氧化铝模板辅助生长一维纳米线阵列及其电学性质研究
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摘要
TCNQ(tetracyanoquinodimethane),全名7,7,8,8-四氰基对苯醌二甲烷,是一种良好的有机电子受体,可以与很多电子给体(如TTF,碱金属或碱金属卤化物,过渡金属,稀土金属等)形成稳定的简单或复合型电荷转移配合物。金属有机配合物M(如Ag,Cu)-TCNQ具有优异的光、电、磁特性,其中Cu-TCNQ、Ag-TCNQ具有良好的开关特性,被认为是理想的分子电子学材料。同时,多孔氧化铝作具有孔洞长径比大、孔径小、透明、绝缘等优点,是辅助生长纳米线阵列的理想模板。
本论文在多孔氧化铝模板中制备生长了M-TCNQ纳米线阵列和金属铜纳米线阵列,表征了其形貌和结构,并分析了M-TCNQ纳米线阵列的电双稳和场发射特性,主要内容如下:
制备了多孔氧化铝模板,研究了各项工艺参数对其形貌、结构的影响。以草酸作为电解液,40 V恒压,5℃条件下,可以得到孔径在40-50纳米的多孔氧化铝模板。调节氧化电压和氧化时间可以改变其孔径和孔深。
在不同的氧化铝模板中生长了Ag-TCNQ和Cu-TCNQ,表征了其形貌,发现采用真空蒸汽输运法在氧化铝模板中生长M-TCNQ纳米线,其填充率达到95%以上。同时XRD测试表明Cu-TCNQ基本上处于电学性能较好的一相(phase I)。在此基础之上,制备了基于Cu-TCNQ纳米线阵列的原型器件。在对器件的电双稳测试中,其高阻态和低阻态电阻比超过10~4,并且有着良好的重复性。器件结构很适合于工业生产,有希望作为高密度存储器件。
对没有模板限制的Cu-TCNQ纳米线进行了场发射的测试,结果表明Cu-TCNQ纳米线场发射阈值电场强度较低,约为5.0 V/μm(电流密度达到10μA/cm~2时)。测试了纳米线阵列的过载电场。从电流和电压的关系来看,其场发射符合F-N理论模型,场发射性能良好,有希望作为有机阴极材料应用于平板显示。
在多孔氧化铝模板中,用交流电沉积的方法获得了铜纳米线阵列。形貌表征显示其填充率很高,纳米线尺寸亦很均匀。
TCNQ(tetracyanoquinodimethane) is a kind of electron ecceptor,which can combined with various electron donors such as TTF,alkali metals,transition metals and rare earth metals,to form stable simple/complex charge-transfer complexes. Metal organic complexes(M-TCNQs) possess excellent photic/ electric/ magnetic properties.Due to the unique on-off properties,Cu-TCNQ and Ag-TCNQ are considered as ideal molectronics materials.On the other hand,the properties such as high aspect ratio,small aperture,transparency and isolation make porous anodic alumina become appropriate template for the synthesis of nanowire array.
In this thesis,M-TCNQ nanowire array and copper nanowire array were synthesized in porous anodic alumina.The morphologies and structures were observed.The properties of electronic bi-stable and field emission of M-TCNQ were also studied.
Porous anodic alumina was prepared.Parameters in process that would affect the morphology and structure were studied.Oxalic acid was employed as electrolyte and anodic alumina template with channels whose diameters are 40-50 nm can be obtained under DC 40 V and 5℃.By modifying anodic voltage and lasting time, channel diameter and depth could be easily controlled.
Ag-TCNQ and Cu-TCNQ were synthesized in different anodic alumina templates.Morphology observing shows M-TCNQ nanowires that synthesized by vacuum vapor induced reaction almost fill every channel in templates.XRD test approves that most Cu-TCNQ is in phaseⅠ.Then,proto-type based on Cu-TCNQ nanowire array was fabricated.The on-off ration of resistance reached 104 in electric test and transition is reproducible.The structure is applicable to industry,so it is promising to be served as information storage device.
Field emission test on Cu-TCNQ nanowires without template showed a low threshold of 5.0 V/μm(when the current density reaches 10μA/cm~2).Overload voltage was also tested.The dependence of emission current density on the electric field follows Fowler-Nordheim relationship.These results indicate that Cu-TCNQ nanowires might be a promising candidate as organic cathode material in FE-based flat panel displays.
Copper nanowire array was also synthesized in porous anodic alumina via AC electrodeposition.Almost every channel was filled and the diameters of copper nanowires are uniform.
本论文在多孔氧化铝模板中制备生长了M-TCNQ纳米线阵列和金属铜纳米线阵列,表征了其形貌和结构,并分析了M-TCNQ纳米线阵列的电双稳和场发射特性,主要内容如下:
制备了多孔氧化铝模板,研究了各项工艺参数对其形貌、结构的影响。以草酸作为电解液,40 V恒压,5℃条件下,可以得到孔径在40-50纳米的多孔氧化铝模板。调节氧化电压和氧化时间可以改变其孔径和孔深。
在不同的氧化铝模板中生长了Ag-TCNQ和Cu-TCNQ,表征了其形貌,发现采用真空蒸汽输运法在氧化铝模板中生长M-TCNQ纳米线,其填充率达到95%以上。同时XRD测试表明Cu-TCNQ基本上处于电学性能较好的一相(phase I)。在此基础之上,制备了基于Cu-TCNQ纳米线阵列的原型器件。在对器件的电双稳测试中,其高阻态和低阻态电阻比超过10~4,并且有着良好的重复性。器件结构很适合于工业生产,有希望作为高密度存储器件。
对没有模板限制的Cu-TCNQ纳米线进行了场发射的测试,结果表明Cu-TCNQ纳米线场发射阈值电场强度较低,约为5.0 V/μm(电流密度达到10μA/cm~2时)。测试了纳米线阵列的过载电场。从电流和电压的关系来看,其场发射符合F-N理论模型,场发射性能良好,有希望作为有机阴极材料应用于平板显示。
在多孔氧化铝模板中,用交流电沉积的方法获得了铜纳米线阵列。形貌表征显示其填充率很高,纳米线尺寸亦很均匀。
TCNQ(tetracyanoquinodimethane) is a kind of electron ecceptor,which can combined with various electron donors such as TTF,alkali metals,transition metals and rare earth metals,to form stable simple/complex charge-transfer complexes. Metal organic complexes(M-TCNQs) possess excellent photic/ electric/ magnetic properties.Due to the unique on-off properties,Cu-TCNQ and Ag-TCNQ are considered as ideal molectronics materials.On the other hand,the properties such as high aspect ratio,small aperture,transparency and isolation make porous anodic alumina become appropriate template for the synthesis of nanowire array.
In this thesis,M-TCNQ nanowire array and copper nanowire array were synthesized in porous anodic alumina.The morphologies and structures were observed.The properties of electronic bi-stable and field emission of M-TCNQ were also studied.
Porous anodic alumina was prepared.Parameters in process that would affect the morphology and structure were studied.Oxalic acid was employed as electrolyte and anodic alumina template with channels whose diameters are 40-50 nm can be obtained under DC 40 V and 5℃.By modifying anodic voltage and lasting time, channel diameter and depth could be easily controlled.
Ag-TCNQ and Cu-TCNQ were synthesized in different anodic alumina templates.Morphology observing shows M-TCNQ nanowires that synthesized by vacuum vapor induced reaction almost fill every channel in templates.XRD test approves that most Cu-TCNQ is in phaseⅠ.Then,proto-type based on Cu-TCNQ nanowire array was fabricated.The on-off ration of resistance reached 104 in electric test and transition is reproducible.The structure is applicable to industry,so it is promising to be served as information storage device.
Field emission test on Cu-TCNQ nanowires without template showed a low threshold of 5.0 V/μm(when the current density reaches 10μA/cm~2).Overload voltage was also tested.The dependence of emission current density on the electric field follows Fowler-Nordheim relationship.These results indicate that Cu-TCNQ nanowires might be a promising candidate as organic cathode material in FE-based flat panel displays.
Copper nanowire array was also synthesized in porous anodic alumina via AC electrodeposition.Almost every channel was filled and the diameters of copper nanowires are uniform.
引文
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