Name: performing in situ closed-cell gas reactions in the transmission electron microscope
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这项研究主要由橡树岭国家实验室（ORNL）的实验室指导研究与开发计划赞助，该项目由UT-Battelle有限责任公司管理，为美国能源部（DOE）提供。将水蒸气引入原位气体电池的部分开发由美国能源部、能源效率和可再生能源办公室、生物能源技术办公室赞助，根据DE-AC05-00OR22725（ORNL）与UT-Battle、LLC签订的合同，并与能源材料网络（EMN）成员生物能源化学催化联盟（ChemCatBio）联盟合作。这项工作部分由国家可再生能源实验室编写，该实验室由可持续能源联盟有限责任公司根据第1号合同为美国能源部运营。德 AC36-08GO28308。部分显微镜是在纳米相材料科学中心（CNMS）进行的，该中心是能源部科学用户设施办公室。原位STEM 功能的早期开发由美国能源部车辆技术办公室的推进材料计划赞助。 我们感谢普罗托奇普斯公司的约翰·达米亚诺博士进行了有益的技术讨论。作者感谢罗斯玛丽·沃克和卡塞·克拉普，ORNL制作团队，对电影制作的支持。本文中表达的观点不一定代表美国国家机关或美国政府的观点。美国政府保留并允许出版商接受该文章进行出版，承认美国政府保留非排他性、付费、不可撤销的全球许可证，用于出版或复制本作品的出版形式，或允许他人为美国政府目的出版或复制该作品。

1. 电子芯片制备
<ol><li>通过从胶体溶液（图2A）滴铸直接沉积粉末。<ol>
<li>如果粉末颗粒聚合物过大，则粉碎粉末。使用小型迫击炮和害虫（碎聚合物应<5 μm大小）来做到这一点。将少量（例如，约0.005毫克，经验确定的量）混合在溶剂的2mL（如异丙酚或乙醇）中。</li>
		<li>将混合物索尼酸约5分钟，以创建胶体悬架。</li>
		<li>将电子芯片放在电子芯片保留夹具上。使用 0.5-2...

<ol>
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在目前的工作中，演示了在有或没有水蒸气的情况下 进行原位 STEM 反应的方法。协议中的关键步骤是电子芯片的准备和在加载过程中保持其完整性。该技术的局限性是（a） 标本大小及其几何形状，以适应配对 （MEMS） 基硅微芯片设备之间的名义 5-μm 间隙，以及 （b） 水蒸气实验中使用的总压力，因为总压力最高取决于水蒸气6的数量。这种方法对现有方法的意义在于，?...

需要获得关于材料在反应性气体暴露和高温下如何经历结构和化学变化的详细信息。专门开发了原位闭电池气体反应 （CCGR） 扫描传输电子显微镜 （STEM），以研究各种材料系统（例如， 催化剂、结构材料、碳纳米管等）在受到高温、不同的气态环境以及从真空到全大气压力的压力时，1、2、3、4、5、6、7、8、9、10、11、12。这种方法在几种情况下是有益的，例如， 加速开发对一些工业转化过程很重要的下一代催化剂，例如乙醇的单步转换 丁烯在Ag-ZrO2/SiO213，催化剂的减氧反应和氢进化反应在燃料电池应用14，15，催化CO2氢化16，我 甲醇脱氢到甲醛或脱水到二甲基乙醚，使用金属催化剂或多壁碳纳米管在甲醇转换反应中存在氧气17。这种原位技术最近应用于催化研究1、2、7、8、10、11、12、18、19、20、21、22，为催化剂动态形状变化10、11、23、面7、增长和移动性8、20、24提供了新的见解。此外，原位CCGR-STEM可用于研究暴露在恶劣环境中的结构材料的高温氧化行为，从燃气轮机发动机到下一代裂变和聚变反应堆，其中不仅强度、断裂韧性、焊接性或辐射性很重要，而且高温氧化电阻25、26、27、28、29。针对结构合金，原位CCGR-STEM实验允许在降低条件下动态跟踪扩散诱导的颗粒边界迁移，并在高温下测量氧化动力学5、6、30。在CCGR技术最近发展之前的几十年里，使用专用的环境TEM（E-TEM）进行了原位气体反应研究。电子-TEM和CCGR-STEM的详细比较之前已经讨论了10：因此，在目前的工作中，没有进一步讨论E-TEM功能。
在这项工作中，使用了一个商业可用的系统（材料表），包括计算机控制的歧管（气体输送系统）和专门设计的CCGR TEM支架，利用一对基于微机电（MEMS）的硅微芯片设备（如垫片和"E芯片"加热器（材料表）。每个电子芯片都支持无定形的电子透明 SixNy膜。垫片具有 50 nm 厚的 SixNy膜，具有 300 x 300 μm2的查看区域和 5μm 厚环氧树脂光分辨率 （SU-8） "间隔器"联系人，这些接触被微晶化，以提供气体流动路径，并在两个配对微芯片（图 1A）之间保持物理偏移。部分电子芯片覆盖低导电性~100纳米SiC陶瓷膜;膜有一个3×2阵列的8μm直径蚀刻孔重叠约30纳米厚无定形SixNy膜（SixNy查看区）（图1A和图2D），通过它记录图像。电子芯片具有标本支持和加热器6的双重作用。Au 接触被微晶化到 E 芯片上，以便对 SiC 膜进行电阻加热。每个电子芯片都使用红外辐射（IR）成像方法（材料表）2校准，并已证明准确到±5%31以内。温度校准独立于气体组成和压力，从而在任何选定的气体条件下对反应温度进行独立控制。薄膜加热器的好处是，温度可达1，000°C，可在毫秒内达到。为了执行反应，E 芯片放置在间隔器芯片的顶部，创建封闭细胞"三明治"，将标本周围的环境与 TEM 柱的高真空隔离开来。此设置的优点是，反应可以从低压到大气压力（760 托尔）与单一或混合气体和静态或流动条件下执行。MEMS 设备使用夹子（图1B）固定，允许将支架插入客观透镜杆片的毫米大小间隙内，插入偏差校正的 S/TEM 仪器 （材料表） （图 1C）中。现代原位S/TEM 支架包括连接到外部不锈钢管的集成微流管（毛细管），后者又连接到气体输送系统（多倍）。电子控制系统允许反应气体通过气体单元进行控制的输送和流动。气体流量和温度由制造商（材料表）10，32提供的基于工作流程的定制软件包操作。该软件控制着三条气体输入线、两个内部实验气体输送罐和一个接收罐，用于在实验期间从电池返回的气体流量（图1D）。
由于材料的变异性及其成形因子，我们首先关注电子芯片上的几种标本沉积方法，然后勾勒出 在原地/操作实验中 进行控制温度、气体混合和流动的定量协议。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Atmosphere Clarity Software</td>
			<td>Protochips</td>
			<td>6.5.14</td>
			<td></td>
		</tr>
		<tr>
			<td>Atmosphere Large Heating E-chips, 300 x 300 window, no spacer</td>
			<td>Protochips</td>
			<td>EAT-33AA-10</td>
			<td>microchip device</td>
		</tr>
		<tr>
			<td>Atmosphere Small E-chips, 300 x 300 micron window, 5 micron SU-8 spacer</td>
			<td>Protochips</td>
			<td>EAB-33W-10</td>
			<td>microchip device</td>
		</tr>
		<tr>
			<td>JEOL 2200FS</td>
			<td>JEOL</td>
			<td></td>
			<td>microscope</td>
		</tr>
		<tr>
			<td>M-bond 610</td>
			<td>Electron Microscopy Sciences</td>
			<td>50410-30</td>
			<td>cyanoacrylate (CA) glue</td>
		</tr>
		<tr>
			<td>Mikron M9103 IR camera</td>
			<td>Micron</td>
			<td></td>
			<td>This is used by Protochips/ not available</td>
		</tr>
		<tr>
			<td>Protochips &#8220;Fusion&#8221; E-chips</td>
			<td>Protochips</td>
			<td></td>
			<td>spacer chip with removed SixNy membrane</td>
		</tr>
		<tr>
			<td>Protochips Atmosphere 200</td>
			<td>Protochips</td>
			<td>prototype</td>
			<td>software</td>
		</tr>
		<tr>
			<td>Residual Gas Analyzer R100 (RGA)</td>
			<td>Stanford Research Systems</td>
			<td>R100 SRS</td>
			<td></td>
		</tr>
	</tbody>
</table>

performing in situ closed-cell gas reactions in the transmission electron microscope

原位电子显微镜研究的气体反应可用于捕捉材料的实时形态和微化学转化，其长度可缩小到原子水平。使用（扫描）传输电子显微镜 （STEM） 进行的原位闭电池气体反应 （CCGR） 研究可以分离和识别局部动态反应，这些反应使用其他特征技术进行捕获极具挑战性。对于这些实验，我们使用了使用基于微机电系统 （MEMS） 的加热微芯片（以下简称"E 芯片"）的 CCGR 支架。此处描述的实验协议详细说明了在反常校正STEM 中在干燥和潮湿气体中执行原位气体反应的方法。这种方法在许多不同的材料系统中具有相关性，例如在大气压力下和存在各种有水蒸气或没有水蒸气的气体时，对结构材料进行催化和高温氧化。在这里，针对各种材料形式因素介绍了几个样品制备方法。在反应过程中，通过残余气体分析仪（RGA）系统获得的质谱，无论有没有水蒸气，进一步验证了反应期间的气体暴露条件。因此，将 RGA 与原位CCGR-STEM 系统集成，可以提供关键见解，将气体组成与反应过程中材料的动态表面演化联系起来。使用这种方法的原位/操作学研究允许对在特定环境条件下（时间、温度、气体、压力）、实时和高空间分辨率发生的基本反应机制和动力学进行详细调查。

基于 MEMS 的闭电池气体反应标本： 通过胶体溶液和面膜的滴铸直接沉积粉末 根据要研究的材料，有许多不同的方法来准备电子芯片 的原位/操作 CCGR-STEM实验。为催化研究准备气体电池通常需要从胶体液体悬架（图2A）或直接从干粉本身（图2B）将催化剂纳米粒子分散到E芯片上。对于较粗的粉末，可能需要粉碎颗粒?...

Watch this Scientific Journal Video about Performing In Situ Closed-Cell Gas Reactions in the Transmission Electron Microscope at JoVE.com

Performing In Situ Closed-Cell Gas Reactions in the Transmission Electron Microscope

在这里，我们提出了一个协议，进行 原位 TEM闭电池气体反应实验，同时详细说明几个常用的样品制备方法。

在传输电子显微镜中执行 原位 闭电池气体反应

Gas reactions studied by in situ electron microscopy can be used to capture the real-time morphological and microchemical transformations of materials at ...

最近，我们分析了某些测试前后的材料。然而，需要获得关于材料在高温下如何在侵略性环境中发生结构和化学变化的详细信息。现场闭电池气体反应、CCGR、扫描传输电镜是专门为此开发的。研究气体环境中高温下的动态变化，在催化剂、结构材料、碳纳米管等多种材料系统中达到全大气压力。此外，这些反应可以在不同的长度尺度上进行研究，从微米到原子尺度水平不等。这一点非常重要，因为在较低的放大倍率下，我们可以学到很多关于整体系统行为和提取动能信息的信息。在原子尺度水平上，我们可以了解在表面发生的反应机制和动力学，以及特定于部位的界面。这是真正了不起的，获得原子分辨率图像在大气压力下，它不能真正做到任何实验技术。该协议强调如何使用原位电镜进行原位闭电池气体反应。它还突出了样品准备及其对不同材料的挑战。通过胶体溶液的滴铸直接沉积粉末。如果粉末颗粒过大，则粉碎粉末。混合少量粉末和两毫升溶剂。数量由实验决定。声波溶液五分钟，以创建胶体悬架。将电子芯片放在电子芯片保留夹具上。使用微型移液器将悬架直接投射到 E 芯片上。在观看时，用吸水纸点清洁黄金接触，然后投射立体显微镜。通过面罩直接沉积粉末。在电子芯片固定固定装置上放置新的清洁电子芯片。使用和掩蔽并直接将其放置在夹具内的电子芯片上。使用顶部板在夹具内将新的清洁电子芯片和面罩夹在一起。使用铲子直接将少量粉末通过面膜存放在新的清洁电子芯片的氮化硅膜上。轻轻振动夹具，将颗粒摇到电子芯片上。这可以通过声波装置和将夹具放入干烧嘴中来完成。甩掉多余的粉末，拆解系统，检查粉末在电子芯片上的位置。通过电子束蒸发、离子或磁子溅射来沉积方法。使用带氮化硅膜和氮化硅微孔 TEM 窗口的垫片创建图案面膜。根据制造商的建议，使用氰酸酯胶水将氮化硅微孔 TEM 窗口面朝下连接到 50 乘 250 微米开口处。然后重复该程序，根据需要为电子芯片准备尽可能多的图案面罩。在电子芯片夹具上放置新的清洁电子芯片。将图案面膜放在电子芯片上。盖住顶部板并夹住它。使用电子束蒸发、离子溅射或磁子溅沉积技术。拆解系统并使用沉积材料检查电子芯片。聚焦离子束或 FIB 铣削。使用 FIB 准备 TEM 跛脚。将 TEM 拉梅拉放在电子芯片上。确保通过将样品连接到电子芯片，您不会损坏氮化硅膜。编制CCGR-TEM支架。下载所需的校准文件。检查电子芯片的阻力。测量碳化硅加热器的电阻，以确保其处于CCGR制造商提供的特定电子芯片校准的电阻范围内。从支架顶部取下夹子。使用吸电纸点或压缩空气清洁 CCGR-TEM 支架的尖端，确保 O 环树林上没有残留的碎屑。将垫片放入 CCGR-TEM 支架中。放置电子芯片，加热器接触器与电气接触器有适当的连接，并带有支架上的弹性电缆。然后扭矩设置螺丝。组装CCGR-TEM支架后，再次测量碳化硅加热器的电阻，以确保其处于CCGR制造商提供的特定电子芯片校准的电阻范围内。准备实验设置。无论是否连接支架，在夜间烘烤和泵送系统。加载支架并连接管子。对于实验，用惰性气体泵送和清除系统。例如，两次从 100 托尔到 0.5 托尔。预制最终泵，从 100 托尔清除到 0.001 托尔。残余气体分析仪。在泵和清除过程中，打开 RGA 系统加热灯丝。将 RGA 与茎上的原位封闭细胞气体反应器系统集成，提供关键测量结果，将气体组成与反应过程中材料的动态表面演化联系起来。连续气体监测对于对混合气体的催化剂和结构材料或交替气体和压力进行反应至关重要，尤其是当水蒸气被纳入气体混合物时。将净化气体连接到 VDS 上，并将操纵杆旋钮连接到排气口，然后转向公园位置。通过流动惰性气体三次或直到没有更多的液体存在，对VDS施加压力。将旋钮转到停车位置，并将 VDS 连接到歧管上。转动旋钮以填充位置，然后删除清除气体线。在气体控制软件中将蒸汽压力设置为 18.7 托尔。泵送VDS真空，这是0.1托尔。将 VDS 装满水，通过注射器和管子填充 2 毫米。请注意，如果需要更高的纯度蒸汽，则需要额外的清除步骤。运行反应。确保所有的气体都连接到歧管。使用命名下的大气软件，为反应设置正确的气体并保存行文件。在设置电子芯片时，为电子芯片选择正确的校准文件并运行校准。在泵下和清除下，请参阅实验设置的准备。在气体控制下，选择气体成分。在温度下，选择加热速率和目标温度。开始实验。开始流动气体。开始成像。记录气体成分。代表性结果。原位 CCGR-STEM 结果的示例。明亮的场 STEM 图像显示了铂纳米粒子在钛支流暴露在水蒸气中的表面演变的一个例子。铂粒子的结构变化表明，在监测气体成分时，结构会重新排列，这与小形状变化有关。结束实验。关闭温度。停止流动气体。结束会话。总结。例如，CCGR-STEM 有利于加速开发耐久性高的下一代催化剂，这对许多催化转化过程非常重要，例如催化快速热解单步将乙醇转换为 N-丁烷以及喷气燃料或 CO2 氢化等。此外，CCGR-STEM还可用于研究侵略性环境中结构材料的高温氧化行为，模仿材料的行为，例如，与燃气轮机发动机环境或下一代裂变或核聚变反应堆类似。

Research

JoVE Journal

Engineering

Performing In Situ Closed-Cell Gas Reactions in the Transmission Electron Microscope

Revealing Dynamic Processes of Materials in Liquids Using Liquid Cell Transmission Electron Microscopy

在液体中使用液体池透射电子显微镜揭示材料的动态过程

The recent development for in situ transmission electron microscopy, which allows imaging through liquids with high spatial resolution, has attracted ...

科研

工程学

In Situ Time-dependent Dielectric Breakdown in the Transmission Electron Microscope: A Possibility to Understand the Failure Mechanism in Microelectronic Devices

In Situ Time-dependent Dielectric Breakdown in the Transmission Electron Microscope: A Possibility to Understand the Failure Mechanism in Microelectronic Devices

在透射电子显微镜原位时间相关的介质击穿：一种可能性，了解微电子器件的失效机理

The time-dependent dielectric breakdown (TDDB) in on-chip interconnect stacks is one of the most critical failure mechanisms for microelectronic devices. ...

Comprehensive Characterization of Extended Defects in Semiconductor Materials by a Scanning Electron Microscope

通过扫描电子显微镜在半导体材料的扩展缺陷的全面表征

Extended defects such as dislocations and grain boundaries have a strong influence on the performance of microelectronic devices and on other applications ...

Studying Dynamic Processes of Nano-sized Objects in Liquid using Scanning Transmission Electron Microscopy

使用扫描透射电子显微镜研究纳米大小的物体的动态过程中的液体

Samples fully embedded in liquid can be studied at a nanoscale spatial resolution with Scanning Transmission Electron Microscopy (STEM) using a ...

Characterization of Ultra-fine Grained and Nanocrystalline Materials Using Transmission Kikuchi Diffraction

超细晶和纳米晶材料的表征采用透射菊池衍射

One of the challenges in microstructure analysis nowadays resides in the reliable and accurate characterization of ultra-fine grained (UFG) and ...

A Method for Obtaining Serial Ultrathin Sections of Microorganisms in Transmission Electron Microscopy

一种在透射电镜中获取微生物连续超薄切片的方法

Observing cells and cell components in three dimensions at high magnification in transmission electron microscopy requires preparing serial ultrathin ...

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

结构转换的原位和原位研究方法: 金属玻璃结晶的实例

We demonstrate the use of two nuclear-based analytical methods that can follow the modifications of microstructural arrangement of iron-based metallic ...

Scalable Quantum Integrated Circuits on Superconducting Two-Dimensional Electron Gas Platform

超导二维电子气体平台上的可扩展量子集成电路

To form a coherent quantum transport in hybrid superconductor-semiconductor (S-Sm) junctions, the formation of a homogeneous and barrier-free interface ...

Single-Digit Nanometer Electron-Beam Lithography with an Aberration-Corrected Scanning Transmission Electron Microscope

用畸变校正扫描透射电镜进行单数字纳米电子束光刻

We demonstrate extension of electron-beam lithography using conventional resists and pattern transfer processes to single-digit nanometer dimensions by ...

在传输电子显微镜中执行 原位 闭电池气体反应

在传输电子显微镜中执行原位闭电池气体反应