纳米ZnO/金刚石复合结构的制备与性质的研究
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摘要
金刚石与氧化锌（ZnO）都是非常重要的宽带隙半导体材料，具有许多优异的化学和物理性质，两者组成的复合结构在半导体异质结、生物电极和太阳能电池等诸多领域具有非常重要的应用前景。本论文的研究内容如下：
1.用水热法在金刚石衬底上制备出硼（B）掺杂ZnO纳米棒，和未掺杂相比，硼掺杂后ZnO纳米棒直径增大，通过X射线衍射和第一性原理的计算得出硼原子掺杂位于ZnO晶格的八面体间隙中，掺硼后导致ZnO晶格常数增大和禁带宽度减小。同时制备出B-ZnO/金刚石异质结并进行光催化实验，通过降解活性黄15得出硼掺杂提高了光催化反应速率，并对其能带结构进行分析。
2.在制备ZnO纳米棒过程中，加入纳米金刚石并研究ZnO光致发光现象，纳米金刚石使ZnO纳米棒形成上端开口的现象，是由于纳米金刚石在ZnO纳米棒的生长过程中抑制其（001）方向生长，掺杂纳米金刚石的ZnO纳米棒光致发光紫外峰位于~380nm，同时有很强的可见发射峰中心在650nm，是由于纳米金刚石的加入增加ZnO纳米棒的氧缺陷，这种上端开口的ZnO纳米棒可应用在紫外传感器、场发射及其它光电装置。
3.在硼掺杂金刚石膜上生长铕（Eu）掺杂ZnO纳米棒，并在ZnO纳米棒的顶部发现具有尖端效应。制作铕掺杂ZnO纳米棒/金刚石异质结结构，研究其电学性能。实验表明，铕掺杂ZnO纳米棒/p型金刚石异质结具有良好的整流特性。
Diamond and zinc oxide (ZnO) are important wide band semiconductor materials.Recently, the combined structures of ZnO and diamond have been paid more attentiondue to their distinguished chemical and physical properties making it suitable for theapplications such as semiconductor heterojunction, biosensor electrodes and solar celldevices. The main content and innovation of this thesis are listed as following:
1．The boron (B)-doped zinc oxide nanorods (ZnO NRs) have been fabricated ondiamond substrate by hydrothermal technique. The mean diameter of the B-dopedZnO NRs is larger than that of the undoped NRs. The results of x-ray diffraction andfirst-principles calculations demonstrate that the boron atoms prefer to occupy theoctahedral interstice positions of ZnO, which lead to the lattice expansion and bandgap shrinkage. The rectifying B-doped ZnO NRs/p-diamond heterojunction structurehas been performed to degrade reactive yellow15solution, showing a highperformance photocatalysis. The photocatalysis mechanism based on the pnheterojunction is discussed.
2. The influence of introducing diamond powder on the growth andphotoluminescence of ZnO nanorods are discussed. The majority of ZnO nanorodsshow open-ended feature due to the addition of diamond powder in the reactionsolution. It is speculated that the diamond fell on the top of the growing ZnOnanorods would suppress the (001) growth at the localized positions to form theopen-ended nanorods. The photoluminescence spectra of the ZnO/diamond productsshow the band-edge-related UV emission of ZnO nanorods at~380nm, in addition toa broad visible band centered at about650nm, which may originate from theemissions related to defects in the open-ended ZnO nanorods and/or in the diamond. The open-ended ZnO nanorods and combined ZnO/diamond nanostructures would befavorable for potential applications including UV sensors, electron field emitter, andvarious photoelectric nanodevices.
3. The Eu doped zinc oxide nanorods (ZnO NRs) have been fabricated onB-diamond substrate. The tip electric field has been found on the top of ZnO. The Eudoped NRs/diamond heterojunctions are constructed and the electrical properties areexamined. The Eu doped ZnO NR/diamond heterojunctions show typical rectifyingcurrent-voltage behavior.
1.用水热法在金刚石衬底上制备出硼（B）掺杂ZnO纳米棒，和未掺杂相比，硼掺杂后ZnO纳米棒直径增大，通过X射线衍射和第一性原理的计算得出硼原子掺杂位于ZnO晶格的八面体间隙中，掺硼后导致ZnO晶格常数增大和禁带宽度减小。同时制备出B-ZnO/金刚石异质结并进行光催化实验，通过降解活性黄15得出硼掺杂提高了光催化反应速率，并对其能带结构进行分析。
2.在制备ZnO纳米棒过程中，加入纳米金刚石并研究ZnO光致发光现象，纳米金刚石使ZnO纳米棒形成上端开口的现象，是由于纳米金刚石在ZnO纳米棒的生长过程中抑制其（001）方向生长，掺杂纳米金刚石的ZnO纳米棒光致发光紫外峰位于~380nm，同时有很强的可见发射峰中心在650nm，是由于纳米金刚石的加入增加ZnO纳米棒的氧缺陷，这种上端开口的ZnO纳米棒可应用在紫外传感器、场发射及其它光电装置。
3.在硼掺杂金刚石膜上生长铕（Eu）掺杂ZnO纳米棒，并在ZnO纳米棒的顶部发现具有尖端效应。制作铕掺杂ZnO纳米棒/金刚石异质结结构，研究其电学性能。实验表明，铕掺杂ZnO纳米棒/p型金刚石异质结具有良好的整流特性。
Diamond and zinc oxide (ZnO) are important wide band semiconductor materials.Recently, the combined structures of ZnO and diamond have been paid more attentiondue to their distinguished chemical and physical properties making it suitable for theapplications such as semiconductor heterojunction, biosensor electrodes and solar celldevices. The main content and innovation of this thesis are listed as following:
1．The boron (B)-doped zinc oxide nanorods (ZnO NRs) have been fabricated ondiamond substrate by hydrothermal technique. The mean diameter of the B-dopedZnO NRs is larger than that of the undoped NRs. The results of x-ray diffraction andfirst-principles calculations demonstrate that the boron atoms prefer to occupy theoctahedral interstice positions of ZnO, which lead to the lattice expansion and bandgap shrinkage. The rectifying B-doped ZnO NRs/p-diamond heterojunction structurehas been performed to degrade reactive yellow15solution, showing a highperformance photocatalysis. The photocatalysis mechanism based on the pnheterojunction is discussed.
2. The influence of introducing diamond powder on the growth andphotoluminescence of ZnO nanorods are discussed. The majority of ZnO nanorodsshow open-ended feature due to the addition of diamond powder in the reactionsolution. It is speculated that the diamond fell on the top of the growing ZnOnanorods would suppress the (001) growth at the localized positions to form theopen-ended nanorods. The photoluminescence spectra of the ZnO/diamond productsshow the band-edge-related UV emission of ZnO nanorods at~380nm, in addition toa broad visible band centered at about650nm, which may originate from theemissions related to defects in the open-ended ZnO nanorods and/or in the diamond. The open-ended ZnO nanorods and combined ZnO/diamond nanostructures would befavorable for potential applications including UV sensors, electron field emitter, andvarious photoelectric nanodevices.
3. The Eu doped zinc oxide nanorods (ZnO NRs) have been fabricated onB-diamond substrate. The tip electric field has been found on the top of ZnO. The Eudoped NRs/diamond heterojunctions are constructed and the electrical properties areexamined. The Eu doped ZnO NR/diamond heterojunctions show typical rectifyingcurrent-voltage behavior.
引文
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