本文主要研究内容
作者蒋庆林（2019）在《芳香酰亚胺的溶液加工及其热电和铁磁性质的研究》一文中研究指出：近年来,有机共轭半导体材料被广泛应用在电致发光、场效应晶体管、有机光伏电池和有机热电等领域。基于活性有机薄膜的器件,如有机发光电子显示屏已经进入了市场,具有高效率、宽视角、高亮度和超轻便等特点。有机共轭半导体材料未来能够在传统无机半导体不能实现的新型应用方面发挥作用,并在材料制备和器件加工方面显示出独特的优势。例如在有机热电领域,有机共轭半导体具有很低的本征热导率,且在室温下就有较好的热电转换性能,而传统无机热电材料热导率较高且大都受限在中高温区工作。例如在有机铁磁材料领域,在过去的几十年,合成纯有机磁性材料一直是化学家和材料科学家关注的焦点。发展有机铁磁材料的一个重要原因是它们具有不同于传统金属和离子晶体磁性材料的独特性质。因此,基于有机光电磁材料的电子产品在不久的未来将成为人类科技的主流,展现出更广阔的发展前景。作为典型的芳香类共轭分子,芳香酰亚胺类衍生物具有优异的化学、光热稳定性和载流子传输特性,逐渐得到了广泛的应用。然而,芳香酰亚胺的应用目前还存在一些科学问题,例如其具有较大的共轭平面,分子刚性较强且聚集严重,这使得其溶解性较差而难以进行溶液加工,这在很大程度上限制了它们的应用。目前报道的方法如通过接枝侧链基团,可以在一定程度上解决其溶解问题,但会牺牲本体材料的某些特性,比如通过修饰后,材料的载流子迁移率会降低等。因此,如何不但能实现芳香酰亚胺类材料的溶液加工,而且还能保留其固有的优点,是有机光电领域亟待解决的科学问题。这对于拓展芳香酰亚胺类材料在有机热电和有机铁磁领域的应用也具有重要意义。我们在本论文中提出利用水合肼还原剂,在高温高压的条件下进行芳香酰亚胺的溶液加工并制备成膜。薄膜中分子排列紧密有序,具有强的相互作用而且氧化后可以得到稳定存在的自由基,在有机热电和有机铁磁领域中具有潜在的应用。在第二章中,针对大环π共轭分子难以进行溶液加工这一科学问题,我们创新地使用水合肼同时作为还原剂和溶剂,在高温高压下把4Cl-PBI分子脱氯并还原成PBI阴离子态（大部分的PBI二价阴离子和少量PBI自由基阴离子）,起到助溶解的作用,并将溶液滴涂制备成平整致密的薄膜。SEM和GIWAXS表明PBI薄膜结晶性好且分子紧密有序排列,π-π间距为3.26?。然后,我们继续尝试将此方法应用于共轭更强且更难溶解的PBI粉末中,也取得了很好的溶液加工效果。最后,我们将这种方法推广到其它芳香酰亚胺类材料如NDI,甚至其它颜料体系中,均取得了较好的结果。以上表明,此方法具有普适性,为有机半导体难溶材料的溶液加工和应用提供了新的机遇。通过上一章的研究,我们发现经过此方法制备的薄膜,不仅分子排列紧密有序,而且含有大量的阴离子,这有利于电导率的提升,因此我们尝试将其应用到有机热电领域中。在第三章中,我们系统地研究了PBI薄膜在氧气掺杂不同时间下的热电性能。首先,通过EPR、拉曼光谱和XPS能谱等表征发现随着氧化掺杂时间的增加,PBI2-被氧化成PBI·-和PBI中性态。在热电性能方面,泽贝克系数迅速增加到–3021μV K-1且电导率依然维持在很高的水平,同时热导率基本不变,ZT值高达0.23,是目前n型溶液加工有机热电材料的最高值。我们还尝试制作了热电微型器件,在温差为10 K且负载为55 kΩ时输出功率达到最大值5.14 nW。这里我们利用的氧气掺杂办法,不仅简单易操作,且不会引入杂质,掺杂效率高。一般情况下掺杂后电导率虽有大幅提升,但泽贝克系数会明显下降。在本工作中,氧气掺杂前,材料的电导率已达到较高的数量级且掺杂后下降较少,而且氧气掺杂可以调节费米能级的位置,增大泽贝克系数,提高ZT值。在前面工作中我们发现PBI分子排列紧密有序,且经过氧化后含有大量稳定存在的自由基,这很符合有机铁磁材料的设计原则。这启发我们去探究其在有机铁磁领域中的应用。为了保证材料的纯度和避免金属杂质的引入对铁磁信号的干扰,我们利用升华的办法得到了PDI单晶材料。然后通过单晶解析,得到了其分子共轭间距为3.34?。随后,我们采用水热反应将刚性骨架PDI晶体溶解在过量的水合肼溶剂中,PDI分子的绝大部分被还原成可溶性二价阴离子。在随后的氧化过程中,产生了大量的PDI·-自由基,同时重新组装为分子间距为3.30?的纳米结构晶体。磁性测量发现,此材料表现出宏观的室温铁磁性,X射线磁圆二色谱证明铁磁性来源于分子间未配对的π电子。我们的发现为实现室温铁磁半导体提供了新的思路,也可以为未来有机自旋电子学器件提供新的选择。
Abstract
jin nian lai ,you ji gong e ban dao ti cai liao bei an fan ying yong zai dian zhi fa guang 、chang xiao ying jing ti guan 、you ji guang fu dian chi he you ji re dian deng ling yu 。ji yu huo xing you ji bao mo de qi jian ,ru you ji fa guang dian zi xian shi bing yi jing jin ru le shi chang ,ju you gao xiao lv 、kuan shi jiao 、gao liang du he chao qing bian deng te dian 。you ji gong e ban dao ti cai liao wei lai neng gou zai chuan tong mo ji ban dao ti bu neng shi xian de xin xing ying yong fang mian fa hui zuo yong ,bing zai cai liao zhi bei he qi jian jia gong fang mian xian shi chu du te de you shi 。li ru zai you ji re dian ling yu ,you ji gong e ban dao ti ju you hen di de ben zheng re dao lv ,ju zai shi wen xia jiu you jiao hao de re dian zhuai huan xing neng ,er chuan tong mo ji re dian cai liao re dao lv jiao gao ju da dou shou xian zai zhong gao wen ou gong zuo 。li ru zai you ji tie ci cai liao ling yu ,zai guo qu de ji shi nian ,ge cheng chun you ji ci xing cai liao yi zhi shi hua xue jia he cai liao ke xue jia guan zhu de jiao dian 。fa zhan you ji tie ci cai liao de yi ge chong yao yuan yin shi ta men ju you bu tong yu chuan tong jin shu he li zi jing ti ci xing cai liao de du te xing zhi 。yin ci ,ji yu you ji guang dian ci cai liao de dian zi chan pin zai bu jiu de wei lai jiang cheng wei ren lei ke ji de zhu liu ,zhan xian chu geng an kuo de fa zhan qian jing 。zuo wei dian xing de fang xiang lei gong e fen zi ,fang xiang xian ya an lei yan sheng wu ju you you yi de hua xue 、guang re wen ding xing he zai liu zi chuan shu te xing ,zhu jian de dao le an fan de ying yong 。ran er ,fang xiang xian ya an de ying yong mu qian hai cun zai yi xie ke xue wen ti ,li ru ji ju you jiao da de gong e ping mian ,fen zi gang xing jiao jiang ju ju ji yan chong ,zhe shi de ji rong jie xing jiao cha er nan yi jin hang rong ye jia gong ,zhe zai hen da cheng du shang xian zhi le ta men de ying yong 。mu qian bao dao de fang fa ru tong guo jie zhi ce lian ji tuan ,ke yi zai yi ding cheng du shang jie jue ji rong jie wen ti ,dan hui xi sheng ben ti cai liao de mou xie te xing ,bi ru tong guo xiu shi hou ,cai liao de zai liu zi qian yi lv hui jiang di deng 。yin ci ,ru he bu dan neng shi xian fang xiang xian ya an lei cai liao de rong ye jia gong ,er ju hai neng bao liu ji gu you de you dian ,shi you ji guang dian ling yu ji dai jie jue de ke xue wen ti 。zhe dui yu ta zhan fang xiang xian ya an lei cai liao zai you ji re dian he you ji tie ci ling yu de ying yong ye ju you chong yao yi yi 。wo men zai ben lun wen zhong di chu li yong shui ge jing hai yuan ji ,zai gao wen gao ya de tiao jian xia jin hang fang xiang xian ya an de rong ye jia gong bing zhi bei cheng mo 。bao mo zhong fen zi pai lie jin mi you xu ,ju you jiang de xiang hu zuo yong er ju yang hua hou ke yi de dao wen ding cun zai de zi you ji ,zai you ji re dian he you ji tie ci ling yu zhong ju you qian zai de ying yong 。zai di er zhang zhong ,zhen dui da huan πgong e fen zi nan yi jin hang rong ye jia gong zhe yi ke xue wen ti ,wo men chuang xin de shi yong shui ge jing tong shi zuo wei hai yuan ji he rong ji ,zai gao wen gao ya xia ba 4Cl-PBIfen zi tuo lv bing hai yuan cheng PBIyin li zi tai （da bu fen de PBIer jia yin li zi he shao liang PBIzi you ji yin li zi ）,qi dao zhu rong jie de zuo yong ,bing jiang rong ye di tu zhi bei cheng ping zheng zhi mi de bao mo 。SEMhe GIWAXSbiao ming PBIbao mo jie jing xing hao ju fen zi jin mi you xu pai lie ,π-πjian ju wei 3.26?。ran hou ,wo men ji xu chang shi jiang ci fang fa ying yong yu gong e geng jiang ju geng nan rong jie de PBIfen mo zhong ,ye qu de le hen hao de rong ye jia gong xiao guo 。zui hou ,wo men jiang zhe chong fang fa tui an dao ji ta fang xiang xian ya an lei cai liao ru NDI,shen zhi ji ta yan liao ti ji zhong ,jun qu de le jiao hao de jie guo 。yi shang biao ming ,ci fang fa ju you pu kuo xing ,wei you ji ban dao ti nan rong cai liao de rong ye jia gong he ying yong di gong le xin de ji yu 。tong guo shang yi zhang de yan jiu ,wo men fa xian jing guo ci fang fa zhi bei de bao mo ,bu jin fen zi pai lie jin mi you xu ,er ju han you da liang de yin li zi ,zhe you li yu dian dao lv de di sheng ,yin ci wo men chang shi jiang ji ying yong dao you ji re dian ling yu zhong 。zai di san zhang zhong ,wo men ji tong de yan jiu le PBIbao mo zai yang qi can za bu tong shi jian xia de re dian xing neng 。shou xian ,tong guo EPR、la man guang pu he XPSneng pu deng biao zheng fa xian sui zhao yang hua can za shi jian de zeng jia ,PBI2-bei yang hua cheng PBI·-he PBIzhong xing tai 。zai re dian xing neng fang mian ,ze bei ke ji shu xun su zeng jia dao –3021μV K-1ju dian dao lv yi ran wei chi zai hen gao de shui ping ,tong shi re dao lv ji ben bu bian ,ZTzhi gao da 0.23,shi mu qian nxing rong ye jia gong you ji re dian cai liao de zui gao zhi 。wo men hai chang shi zhi zuo le re dian wei xing qi jian ,zai wen cha wei 10 Kju fu zai wei 55 kΩshi shu chu gong lv da dao zui da zhi 5.14 nW。zhe li wo men li yong de yang qi can za ban fa ,bu jin jian chan yi cao zuo ,ju bu hui yin ru za zhi ,can za xiao lv gao 。yi ban qing kuang xia can za hou dian dao lv sui you da fu di sheng ,dan ze bei ke ji shu hui ming xian xia jiang 。zai ben gong zuo zhong ,yang qi can za qian ,cai liao de dian dao lv yi da dao jiao gao de shu liang ji ju can za hou xia jiang jiao shao ,er ju yang qi can za ke yi diao jie fei mi neng ji de wei zhi ,zeng da ze bei ke ji shu ,di gao ZTzhi 。zai qian mian gong zuo zhong wo men fa xian PBIfen zi pai lie jin mi you xu ,ju jing guo yang hua hou han you da liang wen ding cun zai de zi you ji ,zhe hen fu ge you ji tie ci cai liao de she ji yuan ze 。zhe qi fa wo men qu tan jiu ji zai you ji tie ci ling yu zhong de ying yong 。wei le bao zheng cai liao de chun du he bi mian jin shu za zhi de yin ru dui tie ci xin hao de gan rao ,wo men li yong sheng hua de ban fa de dao le PDIchan jing cai liao 。ran hou tong guo chan jing jie xi ,de dao le ji fen zi gong e jian ju wei 3.34?。sui hou ,wo men cai yong shui re fan ying jiang gang xing gu jia PDIjing ti rong jie zai guo liang de shui ge jing rong ji zhong ,PDIfen zi de jue da bu fen bei hai yuan cheng ke rong xing er jia yin li zi 。zai sui hou de yang hua guo cheng zhong ,chan sheng le da liang de PDI·-zi you ji ,tong shi chong xin zu zhuang wei fen zi jian ju wei 3.30?de na mi jie gou jing ti 。ci xing ce liang fa xian ,ci cai liao biao xian chu hong guan de shi wen tie ci xing ,Xshe xian ci yuan er se pu zheng ming tie ci xing lai yuan yu fen zi jian wei pei dui de πdian zi 。wo men de fa xian wei shi xian shi wen tie ci ban dao ti di gong le xin de sai lu ,ye ke yi wei wei lai you ji zi xuan dian zi xue qi jian di gong xin de shua ze 。
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论文详细介绍
论文作者分别是来自华南理工大学的蒋庆林，发表于刊物华南理工大学2019-10-23论文，是一篇关于芳香酰亚胺论文,溶液加工论文,有机热电论文,室温铁磁论文,华南理工大学2019-10-23论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自华南理工大学2019-10-23论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：芳香酰亚胺论文; 溶液加工论文; 有机热电论文; 室温铁磁论文; 华南理工大学2019-10-23论文;