半导体/金属微纳结构的设计、制备和光电场下输运特性
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摘要
论文在探索银、镍金属纳米线制备工艺的基础上,进一步设计、制备了基于银、镍纳米线及其氧硫化物半导体纳米材料的异质结构,深入研究了各种类型异质结构在光场和电场作用下的输运特性。利用扫描电子显微镜、透射电子显微镜等设备对纳米结构的微观形貌、化学成分和晶体结构进行了详细观察和表征。
首先,尝试采用AgNO_3溶液法直接制备制备银纳米结构,通过改变溶液浓度以及电场强度,可以得到形态各异的银纳米结构。通过氧化铝模板法制备出了银纳米线阵列,其直径200 nm,长度约为10μm。采用本实验组的固态离子学方法生长的宏观长银纳米线簇,用电镀法制备镍壳/银芯纳米异质结,其长度可达微米量级,镍壳厚度约为100 nm,测试结果表明该微纳结构具有很好的光电响应特性。
其次,采用氧化铝模板法制备了镍纳米线阵列,纳米线直径200 nm,长度可超过50μm。放置于空气中自然氧化12小时后,在镍纳米线表层形成氧化镍纳米层,厚度约为5 nm。使用扫描电子显微镜、透射电子显微镜对镍纳米线及氧化层进行了详细表征,通过测量氧化镍吸收谱得到了氧化镍纳米层的禁带宽度。利用原子力显微镜,实现了对单个NiO-Ni肖特基结的测量,观测到了半导体-金属转变,并在理论上进行了分析。在此基础上,制备了Au-NiO-Ni双肖特基纳米结阵列,两个肖特基结呈“面对面”结构,可以很好地抑制半导体-金属转变前的正向电流,增大开/关状态下的电流比值。通过调控电压,我们得到了可重复的、转变迅速的开关器件。
最后,利用气-固反应法对宏观长银纳米线簇进行硫化处理,得到具有不同厚度比值的硫化银壳/银芯同轴纳米结构,研究发现样品的光电导行为强烈依赖于硫化层厚度,其光电导变化值可以从负转为正,从而为调控纳米材料光电导提供了一种新的途径。
The main topics of this dissertation are about the fabrication of silver and nickel nanowires and the heterojunctions formed by metals and corresponding oxysulfides. The heterojunctions were undergone by exterior laser lighting as well as electric field to study their transport characteristics. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to study the morphologies, components and crystal structures of the nanowires detailedly.
Firstly, attempts to fabricate silver nanowires in AgNO_3 solution show some interesting silver nanostructures, like nanoflakes and dendritic shapes, under different AgNO_3 concentration as well as electronic field. Silver nanowires with diameter of 200 nm and length about 10μm were also made in alumina oxide template through electrochemical deposition. Macro-long Ni/Ag heterojunctions with excellent photo-response were got with the as-prepared silver nanowire bundles by state-ionic method.
Secondly, nickel nanowire arrays were synthesized by the electrochemical deposition method using an anodic aluminum oxide template with a mean diameter of 200 nm and a length of 60μm. Oxidized in the atmosphere for about 12 h, the exposed surface of the Ni nanowire was oxidized and formed a Ni core/NiO shell architecture. SEM and TEM were introduced to characterize the sample and the band gap of NiO nanolayer could be calculated from the absorbance spectrum. With the help of Atomic Force Microscopy (AFM), single NiO-Ni Schottky nanojunction was studied and semiconductor-metal transition was observed. Furthermore, Au-NiO-Ni dual Schottky nanojunctions were formed, manifesting a replicable, fast-responded switch trait after certain treatments. Due to the face-to-face Schottky contact, forward current was restrained and high ratio of ON/OFF current was available.
Finally, through sulfurization of the micro-long silver nanowire bundles, silver sulfide/silver nano-heterojunction was obtained. Unlike the negative photocon- ductivity of silver nanowires, its photoconductivity can change from negative to positive gradually with different silver sulfide thickness, which implies a new approach to manipulate the photoconductivity of nanomaterials.
首先,尝试采用AgNO_3溶液法直接制备制备银纳米结构,通过改变溶液浓度以及电场强度,可以得到形态各异的银纳米结构。通过氧化铝模板法制备出了银纳米线阵列,其直径200 nm,长度约为10μm。采用本实验组的固态离子学方法生长的宏观长银纳米线簇,用电镀法制备镍壳/银芯纳米异质结,其长度可达微米量级,镍壳厚度约为100 nm,测试结果表明该微纳结构具有很好的光电响应特性。
其次,采用氧化铝模板法制备了镍纳米线阵列,纳米线直径200 nm,长度可超过50μm。放置于空气中自然氧化12小时后,在镍纳米线表层形成氧化镍纳米层,厚度约为5 nm。使用扫描电子显微镜、透射电子显微镜对镍纳米线及氧化层进行了详细表征,通过测量氧化镍吸收谱得到了氧化镍纳米层的禁带宽度。利用原子力显微镜,实现了对单个NiO-Ni肖特基结的测量,观测到了半导体-金属转变,并在理论上进行了分析。在此基础上,制备了Au-NiO-Ni双肖特基纳米结阵列,两个肖特基结呈“面对面”结构,可以很好地抑制半导体-金属转变前的正向电流,增大开/关状态下的电流比值。通过调控电压,我们得到了可重复的、转变迅速的开关器件。
最后,利用气-固反应法对宏观长银纳米线簇进行硫化处理,得到具有不同厚度比值的硫化银壳/银芯同轴纳米结构,研究发现样品的光电导行为强烈依赖于硫化层厚度,其光电导变化值可以从负转为正,从而为调控纳米材料光电导提供了一种新的途径。
The main topics of this dissertation are about the fabrication of silver and nickel nanowires and the heterojunctions formed by metals and corresponding oxysulfides. The heterojunctions were undergone by exterior laser lighting as well as electric field to study their transport characteristics. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to study the morphologies, components and crystal structures of the nanowires detailedly.
Firstly, attempts to fabricate silver nanowires in AgNO_3 solution show some interesting silver nanostructures, like nanoflakes and dendritic shapes, under different AgNO_3 concentration as well as electronic field. Silver nanowires with diameter of 200 nm and length about 10μm were also made in alumina oxide template through electrochemical deposition. Macro-long Ni/Ag heterojunctions with excellent photo-response were got with the as-prepared silver nanowire bundles by state-ionic method.
Secondly, nickel nanowire arrays were synthesized by the electrochemical deposition method using an anodic aluminum oxide template with a mean diameter of 200 nm and a length of 60μm. Oxidized in the atmosphere for about 12 h, the exposed surface of the Ni nanowire was oxidized and formed a Ni core/NiO shell architecture. SEM and TEM were introduced to characterize the sample and the band gap of NiO nanolayer could be calculated from the absorbance spectrum. With the help of Atomic Force Microscopy (AFM), single NiO-Ni Schottky nanojunction was studied and semiconductor-metal transition was observed. Furthermore, Au-NiO-Ni dual Schottky nanojunctions were formed, manifesting a replicable, fast-responded switch trait after certain treatments. Due to the face-to-face Schottky contact, forward current was restrained and high ratio of ON/OFF current was available.
Finally, through sulfurization of the micro-long silver nanowire bundles, silver sulfide/silver nano-heterojunction was obtained. Unlike the negative photocon- ductivity of silver nanowires, its photoconductivity can change from negative to positive gradually with different silver sulfide thickness, which implies a new approach to manipulate the photoconductivity of nanomaterials.
引文
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