CN104916777B - 一种锂离子掺杂石墨烯忆阻器及其制备方法 - Google Patents
一种锂离子掺杂石墨烯忆阻器及其制备方法 Download PDFInfo
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Abstract
本发明公开一种锂离子掺杂石墨烯忆阻器,自下而上依次有绝缘衬底、锂离子掺杂的石墨烯层及两个金属电极,或者自下而上依次有绝缘衬底、两个金属电极和锂离子掺杂的石墨烯层。其制备方法如下:1)将石墨烯转移至洁净的绝缘衬底上,再在石墨烯上制作金属电极,或者在洁净的绝缘衬底上先制作金属电极,再将石墨烯转移至绝缘衬底上,获得石墨烯电阻器;2)通过给锂离子电池充电的方式,将锂离子掺入石墨烯层中,获得锂离子掺杂石墨烯忆阻器。本发明的锂离子掺杂石墨烯忆阻器利用石墨烯材料的大比表面积与高载流子率,并利用其表面的缺陷及多层石墨烯与锂离子形成的亚稳定结构,有利于在低成本及简单工艺的基础上制备具有优良电学性能的忆阻器。
Description
技术领域
本发明涉及一种忆阻器及其制备方法,尤其涉及一种锂离子掺杂石墨烯忆阻器及其制备方法,属于微电子器件制备领域。
背景技术
忆阻器是除电阻、电容、电感之外的第四类无源电路元件,于1971年作为一个概念被提出。忆阻器能够在无源的情况下表现出不易失的记忆特性,作为电路元件,相比较实现同样功能的电路单元,其结构简单、集成度高。对忆阻器的研究和普及很可能实现有源器件的无源化。
忆阻器的第一个实物在2008年由惠普实验室两位工程师制得,是一种基于二氧化钛掺杂氧空穴的“三明治”结构。此后各种不同类型的忆阻器实物被不断制造出来。基于“三明治”结构的产品占大多数,器件都是基于三维材料的结构。而且制作成本比较高昂。
自石墨烯材料在2004年首次被稳定制备出来后,越来越多的研究发现石墨烯材料具有优异的电学、光学性质,如极高的载流子迁移率、高透光新、高的杨氏模量等。这些独特的性质使石墨烯有可能广泛的应用于微电子器件的全新领域。已有研究者利用石墨烯开展对忆阻器的研究,包括使用石墨烯作为电极改善性能,使用氧化石墨烯等。而针对石墨烯大比表面积的特点直接将其作为忆阻器的核心部件,目前这方面的研究还比较稀少。
发明内容
本发明的目的在于提供一种性能优良、工艺简单且成本较低的锂离子掺杂石墨烯忆阻器及其制备方法。
本发明的锂离子掺杂石墨烯忆阻器,自下而上依次有绝缘衬底、锂离子掺杂的石墨烯层及两个金属电极;或者自下而上依次有绝缘衬底、两个金属电极和锂离子掺杂的石墨烯层,锂离子掺杂的石墨烯层与两个金属电极均接触。
上述技术方案中,所述的锂离子掺杂的石墨烯层的厚度通常为0.4nm-1μm。
所述的金属电极可以为金、钯、银、钛、铜、铂、铬和镍中的一种或几种复合电极。
制备上述的锂离子掺杂石墨烯忆阻器的方法,包括如下步骤:
1)将石墨烯转移至洁净的绝缘衬底上,再在石墨烯上制作两个金属电极,得到石墨烯电阻器;或者在洁净的绝缘衬底上制作两个金属电极,再将石墨烯转移至绝缘衬底上,并使石墨烯与两个金属电极接触,获得石墨烯电阻器;
2)以上述的石墨烯电阻器作为阴极,以锂离子电池阳极材料作为阳极,置入电解液中,通电1-30分钟,取出洗净并干燥,获得锂离子掺杂石墨烯忆阻器。
所述的锂离子掺杂石墨烯忆阻器的制备方法,其特征在于所述的锂离子电池阳极材料为金属锂、钴酸锂、镊酸锂、锰酸锂、磷酸铁锂、氟化磷酸铁锂、磷酸锰锂、磷酸钛锂中的一种或几种的混合。
所述的电解液是以环状碳酸酯、链状碳酸酯和羧酸酯类中的一种或几种的互溶液为溶剂,以高氯酸锂、六氟磷酸锂、四氟硼酸锂和六氟砷(V)酸锂中的一种或几种为溶质的电解液,其中,环状碳酸酯为PC或EC,链状碳酸酯为DEC、DMC或EMC,羧酸酯类为MF、MA、EA、MA、MP等。
本发明与现有技术相比具有的有益效果是:
相较于各类现有的忆阻器结构而言,本发明的锂离子掺杂石墨烯忆阻器利用石墨烯材料的大比表面积、高导电性以及与锂离子形成的亚稳定结构,能够获得与现有忆阻器相当的忆阻特性。而且本发明的锂离子掺杂石墨烯忆阻器的制备工艺简单,成本较低,有利于实验室的日常制备研究,以及产业化应用。
附图说明
图1为锂离子掺杂石墨烯忆阻器的结构示意图,其中(a)、(b)分别为两种结构的示意图。
具体实施方式
下面结合附图和具体实施例进一步说明本发明。
参照图1,本发明的锂离子掺杂石墨烯忆阻器自下而上依次有绝缘衬底1、锂离子掺杂的石墨烯层3及两个金属电极2,如(a)所示;或者自下而上依次有绝缘衬底1、两个金属电极2和锂离子掺杂的石墨烯层3,锂离子掺杂的石墨烯层3与两个金属电极2均接触,如(b)所示。
所述的锂离子掺杂的石墨烯层3的厚度为0.4nm-1μm。
所述的金属电极2为金、钯、银、钛、铜、铂、铬和镍中的一种或几种复合电极。
实施例1
1)对二氧化硅绝缘衬底进行清洗:分别在去离子水、丙酮、异丙醇中超声5分钟,取出后吹干;
2)在二氧化硅表面用电子束蒸发工艺沉积60纳米厚,1.5毫米宽,间隔5毫米的两个平行金电极,退火后用氧氩等离子体处理1分钟;
3)将0.4纳米厚的石墨烯转移至上述二氧化硅上,并使石墨烯与两个金电极接触,自然阴干半小时,120摄氏度烘干半小时,制成石墨烯电阻器;
4)将3克碳酸乙烯酯(EC)溶于20毫升碳酸二甲酯(DMC)中,加入0.5克无水高氯酸锂晶体溶解,加入适量分子筛除水,制成电解液;
5)称取1克锰酸锂粉末,溶于PVDF溶液,均匀涂于铜箔上并烘干制成锰酸锂阳极;
6)将制备的石墨烯电阻器作为阴极与外接电源负极相连,将锰酸锂阳极与外接电源正极相连,置入上述电解液中,通电1分钟后取出,漂洗干净并吹干,获得锂离子掺杂石墨烯忆阻器。
本例制得的忆阻器,通过测量两个平行金电极两端的I-V曲线、I-t曲线可以表征其忆阻特性。忆阻特性由通过上述方法掺入的锂离子所提供,锂离子所在的地方会引起石墨烯表面电荷的重新分布,在电场的作用下锂离子发生迁移,从而带来整个石墨烯电阻表面电阻率分布的变化,带来忆阻效应,即阻值随通过的电流对时间的积分而改变。
实施例2
1)对二氧化硅绝缘衬底进行清洗:分别在去离子水、丙酮、异丙醇中超声5分钟,取出后加热蒸干;
2)在二氧化硅表面利用磁控溅射沉积两个铬/钛电极,电极60纳米厚,1.5毫米宽,间隔5毫米,退火后用氧氩等离子体处理1分钟;
3)将1微米厚的石墨烯转移至上述二氧化硅上,并使石墨烯与两个电极接触,自然阴干半小时,120摄氏度烘干半小时,制成石墨烯电阻器;
4)将3克碳酸乙烯酯溶于20毫升碳酸甲乙酯(EMC)中,加入0.5克无水六氟磷酸锂晶体溶解,加入适量分子筛除水,制成电解液;
5)称取1克钴酸锂粉末,溶于PVDF溶液,均匀涂于铜箔上并烘干制成钴酸锂阳极;
6)将制备的石墨烯电阻器作为阴极与外接电源负极相连,将钴酸锂阳极与外接电源正极相连,置入上述电解液中,通电30分钟后取出,干燥,获得锂离子掺杂石墨烯忆阻器。
实施例3
1)对二氧化硅绝缘衬底进行清洗:分别在去离子水、丙酮、异丙醇中超声5分钟,取出后加热蒸干,用氧氩等离子体处理1分钟;
2)将10纳米厚的石墨烯转移至上述二氧化硅上,自然阴干半小时,120摄氏度烘干半小时;
3)在石墨烯上磁控溅射两个钛/镍电极,电极60纳米厚,1.5毫米宽,间隔5毫米,得到石墨烯电阻器;
4)将3克碳酸乙烯酯溶于10毫升碳酸甲乙酯和10毫升碳酸二甲酯的混合溶液中,加入0.5克无水四氟硼酸锂晶体溶解,加入适量分子筛除水,制成电解液;
5)称取0.5克钴酸锂粉末和0.5克锰酸锂粉末,溶于PVDF溶液,均匀涂于铜箔上并烘干制成阳极;
6)将制备的石墨烯电阻器作为阴极与外接电源负极相连,将上述阳极与外接电源正极相连,置入上述电解液中,通电10分钟后取出,用去离子水漂洗干净并吹干,获得锂离子掺杂石墨烯忆阻器。
实施例4
1)对二氧化硅绝缘衬底进行清洗:分别在去离子水、丙酮、异丙醇中超声5分钟,取出后加热蒸干,用氧氩等离子体处理1分钟;
2)将10纳米厚的石墨烯转移至上述二氧化硅上,自然阴干半小时,120摄氏度烘干半小时;
3)在石墨烯上利用热蒸发工艺沉积两个镍电极,电极60纳米厚,1.5毫米宽,间隔5毫米,相互平行,得到石墨烯电阻器;
4)将5克碳酸乙烯酯溶于10毫升碳酸甲乙酯和10毫升碳酸二甲酯的混合溶液中,加入0.5克无水四氟硼酸锂晶体溶解,加入适量分子筛除水,制成电解液;
5)称取1克磷酸铁锂粉末,溶于PVDF溶液,均匀涂于铜箔上并烘干制成阳极;
6)将制备的石墨烯电阻器作为阴极与外接电源负极相连,将上述阳极与外接电源正极相连,置入上述电解液中,通电20分钟后取出,干燥,获得锂离子掺杂石墨烯忆阻器。
Claims (6)
1.一种锂离子掺杂石墨烯忆阻器,其特征在于,自下而上依次有绝缘衬底(1)、锂离子掺杂的石墨烯层(3)及两个金属电极(2);或者自下而上依次有绝缘衬底(1)、两个金属电极(2)和锂离子掺杂的石墨烯层(3),锂离子掺杂的石墨烯层(3)与两个金属电极(2)均接触。
2.根据权利要求1所述的锂离子掺杂石墨烯忆阻器,其特征在于所述的锂离子掺杂的石墨烯层(3)的厚度为0.4nm-1μm。
3.根据权利要求1所述的锂离子掺杂石墨烯忆阻器,其特征在于所述的金属电极(2)为金、钯、银、钛、铜、铂、铬和镍中的一种或几种复合电极。
4.制备如权利要求1-3任一项所述的锂离子掺杂石墨烯忆阻器的方法,其特征在于,包括如下步骤:
1)将石墨烯转移至洁净的绝缘衬底上,再在石墨烯上制作两个金属电极,得到石墨烯电阻器;或者在洁净的绝缘衬底上制作两个金属电极,再将石墨烯转移至绝缘衬底上,并使石墨烯与两个金属电极接触,获得石墨烯电阻器;
2)以上述的石墨烯电阻器作为阴极,以锂离子电池阳极材料作为阳极,置入电解液中,通电1-30分钟,取出并干燥,获得锂离子掺杂石墨烯忆阻器。
5.根据权利要求4所述的锂离子掺杂石墨烯忆阻器的制备方法,其特征在于所述的锂离子电池阳极材料为金属锂、钴酸锂、镊酸锂、锰酸锂、磷酸铁锂、氟化磷酸铁锂、磷酸锰锂、磷酸钛锂中的一种或几种的混合。
6.根据权利要求4所述的锂离子掺杂石墨烯忆阻器的制备方法,其特征在于所述的电解液是以环状碳酸酯、链状碳酸酯和羧酸酯类中的一种或几种的互溶液为溶剂,以高氯酸锂、六氟磷酸锂、四氟硼酸锂和六氟砷(V)酸锂中的一种或几种为溶质的电解液。
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