CN105555705B - 硅纳米线阵列的制备方法 - Google Patents

硅纳米线阵列的制备方法 Download PDF

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CN105555705B
CN105555705B CN201480052091.1A CN201480052091A CN105555705B CN 105555705 B CN105555705 B CN 105555705B CN 201480052091 A CN201480052091 A CN 201480052091A CN 105555705 B CN105555705 B CN 105555705B
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尹明汉
李世宁
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Gwangju Institute of Science and Technology
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Abstract

本发明提供一种硅纳米线阵列的制备方法，包括以下步骤：使塑料粒子以均匀随机图案相互隔离地布置于硅基板上；在所述塑料粒子之间形成催化剂层；除去所述塑料粒子；垂直蚀刻与所述催化剂层接触的硅基板部位；及除去所述催化剂层。根据本发明，工艺简单，费用低，通过大面积工艺能够实现批量生产，在资源有限的地方也能够制备纳米线，可以独立控制纳米线的结构。

Description

硅纳米线阵列的制备方法
技术领域
本发明涉及一种硅纳米线阵列的制备方法。
背景技术
纳米线(nano wire)是指作为各种半导体纳米结构物之一，具有纳米级尺寸的线结构体。其涵盖大体上直径从小于10nm到数百nm的纳米线。
关于这些纳米线所提出的制备方法大致分为三种。
首先，提出了通过电子束光刻(e-beam lithography)设备将光刻胶图案化为纳米级图案，通过将图案化的光刻胶用作掩模来对硅进行纳米蚀刻以制得二维硅纳米线的方法。
但根据这些现有硅纳米线的制备方法，纳米线的制备成本高，不适合于大规模生产。
其次，提出了在形成纳米级金属催化剂之后，在保持950℃左右高温的状态下注入反应气体(SiH4)以成长二维硅纳米线的自对准方式的VLS(Vapor-Liquid-Solid)法。
但这些方法难以控制纳米线的结构，且无法控制硅纳米线的成长方向。
最后，提出了利用溶液工艺的蚀刻方法。利用溶液工艺的蚀刻方法与自对准方法相比具有节省时间和费用的效果，而利用溶液工艺的硅纳米线制备方法中作为正确调节硅纳米线的几何学变量(直径、高度、密度等)的方法，主要使用利用纳米结构的六边形格子图案的方法。但此方法无法独立调节纳米线的几何学变量，尤其难以制备大面积纳米线。
发明内容
解决的技术问题
在本发明的一个方面提出能够独立控制纳米线的几何学变量(直径、长度、密度、位置等)，费用低，可以批量生产的纳米线阵列的制备方法。
技术方案
为了达到上述目的，本发明的一个方面提供一种硅纳米线阵列的制备方法，包括以下步骤：使塑料粒子以均匀随机图案相互隔离地布置于硅基板上；在所述塑料粒子之间形成催化剂层；除去所述塑料粒子；垂直蚀刻与所述催化剂层接触的硅基板部位；及除去所述催化剂层。
发明的效果
根据本发明，工艺简单，费用低，通过大面积工艺能够实现批量生产，在资源有限的地方也能够制备纳米线。尤其，可以独立控制纳米线的结构，因此，通过利用纳米结构，可以期待广泛应用于电子元件和太阳能等光能产业、生物传感器等各种产业。
附图说明
图1为根据本发明的一实施例的纳米线阵列的制备方法的工艺图。
图2为示出根据本发明的一实施例的金属催化剂化学蚀刻机制的图。
图3为示出根据本发明的一实施例的根据聚苯乙烯珠粒的大小的硅纳米线的直径的照片。
图4为示出根据本发明的一实施例的根据蚀刻时间的硅纳米线的高度的照片。
图5为示出根据本发明的一实施例的根据聚苯乙烯珠粒的密度的硅纳米线阵列的密度的照片。
图6为根据本发明的一实施例制备的硅纳米线的TEM及EDX分析图。
图7为示出根据本发明的一实施例的垂直结构的硅纳米线阵列(vSiNWA)的图案化工艺的图。
图8为以硅纳米线为模板形成FeOx的核-壳结构的照片。
图9为观察根据不同聚合物层数的不同大小的塑料粒子的分布程度的结果图表。
具体实施方式
本文中所使用的术语“纳米级”或“纳米”可以解释为1至小于1千纳米，但不限于此。
下面，参照附图对本发明的硅纳米线阵列的制备方法进行详细说明，以使所属领域的技术人员可以容易实施本发明。
纳米级材料具有独特的电性、光学及机器特性等新的物理和化学性质，因此，目前作为非常重要的研究领域正在抬头。并且，至今对纳米结构进行的研究显示作为未来的新光元件材料的可能性。尤其，纳米级元件体积小，因此表面积/体积的比增加，在表面上发生的电气和化学反应变得优势，从而可以应用于各种传感器。尤其，垂直结构的硅纳米线阵列(vSiNWA)具有有用的电性质、大表面积、量子局限效应、生物相容性等，因此受到广泛的关注。
然而，大部分的纳米元件很难人为操作，使实际应用遇到困难，因此，作为替代，对容易操作的如纳米线(nanowire)等用于纳米元件的材料进行研究。纳米线可以广泛应用于生物传感器、如激光等光元件、晶体管及存储器元件等各种领域。
目前纳米线大凡通过利用催化剂的成长法制备。根据这些纳米线制备方法，在纳米线形成为预定长度后除去所用的催化剂。但在此情况下，无法自由控制纳米线的直径、长度、密度、位置等。
为了解决上述现有技术的问题，本发明提供通过基于溶液工艺的化学蚀刻方法制备垂直结构的硅纳米线的方法。为此，如图1所示，本发明的一个方面提供一种硅纳米线阵列的制备方法，包括以下步骤：使塑料粒子以均匀随机图案相互隔离地布置于硅基板上；在所述塑料粒子之间形成催化剂层；除去所述塑料粒子；垂直蚀刻与所述催化剂层接触的硅基板部位；及除去所述催化剂层。
在本发明中，作为纳米线的材料选用结晶硅(Si)，但不限于此，对于非晶硅(a-Si)和多晶硅(polycrystalline-Si)也可以通过类似的溶液工艺制备大面积纳米线和纳米图案。
在本发明中，以利用硅制备纳米线阵列的工艺为中心进行说明。
首先，将塑料粒子相互隔离地布置在硅基板上。在所述硅基板上布置塑料粒子之前，可以在所述硅基板上形成聚合物层。为此，通过交替进行在所述硅基板上涂布阳离子聚电解质溶液的工艺和涂布阴离子聚电解质溶液的工艺来一层接一层(layer-by-layer)地形成层状自组装聚合物层。上述工艺可以反复进行多次。所述阳离子聚电解质可以选自由聚芳胺盐酸盐、聚乙烯亚胺、聚二甲基二烯丙基酰胺、聚赖氨酸及其组合构成的组，但不限于此。所述阴离子聚电解质可以选自由聚苯乙烯磺酸、聚丙烯酸、聚乙烯硫酸、肝素及其组合构成的组，但不限于此。
在使用如硅基板等带阴电荷的基板时，可以采取在基板上先涂布带与基板电荷相反的电荷的阳离子聚电解质溶液，然后涂布阳离子聚电解质溶液的方法。优选地，最后涂布的聚电解质溶液带与塑料粒子的电荷相反的电荷。通过上述过程，在基板上可以形成单层或多层的聚合物层。对在基板上涂布聚电解质溶液的方式没有特别限制，可以采用已知方式，也可以采取将基板负载于溶液中的方式。
在所述基板上形成的聚合物层起粘合剂作用，使得塑料粒子附着于基板上。并且，其使静电力作用于塑料粒子之间，以助于塑料粒子均匀隔开。参照图9，可以确定大小分别为100nm、150nm、200nm、350nm的塑料粒子在基板上隔离地布置的分布程度。在将聚合物层分别形成为1层、3层、5层、7层时，结果聚合物层的叠层次数越多，粒子的分布更加均匀。由此可知，聚合物层有助于塑料粒子的均匀分布。
塑料粒子优选为球形，而根据必要可以具有各种形状。所述塑料粒子可以在颗粒状态散布在形成有聚合物层的硅基板上，但也可以在将塑料粒子混合于特定溶液中后以旋涂等方法进行涂布。所述塑料粒子的排列可具有周期性，也可具有非周期性。由此，所述塑料粒子可以以均匀随机图案相互隔离地布置。
所述塑料可以选自由聚乙烯、聚丙烯、聚苯乙烯、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚碳酸酯、聚甲基丙烯酸甲酯、聚苯醚、聚缩醛组成的组，但不限于此。优选地，这些塑料粒子的直径为纳米级。
在塑料粒子分别分散于适当位置时，通过氧等离子体处理来除去聚合物层或溶液成分。接着，在所述塑料粒子之间形成催化剂层，此时可以采用附着有塑料粒子的硅基板上沉积催化剂层的方法。具体地，可以采用溅射、电子束沉积、真空沉积、化学气相沉积、物理气相沉积、原子层沉积(Atomic Layer Deposition；ALD)等方法。
通过所述沉积过程，不但在塑料粒子的露出表面而且在塑料粒子之间的空间形成催化剂层。接着，除去所述塑料粒子，则在塑料粒子停留的位置处于不形成有催化剂层的状态。
所述催化剂层可包括银(Ag)、金(Au)、铂(Pt)、铜(Cu)或其组合。
在本发明中，通过以金属催化剂实现的化学湿蚀刻而形成纳米线阵列。湿蚀刻是指使需要蚀刻的材料与蚀刻液接触，以通过化学反应进行蚀刻的方法。
蚀刻液的实例可包括酸(acid)和过氧化物。所述酸(acid)的代表性的例子可例举氢氟酸(HF)，而所述过氧化物的代表性的例子可例举过氧化氢(H2O2)。如果适当调节包含于所述蚀刻液的酸(acid)和过氧化物的浓度，也就可以调节蚀刻所需的时间。
在与包括金属催化剂的催化剂层接触的硅基板的部位，过氧化氢通过金属催化剂还原，使得在硅内形成孔，而这些孔较多的区域露出于酸(acid)以溶解。
参照图2，具体反应机制如下。
(负极反应式)
H2O2+2H++2e-→2H2O
2H++2e-→H2
(正极反应式)
Si+2H2O→SiO2+4H++4e-
SiO2+6HF→H2SiF6+2H2O
Si+4HF→SiF4+4H++4e-
若反复进行如上反应，则催化剂层下部的硅被溶解以实现垂直蚀刻，而包含于催化剂层的金属向下方的硅下降。反复进行上述过程后，结束蚀刻，最后除去所述金属就可以得到所需的纳米线阵列。
并且，可以使用盐酸和硝酸的混合液即王水来除去包含于催化剂层的金属。
在本发明中，通过适当调节工艺条件来可以控制纳米线的结构变量。独立控制上述结构变量，即，直径、高度、密度、位置等的纳米线可以用于观察神经单位的界面。
作为控制结构变量的一个方法，通过控制塑料粒子的大小来可以调节纳米线的直径。如图3所示，通过使塑料粒子的大小分别变为100nm、150nm、240nm来制备线，结果，由图3(a)可知制得直径100nm的线，由图3(b)可知制得直径150nm的线，由图3(c)可知制得直径240nm的线。
并且，通过控制用蚀刻液进行蚀刻的时间来可以调节纳米线的高度即纳米线的长度，蚀刻时间越长，线的高度或长度变长。如图4所示，在蚀刻时间为1分钟时(图4(a))纳米线的平均高度小于0.9μm，在蚀刻时间为2分钟时(图4(b))纳米线的平均高度为1.4μm，在蚀刻时间为3分钟时(图4(c))纳米线的平均高度为1.8μm。
并且，通过控制所述塑料粒子之间的间隔来可以调节纳米线阵列的密度。在制备工艺上，通过调节用去离子水对包含塑料粒子的溶液进行稀释的倍率来可以调节包含于溶液中的塑料粒子的密度，而通过涂布所述溶液来可以控制涂布的塑料粒子之间的间隔。
如图5所示，如果适当调节包含塑料粒子的溶液的去离子水稀释倍率，就可以制备密度被调节使得每100μm2断面积中纳米线个数分别350以下(图5(a))，700以下(图5(b))，1400以下(图5(c))的纳米线阵列基板。
本发明的纳米线阵列的结构可以通过形成一定图案来制备为具有周期性的结构。即通过结合金属催化剂化学蚀刻(MACE；metal assisted chemical etching)法和光刻(photolithography)法来可以实现。
参照图7，通过形成图案进行蚀刻的过程说明如下。
在硅基板上通过旋涂涂覆光刻胶，使用所需的图案掩模进行光刻工艺。在图案化的硅基板上通过层层自组装法形成聚合物层后，布置所需大小的塑料粒子。通过如上所述的方法沉积金属催化剂层，然后加入蚀刻液中进行化学反应，则可以仅在所需的图案化部分形成垂直型纳米线阵列结构。
并且，通过随意分散塑料粒子进行涂覆来可以制备具有非周期性的纳米结构。即，通过结合层层自组装(layer-by-layer self-assembly)法和纳米球刻蚀(nanospherelithography)法，来不是以六边形格子图案布置而是任意分散纳米球来进行涂覆，从而能够独立调节纳米线的几何学变量，制备排列呈非周期性的纳米线阵列。
通过TEM及EDX对所制得的硅纳米线的特性进行分析，结果如图6所示。
由TEM可确定所制得的硅纳米线的结晶性和表面结构。纳米线的表面以非晶形式存在，且具有通过蚀刻制备时呈现的特点即较多微孔。纳米线的内部具有结晶形式，呈硅晶片本来具有的结晶性。而且，通过EDX测定分析硅纳米线的成分，结果，可确定其包含硅和氧原子，因此，可以类推硅纳米线表面包括氧化硅层。
并且，以硅纳米线为模板，在外表面上涂覆由例如Si、Ge、Cu、Ni、Cr、Fe、Ag、Ti、Co、Zn、Mg、Pt、Pd、Os、Au、Pb、Ir、Mo、V、Al等金属和其合金，如SnO2、Cr2O3、Fe2O3、Fe3O4、FeO、NiO、AgO、TiO2、Co2O3、Co3O4、CoO、ZnO、PtO、PdO、VO2、MoO2及PbO等金属氧化物，如聚酰亚胺等聚合物，或者，例如Ti/TiO2等具有叠层结构的其组合构成的至少一个以上的材料层，从而，可以提供能够赋予预定的光学、电性、磁性、机器或化学功能的核-壳纳米线结构。涂覆于二氧化硅纳米线的所述材料可以通过化学气相沉积、原子层沉积、溅射等公知的薄膜沉积方法来形成。
在部分实施例中，在涂覆所述材料层之后，除去所述硅纳米线，从而可以提供具有仅存留所述至少一个以上的材料层的结构的纳米管阵列结构。如上所示，用作模板的所述硅纳米线根据元件制造方法可以存在于纳米管阵列结构内部，或可以通过利用等离子体的干蚀刻或利用HF的湿蚀刻而被除去。
形成核-壳纳米线结构的方法如下。需要置换使用上述的方法制得的硅纳米线模板的表面的过程。通过溶胶-凝胶法制备FeOx溶液后，将表面处理的硅纳米线模板加入所制得的溶液中。然后，进行氧化水处理，则如图8所示，根据硅纳米线的形状形成FeOx的核-壳结构。

Claims (9)

1.一种硅纳米线阵列的制备方法，其特征在于，包括以下步骤：
使塑料粒子以均匀随机图案相互隔离地布置于形成有层状自组装聚合物层的硅基板上；
通过对形成于所述硅基板上的所述层状自组装聚合物层进行氧等离子体处理，除去所述塑料粒子之间的所述层状自组装聚合物层；
在所述塑料粒子之间形成催化剂层；
除去所述塑料粒子；
通过湿蚀刻工艺，垂直蚀刻与所述催化剂层接触的硅基板部位；及
除去所述催化剂层，
其中，所述硅纳米线阵列的密度通过控制所述塑料粒子之间的间隔来调节，
其中，所述层状自组装聚合物层通过交替进行在所述硅基板上涂布阳离子聚电解质溶液的工艺和涂布阴离子聚电解质溶液的工艺而成。
2.根据权利要求1所述的硅纳米线阵列的制备方法，其特征在于，所述阳离子聚电解质选自由聚芳胺盐酸盐、聚乙烯亚胺、聚二甲基二烯丙基酰胺、聚赖氨酸及其组合构成的组。
3.根据权利要求1所述的硅纳米线阵列的制备方法，其特征在于，所述阴离子聚电解质选自由聚苯乙烯磺酸、聚丙烯酸、聚乙烯硫酸、肝素及其组合构成的组。
4.根据权利要求1所述的硅纳米线阵列的制备方法，其特征在于，所述塑料选自由聚乙烯、聚丙烯、聚苯乙烯、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚碳酸酯、聚甲基丙烯酸甲酯、聚苯醚、聚缩醛组成的组。
5.根据权利要求1所述的硅纳米线阵列的制备方法，其特征在于，所述催化剂层包括银(Ag)、金(Au)、铂(Pt)、铜(Cu)或其组合。
6.根据权利要求1所述的硅纳米线阵列的制备方法，其特征在于，所述形成催化剂层的步骤采用沉积法。
7.根据权利要求4所述的硅纳米线阵列的制备方法，其特征在于，通过使用含有酸(acid)或过氧化物的溶液来进行所述湿蚀刻工艺。
8.根据权利要求1所述的硅纳米线阵列的制备方法，其特征在于，通过控制所述塑料粒子的大小来调节硅纳米线的直径。
9.根据权利要求1所述的硅纳米线阵列的制备方法，其特征在于，通过控制所述蚀刻步骤的蚀刻时间来调节硅纳米线的高度。
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Fabriction of Silicon Nanowire Arrays with Controllaed Diameter, Length, and Density.;Zhipeng Huang, Hui Fang, and Jing Zhu.;《Adv. Mater.》;20070207;第19卷;第744页右栏第1段-第745页右栏第2段，图1-4 *

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CN105555705A (zh) 2016-05-04
KR101827656B1 (ko) 2018-02-08

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