Bulk and Thin Film Synthesis of Compositionally Variant Entropy-stabilized Oxides

Sai Sivakumar; Elizabeth Zwier; Peter Benjamin Meisenheimer; John T. Heron

doi:10.3791/57746

JoVE Journal > Engineering

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Engineering

组分变熵稳定氧化物的体积和薄膜合成

Published: May 29, 2018

doi:

10.3791/57746

Sai Sivakumar*¹, Elizabeth Zwier*¹, Peter Benjamin Meisenheimer*¹, John T. Heron

¹Department of Materials Science and Engineering,University of Michigan

Summary

高质量的散装和薄膜 (Mg_{0.25 (1 x)}Co_x镍_{0.25 (1-x)}铜_{0.25 (1-x)}锌_{0.25 (1-x)}) O 和 (毫克_{0.25 (1 x)}Co_{0.25 (1 x)}镍_{0.25 (1 x)}铜_x锌_{0.25 (1-x)}) O 熵稳定氧化物的提出。

Abstract

这里, 我们提出了合成散装和薄膜多组分 (镁_{0.25 (1 x)}Co_x镍_{0.25 (1-x)}铜_{0.25 (1-x)}锌_{0.25 (1-x)}) O (Co 变体) 和 (毫克_{0.25 (1 x)}Co_{0.25 (1-x)}镍_{0.25 (1 x)}铜_x锌_{0.25 (1-x)}) O (cu 变体) 熵稳定氧化物。相纯和化学均质 (毫克_{0.25 (1 x)}Co_x镍_{0.25 (1-x)}铜_{0.25 (1 x)}锌_{0.25 (1 x)}) O (x = 0.20, 0.27、0.33) 和 (毫克_{0.25 (1 x)}Co_{0.25 (1 x)}镍_{0.25 (1 x)}Cu_x锌_{0.25 (1 x)}) O (x = 0.11, 0.27) 陶瓷颗粒被合成并用于沉积超高质量, 相纯, 单晶薄膜的靶化学计量。本文介绍了用脉冲激光沉积 (001) 取向氧化镁基片沉积光滑、化学均匀、熵稳定氧化物薄膜的详细方法。用 X 射线衍射法确定了大块薄膜材料的相和结晶度。通过 x 射线光电子能谱和能量色散 x 射线光谱法证实了成分和化学均匀性。用扫描探针显微镜测量薄膜的表面形貌。合成高质量, 单晶, 熵稳定的氧化物薄膜, 使研究的界面, 大小, 应变和无序影响的性质, 这一新类高无序氧化物材料。

Introduction

自2004年发现高熵金属合金以来, 高熵材料引起了极大的兴趣, 原因是硬度增加了¹^,²^,³, 韧性⁴^,⁵和耐腐蚀性³^,⁶。最近发现了高熵氧化物⁷^、⁸和硼化^物9, 为物质爱好者开辟了一个大操场。特别是氧化物可以显示有用和动态功能属性, 如铁电^性10、^磁电¹¹^、12^、热电 13^{和超导14。}.熵稳定氧化物 (ESOs) 最近被证明具有有趣的, 组分依赖功能属性¹⁵^,¹⁶, 尽管有重大的障碍, 使这种新的材料类特别令人兴奋。

熵稳定材料是化学上均匀的, 多组分 (通常有五个或更多组分), 单相材料在那里构型熵贡献 () 对吉布斯自由能 () 是重要的足以推动形成单相固体溶液¹⁷。合成多组分 ESOs, 其中阳离子构型紊乱是在阳离子点观察, 需要精确控制的组成, 温度, 沉积速率, 淬火速率和淬火温度⁷^,¹⁶.该方法旨在使从业者能够合成相纯和化学均质的熵稳定氧化物陶瓷小球和相纯, 单晶, 平面薄膜的期望化学计量。可以用大于90% 的理论密度合成大块材料, 从而对电子、磁性和结构特性进行研究, 或用作薄膜物理气相沉积 (PVD) 技术的来源。由于在这里考虑的熵稳定氧化物有五阳离子, 薄膜 PVD 技术, 采用五来源, 如分子束外延 (外延) 或共溅射, 将提出的挑战, 沉积化学均匀薄膜流量漂移。该协议的结果是在化学上均质, 单晶, 扁平 (方根) 粗糙度的 0.15 nm 的熵稳定氧化物薄膜从单一的材料来源, 这表明具有名义化学成分。该薄膜合成协议可通过包含原位电子或光学特性技术来增强, 用于实时监测合成和精制质量控制。这种方法的预期限制来源于激光能量漂移, 这可能会限制高质量薄膜厚度低于1微米。

尽管薄膜氧化物材料的生长和表征有显著的进步¹⁰^,¹⁸^,¹⁹^,²⁰^,²¹, 立体与氧化物中的电子结构可以导致在最终材料中产生显著的差异, 这是由看似微不足道的方法论差异引起的。此外, 多组分熵稳定氧化物的领域是相当新生的, 仅二个当前报告薄膜综合在文献⁷^,¹⁶。ESOs 对这个过程特别好, 规避了化学气相沉积和分子束外延所带来的挑战。在这里, 我们提供了一个详细的综合协议的散装和薄膜 ESOs (图 1), 以尽量减少材料处理困难, 意外的财产变化, 并提高发现在外地的加速。

Protocol

注意: 佩戴必要的个人防护设备 (PPE), 包括近趾鞋、全长长裤、安全眼镜、微粒过滤面罩、实验室大衣和手套, 因为氧化物粉末会对皮肤接触刺激和眼部接触刺激产生风险。在开始之前, 请查阅所有相关的材料安全数据表以补充 PPE 要求。应使用工程控制 (如油烟机) 进行综合。 1. 熵稳定氧化物的批量合成组成氧化物粉体的质量计算通过将所需体积?…

Representative Results

所制备的 X 射线衍射 (XRD) 谱 (Mg0.25 (1 x)Cox镍0.25 (1-x)Cu0.25 (1 x)锌0.25 (1-x)) O (x = 0.20, 0.27, 0.33) 和 (毫克0.25 (1 x)Co0.25 (1-x)镍0.25 (1-x)Cux锌0.25 (1 x)) O (x = 0.11, 0.27) 散装陶瓷 (图 4a) 和沉积薄膜 (图 4b)。这些数据表明, 样品是单相的, 可用于测定晶格常数、?…

Discussion

我们已经描述并显示了一个合成散装和高质量的协议, 单晶薄膜 (镁_{0.25 (1 x)}Co_x镍_{0.25 (1 x)}铜_{0.25 (1 x)}锌_{0.25 (1 x)}) O (x = 0.20, 0.27、0.33) 和 (Mg_{0.25 (1-x)}Co_{0.25 (1 x)}Ni_{0.25 (1 x)}铜_x锌_{0.25 (1 x)}) O (x = 0.11, 0.27) 熵稳定氧化物。我们期望这些合成技术适用于广泛的熵稳定氧化物组成, 更多的发现, 在发展和扩大的领域。此外, 组分变化的熵?…

Disclosures

The authors have nothing to disclose.

Acknowledgements

这项工作是由国家科学基金会资助的一部分。DMR-0420785 (XPS)。我们感谢密歇根大学的密歇根材料鉴定中心 (MC)², 为其提供 XPS 和密歇根大学 Van Vlack 实验室的 XRD。我们还要感谢托马斯. Kratofil 对散装材料的准备工作的协助。

Materials

MAGNESIUM OXIDE 99.95%	Fisher	AA1468422
COBALT(II) OXIDE, 99.995%	Fisher	AA4435414
NICKEL(II) OXIDE 99.998%	Fisher	AA1081914
COPPER(II) OXIDE 99.995%	Fisher	AA1070014
ZINC OXIDE 99.99%	Fisher	AA8781230
TRICHLROETHLENE SEMICNDTR 9	Fisher	AA39744K7
ACETONE SEMICNDTR GRD 99.5%	Fisher	AA19392K7
2-PROPANOL ACS 99.5%	Fisher	A416S4
Mineral oil, pure	Acros Organics	AC415080010
alumina crucible	MTI Corporation	eq-ca-l50w40h20
ZIRCONIA (YSZ) GRINDING MEDIA	Inframat Advanced Materials	4039GM-S010
SiC paper 320/600/800/1200	South Bay Technology	SDA08032-25
MgO (100) substrate, 5x5x0.5 mm, 1SP	MTI Corporation	MGa050505S1
OXYGEN COMPRESSED ULTRA HIGH PURITY GRADE, 99.999%	Cryogenic Gases	OXYUHP
NITROGEN COMPRESSED EXTRA DRY GRADE	Cryogenic Gases	NITEX

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Sivakumar, S., Zwier, E., Meisenheimer, P. B., Heron, J. T. Bulk and Thin Film Synthesis of Compositionally Variant Entropy-stabilized Oxides. J. Vis. Exp. (135), e57746, doi:10.3791/57746 (2018).