CN111235632A - 一种二维超薄BiOBr单晶纳米片的制备方法及其应用 - Google Patents
一种二维超薄BiOBr单晶纳米片的制备方法及其应用 Download PDFInfo
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Abstract
本发明提供一种二维超薄BiOBr单晶纳米片的制备方法及其应用，属于二维纳米材料和纳米器件制备技术领域。本发明通过化学气相沉积，采用已自然氧化后的铜箔作为限域和反应物，通过调节反应温度和时间，制备高质量超薄BiOBr单晶，且暴露晶面为(00l)的固定取向，禁带宽度可达3.69eV；基于本发明二维超薄BiOBr单晶纳米片所制备的光电探测器对245nm到405nm的紫外光都能进行响应，且对可见光波段是基本没有响应的，因此器件被干扰的几率大幅下降；器件在波长为245nm时具有最高的探测性能；除此之外，该器件具有高频响应的特性，在9.5Hz～1000Hz展现了稳定的探测性能，器件探测速率高。
Description
技术领域
本发明属于二维纳米材料和纳米器件制备技术领域，具体涉及一种二维超薄BiOBr单晶纳米片的制备方法及其应用。
背景技术
紫外光电探测器在军事探测、空间光通信、生物探测等多个领域有着极其重要的应用，在实际应用中，高性能的紫外光电探测器需要具备高灵敏度、快速响应、对弱光的高检测等能力。目前，基于ZnO、GaN、Ga2O3等传统宽禁带半导体的紫外探测器存在着响应率低、量子效率低、响应时间长、集成度差、与硅基半导体技术不兼容等问题。
自从石墨烯被发现以来，石墨烯、黑磷、MoTe2、ReS2等一元和二元二维材料因其高载流子迁移率、强的光与物质相互作用、可调带隙等优点，使得基于这些材料制备的光电探测器具有较优的性能。然而，由于这些一元和二元半导体材料的带隙相对较小(<2.5eV)，使得大多数二维半导体材料主要应用于可见光到红外波段。虽然一些基于石墨烯、黑磷的宽谱光电探测器也具有一定紫外光探测的能力，但其探测能力低、探测范围局限于UVA波段阻碍了其实际应用。
近年来，三元二维材料在激子绝缘相、本征铁磁性和超高电子迁移率等方面都取得了较大的进展，更重要的是，三元二维半导体可以有效地通过调节其化学计量比来设计其光电特性，从而可以适应应用场景的变化。新兴的三元二维宽禁带半导体材料如Ga2In4S9和NiPS3，由于其2.7eV和3.0eV的禁带宽度，所以表现出了良好的紫外检测性能，但是，它们的紫外探测性能，特别是对深紫外探测的性能还有待于全面提高。高电子迁移率的三元BiOBr是一种优良的宽禁带光敏材料(2.5～3.69eV)，其层状四方结构由[Bi2O2]2+层与双层Br-离子交织而成，在光催化领域有着广泛的应用。由于其独特的结构，使其具有较强的吸光能力、高导电性和强化学稳定性，使其在光电器件中具有巨大的应用潜力。然而，在过去的报道中，水热法合成的随机堆积、无序形貌且厚的BiOBr纳米片，由于与半导体加工技术不兼容不能用于微纳米器件，并且水热法合成的晶体质量低、不可避免的表面污染和大量的氧缺陷也阻碍了其在光电器件领域的发展。此外，过去报道中的的BiOBr由于纳米片过厚和拉伸应变过大，往往会得到较窄的禁带宽度，这也不适用于紫外检测应用。
发明内容
针对背景技术所存在的问题，本发明的目的在于提供一种二维超薄BiOBr单晶纳米片的制备方法及其应用。本发明通过化学气相沉积法，采用自然氧化后的铜箔作为限域和反应物，通过调节反应温度和时间，制备具有宽带隙的二维超薄BiOBr纳米片，并且该二维纳米片具有较高晶体质量。
为实现上述目的，本发明的技术方案如下：
一种二维超薄BiOBr单晶纳米片的制备方法，包括以下步骤：
步骤1：将BiBr3粉末置于坩埚中，然后将坩埚放置于石英管上游第一加热区中心；将覆盖自然氧化后的铜箔的基片放置于石英管下游第二加热区中心；
步骤2：将石英管内部抽真空至0.1Pa以下，通入Ar气使管内气压保持常压环境，然后继续向管内通入Ar气作为载气流；
步骤3：将第二加热区升温至380～400℃，保持1～60min后，再将第一加热区升温至220～275℃，反应5～30min，反应结束后冷却至室温，取出基片，即可在基片上制备得到所述的二维超薄BiOBr单晶纳米片。
进一步地，步骤1所述BiBr3粉末的质量为2～50mg。
进一步地，步骤1所述自然氧化后的铜箔为将铜箔放置于室温环境下1～2天后得到。
进一步地，步骤2所述Ar气体的流速为25～50sccm。
进一步地，步骤3所述第二加热区的升温速率为10～25℃/min；第一加热区的升温速率为15～30℃/min。
进一步地，步骤3所述冷却为自然冷却或快速冷却，所述快速冷却的冷却速率≥50℃/min。
本发明还公开了一种采用上述制备方法得到的二维超薄BiOBr单晶纳米片，生长晶面为(00l)，厚度0.57nm～200nm，尺寸在0.5～70μm。
基于上述二维超薄BiOBr单晶纳米片制备紫外光电探测器的方法为：采用湿法转移将厚度为0.57nm～20nm的BiOBr单晶纳米片转移至硅基底上，然后通过电子束曝光和热蒸发制作电极，即可得到所述紫外光电器件。
本发明的机理为：利用金属片供源限域生长多种二维材料，由于供源距离非常小，导致高熔点的金属片在较低温度可以通过热扩散的原理，在基底表面得到所需高浓度的源浓度，同时金属片由于自身的片状结构，同时提供了一个合适的限域生长空间，降低了雷洛数，稳定了生长环境，并且金属片可以提供催化的作用，促进二维材料生长。卤素源BiBr3是一类低熔点的钝化剂，抑制二维材料在Z轴的生长进行，辅助二维面内结构的形成，且本身在合适的参数条件下会作为反应源的一种，用于生长卤氧化合物。
本发明BiOBr材料由于二维化后使其具有仅在低维材料中存在的光栅效应，导致了高的光增益，由于低维材料中存在的少数载流子陷阱，束缚了光生载流子中的少数子，延长了多数载流子的寿命，从而提高了光电流值，使得基于该材料制备的光电探测器在深紫外具有高响应率、高外量子效率和高比探测率。
综上所述，由于采用了上述技术方案，本发明的有益效果是：
1.本发明首次通过CVD生长法得到常规水热法难以制备的高质量二维超薄BiOBr单晶纳米片，且暴露晶面为(00l)的固定取向，材料杂质少，纯度高，没有有机物无污染，厚度薄至0.57nm，并且单层BiOBr材料的禁带宽达到3.69eV。
2.本发明基于二维超薄BiOBr单晶纳米片所制备的光电探测器对245nm到405nm的紫外光都能进行响应，且对可见光波段是基本没有响应的，因此器件被干扰的几率大幅下降；器件在波长为245nm时具有最高的探测性能，具体的关键性能参数如：光响应率为2021.9A/W，外量子效率为1.03×106％，比探测率为2.95×1013Jones；除此之外，该器件具有高频响应的特性，在9.5Hz～1000Hz展现了稳定的探测性能，并且其响应上升时间可达110μs，下降时间可达160μs，器件探测速率高。
附图说明
图1为本发明实施例1所制备的BiOBr单晶纳米片的暗场光学显微图。
图2为本发明实施例1所制备的BiOBr单晶纳米片的AFM图。
图3为本发明实施例2所制备的BiOBr单晶纳米片的TEM图，
其中，(a)为低分辨TEM图，(b)为高分辨TEM图。
图4为本发明实施例2所制备的BiOBr单晶纳米片的XRD图谱。
图5为本发明实施例2制备BiOBr单晶纳米片的SEM图。
图6为本发明实施例3制备BiOBr单晶纳米片的SEM图。
图7为基于本发明实施例3所得到的BiOBr单晶纳米片制备的光电探测器件在不同波长光照下的光响应I-V图。
图8为基于本发明实施例3所得到的BiOBr单晶纳米片制备的光电探测器件在高频光照下的单个频率的光响应I-T图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面结合实施方式和附图，对本发明作进一步地详细描述。
一种基于金属片自限域制备超薄二维纳米片的方法，包括以下步骤：
步骤1：将BiBr3粉末置于坩埚中，然后将坩埚放置于石英管上游第一加热区中心，将覆盖金属片的衬底放置于石英管下游第二加热区中心；
步骤2：将石英管内部抽真空，通入Ar气使管内气压保持常压环境，然后向管内通入载气流；
步骤3：加热第二温区，待其温度稳定后，再加热第一温区进行反应，反应结束后冷却至室温，取出基片，即可在基片上制备得到所述的超薄二维单晶纳米片。
实施例1
一种二维超薄BiOBr单晶纳米片的制备方法，包括以下步骤：
步骤1：将10mg的BiBr3粉末置于Al2O3坩埚中，然后将坩埚放置于石英管上游第一加热区中心；然后将云母基底放置在石英板上，再将自然氧化后的铜箔覆盖在云母基底上，将石英板连同云母基底和铜箔一起推至石英管下游的第二加热区中心区域；
步骤2：将石英管内部抽真空至0.1Pa以下，通入Ar气使管内气压保持常压环境，然后继续向管内通入Ar气作为载气流，流速为25sccm；
步骤3：将第二加热区升温至385℃，保持10min后，再将第一加热区升温至220℃，反应30min，反应结束后以50℃/min的冷却速率冷却至室温，取出基片，即可在基片上制备得到所述的二维超薄BiOBr单晶纳米片。
本实施例所制备的BiOBr单晶纳米片的暗场光学显微图如图1所示，AFM图如图2所示。
实施例2
一种二维超薄BiOBr单晶纳米片的制备方法，包括以下步骤：
步骤1：将50mg的BiBr3粉末置于Al2O3坩埚中，然后将坩埚放置于石英管上游第一加热区中心；然后将云母基底放置在石英板上，再将自然氧化后的铜箔覆盖在云母基底上，将石英板连同云母基底和铜箔一起推至石英管下游的第二加热区中心区域；
步骤2：将石英管内部抽真空至0.1Pa以下，通入Ar气使管内气压保持常压环境，然后继续向管内通入Ar气作为载气流，流速为50sccm；
步骤3：将第二加热区升温至385℃，保持30min后，再将第一加热区升温至275℃，反应30min，反应结束后打开CVD炉盖，使石英管快速冷却至室温，取出基片，即可在基片上制备得到所述的二维超薄BiOBr单晶纳米片。
本实施例所制备的BiOBr单晶纳米片的TEM图如图3所示；XRD图谱如图4所示；SEM图如图5所示。
实施例3
一种二维超薄BiOBr单晶纳米片的制备方法，包括以下步骤：
步骤1：将10mg的BiBr3粉末置于Al2O3坩埚中，然后将坩埚放置于石英管上游第一加热区中心；然后将云母基底放置在石英板上，再将自然氧化后的铜箔覆盖在云母基底上，将石英板连同云母基底和铜箔一起推至石英管下游的第二加热区中心区域；
步骤2：将石英管内部抽真空至0.1Pa以下，通入Ar气使管内气压保持常压环境，然后继续向管内通入Ar气作为载气流，流速为37sccm；
步骤3：将第二加热区升温至385℃，保持20min后，再将第一加热区升温至250℃，反应30min，反应结束后以80℃/min的速率冷却至室温，取出基片，即可在基片上制备得到所述的二维超薄BiOBr单晶纳米片。
基于上述二维超薄BiOBr单晶纳米片制备紫外光电探测器的方法为：采用湿法转移将厚度为0.57nm～5nm的BiOBr单晶纳米片转移至硅基底上，然后旋涂光刻胶PMMA，用EBL制备出具有设计好的图案的PMMA，然后再蒸镀Cr/Au电极(Cr/Au电极厚度分别为10nm/50nm)，用丙酮溶液浸泡去除光刻胶，即可得到所述紫外光电器件。
本实施例制备BiOBr单晶纳米片的SEM图如图6所示；基于本实施例所得到的BiOBr单晶纳米片制备的光电探测器件在不同波长光照下的光响应I-V图如图7所示；基于本实施例所得到的BiOBr单晶纳米片制备的光电探测器件在高频光照下的单个频率的光响应I-T图如图8所示。
图1为本发明实施例1所制备的BiOBr单晶纳米片的暗场光显图，从中可以看出该实施例中BiOBr以圆形形貌生长分布在云母片上。图2为实施例1制备的二维BiOBr单晶纳米片的原子力显微图，从图中可以看出，BiOBr纳米片最薄可达0.57nm。图3为本发明实施例2所制备的BiOBr单晶纳米片TEM图谱；其中，图a为二维BiOBr单晶纳米片的低分辨图像，图b为BiOBr单晶纳米片的高分辨图像，得到该纳米片的晶面间距为0.28nm，对应晶面为(110)。图4为本发明实施例2所制备的BiOBr纳米片的XRD图；可以明显观测到定向生长的二维BiOBr特征峰(001)、(002)、(003)、(004)，归属于(00l)晶面，证明了其层状材料的特性。图5为本发明实施例2中所制备的BiOBr的纳米片SEM图，可以看到该实施例条件下制备的纳米片形貌为矩形。图6为本发明实施例3中所制备的BiOBr单晶纳米片SEM图，可以看到纳米片的形貌为等腰直角三角形。图7基于本发明实施例3所得到的BiOBr单晶纳米片制备的光电探测器的光电性能测试；其中，是分别在245nm、295nm、315nm、345nm、375nm、405nm波长下的光响应I-V，表明该探测器在紫外光谱范围内都具有光响应。图8本发明实施例3所得到的BiOBr单晶纳米片制备的光电探测器的光电响应速率测试，其响应上升时间可达110μs，下降时间可达160μs，表明器件探测速率高。
以上所述，仅为本发明的具体实施方式，本说明书中所公开的任一特征，除非特别叙述，均可被其他等效或具有类似目的的替代特征加以替换；所公开的所有特征、或所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，均可以任何方式组合。
Claims (8)
1.一种二维超薄BiOBr单晶纳米片的制备方法，其特征在于，包括以下步骤：
步骤1：将BiBr3粉末置于坩埚中，然后将坩埚放置于石英管上游第一加热区中心；将覆盖自然氧化后的铜箔的基片放置于石英管下游第二加热区中心；
步骤2：将石英管内部抽真空至0.1Pa以下，通入Ar气使管内气压保持常压环境，然后继续向管内通入Ar气作为载气流；
步骤3：将第二加热区升温至380～400℃，保持1～60min后，再将第一加热区升温至220～275℃，反应5～30min，反应结束后冷却至室温，取出基片，即可在基片上得到所述的二维超薄BiOBr单晶纳米片。
2.如权利要求1所述的二维超薄BiOBr单晶纳米片的制备方法，其特征在于，步骤1所述BiBr3粉末的质量为2～50mg。
3.如权利要求1所述的二维超薄BiOBr单晶纳米片的制备方法，其特征在于，步骤1所述自然氧化后的铜箔为将铜箔放置于室温环境下1～2天后得到。
4.如权利要求1所述的二维超薄BiOBr单晶纳米片的制备方法，其特征在于，步骤2所述Ar气体的流速为25～50sccm。
5.如权利要求1所述的二维超薄BiOBr单晶纳米片的制备方法，其特征在于，步骤3所述第二加热区的升温速率为10～25℃/min；第一加热区的升温速率为15～30℃/min。
6.如权利要求1所述的二维超薄BiOBr单晶纳米片的制备方法，其特征在于，步骤3所述冷却为自然冷却或快速冷却，所述快速冷却的冷却速率≥50℃/min。
7.一种采用如权利要求1～6任一所述制备方法得到的二维超薄BiOBr单晶纳米片，其特征在于，所述二维超薄BiOBr单晶纳米片生长晶面为(00l)，厚度0.57nm～200nm，尺寸为0.5～70μm。
8.一种基于权利要求7所述二维超薄BiOBr单晶纳米片制备光电探测器方法，其特征在于，将所述二维超薄BiOBr单晶纳米片从基片上转移至Si/SiO2衬底，然后通过电子束曝光和热蒸发制作电极，即可得到所需紫外光电器件。
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