CN101104513A - 单壁碳纳米管的生长方法 - Google Patents
单壁碳纳米管的生长方法 Download PDFInfo
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Abstract
本发明是关于一种单壁碳纳米管的生长方法,主要包括以下步骤:提供一基底;在基底上形成一氧化铟锡电极,氧化铟锡电极的厚度为5纳米~100纳米;在氧化铟锡电极上沉积一铝过渡层,铝过渡层的厚度为5纳米~40纳米;在铝过渡层上沉积一催化剂层,催化剂层的厚度为3纳米~10纳米;将沉积有催化剂层、铝过渡层和氧化铟锡电极的基底放置在空气中,在300℃~500℃下热处理10分钟~12小时,催化剂层经退火后形成氧化颗粒;将基底放置在反应装置中,在反应装置内通入保护气体,在保护气体的保护下加热至640℃~900℃;以及通入碳源气与保护气体的混合气体,加热至640℃~900℃反应30分钟~60分钟生长出单壁碳纳米管。
Description
技术领域
本发明涉及一种碳纳米管的生长方法,尤其涉及一种低温生长单壁碳纳米管的方法。
背景技术
单壁碳纳米管广泛应用在微电子、纳米器件、材料合成、储氢等许多领域。另外,由于单壁碳纳米管的埸发射域值电压大大低于多壁碳纳米管的埸发射域值电压,因此采用单壁碳纳米管作为埸发射阴极的埸发射器件,可以在较低的电压下工作,其功耗大大低于采用多壁碳纳米管作为埸发射阴极的埸发射器件。
目前,现有技术中生长单壁碳纳米管的方法主要有电弧法、激光蒸发法、太阳能法和催化热解法等。其中,比较适合大规模生长碳纳米管的方法为催化热解法,但是,该类催化热解法的反应温度普遍较高。
因此,确有必要提供一种低温生长单壁碳纳米管的方法。
发明内容
下面将以实施例说明一种单壁碳纳米管的生长方法,该生长方法可以在较低温度下进行。
一种单壁碳纳米管的生长方法,该生长方法主要包括以下步骤:
提供一基底;
在基底上形成一氧化铟锡电极,氧化铟锡电极的厚度为5纳米~100纳米;
在氧化铟锡电极上沉积一铝过渡层,铝过渡层的厚度为5纳米~40纳米;
在铝过渡层上沉积一催化剂层,催化剂层的厚度为3纳米~10纳米;
将沉积有催化剂层、铝过渡层和氧化铟锡电极的基底放置在空气中,在300℃~500℃下热处理10分钟~12小时,催化剂层经退火后形成氧化颗粒;
将基底放置在反应装置中,在反应装置内通入保护气体,在保护气体的保护下加热至640℃~900℃;以及
通入碳源气与保护气体的混合气体,加热至640℃~900℃反应30分钟~60分钟生长出单壁碳纳米管。
与现有技术相比,本发明的单壁碳纳米管的生长方法是在氧化铟锡电极和铝过渡层上直接生长,且生长温度较低。
附图说明
图1是本发明实施例单壁碳纳米管的生长方法的流程示意图。
图2是依据本发明实施例单壁碳纳米管的生长方法所得到的单壁碳纳米管的拉曼散射谱。
图3是依据本发明实施例单壁碳纳米管的生长方法得到的单壁碳纳米管的扫描电子显微镜(Scanning Electron Microscope,SEM)照片。
图4是图3中单壁碳纳米管的高分辨率的透射电子显微镜(TransmissionElectron Microscope,TEM)照片。
具体实施方式
下面将结合附图详细说明本发明实施例单壁碳纳米管的生长方法。
本发明实施例单壁碳纳米管的生长方法包括以下步骤:
(一)提供一个硅或二氧化硅材料的基底10,如硅基底、石英基底或者玻璃基底;
(二)在基底10上形成氧化铟锡电极20,其厚度为5纳米~100纳米;
氧化铟锡电极20可以通过光刻技术、电子束光刻技术结合反应离子刻蚀技术、干法刻蚀技术或者湿法刻蚀技术在基底10上形成,但不以此为限。
采用光刻技术形成氧化铟锡电极20的方法包括以下步骤:
首先将基底10置于真空腔内,以氧化锌(ZnOx)、铌酸锂(LiNbOx)、钛酸锂(LiTiOx)或者钽酸锂(LiTaOx)为溅镀靶材,以氩气(Ar)与氧气为溅镀气体,于该基底10的表面溅镀一个压电薄膜层,溅镀的方法可以为反应性直流溅镀(DC Reactive Sputtering)或反应性射频溅镀(RF Reactive Sputtering),控制反应参数使得压电薄膜层的厚度约为0.02~5微米;在压电薄膜层表面涂覆一层光阻层;然后将一个光罩罩于光阻层表面,该光罩的图案与所需金属电极相对应;用雷射光或紫外光照射该光罩,在光阻表面形成一个曝光区;取下光罩后,将曝光的光阻层置于显影液内,去除曝光区的曝光光阻,露出部分压电薄膜层;接着利用溅镀法在剩余光阻和露出的部分压电薄膜层表面镀一层氧化铟锡层,氧化铟锡层的厚度约为5纳米~100纳米;洗去剩余光阻和附着在光阻上的金属膜层,剩余的氧化铟锡层即形成所需的氧化铟锡电极20。
采用湿法刻蚀技术形成氧化铟锡电极20的方法包括以下步骤:
首先在基底10上利用蒸镀或溅射的方法形成一个氧化铟锡层,氧化铟锡层的厚度约为5纳米~100纳米;将如光致抗蚀剂的刻蚀保护材料涂覆到氧化铟锡层的表面形成刻蚀保护层;曝光或显影去除刻蚀保护层中选定的部分,以便有选择的露出氧化铟锡层;将露出的氧化铟锡层与刻蚀剂反应以便将其去除,其中,刻蚀剂以电解液的形式施加,电化学或化学地刻蚀露出的氧化铟锡层,电解液中包括不能以刻蚀的方式与氧化铟锡层反应的中性盐、酸或碱以及能够以刻蚀方式与露出的氧化铟锡层反应的化学氧化成分;利用有机物溶剂如纯丙酮有机物溶剂去除剩余的刻蚀保护材料,刻蚀保护材料下覆盖的剩余氧化铟锡层即形成所需的氧化铟锡电极20。
(三)在氧化铟锡电极20上利用蒸镀或者溅射的方法形成一个铝层30作为过渡层,铝过渡层30的厚度为5纳米~40纳米,最优地,铝过渡层30的厚度为40纳米;
(四)在铝过渡层30上形成催化剂层40,催化剂可以选用铁(Fe)、钴(Co)、镍(Ni)或者其任意组合的合金之一,催化剂层40的厚度与选择的催化剂种类相对应,当选用铁作为催化剂时,铁催化剂层的厚度为3纳米~10纳米,优选地,铁催化剂层的厚度为5纳米;
(五)将沉积有催化剂层40、铝过渡层30和金属电极20的基底10放置在空气中,在300℃~500℃下热处理10分钟~12小时,催化剂层40经退火后形成氧化颗粒;
(六)将基底10放置在适于化学气相沉积(Chemical Vapor Deposition,CVD)反应的反应装置(图中未显示)中,在反应装置内通入保护气体,在保护气体的保护下加热到一个预定温度,通入碳源气与保护气体的混合气体,加热至640℃~900℃反应30分钟~60分钟从而生长出碳纳米管50。
其中,预先通入保护气体加热到一个预定温度的作用是防止催化剂层形成的氧化颗粒在碳纳米管50的生长过程中进一步被氧化从而影响碳纳米管50的生长条件,该预定温度因使用的催化剂不同而不同,一般为400℃~750℃,当选用铁作为催化剂时,预定温度优选为650℃,另外,预先加热时使用的保护气体为惰性气体或氮气,优选地,保护气体为氩气。在预先加热过程后,可以通入氢气或者氨气还原催化剂层形成的氧化颗粒从而得到纳米级的催化剂颗粒410,但是,在通入碳源气加热时,碳源气分解也可以将氧化颗粒还原形成纳米级的催化剂颗粒410,因此,通入氢气或者氨气还原的过程不是必须,可根据实际情况选择。碳源气与保护气体的混合气体中的碳源气为碳氢化合物,可为乙炔、乙烯等,优选地,碳源气为乙炔;保护气体为惰性气体或者氮气,优选地,保护气体为氩气。
请参阅图2,图2为依据本发明实施例单壁碳纳米管的生长方法所得到的单壁碳纳米管的拉曼散射谱,其中在175cm-1与300cm-1之间的一系列波峰是单壁碳纳米管的呼吸模特征峰。本实施例获得拉曼散射谱的单壁碳纳米管的具体生长步骤大致上包括:提供一个玻璃基底;在玻璃基底上形成氧化铟锡层,然后采用湿法刻蚀技术形成所需的氧化铟锡电极;在氧化铟锡电极上溅射厚度约为40纳米的铝过渡层;在铝过渡层上溅射厚度约为5纳米的铁层作为催化剂层;将沉积有铁催化剂层、氧化铟锡电极和铝过渡层的基底放置在空气中,在约300℃下热处理约10分钟,退火后铁催化剂层形成氧化铁颗粒;将带有氧化铁颗粒的基底放置在石英反应舟中,将反应舟装入管状石英炉中央的反应室内,通入氩气加热至约640℃;通入氢气使氧化铁颗粒还原形成纳米级的铁催化剂颗粒;通入乙炔和氩气的混合气体,加热至约640℃,反应约40分钟生长出单壁碳纳米管。
请参阅图3和图4,图3为依据本发明实施例单壁碳纳米管的生长方法得到的单壁碳纳米管的扫描电子显微镜(Scanning Electron Microscope,SEM)照片;图4为图3中单壁碳纳米管的高分辨率的透射电子显微镜(Transmission ElectronMicroscope,TEM)照片。本实施例获得的SEM、TEM照片中生长单壁碳纳米管的具体步骤大致上包括:提供一个硅基底;在硅基底上蒸镀厚度约为100纳米的氧化铟锡层,然后采用湿法刻蚀技术形成所需的氧化铟锡电极;在氧化铟锡电极上溅射厚度约为40纳米的铝过渡层;在铝过渡层上溅射厚度约为5纳米的铁层作为催化剂层;将沉积有铁催化剂层、氧化铟锡电极和铝过渡层的基底放置在空气中,在约300℃下热处理约10分钟,退火后铁催化剂层形成氧化铁颗粒;将带有氧化铁颗粒的基底放置在石英反应舟中,将反应舟装入管状石英炉中央的反应室内,通入氩气加热至约740℃;通入氢气使氧化铁颗粒还原形成纳米级的铁催化剂颗粒;通入乙炔和氩气的混合气体,加热至约740℃,反应约40分钟生长出碳纳米管。
在未采用氧化铟锡电极或者铝过渡层而其它生长条件与本发明实施例单壁碳纳米管的生长方法中的生长条件相同的现有碳纳米管的生长方法中,仅发现多壁碳纳米管,而未发现单壁碳纳米管。
另外,本领域技术人员还可在本发明精神内作其它变化,当然这些依据本发明精神所作的变化,都应包含在本发明所要求保护的范围内。
Claims (8)
1.一种单壁碳纳米管的生长方法,该生长方法主要包括以下步骤:
提供一基底;
在基底上形成一氧化铟锡电极,氧化铟锡电极的厚度为5纳米~100纳米;
在氧化铟锡电极上沉积一铝过渡层,铝过渡层的厚度为5纳米~40纳米;
在铝过渡层上沉积一催化剂层,催化剂层的厚度为3纳米~10纳米;
将沉积有催化剂层、铝过渡层和氧化铟锡电极的基底放置在空气中,在300℃~500℃下热处理10分钟~12小时,催化剂层经退火后形成氧化颗粒;
将基底放置在反应装置中,在反应装置内通入保护气体,在保护气体的保护下加热至640℃~900℃;以及
通入碳源气与保护气体的混合气体,加热至640℃~900℃反应30分钟~60分钟生长出单壁碳纳米管。
2.如权利要求1所述的单壁碳纳米管的生长方法,其特征在于,所述的氧化铟锡电极可以通过光刻技术、电子束光刻技术结合反应离子刻蚀技术、干法刻蚀技术或者湿法刻蚀技术在基底上形成。
3.如权利要求2所述的单壁碳纳米管的生长方法,其特征在于,所述的铝过渡层采用蒸镀或者溅射的方法沉积在氧化铟锡电极上。
4.如权利要求3所述的单壁碳纳米管的生长方法,其特征在于,所述的基底为硅基底、石英基底或者玻璃基底。
5.如权利要求4所述的单壁碳纳米管的生长方法,其特征在于,在通入碳源气和保护气体的混合气体前,可以通入氢气或者氨气将所述的氧化颗粒还原形成纳米级的催化剂颗粒。
6.如权利要求5所述的单壁碳纳米管的生长方法,其特征在于,所述的催化剂为铁、钴、镍或者其任意组合的合金之一。
7.如权利要求6所述的单壁碳纳米管的生长方法,其特征在于,采用光刻技术形成氧化铟锡电极的方法包括以下步骤:
将基底置于真空腔内,以氧化锌、铌酸锂、钛酸锂或者钽酸锂为溅镀靶材,以氩气与氧气为溅镀气体,在基底的表面溅镀一个压电薄膜层,溅镀的方法可以为反应性直流溅镀或者反应性射频溅镀,控制反应参数使得压电薄膜层的厚度为0.02~5微米;
在压电薄膜层表面涂覆一层光阻层;
将一个光罩罩于光阻层表面,该光罩的图案与所需金属电极相对应;用雷射光或紫外光照射该光罩,在光阻表面形成一个曝光区;
取下光罩后,将曝光的光阻层置于显影液内,去除曝光区的曝光光阻,露出部分压电薄膜层;接着利用溅镀法在剩余光阻和露出的部分压电薄膜层表面镀一层氧化铟锡层,氧化铟锡层的厚度约为5纳米~100纳米;以及
洗去剩余光阻和附着在光阻上的金属膜层,剩余的氧化铟锡层即形成所需的氧化铟锡电极。
8.如权利要求6所述的单壁碳纳米管的生长方法,其特征在于,采用湿法刻蚀技术形成氧化铟锡电极的方法包括以下步骤:
在基底上利用蒸镀或溅射的方法形成一个氧化铟锡层,氧化铟锡层的厚度约为5纳米~100纳米;
将刻蚀保护材料涂覆到氧化铟锡层的表面形成刻蚀保护层;曝光或显影去除刻蚀保护层中选定的部分,以便有选择的露出氧化铟锡层;
将露出的氧化铟锡层与刻蚀剂反应以便将其去除,其中,刻蚀剂以电解液的形式施加,电化学或化学地刻蚀露出的氧化铟锡层,电解液中包括不能以刻蚀的方式与氧化铟锡层反应的中性盐、酸或碱以及能够以刻蚀方式与露出的氧化铟锡层反应的化学氧化成分;以及
利用有机物溶剂去除剩余的刻蚀保护材料,刻蚀保护材料下覆盖的剩余氧化铟锡层即形成所需的氧化铟锡电极。
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