∶1。
该步骤(2)所述Suzuki偶联反应步骤中所述碱性环境的碱为NaOH、Na2CO3、NaHCO3、四乙基氢氧化铵中的至少一种;所述催化剂优选为Pd(PPh3)4、Pd2(dba)3/P(o-Tol)3、Pd(PPh3)2Cl2中的至少一种,其用量为化合物A摩尔百分比的0.05%~20%;所述有机溶剂优选为乙二醇二甲醚、四氢呋喃、乙醚、二氯甲烷、三氯甲烷或乙酸乙酯中的至少一种。该Suzuki偶联反应的温度为优选75~120℃,时间优选为12~72小时。上述该Suzuki偶联反应需要催化剂,因为催化剂一是能有效提高本发明实施例化合物E的得率;二是提高Suzuki偶联反应的反应速率,缩短反应时间,提高生产效率;三是因为该Suzuki偶联反应需要催化剂的参入,在Suzuki偶联反应过程中与其中一反应物生产中间产物,使得本Suzuki偶联反应最终能实现。
上述的Suzuki偶联反应可在有氧环境或者在无氧环境中进行。优选在无氧环境中进行,无氧环境可以采用真空或充满惰性气体来实现,优选充满惰性气体来实现无氧环境,该惰性气体是本技术领域常用的惰性气体,例如氮气、氩气等,优选氮气。这是因为在无氧环境中进行可提高化合物E的得率,因为氧气是个很活泼的成分,能与反应物反应,干扰了反应的顺利进行,从而降低了产物得率。
上述步骤(3)所述溴化反应步骤中所述化合物E与N-溴代丁二酰亚胺的摩尔比优选为1.0∶2.0~2.5;有机溶剂优选为N,N-二甲基甲酰胺(DMF)、四氢呋喃、乙醚、二氯甲烷、三氯甲烷、乙酸乙酯、醋酸中的至少一种。该溴化反应的温度优选为-5~30℃,时间优选为12~48小时。
上述步骤(4)所述缩合反应步骤中所述化合物E的二溴类化合物与丙二腈的摩尔比优选为1.0∶2.0~10;所述有机溶剂优选为乙二醇二甲醚、四氢呋喃、乙醚、二氯甲烷、三氯甲烷或乙酸乙酯中的至少一种;所述缩合剂优选为NaH、醇钠中的至少一种,更优选NaH,其中,醇钠优选但不限于甲醇钠、叔丁醇钠。该缩合反应的温度优选为75~120℃,时间优选为12~72小时;所述催化剂优选为Pd(PPh3)4、Pd2(dba)3、Pd(PPh3)2Cl2中的至少一种,其用量为化合物E的二溴类化合物摩尔百分比的0.05%~20%。
在该醌型硅芴类有机半导体材料制备方法中,只需将反应物按比率添加,无需特殊的设备和环境要求,其制备方法工艺简单,产率高,且条件温和,易于操作和控制,适合于工业化生产。
由于醌型硅芴类有机半导体材料有上述优点,因此,醌型硅芴类有机半导体材料可在有机光电材料、聚合物太阳能电池、有机电致发光器件、有机场效应晶体管、有机光存储器件、有机非线性材料或/和有机激光中应用。
现结合实施例,对本发明进行进一步详细说明。
实施例1
醌型硅芴类有机半导体材料的制备,其结构式如下I1所示:
1)2,7-二溴-9,9-二甲基硅芴的制备,其结构式及制备方法如下:
在氮气保护下,将5.64g的4,4’-二溴-2,2’-二碘联苯溶于40mLTHF中,降温至-25℃,逐滴加入20.00mL正丁基锂溶液(正丁基锂溶液的浓度为1.0mol/L,溶剂为正己烷),反应2小时后,加入1.29g二甲基二氯硅烷,继续反应24小时。反应结束,加入去离子水,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到产物。MALDI-TOF-MS(m/z):368.1(M+);
2)醌型硅芴类有机半导体材料I1的制备,其制备方法如下:
冰浴下将3.14g丙二腈加入至2.45g氢化钠(60%的油溶液)和50mL乙二醇二甲醚的悬浮液中,恢复至室温,搅拌20分钟,加入3.68g的2,7-二溴-9,9-二甲基硅芴和0.54g的PdCl2(PPh3)2。加热至120℃反应12小时后,冷却至0℃,加入饱和Br2/H2O溶液。加入水,抽滤,水洗,干燥,柱层析分离得到产物。MALDI-TOF-MS(m/z):336.4(M+)。
实施例2
醌型硅芴类有机半导体材料的制备,其结构式如下I2所示:
1)2,7-二溴-9,9-二己基硅芴的制备,其结构式及制备方法如下:
在氩气保护下,将6.00g的4,4’-二溴-2,2’-二碘联苯溶于100mLTHF中,降温至-100℃,逐滴加入42.55mL甲基锂溶液(正丁基锂溶液的浓度为1.0M,溶剂为正己烷),反应12小时后,加入5.70g的二己基二氯硅烷,继续反应48小时,反应结束,加入水,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):508.4(M+);
2)2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二己基硅芴的制备,其结构式及制备方法如下:
在-25℃、氮气条件下,将10.00mL(2.00M)正丁基锂溶液加入至盛有5.08g的2,7-二溴-9,9-二己基硅芴和50mL四氢呋喃的反应瓶中,搅拌2小时后缓慢滴加4.17mL2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,继续搅拌24小时,反应结束,将反应液倒入水中,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到固体产物,该产物MALDI-TOF-MS(m/z):602.5(M+);
3)3,7-二(噻吩-2-基)-9,9-二己基硅芴的制备,其结构式及制备方法如下:
在氮气保护下,往含有3.01g的2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二己基硅芴、1.63g2-溴噻吩、0.34gPd(PPh3)4的反应瓶中加入40mL的NaHCO3(1M)水溶液和乙二醇二甲醚(60mL),氮气置换1小时后,加热至120℃,反应12小时,反应结束,过滤,真空干燥,柱层析分离得到固体产物,该产物MALDI-TOF-MS(m/z):514.9(M+);
4)3,7-二(5-溴噻吩-2-基)-9,9-二己基硅芴的制备,其结构式及制备方法如下:
在-5℃下,将0.71g的NBS分批加入至盛有1.30g的5,5-二己基-3,7-二(噻吩-2-基)-4H-二硅芴和20mLDMF的反应瓶中,继续搅拌48小时,反应结束后,将反应液倒入冰水中淬灭,三氯甲烷萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):672.7(M+);
5)醌型硅芴类有机半导体材料I2的制备,其制备方法如下:
冰浴下将1.57g丙二腈加入至0.19g的氢化钠(氢化钠在油溶液中的质量分数为60%)和25mL乙二醇二甲醚的悬浮液中,恢复至室温,搅拌30分钟,加入0.67g的5,5-二己基-3,7-二(5-溴噻吩-2-基)-4H-二硅芴和0.034gPdCl2(PPh3)2,加热至75℃反应72小时后,冷却至0℃,加入饱和Br2/H2O溶液,加入水,抽滤,水洗,干燥,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):640.9(M+)。
实施例3
醌型硅芴类有机半导体材料的制备,其结构式如下I3所示:
1)2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二己基硅芴的制备,具体制备方法详见实施例2中步骤2),其结构式如下:
2)3,7-二(4-己基噻吩-2-基)-9,9-二己基硅芴的制备,其结构式及制备方法如下:
在氮气保护下,往含有3.01g的2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二己基硅芴、2.68g的2-溴-4-己基噻吩、0.15gPd(PPh3)4的反应瓶中加入30mLNaOH(1M)水溶液和三氯甲烷(50mL),氮气置换1小时后,加热至75℃,反应72小时,反应结束,过滤,真空干燥,柱层析分离得到固体产物,MALDI-TOF-MS(m/z):683.2(M+);
3)3,7-二(5-溴-4己基噻吩-2-基)-9,9-二己基硅芴的制备,其结构式及制备方法如下:
在0℃下,将0.89gNBS分批加入至盛有1.37g的5,5-二己基-3,7-二(4-己基噻吩-2-基)-4H-二硅芴和40mLDMF的反应瓶中,继续搅拌12小时,反应结束后,将反应液倒入冰水中淬灭,三氯甲烷萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):841.0(M+);
4)醌型硅芴类有机半导体材料I3的制备,其制备方法如下:
冰浴下将0.25g的丙二腈加入至0.21g的氢化钠(氢化钠在油溶液中的质量分数为60%)和30mL乙二醇二甲醚的悬浮液中,恢复至室温,搅拌30分钟,加入0.84g的5,5-二己基-3,7-二(5-溴-4己基噻吩-2-基)-4H-二硅芴和0.038g的PdCl2(PPh3)2,加热至90℃反应52小时后,冷却至0℃,加入饱和Br2/H2O溶液,加入水,抽滤,水洗,干燥,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):809.3(M+)。
实施例4
醌型硅芴类有机半导体材料的制备,其结构式如下I4所示:
1)2,7-二溴-9,9-双二十基硅芴的制备,其结构式及制备方法如下:
将6.00g的4,4’-二溴-2,2’-二碘联苯溶于100mL按体积比1∶1的二氯甲烷与乙酸乙酯混合溶剂中,降温至-75℃,逐滴力入30.00mL苯基锂溶液(正丁基锂溶液的浓度为1.0M,溶剂为正己烷),反应10小时后,加入14.56g的双二十基二氯硅烷,继续反应34小时,反应结束后,加入水,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):901.2(M+);
2)2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-双二十烷基硅芴的制备,其结构式及制备方法如下:
在-78℃、氮气条件下,将20.00mL(1.00M)正丁基锂溶液加入至盛有4.50g的2,7-二溴-9,9-双二十烷基硅芴和100mL乙醚的反应瓶中,搅拌12小时后慢慢滴加4.17mL的2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,继续搅拌48小时,反应结束后,将反应液倒入水中,乙醚萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到固体产物,该产物MALDI-TOF-MS(m/z):995.3(M+);
3)3,7-二(4-二十基噻吩-2-基)-9,9-双二十基硅芴的制备,其结构式及制备方法如下:
在氮气保护下,往含有3.00g的2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-双二十烷基硅芴、2.92g的2-溴-4-二十基噻吩、0.25g的Pd2(dba)3/P(o-Tol)3、的反应瓶中加入30mL四乙基氢氧化铵(1M)水溶液和乙二醇二甲醚(50mL),氮气置换1小时后,加热至90℃,反应28小时,反应结束后,过滤,真空干燥,柱层析分离得到固体产物,该产物MALDI-TOF-MS(m/z):1468.7(M+);
4)3,7-二(5-溴-4-二十基噻吩-2-基)-9,9-双二十基硅芴的制备,其结构式及制备方法如下:
在30℃下,将0.73g的NBS分批加入至盛有2.94g的5,5-双二十基-3,7-二(4-二十基噻吩-2-基)-4H-二硅芴和40mLDMF的反应瓶中,继续搅拌18小时,反应结束后,将反应液倒入冰水中淬灭,三氯甲烷萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):1626.5(M+);
5)醌型硅芴类有机半导体材料I4的制备,其制备方法如下:
冰浴下将0.88g丙二腈加入至0.20g氢化钠(氢化钠在油溶液中的质量分数为60%)和40mL乙二醇二甲醚的悬浮液中,恢复至室温,搅拌30分钟,加入1.63g的5,5-双二十基-3,7-二(5-溴-4-二十基噻吩-2-基)-4H-二硅芴和0.055gPdCl2(PPh3)2,加热至100℃反应25小时后,冷却至0℃,加入饱和Br2/H2O溶液,再加入水,抽滤,水洗,干燥,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):1594.7(M+);
实施例5
醌型硅芴类有机半导体材料的制备,其结构式如下I5所示:
1)2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二己基硅芴的制备,具体制备方法详见实施例2中步骤2),其结构式如下:
2)3,7-二(2,2’-联二噻吩-5-基)-9,9-二己基硅芴的制备,其结构式及制备方法如下:
在氮气保护下,往含有3.01g的2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二己基硅芴、2.50g的5-溴-2,2’-联二噻吩、0.21g的Pd(PPh3)2Cl2的反应瓶中加入30mLNaHCO3(1M)水溶液和乙二醇二甲醚(50mL)。氮气置换1小时后,加热至100℃,反应25小时,反应结束后,过滤,真空干燥,柱层析分离得到固体产物,该产物MALDI-TOF-MS(m/z):679.1(M+);
3)3,7-二(5’-溴-2,2’-联二噻吩-5-基)-9,9-二己基硅芴的制备,其结构式及制备方法如下:
在10℃下,将0.71gNBS分批加入至盛有1.36g的5,5-二己基-3,7-二(2,2’-联二噻吩-5-基)-4H-二硅芴和20mL三氯甲烷的反应瓶中,继续搅拌12小时,反应结束后,将反应液倒入冰水中淬灭,三氯甲烷萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):836.9(M+);
4)醌型硅芴类有机半导体材料I5的制备,其制备方法如下:
冰浴下将0.33g丙二腈加入至0.20g甲醇钠和40mL乙二醇二甲醚的悬浮液中,恢复至室温,搅拌30分钟,加入0.84g的5,5-二己基-3,7-二(5’-溴-2,2’-联二噻吩-5-基)-4H-二硅芴和0.043g的PdCl2(PPh3)2,加热至110℃反应33小时后,冷却至0℃,加入饱和Br2/H2O溶液,再加入水,抽滤,水洗,干燥,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):805.2(M+)。
实施例6
醌型硅芴类有机半导体材料的制备,其结构式如下I6所示:
1)2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-双二十烷基硅芴的制备,具体制备方法详见实施例2中步骤2),其结构式如下:
2)3,7-二(4,4’-双二十基-2,2’-联二噻吩-5-基)-9,9-双二十基硅芴的制备,其结构式及制备方法如下:
在往含有9.95g的2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-双二十烷基硅芴、16.20g的5-溴-4,4’-双二十基-2,2’-联二噻吩、0.55g的Pd(PPh3)4的反应瓶中加入60mLNaHCO3(1M)水溶液和按体积比1∶1乙醚与二氯甲烷混合溶剂(100mL),加热至85℃,反应32小时,反应结束后,过滤,真空干燥,柱层析分离得到固体产物,该产物MALDI-TOF-MS(m/z):2194.0(M+);
3)3,7-二(5’-溴-4,4’-双二十基-2,2’-联二噻吩-5-基)-9,9-双二十基硅芴的制备,其结构式及制备方法如下:
在25℃下,将0.77gNBS分批加入至盛有2.19g的5,5-双二十基-3,7-二(4,4’-双二十基-2,2’-联二噻吩-5-基)-4H-二硅芴和40mL按体积比1∶3四氢呋喃与乙酸乙酯混合溶剂的反应瓶中,继续搅拌18小时,反应结束后,将反应液倒入冰水中淬灭,三氯甲烷萃取,无水硫酸镁干燥,旋蒸,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):2351.8(M+);
4)醌型硅芴类有机半导体材料I6的制备,其制备方法如下:
冰浴下将0.49g丙二腈加入至0.10g叔丁醇钠(氢化钠在油溶液中的质量分数为60%)和20mL乙二醇二甲醚的悬浮液中,恢复至室温,搅拌40分钟,加入1.18g的5,5-双二十基-3,7-二(5’-溴-4,4’-双二十基-2,2’-联二噻吩-5-基)-4H-二硅芴和0.033g的PdCl2(PPh3)2,加热至95℃反应42小时后,冷却至0℃,加入饱和Br2/H2O溶液,再加入水,抽滤,水洗,干燥,柱层析分离得到产物,该产物MALDI-TOF-MS(m/z):2320.1(M+)。
应用实施例7
以实施例1制备的醌型硅芴类有机半导体材料作为活性层的太阳能电池器件的制备:
请参阅图2,该太阳能电池器件包括依次层叠的玻璃基层11、透明阳极12、中间辅助层13、活性层14、阴极15,中间辅助层13采用聚乙烯二氧基噻吩:聚苯乙烯-磺酸复合材料(简称为PEDOT:PSS),活性层14包括电子给体材料和电子受体材料,电子给体材料采用实施例1制备的醌型硅芴类有机半导体材料,电子受体材料可以是[6,6]苯基-C61-丁酸甲酯(简称为PCBM)。透明阳极12可采用氧化铟锡(简称为ITO),优选为方块电阻为10-20Ω/的氧化铟锡。阴极15可采用铝电极或者双金属层电极,例如Ca/Al或Ba/Al等。其中,玻璃基层11可作为底层,制作时,选取ITO玻璃,并经超声波清洗后,用氧-Plasma处理,在ITO玻璃上涂覆中间辅助层13,再将实施例1制备的醌型硅芴类有机半导体材料和电子受体材料通过共混后涂覆于中间辅助层13上,形成活性层14,然后再通过真空蒸镀技术在活性层14上沉积阴极15,获得上述太阳能电池器件。在一个优选的实施例中,透明阳极12、中间辅助层13、活性层14、双金属层Ca和Al层的厚度分别为170、40、150、70nm。
如图2所示,在光照下,光透过玻璃基层11和ITO电极12,活性层14中的实施例1制备的醌型硅芴类有机半导体材料吸收光能,并产生激子,这些激子再迁移到电子给体/受体材料的界面处,并将电子转移给电子受体材料,如PCBM,实现电荷的分离,从而形成自由的载流子,即自由的电子和空穴。这些自由的电子沿电子受体材料向金属阴极传递并被阴极所收集,自由的空穴沿电子给体材料向ITO阳极传递并被阳极所收集,从而形成光电流和光电压,实现光电转换,外接负载16时,可对其进行供电。在此过程中,实施例1制备的醌型硅芴类有机半导体材料由于其具有很宽的光谱响应范围,能够更充分地利用光能,以获得更高的光电转换效率,增加太阳能电池器件的产电能力。而且这种有机材料还能减轻太阳能电池器件的质量,并通过旋涂等技术即可制作,便于大批量的制备。
应用实施例8
含实施例1制备的醌型硅芴类有机半导体材料有机电致发光器件的制备:
请参阅图3,显示采用实施例1制备的醌型硅芴类有机半导体材料有机电致发光器件,其包括依次层叠设置的玻璃基层21、透明阳极22、发光层23、缓冲层24、阴极25。透明阳极22可采用氧化铟锡(简称为ITO),优选为方块电阻为10-20Ω/的氧化铟锡。发光层23包含实施例1制备的醌型硅芴类有机半导体材料。缓冲层24可采用LiF等,但不限于此。阴极25可以是但不限于金属Al等。因而,在一个具体实施例中,有机电致发光器件结构表示为:ITO/实施例1制备的醌型硅芴类有机半导体材料/LiF/Al。各层可采用现有方法形成,而实施例1制备的醌型硅芴类有机半导体材料可通过旋涂技术形成于ITO上。在此发光层上可采用真空蒸镀LiF缓冲层,在缓冲层上可采用蒸镀金属Al,作为器件的阴极。
应用实施例9
含聚实施例1制备的醌型硅芴类有机半导体材料有机场效应晶体管的制备:
请参阅图4,该有机场效应晶体管包括依次层叠设置的衬底31、绝缘层32、修饰层33、有机半导体层34以及设于有机半导体层34上的源电极35和漏电极36。其中,衬底31可以是但不限于高掺杂的硅片(Si),绝缘层32可以是但不限于微纳米(如450nm)厚的SiO2。有机半导体层34采用实施例1制备的醌型硅芴类有机半导体材料。源电极35和漏电极36均可采用但不限于金。修饰层33可以是但不限于十八烷基三氯硅烷(OTS)。衬底31、绝缘层32、修饰层33以及源电极35和漏电极36都可采用现有的方法形成。有机半导体层34可以是将实施例1制备的醌型硅芴类有机半导体材料在真空度接近10-4Pa下旋涂于由修饰层33修饰的绝缘层32上。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种硅芴类有机半导体材料,其分子结构式为:
2.一种硅芴类有机半导体材料制备方法,包括如下步骤:
选取如下结构式表示的化合物:
在催化剂、缩合剂和有机溶剂存在的条件下,将所述化合物与丙二腈进行缩合反应,得到如下结构的所述硅芴类有机半导体材料:
3.根据权利要求2所述的硅芴类有机半导体材料制备方法,其特征在于:
所述催化剂为Pd(PPh3)4、Pd2(dba)3/P(o-Tol)3、Pd(PPh3)2Cl2中的至少一种;所述有机溶剂为乙二醇二甲醚、四氢呋喃、乙醚、二氯甲烷、三氯甲烷或乙酸乙酯中的至少一种。
4.根据权利要求2所述的硅芴类有机半导体材料制备方法,其特征在于:
所述缩合剂为NaH、醇钠中的至少一种。
5.根据权利要求1所述的硅芴类有机半导体材料在有机光电材料、聚合物太阳能电池、有机电致发光器件、有机场效应晶体管、有机光存储器件、有机非线性材料或/和有机激光中的应用。
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EP2068379A1 (en) * | 2006-09-12 | 2009-06-10 | Hiroshima University | Organic semiconductor material, organic semiconductor device using the same, and their production methods |
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