CN1277145A - 利用热cvd法在大尺寸基片上大规模合成垂直排列的高纯碳纳米管的方法 - Google Patents
利用热cvd法在大尺寸基片上大规模合成垂直排列的高纯碳纳米管的方法 Download PDFInfo
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Abstract
一种利用热化学汽相淀积(CVD)在大尺寸基片上合成垂直排列的高纯碳纳米管的方法。该合成方法中,通过腐蚀在基片上形成隔离的纳米级催化金属颗粒,并通过利用碳源气的热CVD,由催化金属颗粒生长垂直排列的净化碳纳米管。
Description
本发明涉及碳纳米管的合成方法,特别涉及在大面积基片上大规模合成垂直排列的高纯碳纳米管的方法。
为扶手椅形时具有导电性、为锯齿形时具有半导电性的碳纳米管可用作场发射器件、白光源、锂二次电池、储氢电池、阴极射线管的晶体管的电子发射源。对于碳纳米管的这种工业应用来说,有益的是在大面积基片上合成垂直排列形式的高纯碳纳米管。另外,另一个令人关注的是对于碳纳米管的合成来说,容易控制碳纳米管的直径和长度及所用衬底的密度和均匀性。
现有碳纳米管合成技术包括放电法、激光淀积法、气相合成法、热化学汽相淀积(CVD)法、等离子CVD法等。
放电法(C.Journet等人,Nature,388,756(1997)和D.S.Bethune等人,Nature,363,605(1993))和激光淀积法(R.E.Smally等人,Science,273,483(1996))不能控制碳纳米管的直径或长度,并且使用这些方法的产量低。另外,还会与碳纳米管一起产生额外的非晶碳块,所以需要复杂的净化工艺。所以,利用这些方法,很难在大尺寸基片上大规模生长碳纳米管。
同时,适于大规模合成碳纳米管的气相合成法(R.Andrews等人,Chem.Phys.Lett.,303,468,1999)是在不用基片的情况下,利用处于炉中的碳源气的热解在气相中形成碳纳米管。然而,该方法也难以控制碳纳米管的直径或长度,并会使金属催化剂块粘附于碳纳米管的内壁或外壁上。所以,这种方法不能满足高纯碳纳米管的需要,并且不能在基片上得到垂直排列的碳纳米管。
热CVD法涉及在多孔硅石(W.Z.Li等人,Science,274,1701(1996))或沸石(Shinohara等人,Japanese J. of Appl.Phys.,37,1357(1998))基片上生长碳纳米管。然而,用金属催化剂填充基片的小孔是一种复杂且耗时的过程。另外,不容易控制碳纳米管的直径,而且产量也低。所以,热CVD法局限于在较大基片上生长大块碳纳米管。
等离子CVD法(Z.F.Ren等人,Science,282,1105(1998))是垂直排列碳纳米管的合适技术,具有优异的性能。然而,问题是等离子能量会损坏碳纳米管,而且由于低温合成工艺,碳纳米管结构不稳定。此外,许多碳颗粒会粘附于碳纳米管的表面上。
为解决上述问题,本发明的目的是提供一种在大尺寸基片上大规模合成垂直排列的高纯碳纳米管的方法。
借助包括在基片上形成金属催化层的合成碳纳米管的方法,可以实现本发明的目的。腐蚀金属催化层,形成隔离的纳米级催化金属颗粒,并利用热化学汽相淀积(CVD),由每个隔离的纳米级催化金属颗粒生长碳纳米管,其中碳源气供应到热CVD设备中,碳纳米管垂直排列于基片上。
优选是利用气体腐蚀法形成隔离的纳米级催化金属颗粒,该方法中,选自氨气、氢气和氢化物气的一种腐蚀气热分解,用于腐蚀。可以利用等离子腐蚀或使用氢氟酸系列腐蚀剂的湿法腐蚀形成隔离的纳米级催化金属颗粒。
优选地,腐蚀气是氨气,在温度为700-1000℃,同时以80-400sccm的流量供应氨气10-30分钟的条件下进行气体腐蚀的方法。
优选地,在温度为700-1000℃,同时以20-200sccm的流量供应碳源气10-60分钟的条件下形成碳纳米管。
优选地,在相同的热CVD设备中,原位形成催化金属颗粒和碳纳米管。
优选地,在形成碳纳米管时,与碳源气一起,向热CVD设备供应选自氨气、氢气、和氢化物气中的一种气体。
优选地,在形成碳纳米管后,该合成方法还包括利用惰性气体,排出热CVD设备中的碳源气。
优选地,在形成碳纳米管后,该合成方法还包括在相同热CVD设备中,原位净化碳纳米管。优选是用选自氨气、氢气、氧气和这些气体的混合气中的一种净化气,原位净化该碳纳米管。
优选地,在原位净化碳纳米管后,该合成方法还利用惰性气体,排出热CVD设备中的净化气。
通过结合附图详细介绍本发明的优选实施方案,本发明的上述目的和优点将变得更清楚,各附图中:
图1是展示本发明合成碳纳米管的方法的流程图;
图2A和2B是具有金属催化层的基片的剖面图;
图3是用于本发明优选实施方案的热化学汽相淀积(CVD)设备的示意图;
图4是展示形成独立隔离的催化金属颗粒情况的示意图;且
图5是展示形成从隔离催化金属颗粒突起的碳纳米管情况的剖面图;
图6A-6C是展示从隔离的催化金属颗粒生长碳纳米管的机理的示意图;
图7是展示应用于使用净化气的原位净化工艺中的气体脉冲技术的时序图;以及
图8A-8C是展示利用光刻技术形成纳米级催化金属颗粒的情况的剖面图。
下面结合展示了本发明优选实施方案的各附图更完整地介绍本发明。然而,本发明可按许多不同方式实施,不应当认为本发明限于这里所记载的各实施方案。而且,提供这些实施方案的目的是使本公开彻底完全,向所属领域的技术人员充分传达本发明的思想。为了解释,大致示出了热化学汽相淀积(CVD)设备的示意图。各附图中,为清楚起见放大了基片、催化金属层和催化金属颗粒的厚度和比例。还应注意,各附图中,类似的参考标记可用于指明相同或相应的部分。
实施方案1
下面结合图1、图2A和2B和图3描述根据本发明合成碳纳米管的方法,其中图1是展示该合成方法的流程图,图2A和2B是将于其上形成碳纳米管的基片的剖面图,图3是用于该合成的热化学汽相淀积(CVD)设备的示意图。该流程图中,该合成法必须的步骤示于实线框内,而该合成法的任选步骤示于虚线框内。
参见图1,在其上将要形成碳纳米管的基片(图2A中的110)上,形成金属催化层(图2A中的130)(步骤20)。关于基片110,可以用玻璃、石英、硅或氧化铝(Al2O3)基片。金属催化层130由钴(Co)、镍(Ni)、铁(Fe)或它们的合金(Co-Ni,Co-Fe或Ni-Fe)构成。金属催化层130利用热淀积、电子束淀积或溅射法等形成于基片110上,厚度为几纳米到几百纳米,优选为2-200nm。
在由硅构成的基片110、金属催化层130由Co、Ni或它们的合金构成时,在形成金属催化层130前,在基片110上形成绝缘层(图2B中的120),用于防止由于金属催化层130与基片11O间反应产生硅化物膜(步骤10)。可以形成氧化硅或氧化铝层作绝缘层120。
然后,腐蚀金属催化层130,形成独立隔离的纳米级催化金属颗粒(步骤30)。
具体说,参见图3,将具有金属催化层130或绝缘层120和金属催化层130的基片彼此间隔预定距离装入热CVD设备的舟310中,将舟310装入热CVD设备的反应炉中。这里,装载舟310使形成于基片上的金属催化层130的表面在箭头315所示的与气流相反的方向面向下,如图3所示。基片110设置成使金属催化层130的表面不面向气流的原因是,通过均匀控制腐蚀气的大规模流动,在由金属催化层130涂敷的基片110上进行均匀反应。另外,将基片110插入舟310,使金属催化层130的表面面向下,为的是防止不稳定反应产物造成的缺陷,或碳颗粒从反应炉300的壁上落下。
将舟310装入反应炉后,反应炉300的压力保持大气压(在使用常压CVD设备时),或保持在几百毫乇到几乇的量级(使用低压CVD设备的情况下)。然后,利用安装在反应炉300外壁周围的电阻线圈330,将反应炉300的温度升高到700-1000℃。在反应炉300的温度达到预定处理温度时,第一阀门400打开,允许腐蚀气通过气体输入管320,从腐蚀气供应源410流到反应炉300内。腐蚀气可以是氨气、氢气或氢化物气,但优选氨气。如果氨气用作腐蚀气,则以80-400sccm的流量,供应氨气10-30分钟。处理温度的下限,700℃,对应于腐蚀气可以分解以便进行腐蚀的最低温度。
如图4所示,引入反应炉300的腐蚀气200沿晶界腐蚀金属催化层130,在基片110上,高密度并且均匀地形成独立隔离的纳米级催化金属颗粒130P。本说明书使用的术语“纳米级”是指几纳米到几百纳米的尺寸。隔离的纳米级催化金属颗粒的尺寸和形状随腐蚀条件而改变。另外,催化金属颗粒的形状影响随后工艺中形成的碳纳米管的形状。
然后,向热CVD设备供应碳源气,以便在基片110上生长碳纳米管(步骤40)。
碳纳米管的生长(步骤40)与纳米级催化金属颗粒的形成(步骤30)在原位进行。具体地说,图3的第一阀门400关闭,切断氨气供应,第二阀门420打开,通过气体输入管320,从气体供应源430向反应炉300供应碳源气。反应炉300的温度保持与形成纳米级隔离的催化金属颗粒130P时相同,即,为700-1000℃。碳源气以20-200sccm的流量供应10-60分钟。另外,用具有1-3个碳原子的碳氢化合物作碳源气。优选乙炔、乙烯、乙烷、丙烯、丙烷或甲烷气作碳源气。处理温度的下限,即700℃,对应于碳源气能充分热解的最低温度。
为控制碳纳米管的生长速度和时间,通过打开第三阀门440,可以与碳源气一起,从携带和/或稀释气供应源450,向反应炉300供应携带气(惰性气体,例如,氢或氩)和/或稀释气体(氢化物气体)。
通过以预定比例,与碳源气一起供应腐蚀气(氨气、氢气或氢化物气),还可以控制基片上合成的碳纳米管的密度和生长图形。较好以2∶1-3∶1的体积比供应碳源气和腐蚀气。
如图5所示,供应到反应炉300中的碳源气热解,从而生长从纳米级催化金属颗粒130P突出的碳纳米管。
图6A-6C是基本生长模式的示意图。下面结合图6A-6C介绍该生长机理。首先,如图6A所示,供应到热CVD设备的反应炉300中的碳源气(例如,乙炔气(C2H2))汽相热解成碳单元(C=C或C)或自由氢(H2)。碳单元吸附到催化金属颗粒130P的表面上,并扩散到催化金属颗粒130P中。在催化金属颗粒130P被溶解的碳单元过饱和时,碳纳米管150开始生长。随着碳单元向催化金属颗粒130P侵入的继续,在催化金属颗粒130P的催化作用下,碳纳米管150象竹子一样生长,如图6C所示。如果催化金属颗粒130P具有圆头或钝头,碳纳米管150生长为具有圆头或钝头。尽管图中未示出,但如果纳米级金属催化颗粒130P具有尖头,则碳纳米管生长为具有尖头。
尽管结合卧式热(CVD)设备介绍了第一实施方案,但应理解,也可以使用立式、直线型或传送带型CVD设备。
第一实施方案的合成方法可以形成直径为几纳米到几百纳米例如1-400nm、长度为几微米到几百微米例如0.5-300微米的碳纳米管。
碳纳米管的合成完成后,任选可以对碳纳米管150进行原位净化(步骤60)。在原位去掉存在于所生长的碳纳米管150表面上作为碳纳米管生长(步骤40)一部分的碳块或碳颗粒。
具体说,图3的第二阀门420关闭,切断碳源气的供应,第四阀门460打开,通过气体输入管320,从净化气供应源470向反应炉300供应净化气。氨气、氢气、氧气或这些气体的混合气可用作净化气。在选择氨气或氢气作净化气时,可以从腐蚀气供应源410或携带气和/或稀释气供应源450供应净化气,而不需要净化气供应源470。
净化工艺期间,反应炉300的温度保持在500-1000℃,以40-200sccm的流量,向反应炉300供应净化气10-30分钟。
氨气或氢气热分解产生的氢离子(H+)去除不必要的碳块或碳颗粒。在用氧气作净化气体时,氧气热分解衍生的氧离子(O2-)燃烧,并去除碳块或碳颗粒。净化的结果是,从碳纳米管150的表面上完全去除了碳块、碳颗粒等,形成净化的碳纳米管。
优选地,在净化(步骤60)前,以200-500sccm的流量,向反应炉300供应惰性气体,如图7所示,通过排气孔340,排出反应炉300中的残余的碳源气(图1中的步骤50)。优选用氩气作惰性气体。这样做,可以精确控制所生长的碳纳米管的长度,并可以防止碳纳米管合成后残余碳源气造成的不希望的反应。
还优选在净化(步骤60)后,以200-500sccm的流量,向反应炉300供应惰性气体,以便通过排气孔340,排出反应炉300中的残余净化气(图1中的步骤70)。排出净化气期间,优选是降低反应炉300的温度。净化气的排出(步骤70)可以防止反应炉300的温度降低时,净化气对碳纳米管150的局部损坏。
根据合成方法的第一实施方案,适用于生长碳纳米管的纳米级催化金属颗粒以高密度彼此隔离,而不聚集,所以在合成碳纳米管时,不会产生非晶碳块。所以,可以在基片上垂直列高纯碳纳米管。
通过腐蚀形成于基片上的金属催化层,在基片上均匀且高密度地形成隔离的纳米级催化金属颗粒。于是,在采用大尺寸基片时,无论基片上的位置如何,碳纳米管都可在垂直方向均匀致密地在大基片上生长。
另外,由于通过改变例如氨气等腐蚀气的流量、腐蚀温度和时间等腐蚀条件,可以控制催化金属颗粒的密度和尺寸,所以,容易控制碳纳米管的密度和直径。
本发明第一实施方案的优点是,通过改变例如流量等碳源气的流动条件、反应温度和时间,可以容易控制碳纳米管的长度。
此外,采用热CVD设备,可以进行批量合成,即,可以同时在设备中装入大量基片,进行碳纳米管的合成,所以提高了产量。
形成催化金属颗粒和利用碳源气形成碳纳米管的可在相同的温度范围内原位进行。另外,碳纳米管的净化可作为合成过程的一部分原位进行。于是,与每步工艺需要不同处理室的其它合成方法相比,可以减少室到室间的传递需要的时间和每个室升高到合适温度需要的时间。另外,净化工艺简单。所以,具有可以将净化碳纳米管的产率提高到最高水平的优点。
实施方案2
与第一实施方案的不同在于,第二实施方案中,通过等离子腐蚀而不是通过利用热分解气体的腐蚀进行纳米级催化金属颗粒的形成(步骤30)。等离子腐蚀的优点在于,腐蚀可以在低温下进行,容易控制反应。
等离子腐蚀可以在等离子腐蚀设备中单独进行,或可以在与用于随后形成碳纳米管的热CVD设备组合的等离子腐蚀设备中进行。组合型系统可以是多室系统,其中等离子腐蚀设备和热CVD设备组装在一个组中,或远距离等离子系统和热CVD设备组合在一起。优选组合型系统,可以减少基片传递所耗用的时间,防止基片暴露于空气中被沾污。
对于独立的等离子腐蚀设备来说,通过以30-300sccm的流量,向反应室供应氨气、氢气或氢化物气体,在频率为13.6MHz、气压为0.1-10乇、功率为50-200瓦的处理条件下,产生等离子体。然后,在350-600℃,以与第一实施方案相同的方式,用等离子体腐蚀形成于基片上的金属催化层5-30分钟,形成隔离的纳米级催化金属颗粒。
对于包括远距离等离子设备和化学CVD系统的组合型系统来说,施加13.6MHz的频率,并以30-300sccm的流量,向远距离等离子设备供应氨气、氢气或氢化物气体,产生等离子体,然后,将产生的等离子体供应到化学CVD设备中,从而形成隔离的纳米级催化金属颗粒。这里,在350-600℃,进行5-30分钟等离子腐蚀。
最优选的是,等离子体由氨气产生。
然后,与第一实施方案一样,形成碳纳米管。
实施方案3
第三实施方案与前述的第一和第二实施方案的不同在于,通过湿法腐蚀而非干法腐蚀形成隔离的纳米级催化金属颗粒。具体说,将具有催化层的基片浸入例如氢氟酸系列腐蚀剂(用去离子水稀释的HF溶液,或HF与NH4F的混合溶液)的腐蚀剂1-5分钟,形成隔离的纳米级催化金属颗粒。该湿法腐蚀技术的优点在于,可以在低温下进行腐蚀。
然后,与第一实施方案一样,形成碳纳米管。
实施方案4
第四实施方案是第一和第三实施方案的结合。首先,象第三实施方案一样,进行湿法腐蚀,然后,象第一实施方案一样,用气体进行干法腐蚀。具体说,在腐蚀剂(用去离子水稀释的HF溶液)中腐蚀具有金属催化层的基片1-5分钟,并干燥。然后,象第一实施方案一样,将基片装入热CVD设备,以60-300sccm的流量,向设备引入氨气作腐蚀气,时间为5-20分钟,在基片上形成隔离的纳米级催化金属颗粒。
然后,象第一实施方案一样,形成碳纳米管。
实施方案5
与第一实施方案的不同在于,利用光刻技术而非通过用热分解气体的腐蚀,形成纳米级催化金属颗粒(步骤30)。
具体地说,如图8A所示,用光刻胶涂敷金属催化层130,并进行曝光和显影处理,形成例如具有几纳米到几百纳米尺寸的纳米级光刻胶图形PR。
然后,用光刻胶图形PR作腐蚀掩模,腐蚀金属催化层130,形成纳米级催化金属颗粒130P,如图8B所示。然后,象第一实施方案一样,由催化金属颗粒130P形成碳纳米管150,如图8C所示。
本实施方案中,利用光刻法形成催化金属颗粒,通过控制光刻胶图形的尺寸和密度,容易控制催化金属颗粒的尺寸和密度。于是,可以任意控制碳纳米管的直径和密度。
以下将利用以下各实例详细介绍本发明。以下的各实例仅是为了说明的目的,并不想限制本发明的范围。
(实例1)
在尺寸为2cm×3cm、厚为1500埃的硅基片上,形成氧化硅膜,并利用热淀积,在氧化硅膜上形成厚100nm的铁(Fe)膜。将具有Fe膜的基片装入热CVD设备。然后,使CVD设备的炉压力保持在760乇,炉温升高到950℃。然后,以100sccm的流量,向炉内引入氨气,时间为20分钟,形成隔离的铁颗粒。在保持温度为950℃的同时,以40sccm的流量,供应乙炔气,时间为10分钟,由每个铁颗粒生长碳纳米管。扫描电子显微镜(SEM)观察发现,碳纳米管垂直且均匀地生长于基片上。透射电子显微镜(TEM)的测量结果是,所得碳纳米管的直径为约80nm,长度为约120微米。
(实例2)
为了合成碳纳米管,除用镍(Ni)膜代替Fe膜作金属催化层外,采用与实例1相同的工艺。SEM观察发现,碳纳米管垂直且均匀生长于基片上。TEM的测量结果是,所得碳纳米管的直径为约50nm,长度为约80微米。
(实例3)
为了合成碳纳米管,除用钴(Co)膜代替Fe膜作金属催化层外,采用与实例1相同的工艺。SEM观察发现,碳纳米管垂直且均匀生长于基片上。TEM的测量结果是,所得碳纳米管的直径为约70nm,长度为约30微米。
(实例4)
为了合成碳纳米管,除用Co-Ni合金膜代替单层Fe膜作金属催化层外,采用与实例1相同的工艺。SEM观察发现,碳纳米管垂直且均匀生长于基片上。TEM的测量结果是,所得碳纳米管的直径为约90nm,长度为约100微米。
(实例5)
为了合成碳纳米管,除用Co-Fe合金膜代替Co-Ni合金膜作金属催化层外,采用与实例4相同的工艺。SEM观察发现,碳纳米管垂直且均匀生长于基片上。TEM的测量结果是,所得碳纳米管的直径为约90nm,长度为约80微米。
(实例6)
为了合成碳纳米管,除用Ni-Fe合金膜代替Co-Ni合金膜作金属催化层外,采用与实例4相同的工艺。SEM观察发现,碳纳米管垂直且均匀生长于基片上。TEM的测量结果是,所得碳纳米管的直径为约80nm,长度为约80微米。
(实例7)
在大小为2cm×3cm、厚为1500埃的硅基片上,形成氧化硅膜,并利用溅射,在氧化硅膜上形成厚100nm的镍(Ni)膜。具有Ni膜的基片装入等离子腐蚀设备。使等离子腐蚀设备的压力设置在1.5乇,设备频率设定为13.6MHz。将等离子腐蚀设备的温度升高到550℃后,以200sccm的流量,向设备供应氨气,产生等离子体。用等离子体腐蚀形成于基片上的Ni膜,时间为15分钟。用等离子体腐蚀后,从等离子腐蚀设备中取出基片,并装入热CVD设备。反应炉的压力保持在766乇,炉温升高到950℃。然后,以40sccm的流量,向反应炉供应乙炔气,时间为10分钟,由形成于基片上的隔离的Ni颗粒生长碳纳米管。SEM观察发现,碳纳米管垂直且均匀地生长于基片上。TEM测量结果是,所得碳纳米管的直径为约60nm,长度为约50微米。
(实例8)
在大小为2cm×3cm、厚为1500埃的硅基片上,形成氧化硅膜,并利用热淀积,在氧化硅膜上形成厚100nm的Co-Ni合金膜。将具有Co-Ni合金膜的基片浸入HF溶液,时间为140秒,进行腐蚀,并干燥。然后,将所得基片装入化学CVD设备的反应炉内,反应炉的压力升高到760乇,温度升高到950℃。然后,以80sccm的流量,向反应炉供应氨气,时间为10分钟,形成隔离的Co-Ni合金颗粒。在保持温度为950℃的同时,以40sccm的流量,向反应炉供应乙炔气,时间为10分钟,由每个Co-Ni合金颗粒生长碳纳米管。SEM观察发现,碳纳米管垂直且均匀地生长于基片上。TEM测量结果是,所得碳纳米管的直径为约100nm,长度为约100微米。
在根据本发明的碳纳米管合成方法中,可以形成彼此隔离而非聚集的高密度催化金属颗粒,所以可以在基片上垂直排列高纯碳纳米管。另外,通过均匀腐蚀金属催化层,可以得到隔离的纳米级催化金属颗粒,使得无论在基片上的位置如何,碳纳米管都可以均匀分布于大尺寸基片上。此外,通过调节腐蚀气和碳源气的流量及处理温度和时间,容易改变碳纳米管的密度、直径和长度。使用热CVD设备的本发明碳纳米管合成方法可用于批量合成,即同时在数个基片上生长碳纳米管。所以,可以在大尺寸基片上高纯、高产率地合成垂直排列的碳纳米管。另外,容易作为合成工艺的一部分在原位净化碳纳米管,所以具有最高合成效率。
尽管以上结合优选实施方案具体展示和介绍了本发明,但所属领域的技术人员应理解,在形式上和细节上,可以对本发明做出各种改变,而不会脱离如所附权利要求所限定的本发明的精神和范围。
Claims (14)
1.一种合成碳纳米管的方法,包括:
在基片上形成金属催化层;
腐蚀金属催化层,形成隔离的纳米级催化金属颗粒;以及
利用热化学汽相淀积(CVD),由每个隔离的纳米级催化金属颗粒生长碳纳米管,其中碳源气供应到热CVD设备中,碳纳米管垂直排列于基片上。
2.根据权利要求1的方法,其中金属催化层由钴、镍、铁或它们的合金构成。
3.根据权利要求1的方法,其中利用气体腐蚀法形成隔离的纳米级催化金属颗粒,该方法中,选自氨气、氢气和氢化物气的一种腐蚀气热分解,用于腐蚀。
4.根据权利要求1的方法,其中腐蚀气是氨气,在温度为700-1000℃、同时以80-400sccm的流量供应氨气10-30分钟的条件下进行气体腐蚀。
5.根据权利要求1的方法,其中在温度为700-1000℃、同时以20-200sccm的流量供应碳源气10-60分钟的条件下形成碳纳米管。
6.根据权利要求3的方法,其中在同一热CVD设备中,原位形成催化金属颗粒和形成碳纳米管。
7.根据权利要求1的方法,其中利用等离子腐蚀法形成隔离的纳米级催化金属颗粒,其中采用选自氨气、氢气和氢化物气的一种气体,产生等离子体,用于腐蚀。
8.根据权利要求1的方法,其中通过使用氢氟酸系列腐蚀剂的湿法腐蚀法,形成隔离的纳米级催化金属颗粒。
9.根据权利要求1的方法,其中通过使用光刻胶图形作腐蚀掩模的光刻法形成隔离的纳米级催化金属颗粒。
10.根据权利要求1的方法,其中在形成碳纳米管时,与碳源气一起,向热CVD设备供应选自氨气、氢气和氢化物气体中的一种气体。
11.根据权利要求1的方法,在形成金属催化层前,还包括形成绝缘层,以防止基片与金属催化层间的反应。
12.根据权利要求1的方法,在形成碳纳米管后,还包括利用惰性气体,排出热CVD设备中的碳源气。
13.根据权利要求1的方法,在形成碳纳米管后,还包括在相同热CVD设备中,原位净化碳纳米管。
14.根据权利要求13的方法,其中用选自氨气、氢气、氧气和这些气体的混合气中的一种净化气,原位净化碳纳米管。
15.根据权利要求14的方法,在原位净化碳纳米管后,还包括利用惰性气体,排出热CVD设备中的净化气。
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CN103879995B (zh) * | 2012-12-20 | 2016-01-13 | 海洋王照明科技股份有限公司 | 碳纳米壁粉末的制备方法及石墨烯纳米带的制备方法 |
CN103935975A (zh) * | 2013-01-18 | 2014-07-23 | 海洋王照明科技股份有限公司 | 碳纳米壁及石墨烯纳米带的制备方法 |
CN103935980B (zh) * | 2013-01-18 | 2016-02-10 | 海洋王照明科技股份有限公司 | 石墨烯纳米带的制备方法 |
CN103935980A (zh) * | 2013-01-18 | 2014-07-23 | 海洋王照明科技股份有限公司 | 石墨烯纳米带的制备方法 |
CN105734525A (zh) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | 一种化学气相沉积法制备石墨烯薄膜的方法 |
CN105984862A (zh) * | 2015-02-16 | 2016-10-05 | 北京大学深圳研究生院 | 用于生长碳纳米管的方法 |
CN105984862B (zh) * | 2015-02-16 | 2018-08-28 | 北京大学深圳研究生院 | 用于生长碳纳米管的方法 |
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CN1189390C (zh) | 2005-02-16 |
JP3442032B2 (ja) | 2003-09-02 |
EP1059266A3 (en) | 2000-12-20 |
EP1059266A2 (en) | 2000-12-13 |
JP2001020071A (ja) | 2001-01-23 |
US6350488B1 (en) | 2002-02-26 |
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