ZnO晶体形貌调控、离子掺杂及其生长动力学
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摘要
ZnO作为宽禁带氧化物半导体具有优异的光学性能，近年其发光性能、磁学特性的研究成为热点。本文在水热条件下，系统研究了矿化剂、金属离子对ZnO晶体生长特性的影响，获得了较高浓度磁性金属离子掺杂的ZnO半导体，并进行了光、电、磁学性能的表征。利用基于密度泛函理论的第一性原理，从原子层次探讨了水热合成纤锌矿ZnO晶体形态的物理机制。主要研究结果如下：
1、用强碱性化合物（KOH、NaOH）作为矿化剂时，氧化锌晶体显现极性生长特征，C轴方向生长速度较快，有利于晶体生长，但快速的极性生长容易出现更多缺陷。而盐类矿化剂（KBr、NaCO3）条件下因为ZnO溶蚀度低，晶体生长相对较慢。在强碱性矿化剂的反应体系中分别加入适量的LiOH、CaO、Mg(OH)2，可以抑制ZnO晶体C轴方向生长速度。其中添加CaO制备的ZnO晶体发光光谱中有较强的紫外带间跃迁发光。
2、在强碱性矿化剂的反应体系中添加适量金属离子（Sb、Sn、In）可以控制ZnO晶体的形貌。其中添加Sn、In离子时，ZnO晶体C轴生长速度明显低于a、b轴，晶体始终大面积显露{0001}晶面，并且表现出良好的导电性能。其中添加In离子制备的ZnO晶体发光光谱中有较强的紫外带间跃迁发光。而添加Sb离子时，生成晶体完全不显露{0001}和{000}面。
3、填充度35%条件下，反应体系中分别加入MnCl2、CoCl2·6H2O，采用磁选分离对合成产物进行处理，分别得到了Mn掺杂浓度7%，Co掺杂浓度0.64-2.87%的均匀掺杂ZnO晶体，SQUID测量表明，这些均匀掺杂Mn、Co的ZnO晶体分别表现出反铁磁性和顺磁性，生成产物中同时伴生铁磁性Co单质存在。
4、为了提高Co掺杂浓度，采用耐压性能更好的反应釜，将填充度提高到70%，在反应体系中添加CoO，合成产物经磁选分离后获得了Co:Zn最高超过10at%的高浓度Co均匀掺杂ZnO晶体，测试结果表明该晶体表现出顺磁性。
5、利用基于密度泛函理论的第一性原理方法，对水热合成纤锌矿ZnO晶体形态的物理机制进行了理论研究。分析了纤锌矿ZnO晶体的原子结构、能带结构和态密度，并利用乌尔夫定理得到平衡态ZnO晶体形态图。构建金属原子在极性和半极性表面上的吸附结构模型，计算K、Na、Li、Ca、Mg五种金属原子在负极面（0001）和负锥面（1011）的O原子截断面上单类和混合吸附后的表面能的变化，并预测吸附后ZnO晶体形态图。从原子层次探讨了水热合成ZnO晶体形态的物理机制，我们认为添加剂中的金属原子对其表面悬挂键的饱和作用，直接影响表面能的大小，进而影响最终生成的晶体形态。
主要创新：
1、弄清了矿化剂离子以及金属离子对ZnO晶体极性生长的影响关系，建立了水热条件下ZnO晶体形貌调控技术路线。
2、在水热条件下实现了Mn/Co高浓度均匀掺杂，得到了高浓度均匀掺杂的高质量ZnO晶体，证实在Mn（Co）掺杂浓度超过7at%（10at%）时ZnO晶体不会产生铁磁性。
3、利用基于密度泛函理论的第一性原理方法，从原子层次探讨了水热合成ZnO晶体形态的物理机制，得到了与实验比较吻合的结果。
In recent years, the study is focused on the luminescent properties and magneticcharacteristics of the wide bandgap oxide semiconductor ZnO because of its excellent opticalperformance. In this work, the effect on the growth of ZnO crystal by mineralizing agent andmetal ions is systematically studied under hydrothermal conditions. Higher concentration ofmagnetic metal ions doped in the semiconductor ZnO was obtained, and its optical properties,electrical properties, and magnetic properties were characterized. The mechanism of theformation of wurtzite ZnO crystal is studied using first-principles density functional theorymethods.
1、Zinc oxide crystals show anosotropic growth characteristics with strong alkalinecompounds （KOH、NaOH）as mineralizer. The result is that the growth is faster at the c-axisdirection and it is conducive to the growth of crystal. However, the rapid growth of thepolarity is prone to more defects. The speed of growth was slow because of the dissolution islow with salts as mineralizer （KBr、NaCO3）. The speed of growth of ZnO crystal along thec–axis was weakened obviously by adding appropriate amount of LiOH、CaO or Mg(OH)2inthe strong alkaline mineralizers in the reaction system.
2、The ZnO crystal morphology could be controlled by adding appropriate amount ofmetal ions（Sb、Sn、In）in the strong alkaline mineralizer in the reaction system. The speedof growth of ZnO crystal along c–axis was weakened obviously compared with a–axis andb–axis by adding Sn or In ions. Large exposures of the positive polar face{0001} of ZnOcrystals is obtained.. Meanwhile, it exhibits good conduction properties. However, the the{0001} and {000} surfaces of ZnO crystal are not exposed in.
3、At the fill factor of35%of adding MnCl2、CoCl2.6H2O in the reaction system, theuniformly doped ZnO crystals were obtained with7mole%Mn and0.64-2.87mole%Cocontent after magnetic separation. SQUID test showed that the samples were mainlyparamagnetic in the uniformly doped ZnO crystals, and some Co single phase appearedsimultaneously.
4、In order to enhance the content of Co, more pressure-resistive reactor was used, andthe fill factor was enhanced to70%.Some CoO were added in the reaction system at the sametime. After magnetic separation, high content of Co, uniformly doped in ZnO crystals, wereobtained with the ratio of Co:Zn reaching10at%. The results showed that the samples weremainly paramagnetic.
5、The physical mechanisms of wurtzite ZnO crystal morphology were studied usingdensity functional theory. The atomistic structure, the energy band structure, and density ofstates of ZnO crystal were analyzed, and the aspect-graph of the equilibrium state of ZnOcrystal was obtained by using Ulf Theorem. The adsorption structure of metal atoms on thesurface of polar and semi-polar was set up. The adsorption energies of K、Na、Li、Ca、Mgatom, singly adsorbed or in mixture, at the truncated surfaces of O atoms located at thenegative face and negative cone face were obtained., The ZnO crystal morphology diagramafter adsorption was predicted. The physical mechanism of the hydrothermal synthesis of ZnOcrystal morphology was discussed from the atomic level. We believe that the surface energiesare directly correlated with the saturation of dangling bonds from the metal atoms in theadditive and the crystal morphology was affected in turn.
Innovations of this work:
1、the relationship between the growth of ZnO crystal and the mineralizing agent andmetal ions were clarified and technical routes of controlling ZnO crystal morphology underthe hydrothermal conditions were obtained.
2、 High concentrations of Mn/Co uniformly doped in the ZnO crystal underhydrothermal conditions were achieved and high qualities of ZnO crystals uniformly doped athigh concentrations were obtained. The results show that ZnO crystals doped high than7at%(10at%) of Mn（Co）do not show ferromagnetism.
3、The physical mechanisms of wurtzite ZnO crystal morphology synthesized byhydrothermal method were studied from the atomistic level using density functional theoryand the results are consistent with experiments.
1、用强碱性化合物（KOH、NaOH）作为矿化剂时，氧化锌晶体显现极性生长特征，C轴方向生长速度较快，有利于晶体生长，但快速的极性生长容易出现更多缺陷。而盐类矿化剂（KBr、NaCO3）条件下因为ZnO溶蚀度低，晶体生长相对较慢。在强碱性矿化剂的反应体系中分别加入适量的LiOH、CaO、Mg(OH)2，可以抑制ZnO晶体C轴方向生长速度。其中添加CaO制备的ZnO晶体发光光谱中有较强的紫外带间跃迁发光。
2、在强碱性矿化剂的反应体系中添加适量金属离子（Sb、Sn、In）可以控制ZnO晶体的形貌。其中添加Sn、In离子时，ZnO晶体C轴生长速度明显低于a、b轴，晶体始终大面积显露{0001}晶面，并且表现出良好的导电性能。其中添加In离子制备的ZnO晶体发光光谱中有较强的紫外带间跃迁发光。而添加Sb离子时，生成晶体完全不显露{0001}和{000}面。
3、填充度35%条件下，反应体系中分别加入MnCl2、CoCl2·6H2O，采用磁选分离对合成产物进行处理，分别得到了Mn掺杂浓度7%，Co掺杂浓度0.64-2.87%的均匀掺杂ZnO晶体，SQUID测量表明，这些均匀掺杂Mn、Co的ZnO晶体分别表现出反铁磁性和顺磁性，生成产物中同时伴生铁磁性Co单质存在。
4、为了提高Co掺杂浓度，采用耐压性能更好的反应釜，将填充度提高到70%，在反应体系中添加CoO，合成产物经磁选分离后获得了Co:Zn最高超过10at%的高浓度Co均匀掺杂ZnO晶体，测试结果表明该晶体表现出顺磁性。
5、利用基于密度泛函理论的第一性原理方法，对水热合成纤锌矿ZnO晶体形态的物理机制进行了理论研究。分析了纤锌矿ZnO晶体的原子结构、能带结构和态密度，并利用乌尔夫定理得到平衡态ZnO晶体形态图。构建金属原子在极性和半极性表面上的吸附结构模型，计算K、Na、Li、Ca、Mg五种金属原子在负极面（0001）和负锥面（1011）的O原子截断面上单类和混合吸附后的表面能的变化，并预测吸附后ZnO晶体形态图。从原子层次探讨了水热合成ZnO晶体形态的物理机制，我们认为添加剂中的金属原子对其表面悬挂键的饱和作用，直接影响表面能的大小，进而影响最终生成的晶体形态。
主要创新：
1、弄清了矿化剂离子以及金属离子对ZnO晶体极性生长的影响关系，建立了水热条件下ZnO晶体形貌调控技术路线。
2、在水热条件下实现了Mn/Co高浓度均匀掺杂，得到了高浓度均匀掺杂的高质量ZnO晶体，证实在Mn（Co）掺杂浓度超过7at%（10at%）时ZnO晶体不会产生铁磁性。
3、利用基于密度泛函理论的第一性原理方法，从原子层次探讨了水热合成ZnO晶体形态的物理机制，得到了与实验比较吻合的结果。
In recent years, the study is focused on the luminescent properties and magneticcharacteristics of the wide bandgap oxide semiconductor ZnO because of its excellent opticalperformance. In this work, the effect on the growth of ZnO crystal by mineralizing agent andmetal ions is systematically studied under hydrothermal conditions. Higher concentration ofmagnetic metal ions doped in the semiconductor ZnO was obtained, and its optical properties,electrical properties, and magnetic properties were characterized. The mechanism of theformation of wurtzite ZnO crystal is studied using first-principles density functional theorymethods.
1、Zinc oxide crystals show anosotropic growth characteristics with strong alkalinecompounds （KOH、NaOH）as mineralizer. The result is that the growth is faster at the c-axisdirection and it is conducive to the growth of crystal. However, the rapid growth of thepolarity is prone to more defects. The speed of growth was slow because of the dissolution islow with salts as mineralizer （KBr、NaCO3）. The speed of growth of ZnO crystal along thec–axis was weakened obviously by adding appropriate amount of LiOH、CaO or Mg(OH)2inthe strong alkaline mineralizers in the reaction system.
2、The ZnO crystal morphology could be controlled by adding appropriate amount ofmetal ions（Sb、Sn、In）in the strong alkaline mineralizer in the reaction system. The speedof growth of ZnO crystal along c–axis was weakened obviously compared with a–axis andb–axis by adding Sn or In ions. Large exposures of the positive polar face{0001} of ZnOcrystals is obtained.. Meanwhile, it exhibits good conduction properties. However, the the{0001} and {000} surfaces of ZnO crystal are not exposed in.
3、At the fill factor of35%of adding MnCl2、CoCl2.6H2O in the reaction system, theuniformly doped ZnO crystals were obtained with7mole%Mn and0.64-2.87mole%Cocontent after magnetic separation. SQUID test showed that the samples were mainlyparamagnetic in the uniformly doped ZnO crystals, and some Co single phase appearedsimultaneously.
4、In order to enhance the content of Co, more pressure-resistive reactor was used, andthe fill factor was enhanced to70%.Some CoO were added in the reaction system at the sametime. After magnetic separation, high content of Co, uniformly doped in ZnO crystals, wereobtained with the ratio of Co:Zn reaching10at%. The results showed that the samples weremainly paramagnetic.
5、The physical mechanisms of wurtzite ZnO crystal morphology were studied usingdensity functional theory. The atomistic structure, the energy band structure, and density ofstates of ZnO crystal were analyzed, and the aspect-graph of the equilibrium state of ZnOcrystal was obtained by using Ulf Theorem. The adsorption structure of metal atoms on thesurface of polar and semi-polar was set up. The adsorption energies of K、Na、Li、Ca、Mgatom, singly adsorbed or in mixture, at the truncated surfaces of O atoms located at thenegative face and negative cone face were obtained., The ZnO crystal morphology diagramafter adsorption was predicted. The physical mechanism of the hydrothermal synthesis of ZnOcrystal morphology was discussed from the atomic level. We believe that the surface energiesare directly correlated with the saturation of dangling bonds from the metal atoms in theadditive and the crystal morphology was affected in turn.
Innovations of this work:
1、the relationship between the growth of ZnO crystal and the mineralizing agent andmetal ions were clarified and technical routes of controlling ZnO crystal morphology underthe hydrothermal conditions were obtained.
2、 High concentrations of Mn/Co uniformly doped in the ZnO crystal underhydrothermal conditions were achieved and high qualities of ZnO crystals uniformly doped athigh concentrations were obtained. The results show that ZnO crystals doped high than7at%(10at%) of Mn（Co）do not show ferromagnetism.
3、The physical mechanisms of wurtzite ZnO crystal morphology synthesized byhydrothermal method were studied from the atomistic level using density functional theoryand the results are consistent with experiments.
引文
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