金属硼化物体系纳米材料的制备与性能
摘要
稀土六硼化物(RB6)由于特殊的结构使其具有一系列其它材料无法比拟的优良特性,比如功函数小、硬度大、熔点高、导电率高、热稳定性好、化学稳定强等。正是由于该材料具有良好的化学稳定性,用它制备的场发射器件性能稳定,使用寿命长,这是其具有广阔应用前景的重要原因之一,因此该系列材料广泛用于民用工业和国防工业。理论和实验表明金属硼化物纳米材料具有丰富的结构形态和优异的物理化学特性,但是稀土金属单质和硼单质都具有高熔点、高沸点的物理性质使得金属硼化物的合成比较困难。同时,如何方便、安全、低廉地制备大量、尺寸均匀、生长整齐、光滑且致密的稀土金属六硼化物和A182化合物的一维纳米材料,以及对它们性能的研究还比较少。
本论文采用化学气相沉积工艺,在不同催化剂(Ni(NO3)2、Cu(NO3)2或Au)的催化作用下制备了一系列稀土金属六硼化物和二硼化铝的纳米管和纳米线,用X射线粉末衍射、拉曼光谱、场发射扫描电镜、透射电镜、电子能谱等分析技术对所制备的纳米材料进行了表征,并探讨了其生长机制。
主要研究内容包括：
(1)通过稀土金属镧(La)粉末和三氯化硼(BC13)气体反应,硝酸镍(Ni(NO3)2)或金(Au)为催化剂,在氢氩混合气氛下,成功地得到了大面积、排列整齐、尺寸均匀、表面光滑的六硼化镧(LaB6)纳米管和纳米线。用此方法制备大量、均匀的LaB6纳米管的工作属于首创。X射线粉末衍射结果表明所制备的样品为简单立方结构的六硼化镧,扫描电镜和透射电镜结果显示所制备的纳米管和纳米线都具有单晶结构,结晶性好,表面光滑而致密。对不同反应温度、反应时间和反应气体流量等因素对LaB6纳米管和纳米线生长的影响进行了研究,并探讨了LaB6纳米管和纳米线的生长机制。
(2)首次分别用Ni(NO3)2或Au为催化剂,以金属钕(Nd)粉末、三氯化硼气体(BC13)作前驱体,采用CVD方法,在单晶Si片衬底上成功制备了大面积、尺寸均匀的NdB6纳米线。Ni(NO3)2催化法所制备的NdB6纳米线呈圆柱状,其长度超过20μm,直径大致有200nm、126nm、50nm等几个尺寸。高分辨透射和选区电子衍射分析结果显示,Ni(NO3)2催化法所制备的NdB6纳米线具有典型的孪晶结构。而Au催化生长的纳米线呈棱柱状的,其中有四棱柱状也有六棱柱状。在Ni(NO3)2或Au催化法制备NdB6纳米线的顶端都不同程度的观察到了金属颗粒,说明它们的生长过程是典型的VLS生长过程。
对自催化法(即不用任何催化剂,以金属Nd粉与BC13直接反应)在单晶Si片衬底得到的大面积、排列整齐、尺寸一致、表面光滑的NdB6纳米线的场发射测试结果显示,NdB6纳米线是一种性能优良的场发射材料。该工作属于首创。
(3)首次以金属镨(Pr)粉末、三氯化硼气体(BC13)作为前驱体,分别以Ni(NO3)2、 Cu(NO3)2或Au作为催化剂,在氢/氩混合气氛中反应,成功地制备了大面积、尺寸均匀的PrB6纳米线和纳米管。扫描电镜表明Ni(NO3)2或Cu(NO3)2作为催化剂所制备的PrB6纳米线长度超过20μm,直径约100nm。而Au作为催化剂制备出大量的PrB6纳米管,长度约1μm,直径约80～100nm,纳米管壁较薄约6.6nm,并且纳米管表面不光滑、不致密。
(4)以金属铝(A1)粉末和三氯化硼气体(BC13)反应,Ni(NO3)2或Au作为催化剂,采用CVD工艺在氢/氩混合气氛中,成功地制备了大面积且尺寸均匀的A182纳米线。该工作属于首创。X射线粉末衍射所得到的结果表明样品是六角结构的AIB2单相。Ni(NO3)2作为催化剂所制备AlB2纳米线,直径约200nm,长度约几微米,表面光滑；喷金一次所制备的AlB2纳米线在硅基片上纵横交错,长度可达几十微米,直径约50nm,表面光滑,无分支结构。而喷金两次所制备的AlB2纳米线在硅基片上呈现出大量的、尺寸均匀的、生长方向整齐排列的特征。纳米线的直径约500～600nm,长度约几个微米,表面光滑,且每根纳米线顶端都有与纳米线同样尺寸的金催化剂颗粒存在。我们发现,无论是Ni(NO3)2还是Au作催化所制备AlB2纳米线在高压电子束的照射下都有分解变质的现象,并且随着加速电压的增大照射电子的能量增高对A182纳米线晶格结构形成了破坏,由晶态变成非晶态。在实验结果的基础上,结合常规纳米材料合成工艺的生长机制,讨论了AlB2纳米线的生长机制。
Rare-earth metal hexaboredes (RB6) have excellent physical and chemical properties, such as low work function, high hardness, high melting point, high conductivity, high thermic stability, high chemical stability, respectively. It can be used as the field emission cathode materials for high stability and longer life equipment due to their excellent chemical stability. Therefore, the RB6materials have extensive applications in the civil and national defence industry. Theories and experiments results reveal that the metal borides have abundant structural and excellent physical and chemical properties. However, it is more difficult to synthesize the metal borides because of the high melting and boiling point of rare-earth metal and boron. Until now, the research on the inexpensively, safely and conveniently synthesis and properties of RB6nanostructural meterials with a large-scal, well-aligned, and smooth and dense on surface is not widely carried out. To our best knowledge, no results on the synthesis of AlB2one-dimentional nanometerials has been reported yet.
In this desertion, the RB6nanotubes and nanowires and AIB2nanowires were synthesised by chemical vapor deposition method under the assistance of diffirent catalysts (such as Ni(NO3)2, Cu(NO3)2or Au). The structure, morphology and field-emission properties were characterized using X-ray diffractometer (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and field-emission measurement system. The growth mechanism of these nanotubes and nanowires was discussed.
(1) Large-scale and uniform lanthanum hexaboredes (LaB6) nanotubes and nanowires have been successfully fabricated for the first time under the hydrogen and argon atmosphere, where lanthanum (La) powders and boron trichloride (BCl3) gas as the reactant and Ni(NO3)2or Au as the catalyst. The results of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM) indicate that the nanomaterials with smooth surfaces were single crystal lanthanum hexaboride with cubic structure. The preparation conditions of LaB6nanotubes and nanowires, such as reaction temperature, reaction time and the gas flow rate, were compared. The growth mechanism of LaB6nanotubes and nanowires was also discussed.
(2)The column-like neodymium hexaboredes (NdB6) nanowires have been successfully fabricated for the first time using the Ni(NO3)2as the catalyst. The XRD patterns confirm that a single phase NdB6can be obtained under our experimental procedure. The result of scanning electron microscopy (SEM) show that the surfaces of nanowires under the assistance of Ni(NO3)2catalysts are smooth and the distribution of the diameters of nanowires are200nm,126nm,50nm, respectively. The results of the high resolution transmission electron microscopy (HRTEM) and selected area electronic diffraction (SAED) images clearly reveal that the neodymium hexaboride adopt the twin crystal. However, if Au was used as catalyst, NdB6nanowires obtained here have the morphologies of quadrangular and hexagonal prism.
The Raman spectra and the field emission measurement were conducted for the first time with the neodymium hexaboride (NdB6) nanowires which has been fabricated using a catalysis-free method. The field emission of these one-dimensional NdB6nanowires shows that NdB6nanowires has the good performance for field emission.
(3) A large-scale single-crystalline PrB6nanotubes and nanowires can be obtained using Pr and BCl3as starting materials and Ni(NO3)2, Cu(NO3)2or Au as the catalysts. The results of scanning electron microscopy (SEM) images show that PrB6nanowires obtained using Ni(NO3)2and Cu(NO3)2as the catalysts have the lenght of more20μm and the diameters about100nm. A large number of PrB6nanotubes can be obtained when using Au as the catalyst. The length of PrB6nanotubes obtained here can reach more than one micrometers, and the diameter is in the range of80～100nm..
(4) Large-scale aluminum diboride (AIB2) nanowires have been successfully fabricated for the first time under the hydrogen and argon atmosphere, where aluminum (Al) powders and boron trichloride (BCl3) gas as the reactant and Ni(NO3)2or Au as the catalyst. The XRD patterns confirm that aluminum diboride obtained under our experimental procedure has hexagonal symmetry. The result of scanning electron microscopy (SEM) images show that the lenght of AlB2nanowires with smooth surface obtained using Ni(NO3)2as the catalyst can reach more than several micrometers and the diameters about200nm. The SEM images show that a large-scale, smooth and well-aligned AlB2nanowires were formed uniformly over the Si substrate when using Au as the catalyst. The AlB2nanowires have the length of several micronmeters with diameters in the range of500-600nm. The gold catalyst particles with same size as the diameters of AlB2nanowires can be observed on the top of each nanowire. HRTEM as well as the SAED resutls reveal that AlB2nanowires obtained in our experiments adopt single crystal structure, but it is unstable after exposing in air or under electron beam intensity. The growth mechanism dominated the AIB2nanowires growing process under this study was also discussed.
本论文采用化学气相沉积工艺,在不同催化剂(Ni(NO3)2、Cu(NO3)2或Au)的催化作用下制备了一系列稀土金属六硼化物和二硼化铝的纳米管和纳米线,用X射线粉末衍射、拉曼光谱、场发射扫描电镜、透射电镜、电子能谱等分析技术对所制备的纳米材料进行了表征,并探讨了其生长机制。
主要研究内容包括：
(1)通过稀土金属镧(La)粉末和三氯化硼(BC13)气体反应,硝酸镍(Ni(NO3)2)或金(Au)为催化剂,在氢氩混合气氛下,成功地得到了大面积、排列整齐、尺寸均匀、表面光滑的六硼化镧(LaB6)纳米管和纳米线。用此方法制备大量、均匀的LaB6纳米管的工作属于首创。X射线粉末衍射结果表明所制备的样品为简单立方结构的六硼化镧,扫描电镜和透射电镜结果显示所制备的纳米管和纳米线都具有单晶结构,结晶性好,表面光滑而致密。对不同反应温度、反应时间和反应气体流量等因素对LaB6纳米管和纳米线生长的影响进行了研究,并探讨了LaB6纳米管和纳米线的生长机制。
(2)首次分别用Ni(NO3)2或Au为催化剂,以金属钕(Nd)粉末、三氯化硼气体(BC13)作前驱体,采用CVD方法,在单晶Si片衬底上成功制备了大面积、尺寸均匀的NdB6纳米线。Ni(NO3)2催化法所制备的NdB6纳米线呈圆柱状,其长度超过20μm,直径大致有200nm、126nm、50nm等几个尺寸。高分辨透射和选区电子衍射分析结果显示,Ni(NO3)2催化法所制备的NdB6纳米线具有典型的孪晶结构。而Au催化生长的纳米线呈棱柱状的,其中有四棱柱状也有六棱柱状。在Ni(NO3)2或Au催化法制备NdB6纳米线的顶端都不同程度的观察到了金属颗粒,说明它们的生长过程是典型的VLS生长过程。
对自催化法(即不用任何催化剂,以金属Nd粉与BC13直接反应)在单晶Si片衬底得到的大面积、排列整齐、尺寸一致、表面光滑的NdB6纳米线的场发射测试结果显示,NdB6纳米线是一种性能优良的场发射材料。该工作属于首创。
(3)首次以金属镨(Pr)粉末、三氯化硼气体(BC13)作为前驱体,分别以Ni(NO3)2、 Cu(NO3)2或Au作为催化剂,在氢/氩混合气氛中反应,成功地制备了大面积、尺寸均匀的PrB6纳米线和纳米管。扫描电镜表明Ni(NO3)2或Cu(NO3)2作为催化剂所制备的PrB6纳米线长度超过20μm,直径约100nm。而Au作为催化剂制备出大量的PrB6纳米管,长度约1μm,直径约80～100nm,纳米管壁较薄约6.6nm,并且纳米管表面不光滑、不致密。
(4)以金属铝(A1)粉末和三氯化硼气体(BC13)反应,Ni(NO3)2或Au作为催化剂,采用CVD工艺在氢/氩混合气氛中,成功地制备了大面积且尺寸均匀的A182纳米线。该工作属于首创。X射线粉末衍射所得到的结果表明样品是六角结构的AIB2单相。Ni(NO3)2作为催化剂所制备AlB2纳米线,直径约200nm,长度约几微米,表面光滑；喷金一次所制备的AlB2纳米线在硅基片上纵横交错,长度可达几十微米,直径约50nm,表面光滑,无分支结构。而喷金两次所制备的AlB2纳米线在硅基片上呈现出大量的、尺寸均匀的、生长方向整齐排列的特征。纳米线的直径约500～600nm,长度约几个微米,表面光滑,且每根纳米线顶端都有与纳米线同样尺寸的金催化剂颗粒存在。我们发现,无论是Ni(NO3)2还是Au作催化所制备AlB2纳米线在高压电子束的照射下都有分解变质的现象,并且随着加速电压的增大照射电子的能量增高对A182纳米线晶格结构形成了破坏,由晶态变成非晶态。在实验结果的基础上,结合常规纳米材料合成工艺的生长机制,讨论了AlB2纳米线的生长机制。
Rare-earth metal hexaboredes (RB6) have excellent physical and chemical properties, such as low work function, high hardness, high melting point, high conductivity, high thermic stability, high chemical stability, respectively. It can be used as the field emission cathode materials for high stability and longer life equipment due to their excellent chemical stability. Therefore, the RB6materials have extensive applications in the civil and national defence industry. Theories and experiments results reveal that the metal borides have abundant structural and excellent physical and chemical properties. However, it is more difficult to synthesize the metal borides because of the high melting and boiling point of rare-earth metal and boron. Until now, the research on the inexpensively, safely and conveniently synthesis and properties of RB6nanostructural meterials with a large-scal, well-aligned, and smooth and dense on surface is not widely carried out. To our best knowledge, no results on the synthesis of AlB2one-dimentional nanometerials has been reported yet.
In this desertion, the RB6nanotubes and nanowires and AIB2nanowires were synthesised by chemical vapor deposition method under the assistance of diffirent catalysts (such as Ni(NO3)2, Cu(NO3)2or Au). The structure, morphology and field-emission properties were characterized using X-ray diffractometer (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and field-emission measurement system. The growth mechanism of these nanotubes and nanowires was discussed.
(1) Large-scale and uniform lanthanum hexaboredes (LaB6) nanotubes and nanowires have been successfully fabricated for the first time under the hydrogen and argon atmosphere, where lanthanum (La) powders and boron trichloride (BCl3) gas as the reactant and Ni(NO3)2or Au as the catalyst. The results of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM) indicate that the nanomaterials with smooth surfaces were single crystal lanthanum hexaboride with cubic structure. The preparation conditions of LaB6nanotubes and nanowires, such as reaction temperature, reaction time and the gas flow rate, were compared. The growth mechanism of LaB6nanotubes and nanowires was also discussed.
(2)The column-like neodymium hexaboredes (NdB6) nanowires have been successfully fabricated for the first time using the Ni(NO3)2as the catalyst. The XRD patterns confirm that a single phase NdB6can be obtained under our experimental procedure. The result of scanning electron microscopy (SEM) show that the surfaces of nanowires under the assistance of Ni(NO3)2catalysts are smooth and the distribution of the diameters of nanowires are200nm,126nm,50nm, respectively. The results of the high resolution transmission electron microscopy (HRTEM) and selected area electronic diffraction (SAED) images clearly reveal that the neodymium hexaboride adopt the twin crystal. However, if Au was used as catalyst, NdB6nanowires obtained here have the morphologies of quadrangular and hexagonal prism.
The Raman spectra and the field emission measurement were conducted for the first time with the neodymium hexaboride (NdB6) nanowires which has been fabricated using a catalysis-free method. The field emission of these one-dimensional NdB6nanowires shows that NdB6nanowires has the good performance for field emission.
(3) A large-scale single-crystalline PrB6nanotubes and nanowires can be obtained using Pr and BCl3as starting materials and Ni(NO3)2, Cu(NO3)2or Au as the catalysts. The results of scanning electron microscopy (SEM) images show that PrB6nanowires obtained using Ni(NO3)2and Cu(NO3)2as the catalysts have the lenght of more20μm and the diameters about100nm. A large number of PrB6nanotubes can be obtained when using Au as the catalyst. The length of PrB6nanotubes obtained here can reach more than one micrometers, and the diameter is in the range of80～100nm..
(4) Large-scale aluminum diboride (AIB2) nanowires have been successfully fabricated for the first time under the hydrogen and argon atmosphere, where aluminum (Al) powders and boron trichloride (BCl3) gas as the reactant and Ni(NO3)2or Au as the catalyst. The XRD patterns confirm that aluminum diboride obtained under our experimental procedure has hexagonal symmetry. The result of scanning electron microscopy (SEM) images show that the lenght of AlB2nanowires with smooth surface obtained using Ni(NO3)2as the catalyst can reach more than several micrometers and the diameters about200nm. The SEM images show that a large-scale, smooth and well-aligned AlB2nanowires were formed uniformly over the Si substrate when using Au as the catalyst. The AlB2nanowires have the length of several micronmeters with diameters in the range of500-600nm. The gold catalyst particles with same size as the diameters of AlB2nanowires can be observed on the top of each nanowire. HRTEM as well as the SAED resutls reveal that AlB2nanowires obtained in our experiments adopt single crystal structure, but it is unstable after exposing in air or under electron beam intensity. The growth mechanism dominated the AIB2nanowires growing process under this study was also discussed.
引文
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