CN115613130A - 一种在常压下化学气相沉积制备六方氮化硼薄膜的方法 - Google Patents
一种在常压下化学气相沉积制备六方氮化硼薄膜的方法 Download PDFInfo
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Abstract
本发明提供一种在常压下化学气相沉积制备六方氮化硼薄膜的方法,通过超声清洗、电化学抛光、化学腐蚀、高温退火后的铜箔表面表面平整,粗糙度较低,具有较少的成核位点,为生长大尺寸高质量六方氮化硼薄膜H‑BN提供必要条件,通过多种处理方式合理搭配,将基片处理为适合H‑BN生长的状态,并通过对化学气相沉积过程中的热力学和动力学的分析,分析并调整在H‑BN的合适生长参数,在常压环境和低气流条件下得到大尺寸、高质量的H‑BN,低气流的生长降低了气流的使用,提高了经济效益,且在常压下进行H‑BN的生长,降低了对生长设备的要求,提高了安全系数。
Description
技术领域
本发明涉及纳米材料领域,特别涉及一种在常压下化学气相沉积制备六方氮化硼薄膜的方法。
背景技术
石墨烯研究的巨大成功引发了人们对开发各种具有独特结构和电子性质的互补的、原子薄的二维材料的巨大兴趣。六方氮化硼(H-BN)在结构上与石墨烯极其相似,且具有较宽的带隙等条件,具有优异的化学惰性和电绝缘性、高的弹性模量和热导率等性能,在深紫外发射器、内场效应隧道晶体管的隧道势垒以及量子光子发射器等方向得到广泛应用。但由于生长条件苛刻,较难获得表面平整,且高纯度、高结晶质量的六方氮化硼薄膜。
目前通过化学气相沉积法生长H-BN的方法得到广泛的应用,化学气相沉积法可以通过合理的设计实验方案和对生长参数的调整可以对H-BN的尺寸、形貌、层数等方面进行调控,从而实现H-BN的可控制备。为提高H-BN薄膜的质量,科研人员做了大量的工作,例如促进均匀性,降低缺陷,特别是扩大单个薄片的粒度。目前主要应用的是电化学抛光、长时间退火甚至熔化和溶解铜基底来用于H-BN的成核抑制。此外,在生长过程中,也可以通过降低原料浓度来抑制成核。通过改善基底状态和调控化学气相沉积法所涉及的生长参数,实现H-BN的大尺寸和多层次的均匀性生长。
发明内容
鉴以此,本发明提出一种在常压下化学气相沉积制备六方氮化硼薄膜的方法,来解决上述问题。
本发明的技术方案是这样实现的:一种在常压下化学气相沉积制备六方氮化硼薄膜的方法,包括以下步骤:
S1、预处理:将商用铜箔裁剪为0.5~2cm×1~1.2cm的基片,并通过压力设备将基片压平整。商用铜箔的使用降低了经济成本,相比于单晶铜,商用铜箔的制造工艺和成本相对较低,更适合大批量的生产。经过处理的商用铜箔成核位点减少,经过进行多种工艺处理后可以成为适合生长的基片,有利于六方氮化硼薄膜(H-BN)的大尺寸高质量生长;基片的裁剪可用剪刀或其他剪切机,基片的锻压可用各类压力机。
S2、超声清洗:将基片先后放置在丙酮、异丙醇、乙醇、超纯水中进行超声清洗,超声时间为8~12min,以除去基片表面的灰尘和有机物,从而获得表面干净的基片。
S3、电化学抛光:将磷酸、异丙醇、乙醇、超纯水加尿素配成电解液,将基片通过电化学工作站恒流模式进行抛光,以除去基片表面的氧化层;电化学工作站的恒流模式相对于其他模式抛光出来的铜箔表面更加平整;
S4、化学腐蚀:抛光后的基片放入弱酸水中浸泡10~60s,除去基片上的天然氧化物,用乙醇冲洗掉表面的试剂,最后用N2吹干基片,从而得到未被氧化的基片,备用;
S5、高温退火:生长设备为三温区管式炉,使用闭式石英舟称取10~100mg 的氨硼烷络合物,放置在管式炉第一温区,将处理干净的基片倒置在开式石英舟上,基片与石英舟的间隙保持在0.3~0.8cm,基片放置在第三温区,基片的温度变化主要包括四部分,分别是升温、退火、生长和冷却,以得到尺寸大且均匀的六方氮化硼薄膜;在高温退火过程中,铜原子重排会改善基底的形貌,并释放铜箔内部应力,退火后的衬底晶界尺寸由几微米增加到了几百微米,有利于大尺寸H-BN的生长。退火后的铜表面的杂质减少,表面粗糙度降低,使其表面更平整,铜箔表面平整度的增加有助于减少成核点,进而为制备大尺寸的单晶h-BN提供了一种可能性。平整的表面相对高能区域减少,这样分子在其表面吸附位点减少,有利于减少成核点,制备大尺寸高质量H-BN。
进一步的,所述S2中丙酮、异丙醇、乙醇、超纯水的体积比为1:1~1.2: 1~3:2~4。
进一步的,所述S3中电解液分别由25ml磷酸、5ml异丙醇、25ml乙醇、 50ml超纯水、0.5g尿素配制而成。
进一步的,所述S3中电化学工作站选择恒流模式为起始电压2.8~3.2V,最高电压3.5~4V,抛光时间60~100s。
进一步的,所述S4中弱酸水的pH至在3.5~6.5之间,取1-10μl硝酸与10-20L 超纯水混合而成,配好的弱酸水溶液可重复利用100-200次。
进一步的,所述S5中药品升华温度控制在100~150℃,基片的退火温度 950~1050℃,升温速率15~25℃/min,退火时间20~40min,退火过程需通入混合气Ar/H2,流速为90~120sccm,退火完成后在950~1050℃下继续进行生长,生长时间为10~30min,生长过程继续通入Ar/H2,混合气Ar/H2中,Ar和H2比值为8~10:1N/m3,流速为50~100sccm,退火完成将气体换成流速为50sccm的 Ar,直到降至室温;在适合H-BN生长的温度范围,温度越高,越容易形核。在高温下,环硼吖嗪的分解和聚合速度随之加快,铜的催化活性增强,导致H-BN 的生长速率增加。此外,随着温度升高,铜表面的条纹、点缺陷以及氧化铜、氧化亚铜进一步消除,高温下进行的重结晶形成更为平坦的尺寸大的铜晶粒,有利于大尺寸高质量的H-BN的生长。
进一步的,在整个过程中气流始终保持低气速,腔室内始终保持在常压环境,在降低操作难度的同时降低了生产成本。压力对表面自由能的影响与氨硼烷分解生成硼吖嗪并迁移到表面区时的摩尔分子体积变化有关,根据热力学定律可以推出表面自由能随压力的增大而增大。适当增大管式炉内的气压能增大 H-BN在形核过程中所需的最大能力△Gmax,可以抑制形核;同时使临界晶核半径rc增大,形核数目减小,使沉积的H-BN尺寸更大。此外,气体流速的增加,可以将产生的前驱体迅速输送到铜的表面,硼吖嗪在运输过程中也会分解,这样通过气象输运的前驱体也随之增多,在铜表面参与脱氢反应的前驱体浓度就会比低流量大,使H-BN更容易生长。
与现有技术相比,本发明的有益效果是:
本发明的目的是通过超声清洗、电化学抛光、化学腐蚀、高温退火结合的方式处理商用铜箔得到适合H-BN生长的基片,其表面平整,粗糙度较低,具有较少的成核位点,为生长大尺寸高质量H-BN提供必要条件,并通过构造合适的模型实现在常压环境下通过低气速实现高质量生长,较大的降低生产成本。
附图说明
图1是实施例3H-BN薄膜的光学显微镜图片;
图2是实施例3H-BN薄膜的XPS图片,图中,Binding Energy:结合能;
图3是实施例3H-BN薄膜的拉曼图;
图4是实施例3H-BN薄膜的AFM图。
具体实施方式
为了更好理解本发明技术内容,下面提供具体实施例,对本发明做进一步的说明。
本发明实施例所用的实验方法如无特殊说明,均为常规方法。
本发明实施例所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1
一种在常压下化学气相沉积制备六方氮化硼薄膜的方法,包括以下步骤:
S1、预处理:将铜箔裁剪为0.5~2cm×1cm的基片,并通过压力设备将基片压平整。
S2、超声清洗:将基片先后放置在丙酮、异丙醇、乙醇、超纯水中进行超声清洗,丙酮、异丙醇、乙醇、超纯水的体积比1:1:2:3,超声时间为8min,从而获得表面干净的基片。
S3、电化学抛光:由25ml磷酸、5ml异丙醇、25ml乙醇、50ml超纯水、 0.5g尿素配制而成电解液,基片通过电化学工作站恒流模式进行抛光,电化学工作站选择恒流模式为起始电压2.8V,最高电压3.5V,抛光时间60s;
S4、化学腐蚀:抛光后的基片放入pH值为3.5的弱酸水中浸泡10s,弱酸水为5μl硝酸与15L超纯水混合而成,配好的弱酸水溶液可重复利用100次,用乙醇冲洗掉基片表面的试剂,最后用N2吹干基片,从而得到未被氧化的基片,备用;
S5、高温退火:生长设备为三温区管式炉,称取10mg的氨硼烷络合物,放置在管式炉第一温区,将处理干净的基片放置在管式炉第三温区,基片的温度变化主要包括四部分,分别是升温、退火、生长和冷却,升华温度控制在100℃,基片的退火温度950℃,升温速率15℃/min,退火时间20min,退火过程需通入混合气Ar/H2,Ar和H2比值为9:1,流速为90sccm,退火完成后在950℃下继续进行生长,生长时间为10min,生长过程继续通入Ar/H2,流速为50sccm,退火完成将气体换成流速为50sccm的Ar,直到降至室温以得到尺寸大且均匀的六方氮化硼薄膜。
实施例2
一种在常压下化学气相沉积制备六方氮化硼薄膜的方法,包括以下步骤:
S1、预处理:将铜箔裁剪为0.5~2cm×1cm的基片,并通过压力设备将基片压平整。
S2、超声清洗:将基片先后放置在丙酮、异丙醇、乙醇、超纯水中进行超声清洗,丙酮、异丙醇、乙醇、超纯水的体积比1:1:2:3,超声时间为12min,从而获得表面干净的基片。
S3、电化学抛光:由25ml磷酸、5ml异丙醇、25ml乙醇、50ml超纯水、 0.5g尿素配制而成电解液,基片通过电化学工作站恒流模式进行抛光,电化学工作站选择恒流模式为起始电压3.2V,最高电压4V,抛光时间100s;
S4、化学腐蚀:抛光后的基片放入pH值为6.5的弱酸水中浸泡60s,弱酸水为1μl硝酸与10超纯水混合而成,配好的弱酸水溶液可重复利用100次,用乙醇冲洗掉基片表面的试剂,最后用N2吹干基片,从而得到未被氧化的基片,备用;
S5、高温退火:生长设备为三温区管式炉,称取10~100mg的氨硼烷络合物,放置在管式炉第一温区,将处理干净的基片放置在管式炉第三温区,基片的温度变化主要包括四部分,分别是升温、退火、生长和冷却,升华温度控制在150℃,基片的退火温度1050℃,升温速率25℃/min,退火时间40min,退火过程需通入混合气Ar/H2,Ar和H2比值为9:1,流速为120sccm,退火完成后在1050℃下继续进行生长,生长时间为30min,生长过程继续通入Ar/H2,流速为100sccm,退火完成将气体换成流速为50sccm的Ar,直到降至室温以得到尺寸大且均匀的六方氮化硼薄膜。
实施例3
一种在常压下化学气相沉积制备六方氮化硼薄膜的方法,包括以下步骤:
S1、预处理:将铜箔裁剪为0.5~2cm×1cm的基片,并通过压力设备将基片压平整。
S2、超声清洗:将基片先后放置在丙酮、异丙醇、乙醇、超纯水中进行超声清洗,丙酮、异丙醇、乙醇、超纯水的体积比1:1:2:3,超声时间为10min,从而获得表面干净的基片。
S3、电化学抛光:由25ml磷酸、5ml异丙醇、25ml乙醇、50ml超纯水、 0.5g尿素配制而成电解液,基片通过电化学工作站恒流模式进行抛光,电化学工作站选择恒流模式为起始电压3V,最高电压3.8V,抛光时间80s;
S4、化学腐蚀:抛光后的基片放入pH值为5的弱酸水中浸泡30s,弱酸水为10μl硝酸与20L超纯水混合而成,配好的弱酸水溶液可重复利用200次,用乙醇冲洗掉基片表面的试剂,最后用N2吹干基片,从而得到未被氧化的基片,备用;
S5、高温退火:生长设备为三温区管式炉,称取50mg的氨硼烷络合物,放置在管式炉第一温区,将处理干净的基片放置在管式炉第三温区,基片的温度变化主要包括四部分,分别是升温、退火、生长和冷却,升华温度控制在130℃,基片的退火温度1000℃,升温速率20℃/min,退火时间30min,退火过程需通入混合气Ar/H2,Ar和H2比值为9:1,流速为100sccm,退火完成后在1000℃下继续进行生长,生长时间为20min,生长过程继续通入Ar/H2,流速为80sccm,退火完成将气体换成流速为50sccm的Ar,直到降至室温以得到尺寸大且均匀的六方氮化硼薄膜。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种在常压下化学气相沉积制备六方氮化硼薄膜的方法,其特征在于:包括以下步骤:
S1、预处理:将铜箔裁剪为0.5~2cm×1~1.2cm的基片,并通过压力设备将基片压平整;
S2、超声清洗:将基片先后放置在丙酮、异丙醇、乙醇、超纯水中进行超声清洗,超声时间为8~12min,从而获得表面干净的基片;
S3、电化学抛光:将磷酸、异丙醇、乙醇、超纯水加尿素配成电解液,基片通过电化学工作站恒流模式进行抛光;
S4、化学腐蚀:抛光后的基片放入弱酸水中浸泡10~60s,用乙醇冲洗掉表面的试剂,最后用N2吹干基片,从而得到未被氧化的基片,备用;
S5、高温退火:生长设备为三温区管式炉,称取氨硼烷络合物放置在管式炉第一温区,将处理干净的基片放置在管式炉第三温区,基片的温度变化主要包括四部分,分别是升温、退火、生长和冷却,以得到尺寸大且均匀的六方氮化硼薄膜。
2.如权利要求1所述的在常压下化学气相沉积制备六方氮化硼薄膜的方法,其特征在于:所述S2中丙酮、异丙醇、乙醇、超纯水的体积比为1:1~1.2:1~3:2~4。
3.如权利要求1所述的在常压下化学气相沉积制备六方氮化硼薄膜的方法,其特征在于:所述S3中电解液分别由25ml磷酸、5ml异丙醇、25ml乙醇、50ml超纯水、0.5g尿素配制而成。
4.如权利要求1所述的在常压下化学气相沉积制备六方氮化硼薄膜的方法,其特征在于:所述S3中电化学工作站选择恒流模式为起始电压2.8~3.2V,最高电压3.5~4V,抛光时间60~100s。
5.如权利要求1所述的在常压下化学气相沉积制备六方氮化硼薄膜的方法,其特征在于:所述S4中弱酸水的pH值在3.5~6.5之间,取1-10μl硝酸与10-20L超纯水混合而成,配好的弱酸水溶液可重复利用100-200次。
6.如权利要求1所述的在常压下化学气相沉积制备六方氮化硼薄膜的方法,其特征在于:所述S5中氨硼烷络合物称取重量为10~100mg。
7.如权利要求1所述的在常压下化学气相沉积制备六方氮化硼薄膜的方法,其特征在于:所述S5中药品升华温度控制在100~150℃,基片的退火温度950~1050℃,升温速率15~25℃/min,退火时间20~40min,退火过程需通入混合气Ar/H2,流速为90~120sccm,退火完成后在950~1050℃下继续进行生长,生长时间为10~30min,生长过程继续通入Ar/H2,流速为50~100sccm,退火完成将气体换成流速为50sccm的Ar,直到降至室温。
8.如权利要求6所述的在常压下化学气相沉积制备六方氮化硼薄膜的方法,其特征在于:所述混合气Ar/H2中,Ar和H2比值为8~10:1N/m3。
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