CN112624089A - 一种合成螺旋碳纳米管-碳纳米管异质结的方法 - Google Patents
一种合成螺旋碳纳米管-碳纳米管异质结的方法 Download PDFInfo
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- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 36
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Abstract
本发明公开了一种合成螺旋碳纳米管‑碳纳米管异质结的方法，取纳米氧化镍颗粒放入管式炉内，在氢气氛围下加热至400℃并保持1小时获得镍纳米颗粒；镍纳米颗粒为催化剂，在管式炉中通入乙炔和氨气的混合气体，加热至450±25℃并保持4小时；关闭乙炔和氨气并通入氩气，在氩气氛围下自然冷却至室温得到螺旋碳纳米管‑碳纳米管异质结。本发明简单易行，可高效率获得螺旋碳纳米管‑碳纳米管异质结，且易于分散，为碳纳米管异质结家族增添了新的成员，在低维纯碳异质结的研究和应用方面都具有重要的价值。
Description
技术领域
本发明涉及一种合成螺旋碳纳米管-碳纳米管异质结的方法，在低维纯碳异质结的研究和应用方面都具有重要的价值。
背景技术
异质结或同质结主要作为组件应用于电子电路或光电领域，在人类社会的发展和科技的进步中起着至关重要的作用。随着集成度越来越高，新一代异质结或同质结组件必然为纳米量级。纯碳异质结由于具有诸多优越性能而广受究者们青睐。
上世纪90年代，研究者们就通过在单根碳纳米管的6元环网络中引入5元环和7元环缺陷的方法，设计并构建了纯碳纳米管的异质结模型。2001年，研究人员利用扫描隧道显微镜首次在实验上明确地观测到由不同手征指数的碳纳米管头对头连接而成的异质结(Ouyang et al.，《Science》2001年第291卷第97-100页)，推开了纳米集成电路的大门。由于碳纳米管根据其直径和手征指数的不同，可表现出金属或半导体性质，因此，CNTs异质结可以是金属-金属结、金属-半导体结，以及半导体-半导体结，这些不同的异质结可以制成单根碳纳米管的二极管、整流器，以及电光器件等，在即将快速兴起的微纳时代中将占据重要地位，并发挥出极其重要的作用。
目前已报道的碳纳米管异质结均为直杆的碳纳米管相互连接，而发明人合成的则是由螺旋碳纳米管与直杆碳纳米管相互连接组成的纯碳异质结。螺旋碳纳米管是在直杆的碳纳米管的6元环网络中周期性的插入5元环和7元环而构成的一种类似弹簧状的螺旋形结构，它在形貌结构上与碳纳米管有很大的不同。显然，螺旋碳纳米管-碳纳米管异质结是一种新型的准一维纯碳异质结，其能带结构、电学及光学性能等可能都与直杆的碳纳米管异质结不同，在未来的纳米集成电路以及纳米电光器件等方面可能有着重要的应用价值。
发明内容
本发明的目的是提供一种易于操控，实用的合成螺旋碳纳米管-碳纳米管异质结的方法。
具体步骤为：
一种合成螺旋碳纳米管-碳纳米管异质结的方法，采用催化化学气相沉积法，催化剂采用镍纳米颗粒。具体步骤为：
(1)取纳米氧化镍颗粒放入管式炉内，在氢气氛围下加热至400℃并保持1小时获得镍纳米颗粒；
(2)以步骤(1)中所获得的镍纳米颗粒为催化剂，在管式炉中通入乙炔和氨气的混合气体，加热至450±25℃并保持4小时；关闭乙炔和氨气并通入氩气，在氩气氛围下自然冷却至室温得到螺旋碳纳米管-碳纳米管异质结。
其中，所述的纳米氧化镍颗粒的制备方法为：
(a)将镍盐和柠檬酸按摩尔比1:3溶于无水乙醇中；
(b)水浴60℃条件下持续搅拌6小时；
(c)搅拌后的溶液在85℃将其基本烘干，再175℃完全烘干；
(d)烘干后的产物在马弗炉中400℃煅烧4小时，此时获得纳米氧化镍颗粒。
进一步的，所述的镍盐为硝酸镍、氯化镍或醋酸镍。
上述过程中所使用原料的纯度应至少为分析纯。
本发明的过程在化学气相沉积系统中完成。反应器可采用石英管，水平管式炉升温前需先排尽反应器中的空气，以免爆炸。
400℃升温至450±25℃时的升温速率为5℃/min。
所使用的乙炔应为工业纯，氢气、氨气、氩气为高纯。乙炔和氨气同时输入，其比例可利用流量计控制。
由于镍纳米颗粒在空气中容易氧化，因此氢气还原只取少量在合成螺旋碳纳米管-碳纳米管异质结的时候完成。称取纳米氧化镍颗粒0.025g置于水平管式炉中，输入氢气，400℃还原1小时，获得镍纳米颗粒。
本发明简单易行，可高效率获得螺旋碳纳米管-碳纳米管异质结，且易于分散，为碳纳米管异质结家族增添了新的成员，在低维纯碳异质结的研究和应用方面都具有重要的价值。
附图说明
图1a为本发明实施例1获得的螺旋碳纳米管-碳纳米管异质结的场发射扫描电子显微镜照片；
图1b为本发明实施例1获得的螺旋碳纳米管-碳纳米管异质结的透射电子显微镜照片；
图2a为本发明实施例2获得的螺旋碳纳米管-碳纳米管异质结的场发射扫描电子显微镜照片；
图2b为本发明实施例2获得的螺旋碳纳米管-碳纳米管异质结的透射电子显微镜照片；
图3a为本发明实施例3获得的螺旋碳纳米管-碳纳米管异质结的场发射扫描电子显微镜照片；
图3b为本发明实施例3获得的螺旋碳纳米管-碳纳米管异质结的透射电子显微镜照片。
具体实施方式
结合实施例说明本发明的具体技术方案。
实施例1：
(1)称取0.01mol六水合硝酸镍和0.03mol一水合柠檬酸于盛有100ml无水乙醇的三角烧瓶中。水浴加热至60℃并电动搅拌，保持6小时后转入烧杯中，85℃将其烘干后，再175℃将其完全烘干。最后在马弗炉中400℃煅烧4小时，即得到镍的氧化物纳米颗粒。
(2)称取步骤(1)的产物0.025g于瓷舟中放入化学气相沉积系统的反应器(水平管式炉，管径50mm)内，输入20ml/min流量的氢气后加热至400℃并保持1小时。
(3)关闭氢气，输入乙炔和氨气(流量分别为30ml/min和5ml/min)，加热至425℃并保持4小时。最后关闭乙炔和氨气，输入氩气，在氩气的保护下降至室温，得到螺旋碳纳米管-碳纳米管异质结大约1.52g左右。
上述实施例获得的产物的场发射扫描电子显微镜照片和透射电子显微镜照片如图1a和图1b。
实施例2：
将实施例1步骤(3)中炉温加热至450℃，其他条件完全同于实施例1，得到螺旋碳纳米管-碳纳米管异质结大约1.21g左右。
上述实施例获得的产物的场发射扫描电子显微镜照片和透射电子显微镜照片如图2a和图2b。
实施例3：
将实施例1步骤(3)中炉温加热至475℃，其他条件完全同于实施例1，得到螺旋碳纳米管-碳纳米管异质结大约1.89g左右。
上述实施例获得的产物的场发射扫描电子显微镜照片和透射电子显微镜照片如图3a和图3b。
虽然本发明已有技术方案和实施例陈述如上，然其并非用以限定本发明。本发明所属技术领域中具有通常知识者，在不脱离本发明的精神和范围内，当可作各种的变化、更替与润饰。因此，本发明的保护范围当视权利要求书所界定者为准。
Claims (7)
1.一种合成螺旋碳纳米管-碳纳米管异质结的方法，其特征在于，采用催化化学气相沉积法，催化剂采用镍纳米颗粒。
2.根据权利要求1所述的一种合成螺旋碳纳米管-碳纳米管异质结的方法，其特征在于，具体步骤为：
(1)取纳米氧化镍颗粒放入管式炉内，在氢气氛围下加热至400℃并保持1小时获得镍纳米颗粒；
(2)以步骤(1)中所获得的镍纳米颗粒为催化剂，在管式炉中通入乙炔和氨气的混合气体，加热至450±25℃并保持4小时；关闭乙炔和氨气并通入氩气，在氩气氛围下自然冷却至室温得到螺旋碳纳米管-碳纳米管异质结。
3.根据权利要求2所述的一种合成螺旋碳纳米管-碳纳米管异质结的方法，其特征在于，所述的纳米氧化镍颗粒的制备方法为：
(a)将镍盐和柠檬酸按摩尔比1:3溶于无水乙醇中；
(b)水浴60℃条件下持续搅拌6小时；
(c)搅拌后的溶液在85℃将其基本烘干，再175℃完全烘干；
(d)烘干后的产物在马弗炉中400℃煅烧4小时，此时获得纳米氧化镍颗粒。
4.根据权利要求3所述的一种合成螺旋碳纳米管-碳纳米管异质结的方法，其特征在于，所述的镍盐为硝酸镍、氯化镍或醋酸镍。
5.根据权利要求2所述的一种合成螺旋碳纳米管-碳纳米管异质结的方法，其特征在于，在化学气相沉积系统中完成。
6.根据权利要求2所述的一种合成螺旋碳纳米管-碳纳米管异质结的方法，其特征在于，400℃升温至450±25℃时的升温速率为5℃/min。
7.根据权利要求2所述的一种合成螺旋碳纳米管-碳纳米管异质结的方法，其特征在于，所使用的乙炔应为工业纯，氢气、氨气、氩气为高纯。
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