非晶钯基纳米颗粒及热电材料的透射电镜研究

材料科学的发展与新材料的研发及材料表征技术的进步紧密相连，其中非晶材料与热电材料显示出在储能领域的应用潜力而备受关注。非晶的本质、结构及玻璃形成能力是非晶材料研究常关注的几个问题。单质金属非晶因可以为非晶基本问题的研究提供理想的样品体系，其制备研究一直被视为非晶领域皇冠上的明珠。然而，受限于单质非晶态的玻璃形成条件苛刻等因素，其形成液体的调控及玻璃转变过程的研究少有文献报道。透射电子显微镜作为分析固液相材料微观形貌与结构动态过程的有力工具，已逐渐成为从原子层次窥探材料的合成、相变过程的有效途径。

本论文主要利用透射电子显微镜，重点关注纳米单质非晶的合成、流变行为与电镜分析方法在热电晶体掺杂原子占位上的应用。首先通过合成新的单质金属非晶态，并分析其形成机制与结构演化行为，从微观甚至原子尺度窥探单质非晶形成能力不高的内在原因，为更多单质非晶的制备及相关探索提供有用的实验指导；其次，通过利用电子束在晶体样品中的通道效应拓宽热电材料异质原子的占位表征方法。具体研究内容和主要结果如下：

（1）通过将晶体前驱体Pd与非晶氮化硅组成的体系加热至1073 K，保温20分钟后冷却至室温，制备出了单质非晶Pd纳米颗粒。运用透射电镜成像，分析了非晶Pd颗粒的物相信息。利用电子能量损失谱结合三维原子探针技术，表征了获得的非晶Pd纳米颗粒的成分信息。通过原位透射电镜，分析了非晶Pd颗粒的形成机制。EELS和APT结果分析发现合成的非晶Pd纳米颗粒的纯度为99.35±0.23 at %。原位电镜观察发现在1073 K温度下晶体Pd熔化并与非晶氮化硅基底发生化学反应，在冷却过程中Si原子从PdSi液体中析出形成非晶Si。单质非晶Pd纳米颗粒的形成机制是冷却过程中Si与Pd的相分离。

（2）以非晶Pd颗粒为研究对象，利用电子衍射分析了非晶Pd的结构特征。利用透射电镜高分辨成像，观察了非晶颗粒在受电子束辐照时的晶化过程，研究了颗粒尺寸、电压、温度对晶化的影响，并根据实验结果建立了非晶晶化的自由能模型。通过运用高分辨TEM成像研究粒径为30 nm非晶颗粒，发现剂量率为6680 e/Å2s 的300 keV高能电子束辐照下非晶Pd颗粒逐渐晶化，达到平衡时形成非晶-晶体的核-壳结构，晶体壳层平衡厚度为5 nm。通过观察不同尺寸非晶Pd颗粒的结晶现象，发现半径小于7 nm的非晶Pd颗粒全部晶化，半径大于7 nm的非晶Pd颗粒形成核-壳结构。通过在不同温度下对非晶颗粒进行电子束辐照，发现温度对平衡晶体层的厚度具有调控作用。通过对颗粒的自由能进行分析，发现小颗粒完全晶化的原因源自于非晶自由能拖尾的交叠，大颗粒则随着自由能的降低出现晶化不完全的特征。

（3）以引入异质元素的方式，研究了Au元素添加对PdSi熔体的影响。通过把Au-Pd核-壳纳米棒作为催化剂前驱体放置于非晶氮化硅衬底上，并把该体系加热至1338 K，发现纳米棒会熔化并以液体形式在非晶氮化硅上移动，并在移动后端形成晶体纳米薄膜。透射电镜成像及谱学分析发现该晶体膜结构为β-Si3N4。通过原位电镜分析其形成机制，发现β-Si3N4的合成是一个固-液-固过程：Au-Pd核-壳结构在1338 K温度下形成AuPd熔体并与氮化硅发生反应，氮化硅中的Si原子被吸收进熔体中，熔体中Si原子达到过饱和后在熔体行进后侧析出并与N原子重新结合形成高稳定性的晶体相β-Si3N4。熔体运动的驱动力为非晶基底与晶体氮化硅之间的化学势差。同时，我们还在低温条件下利用EELS研究了非晶Pd颗粒的氢气吸附过程，发现非晶Pd颗粒在吸氢过程中不产生体积膨胀的现象，突出了非晶Pd作为新型储能材料的应用潜力。

（4）异质元素添加对材料稳定性的影响较大，拓展电镜研究方法去量化材料的异质原子含量是非常必要的。在最后一部分内容中，我们以热电晶体材料为模板，通过选取Mn掺杂的SnTe晶体为对象，利用基于通道效应的ALCHEMI技术表征了Mn原子在SnTe晶格中的占位信息，给出了Mn在各原子面上的占位比例。通过分析，发现Mn原子倾向于占据Sn位置。ALCHEMI技术的成功实施，拓展了热电材料等晶体材料中异质原子占位的表征方法。

本文研究结果对认识非晶相的形成机理，探索单质非晶的结构，揭示非晶的本质及玻璃形成能力的来源，从而开发出更多种类的单质非晶态具有重要意义。

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