CN108558933B - 一类具有电荷存储能力的芳香胺材料的开发与应用 - Google Patents
一类具有电荷存储能力的芳香胺材料的开发与应用 Download PDFInfo
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- 238000003860 storage Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 23
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- LQFLWKPCQITJIH-UHFFFAOYSA-N n-allyl-aniline Chemical compound C=CCNC1=CC=CC=C1 LQFLWKPCQITJIH-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- SKJCWIFHLDWPEO-UHFFFAOYSA-N 3-benzyl-4-phenylbutan-2-one Chemical class C=1C=CC=CC=1CC(C(=O)C)CC1=CC=CC=C1 SKJCWIFHLDWPEO-UHFFFAOYSA-N 0.000 claims description 2
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
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- 238000010438 heat treatment Methods 0.000 claims description 2
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- 238000012423 maintenance Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- -1 tri-tert-butylphosphine tetrafluoroborate Chemical compound 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 2
- 238000000926 separation method Methods 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 238000003851 corona treatment Methods 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- 230000005669 field effect Effects 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000011232 storage material Substances 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 230000005055 memory storage Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- 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
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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Abstract
本专利主要是设计与合成一类具有电荷存储能力的芳香胺材料:其化学结构为结构中Ar1为以下芳香单元的一种:,结构中Ar2为以下芳香单元的一种:,结构中n为1~16烷基直链,X=Cl,OCH3或者OC2H5。本发明提供该类材料在介电层SiO2表面形成电荷存储层及该电荷存储层可应用在非易失性有机场效应晶体管存储器,展示出在有机存储器、有机光探测器、有机发光等领域潜在而广泛的应用前景。
Description
技术领域
本发明涉及电荷存储芳香胺材料的设计、合成及在非易失性有机场效应晶体管存储器中的应用。
背景技术
存储器件在现代信息存储、数据处理与通信技术中起着非常重要的作用。存储性能是通过对栅电极施加正向或反向电压实现阈值电压的可逆性漂移。存储窗口和开关比是场效应晶体管存储器的两个重要性能衡量参数。存储窗口是指不同存储状态下阈值电压的差值,开关比是用漏电流的比值来衡量不同的存储状态;两个性能参数值越大,存储性能越好。
相对于无机材料的存储器,有机材料存储器具有成本低、重量轻、可大面积制备等优点。有机场效应晶体管存储器是在栅极介电层与有机半导体层之间引入电荷存储层,当在栅极加一外电压,载流子被限制,施加一个反向电压,载流子被释放,从而实现信息存储。自组装是有机材料通过化学键合或物理吸附在衬底成膜的有效办法,制备工艺简单,膜的疏水性、形貌、膜的致密性等可进行调控。具有电荷存储性能的有机界面材料的自组装单分子层用于存储器中已有报道,但存储窗口较小(C.W.Tseng,D.C.Huang and Y.T.Tao,ACSAppl. Mater.Interfaces.,2015,7,9767-9775)。
通过键合基团三甲氧基硅烷基与介电层SiO2表面上活化羟基进行化学反应,3-氨丙基三甲氧基硅烷可在SiO2/Si衬底形成自组装膜(A.K.Chauhan,D.K.Aswal,S.P.Koiry,S.K. Gupta,J.V.Yakhmi,C.Sürgers,D.Guerin,S.Lenfant and D.Vuillaume,Appl.Phys.A.,2008, 90,581-589;A.Wang,H.Tang,T.Cao,S.O.Salley,K.Y.Ng,J.ColloidInterf.Sci.2005,291, 438-447.),其单分子层用于场效应晶体管存储器中,表现出微弱的存储性能(H.M.Lv,H.Q. Wu,C.Huang,Y.D.Wang and H.Qian,Appl.Phys.Express.,2014,7,045101.),因此在本领域中需要开发基于有机材料的高性能场效应晶体管存储器。
发明内容
1.本发明的特征是设计一类具有电荷存储能力的芳香胺材料,化学结构包括三部分:具有电荷存储功能的带有芳香基及芳香杂环基的胺基、键合基团及烷基链,该材料分子可在SiO2表面通过自组装及聚集,形成电荷存储层。
2.本发明提供的电荷存储芳香胺材料,化学结构式为
结构中Ar1为以下芳香单元的一种:
结构中Ar2为以下芳香单元的一种:
结构中n为1~16烷基直链,X=Cl,OCH3或者OC2H5。
3.上述的Ar1为Ar2为n为3,X为OC2H5,材料为PyPN,结构式为
4.本发明提供用于上述材料PyPN的合成方法。
5.本发明提供该类材料可在SiO2表面自组装及聚集形成电荷存储层的方法。
6.本发明将该类电荷存储材料应用在非易失性有机场效应晶体管存储器。
附图说明
结合如下附图及详细描述将会更清楚地理解本发明的上述和其它特征及优点,其中:
图1 N-烯丙基苯胺核磁氢谱;
图2 N-烯丙基-N-(3-吡啶基)苯胺核磁氢谱;
图3 电荷存储材料PyPN核磁氢谱;
图4 电荷存储材料PyPN核磁碳谱;
图5 电荷存储材料PyPN在氯仿溶液中的紫外吸收光谱;从图中可以看出,PyPN的最大吸收波长位于297nm与249nm。
图6 电荷存储材料PyPN在溶液中CV曲线图;
图7 PyPN电荷存储层的形貌AFM图;从图中可以看出,电荷存储层表面分布粒径为200nm的聚集体,分子间聚集是由于N原子对分子间聚集的自催化作用及N与羟基之间的氢键作用;表面呈现疏水性,水滴的接触角为86.3°。
图8 位于PyPN电荷存储层上面pentacene层的AFM图;从图中可以看出,pentacene晶粒粒径平均为120nm,表面粗糙度为6.50nm。
图9 有机场效应晶体管存储器结构示意图;沟道的长和宽分别为100μm与2000μm。
图10 存储器功能材料能级图;从图中可以看出,半导体材料pentacene与电荷存储层之间的HOMO能级接近,有利于空穴传输,而LUMO能级相差大,阻碍电子传输。
图11 晶体管的源漏极电流随栅源极电压变化的转移特征曲线;由图可以观察到,当栅源极电压VGS向负方向移动时,源漏极电流随着栅源极电压的增大而增大。与此相反,当栅源极电压VGS向正方向移动时,源漏极电流会随着栅源极电压的增大而减小。
图12 晶体管的源漏极电流随源漏极电压变化的输出特征曲线;
图13 电压写入光照擦除模式下的存储转移曲线;电压写入光照擦除模式下,写入电压为栅源极电压-80V时间1s,转移曲线向负方向移动,表明空穴载流子在栅压电场作用下,从 pentacene半导体层转移到PyPN电荷存储层,这是存储器的“写”操作;将发光二极管光源对着存储器器件的正上方照射1s后,可以观察到转移曲线几乎回到初始位置,这是存储器的“擦”操作。
图14 电压写入光照擦除模式下的读写擦循环曲线;在栅源极电压-80V时间1s时写入,在栅源极电压-40V时读取,在光照射1s进行擦除,这样的读写擦循环高达150次。
图15 电压写入光照擦除模式下的存储维持时间曲线;器件在“ON”态与“OFF”态能够稳定维持10000s。
非易失性有机场效应晶体管存储器性能参数
具体实施方式
下面对本发明的优选实施案例进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解。下面对电荷存储材料PyPN化学合成作详细说明。
实施案例1:材料PyPN的合成:
合成如下:
化合物N-烯丙基苯胺的合成
在250ml三口烧瓶中加入100ml N,N-二甲基甲酰胺、碳酸钾(33.8g,0.245mol)与苯胺(20ml,0.22mol),在N2气氛下冷却至0℃并搅拌30分钟。然后向其中缓慢加入3-溴丙烯(19ml,0.22mol)。室温下反应6h后将该反应液倒入500ml的冰水中。然后用二氯甲烷萃取三次,合并有机相,分别用水和饱和食盐水洗涤,加入无水MgSO4。过滤除去MgSO4,旋蒸除去二氯甲烷,层析柱分离提纯(淋洗液为石油醚与乙酸乙酯混合溶液,体积比为35∶1) 得到淡黄色油状物,产率为48%。1H NMR(300MHz,CDCl3)δ:7.19(m,2H),6.73(m,1H),6.65 (m,2H),5.97(m,1H),5.24(m,2H),3.79(d,2H),3.41(s,1H)。
化合物N-烯丙基-N-(3-吡啶基)苯胺的合成
将化合物N-烯丙基苯胺(2.1g,15.7mmol)、3-溴吡啶(1.91g,12.1mmol)、叔丁醇钠(1.75g,18.2mmol)与干燥的甲苯(20mL)加到Schlenk反应瓶中,用N2置换空气后,加入三叔丁基膦四氟硼酸盐(14mg)与双(二亚芐基丙酮)钯(35mg)。将体系加热到100℃反应4h,冷却到室温,过滤收集母液。蒸掉溶剂后用石油醚与乙酸乙酯混合溶液(体积比为 3∶1)进行柱分离提纯,得到产物2.34g,产率为92%。1H NMR(300MHz,CDCl3)δ:8.28(d,1H), 8.10(m,1H),7.33(m,2H),7.22(m,1H),7.11(m,4H),5.90(m,1H),5.24(m,2H),4.36(m,2H)。
电荷存储材料PyPN合成
在Schlenk反应瓶中,加入N-烯丙基-N-(3-吡啶基)苯胺(0.42g,2mmol)、三乙氧基硅烷 (0.49g,3mmol)与Karstedt催化剂(platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane)(2 mg),用N2置换空气后,在95℃加热搅拌下12h。冷却到室温,旋转蒸馏后,层析柱分离提纯(淋洗液为石油醚与乙酸乙酯混合溶液,体积比为4∶1),得到淡黄色油状液体,产率为50%。1H NMR(300MHz,CDCl3)δ:8.23(d,1H),8.08(m,1H),7.33(m,2H),7.22(m,1H),7.12(m, 4H),3.79(q,6H),3.70(t,2H),1.79(m,2H),1.20(t,9H),0.63(m,2H).13C NMR(75MHz,CDCl3) δ:146.86,144.64,140.52,129.80,125.08,123.67,123.53,123.45,58.57,54.63,20.67,18.39, 7.58。
实施案例2:电荷存储层的制备
(1)SiO2(300nm厚)/Si(n型)衬底依次在丙酮、乙醇、去离子水超声5min后,在烘箱里 100℃干燥。用氧等离子体处理10min。
(2)将处理好的SiO2/Si浸泡到PyPN的无水甲苯溶液里(3mM),维持在80℃共60h。从溶液中取出,用甲苯充分冲洗,转移到烘箱里,在110℃维持30min。
实施案例3:有机场效应晶体管存储器的制备
将带有电荷存储层的衬底放入真空蒸镀室,在真空度为3x10-4Pa、蒸镀速率为下依次蒸镀50nm有机半导体材料pentance,然后蒸镀50nm Au作为源、漏电极,晶体管沟道的长和宽分别为100μm与2000μm。器件结构为SiO2/Si/电荷存储层/pentacene(50nm)/Au (50nm)。
实施案例4:器件性能测试
使用Keithley2400对器件进行性能测试。
Claims (5)
1.一类具有电荷存储能力的芳香胺材料,其特征在于,材料的化学结构式为
结构中Ar1为以下芳香单元的一种:
结构中Ar2为以下芳香单元的一种:
结构中n为1~16烷基直链,X = Cl, OCH3 或者OC2H5。
2.根据权利要求1所述的芳香胺材料,其特征在于,Ar1为,Ar2为,n为3,X为
OC2H5,材料为PyPN,结构式为。
3.根据权利要求2所述的芳香胺材料,其特征在于,PyPN的合成路线为:
其合成步骤为:
(1) 化合物N-烯丙基苯胺的合成:在250 ml 三口烧瓶中加入100 ml的N,N-二甲基甲酰胺、33.8 g的碳酸钾与20 ml的苯胺,在N2气氛下冷却至0 ℃并搅拌30分钟;向其中缓慢加入19 ml 的3-溴丙烯,室温下反应6 h后将该反应液倒入500 ml的冰水中;用二氯甲烷萃取三次,合并有机相,分别用水和饱和食盐水洗涤,加入无水MgSO4干燥后,用石油醚与乙酸乙酯通过层析柱分离提纯,得到淡黄色油状物,产率为48%;
(2) 化合物N-烯丙基-N-(3-吡啶基)苯胺的合成:将2.1 g的化合物N-烯丙基苯胺、1.91 g的3-溴吡啶、1.75 g的叔丁醇钠与20 ml干燥的甲苯加到Schlenk反应瓶中,用N2置换空气后,加入14 mg的三叔丁基膦四氟硼酸盐与35 mg的双(二亚芐基丙酮)钯;将体系加热到100 ℃反应4 h,冷却到室温,过滤收集母液;蒸掉溶剂后用石油醚与乙酸乙酯混合溶液进行柱分离提纯,得到产物2.34 g,产率为92%;
(3) PyPN的合成:在Schlenk反应瓶中,加入0.42 g的化合物N-烯丙基-N-(3-吡啶基)苯胺、0.49 g的三乙氧基硅烷与2 mg 的Karstedt催化剂,用N2置换空气后,在95 ℃加热搅拌下12 h;冷却到室温,旋转蒸馏后,用石油醚与乙酸乙酯混合溶液进行柱分离提纯,得到淡黄色油状液体,产率为50%。
4.根据权利要求2所述的芳香胺材料,其特征在于,材料PyPN在SiO2表面形成电荷存储层的方法:
(1) SiO2/Si衬底依次在丙酮、乙醇、去离子水超声5 min后,在烘箱里100 ℃干燥,用氧等离子体处理10 min;
(2) 将处理好的SiO2/Si浸泡到浓度为3 mM的PyPN的无水甲苯溶液里,在80℃维持60h;从溶液中取出,用甲苯充分冲洗,转移到烘箱里,在110℃维持30 min。
5.根据权利要求1所述一类具有电荷存储能力的芳香胺材料在非易失性有机场效应晶体管存储器中的应用。
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