一维纳米ZnO半导体材料的掺杂及器件制备
摘要
采用化学气相沉积(CVD)法,以高纯ZnO和活性碳混合粉末为原料,分别以Mg和N为掺杂元素,在Si(111)衬底上制备了不同掺杂浓度的取向ZnO纳米线阵列。用X射线衍射仪(XRD),扫描电镜(SEM),能量色散X射线分析(EDAX),拉曼光谱,透射电镜(TEM)及荧光光谱分析仪(PL)对样品的晶体结构,形貌、成分组成和光致发光特性等进行了分析。用霍尔效应测量系统测试了不同配比样品的载流子浓度。
以Mg为掺杂元素制备Zn_(1-x)Mg_xO纳米线阵列。实验发现,Zn_(1-x)Mg_xO纳米线阵列中Mg原子相对Zn原子摩尔比X值较小时(X＜0.29),XRD衍射谱中只有ZnO晶体标准衍射峰,没有MgO晶体衍射峰,说明此时制备的Zn_(1-x)Mg_xO纳米线样品晶格结构以ZnO纤锌矿结构为主,Mg原子只是作为替位或填隙原子分布在ZnO晶体中。但当样品中X＞0.53时,ZnO与MgO的特征衍射峰同时出现在样品的衍射谱图中,说明随原料中Mg原子摩尔比的增加,制备的Zn_(1-x)Mg_xO纳米阵列样品中ZnO纤锌矿结构与MgO岩盐结构将同时存在,样品呈现多晶体结构形式。实验还对比了制备的纯ZnO与不同配比的Zn_(1-x)M_xO纳米线阵列的PL光谱和载流子浓度,发现随Mg含量的增加,Zn_(1-x)Mg_xO阵列紫光发光峰出现了较明显的蓝移现象,同时,测试结果也表明,随Mg含量的增加,Zn_(1-x)Mg_xO阵列的紫光(376nm)和绿光峰(535nm)发光强度都有所减弱,样品的载流子浓度也随之下降。
在以N为掺杂元素制备的ZnO:N纳米线阵列中,N原子作为填隙原子确实掺杂进入ZnO晶体的晶体结构中,并且随着反应中NH_3气体流量的增加,掺杂到ZnO:N晶体中的N原子逐渐增多。XRD测试结果显示,随着N原子掺杂含量的增加,ZnO:N晶体的(002)易生长面减少。掺杂后的ZnO:N晶体仍为ZnO纤锌矿结构,未产生相分离。扫描电镜显示,NH_3气体在ZnO:N晶体的生长过程中影响了产物的表明形貌。最后,实验采用两步法,制备了一维纳、微米尺度的ZnO:N/ZnO结构P-N结。测试了微米尺度ZnO:N/ZnO结构P-N结的I-V特性,并对比ZnO:N微米线I-V特性的测试结果分析了ZnO:N/ZnO结构P-N结的电学性质。
The aligned doped ZnO nanowire arrays have been successfully prepared on Si(111) substrates via the chemical vapor deposition method with a mixture of ZnO and activated carbon powders as reactants.The Mg and N were inctoduced as the dopant,respectively.The microstructures and optical properties of synthesized nanowire arrays were investigated by X-ray diffraction(XRD),Scanning Electron Microscopy(SEM),Energy Dispersive Analysis of X-ray(EDAX),Raman Spectroscopy,Transmission Electron Microscope(TEM),and Photoluminescence Spectrum(PL) analytic apparatus,respectively.
The aligned Zn_(1-x)Mg_xO nanowire arrays have been successfully prepared on Si(111) substrates via the chemical vapor deposition method with a mixture of ZnO,Mg and activated carbon powders as reactants.While Mg content was achieved or less about 29 at.%in ZnO lattice,the crystal lattice of the synthesized samples exhibited wurtzite structure.The Mg atoms were distributed into the ZnO crystal as the interstitial and displaced atoms,and there was no a phase separation in the preparing Zn_(1-x)Mg_xO nanowire arrays.However,as the Mg content was up to 53 at.%in the fabricating Zn_(1-x)Mg_xO samples,a clear phase separation phenomena appeared in the Zn_(1-x)Mg_xO crystal.Compared with the PL spectrum of the pure ZnO nanowire arrays,the analytic results showed that a blue-shift of the near-band edge emission with increasing Mg content was observed in the Zn_(1-x)Mg_xO arrays.And the relative intensity of green peak at～535nm and UV emission peak at～376nm were all restrained.
The aligned N-doped ZnO(ZnO:N) nanowire arrays have been prepared on Si(111) substrates by CVD method with NH_3 gas as nitrogen source.Raman scattering spectra testify the nitrogen atoms were indeed doped into the wurtzite structure ZnO:N nano/microwire crystal as the substitutional atoms.And the content of N atoms in the ZnO crystal is increaseing as the NH_3 gas flux.The XRD pictures reveal that the(002) planes of ZnO:N crystal were decreased as the NH_3 gas increaseing in the reaction.The crystal lattice of the synthesized ZnO:N samples exhibited wurtzite structure,and no phase separation phenomena appeared in the ZnO:N crystal..The SEM images reveal that the growth morphology of the synthesized ZnO:N samples can be influenced by the quantities of doped NH_3 gas.Meanwhile, one dimensional ZnO:N microwire and ZnO:N/ZnO microwire junction devices have been fabricated.TheⅠ-Ⅴcharacters of the devices have been discussed.And the electron properties have been analyzed by compareing theⅠ-Ⅴcharacters of ZnO:N microwires.
以Mg为掺杂元素制备Zn_(1-x)Mg_xO纳米线阵列。实验发现,Zn_(1-x)Mg_xO纳米线阵列中Mg原子相对Zn原子摩尔比X值较小时(X＜0.29),XRD衍射谱中只有ZnO晶体标准衍射峰,没有MgO晶体衍射峰,说明此时制备的Zn_(1-x)Mg_xO纳米线样品晶格结构以ZnO纤锌矿结构为主,Mg原子只是作为替位或填隙原子分布在ZnO晶体中。但当样品中X＞0.53时,ZnO与MgO的特征衍射峰同时出现在样品的衍射谱图中,说明随原料中Mg原子摩尔比的增加,制备的Zn_(1-x)Mg_xO纳米阵列样品中ZnO纤锌矿结构与MgO岩盐结构将同时存在,样品呈现多晶体结构形式。实验还对比了制备的纯ZnO与不同配比的Zn_(1-x)M_xO纳米线阵列的PL光谱和载流子浓度,发现随Mg含量的增加,Zn_(1-x)Mg_xO阵列紫光发光峰出现了较明显的蓝移现象,同时,测试结果也表明,随Mg含量的增加,Zn_(1-x)Mg_xO阵列的紫光(376nm)和绿光峰(535nm)发光强度都有所减弱,样品的载流子浓度也随之下降。
在以N为掺杂元素制备的ZnO:N纳米线阵列中,N原子作为填隙原子确实掺杂进入ZnO晶体的晶体结构中,并且随着反应中NH_3气体流量的增加,掺杂到ZnO:N晶体中的N原子逐渐增多。XRD测试结果显示,随着N原子掺杂含量的增加,ZnO:N晶体的(002)易生长面减少。掺杂后的ZnO:N晶体仍为ZnO纤锌矿结构,未产生相分离。扫描电镜显示,NH_3气体在ZnO:N晶体的生长过程中影响了产物的表明形貌。最后,实验采用两步法,制备了一维纳、微米尺度的ZnO:N/ZnO结构P-N结。测试了微米尺度ZnO:N/ZnO结构P-N结的I-V特性,并对比ZnO:N微米线I-V特性的测试结果分析了ZnO:N/ZnO结构P-N结的电学性质。
The aligned doped ZnO nanowire arrays have been successfully prepared on Si(111) substrates via the chemical vapor deposition method with a mixture of ZnO and activated carbon powders as reactants.The Mg and N were inctoduced as the dopant,respectively.The microstructures and optical properties of synthesized nanowire arrays were investigated by X-ray diffraction(XRD),Scanning Electron Microscopy(SEM),Energy Dispersive Analysis of X-ray(EDAX),Raman Spectroscopy,Transmission Electron Microscope(TEM),and Photoluminescence Spectrum(PL) analytic apparatus,respectively.
The aligned Zn_(1-x)Mg_xO nanowire arrays have been successfully prepared on Si(111) substrates via the chemical vapor deposition method with a mixture of ZnO,Mg and activated carbon powders as reactants.While Mg content was achieved or less about 29 at.%in ZnO lattice,the crystal lattice of the synthesized samples exhibited wurtzite structure.The Mg atoms were distributed into the ZnO crystal as the interstitial and displaced atoms,and there was no a phase separation in the preparing Zn_(1-x)Mg_xO nanowire arrays.However,as the Mg content was up to 53 at.%in the fabricating Zn_(1-x)Mg_xO samples,a clear phase separation phenomena appeared in the Zn_(1-x)Mg_xO crystal.Compared with the PL spectrum of the pure ZnO nanowire arrays,the analytic results showed that a blue-shift of the near-band edge emission with increasing Mg content was observed in the Zn_(1-x)Mg_xO arrays.And the relative intensity of green peak at～535nm and UV emission peak at～376nm were all restrained.
The aligned N-doped ZnO(ZnO:N) nanowire arrays have been prepared on Si(111) substrates by CVD method with NH_3 gas as nitrogen source.Raman scattering spectra testify the nitrogen atoms were indeed doped into the wurtzite structure ZnO:N nano/microwire crystal as the substitutional atoms.And the content of N atoms in the ZnO crystal is increaseing as the NH_3 gas flux.The XRD pictures reveal that the(002) planes of ZnO:N crystal were decreased as the NH_3 gas increaseing in the reaction.The crystal lattice of the synthesized ZnO:N samples exhibited wurtzite structure,and no phase separation phenomena appeared in the ZnO:N crystal..The SEM images reveal that the growth morphology of the synthesized ZnO:N samples can be influenced by the quantities of doped NH_3 gas.Meanwhile, one dimensional ZnO:N microwire and ZnO:N/ZnO microwire junction devices have been fabricated.TheⅠ-Ⅴcharacters of the devices have been discussed.And the electron properties have been analyzed by compareing theⅠ-Ⅴcharacters of ZnO:N microwires.
引文
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