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(This page is in Chinese only.  For details, please kindly contact our representative.)   锂离子电池（LIB）作为一种重要的储能技术，已经广泛应用于便携式电子设备、电动汽车和电网储能等领域。然而，锂离子电池技术方面仍然存在诸多挑战，特别是现有的锂离子电池电极材料在极端条件（如高低温环境）下不良的快充特性和安全隐患严重阻碍了其在电动汽车领域中的进一步发展。值得注意的是，如果从LIB的外部或内部加热或冷却来改变工作温度，不仅会增加系统的复杂性，还会降低能源效率和能量/功率密度。因此，研发一种适用于变温的新型负极材料以及深入理解其在充放电过程中的电化学变化是当前研究的重点。   X射线光电子能谱仪（XPS）作为表面分析领域重要的大型科学仪器，可以提供高表面灵敏（<10 nm）和高空间分辨(<10 um)的元素组分和化学态解析能力，还可以对膜层结构提供深度分析。因此XPS已经广泛用于锂电池的研究中，例如锂电池的负极材料、正极材料、隔膜和电解质界面等。   青岛大学能源与环境材料研究院（Institute of Materials for Energy and Environment）主要致力于二次电池（锂离子电池、锂硫电池、锂空气电池和钠离子电池等）、超级电容器、燃料电池及新型功能材料等研究。为了对电池开展深入研究，该研究院采购了PHI XPS 设备（PHI 5000 Versaprobe III）。在PHI 公司售后和应用团队的支持下，该设备一直保持着出色的运行状态，为相关研究提供了大量重要实验数据，至今已在Advanced Science、Advance Energy Materials、ACS Energy Letters、Carbon及Chemical Engineering Journal等国内外顶级期刊发表学术文章累计达70余篇。[1]   图1. 青岛大学能源与环境材料研究院PHI XPS设备。   下面我们来欣赏一下青岛大学能源与环境材料研究院利用PHI XPS所发表的研究成果：   研究成果一 通过固态反应法合成了一种镍铌氧化物（Ni2Nb34O87）电极，并研究了其在不同温度下（−10、25和60 ℃）的锂离子存储性能。   图2. Ni2Nb34O87的晶体结构。   为探究样品在充放电过程中发生的化学反应，在本项工作中利用XPS分析技术获取样品中Nb元素的化学状态。XPS结果表明原始样品的Nb为Nb5+；在0.8 V放电锂化过程中，部分Nb5+被还原为Nb4+和Nb3+；然而，在3.0 V充电去锂化过程中，Nb元素全部被氧化为Nb5+。研究结果证明了Nb4+/Nb5+和Nb3+/Nb4+可以发生可逆的氧化还原反应，该电极具有良好的循环稳定性。相关研究成果发表在《Advance Energy Materials》期刊。[2]   图3. Ni2Nb34O87在（I）原始、（II）0.8 V放电和（III）3.0 V充电状态下Nb 3d的XPS图谱。   研究成果二 通过静电纺丝及分步煅烧法合成部分还原的TiNb24O62（PR-TNO）纤维，利用XPS进一步揭示PR-TNO的工作机理。   图4. TNO和PR-TNO的制备过程。   首先，XPS结果证实了Nb4+/Nb5+和Nb3+/Nb4+的高度可逆氧化还原反应。此外，PR-TNO中部分还原的Ti3+和Nb4+增强了电子导电性。因此在−20℃下，锂离子电池达到了较大的可逆容量。相关研究成果发表在《Advanced Science》期刊。[3]   图5. PR-TNO在（I）原始、（II）0.8 V放电和（III）3.0 V充电状态下Nb 3d的XPS图谱。   ULVAC-PHI作为全球技术领先的表面分析仪器厂商，一直致力于提供最先进的技术和最优质的服务，并期盼与我们的用户共同推动表面分析技术的应用和发展，以及提升大型科学仪器的“创新服务产出”水平。   参考文献： [1] https://imee.qdu.edu.cn/info/1046/2477.htm [2] https://doi.org/10.1002/aenm.202102550 [3] https://doi.org/10.1002/advs.202105119

(This page is in Chinese only.  For details, please kindly contact our representative.)   1.　简介 扫描俄歇纳米探针，又称俄歇电子能谱（Auger Electron Spectroscopy，简称AES）是一种表面科学和材料科学的分析技术。根据分析俄歇电子的基本特性得到材料表面元素成分（部分化学态）定性或定量信息。可以对纳米级形貌进行观察和成分表征。近年来，随着超高真空和能谱检测技术的发展，扫描俄歇纳米探针作为一种极为有效的表面分析工具，为探索和研究表面现象的理论和工艺问题，做出了巨大贡献，日益受到科研工作者的普遍重视。 俄歇电子能谱常常应用在包括半导体芯片成分表征等方向   2.　发展历史 近年来，固体表面分析方法获得了迅速的发展，它是目前分析化学领域中最活跃的分支之一。 它的发展与催化研究、材料科学和微型电子器件研制等有关领域内迫切需要了解各种固体表面现象密切相关。各种表面分析方法的建立又为这些领域的研究创造了很有利的条件。在表面组分分析方法中，除化学分析用光电子能谱以外，俄歇电子能谱是最重要的一种。目前它已广泛地应用于化学、物理、半导体、电子、冶金等有关研究领域中。   俄歇现象于1925年由P.Auger发现。28 年以后，J.J.Lander从二次电子能量分布曲线中第一次辨认出俄歇电子谱线， 但是由于俄歇电子谱线强度低，它常常被淹没在非弹性散射电子的背景中，所以检测它比较困难。   1968年，L.A.Harris 提出了一种“相敏检测”方法，大大改善了信噪比，使俄歇信号的检测成为可能。以后随着能量分析器的完善,使俄歇谱仪达到了可以实用的阶段。   1969年圆筒形电子能量分析器应用于AES, 进一步提高了分析的速度和灵敏度。   1970年通过扫描细聚焦电子束,实现了表面组分的两维分布的分析(所得图像称俄歇图)，出现了扫描俄歇微探针仪器。   1972年，R.W.Palmberg利用离子溅射，将表面逐层剥离，获得了元素的深度分析，实现了三维分析。至此，俄歇谱仪的基本格局已经确定， AES已迅速地发展成为强有力的固体表面化学分析方法，开始被广泛使用。   3.　基本原理 俄歇电子是由于原子中的电子被激发而产生的次级电子。当原子内壳层的电子被激发形成一个空穴时，电子从外壳层跃迁到内壳层的空穴并释放出光子能量；这种光子能量被另一个电子吸收，导致其从原子激发出来。这个被激发的电子就是俄歇电子。这个过程被称为俄歇效应。 Auger electron emission   入射电子束和物质作用，可以激发出原子的内层电子。外层电子向内层跃迁过程中所释放的能量，可能以X光的形式放出，即产生特征X射线，也可能又使核外另一电子激发成为自由电子，这种自由电子就是俄歇电子。对于一个原子来说,激发态原子在释放能量时只能进行一种发射：特征X射线或俄歇电子。原子序数大的元素，特征X射线的发射几率较大，原子序数小的元素，俄歇电子发射几率较大，当原子序数为33时，两种发射几率大致相等。因此，俄歇电子能谱适用于轻元素的分析。   如果电子束将某原子K层电子激发为自由电子，L层电子跃迁到K层，释放的能量又将L层的另一个电子激发为俄歇电子，这个俄歇电子就称为KLL俄歇电子。同样，LMM俄歇电子是L层电子被激发，M层电子填充到L层，释放的能量又使另一个M层电子激发所形成的俄歇电子。     只要测定出俄歇电子的能量，对照现有的俄歇电子能量图表，即可确定样品表面的成份。由于一次电子束能量远高于原子内层轨道的能量，可以激发出多个内层电子，会产生多种俄歇跃迁，因此,在俄歇电子能谱图上会有多组俄歇峰，虽然使定性分析变得复杂，但依靠多个俄歇峰,会使得定性分析准确度很高，可以进行除氢氦之外的多元素一次定性分析。同时,还可以利用俄歇电子的强度和样品中原子浓度的线性关系,进行元素的半定量分析,俄歇电子能谱法是一种灵敏度很高的表面分析方法。其信息深度为5nm以内,检出限可达到0.1%atom。是一种很有用的分析方法。   4.　系统组成 AES主要由超高真空系统、肖特基场发射电子枪、CMA同轴式筒镜能量分析器、五轴样品台、离子枪等组成。以ULVAC-PHI的PHI 710举例，其核心分析能力为25 kV肖特基热场发射电子源，与筒镜式电子能量分析器CMA同轴。伴随着这一核心技术是闪烁二次电子探测器、 高性能低电压浮式氩溅射离子枪、高精度自动的五轴样品台和PHI创新的仪器控制和数据处理软件包： SmartSoft AES ™ 和 MultiPak ™。并且，目前ULVAC-PHI的PHI 710可以扩展冷脆断样品台、EDS、EBSD、BSE、FIB等技术，深受广大用户认可。 PHI710激发源，分析器和探测器结构示意图：   为满足当今纳米材料的应用需求，PHI 710提供了最高稳定性的 AES 成像平台。隔声罩、 低噪声电子系统、 稳定的样品台和可靠的成像匹配软件可实现 AES对纳米级形貌特征的成像和采谱。   真正的超高真空（UHV）可保证分析过程中样品不受污染，可进行明确、准确的表面表征。测试腔室的真空是由差分离子泵和钛升华泵（TSP）抽气实现的。肖特基场发射源有独立的抽气系统以确保发射源寿命。最新的磁悬浮涡轮分子泵技术用于系统粗抽，样品引入室抽真空，和差分溅射离子枪抽气。为了连接其他分析技术，如EBSD、 FIB、 EDS 和BSE，标配是一个多技术测试腔体。   PHI 710 是由安装在一个带有 Microsoft Windows ® 操作系统的专用 PC 里的PHI SmartSoft-AES 仪器操作软件来控制的。所有PHI电子光谱产品都包括执行行业标准的 PHI MultiPak 数据处理软件用于获取数据的最大信息。710 可应用互联网，使用标准的通信协议进行远程操作。   5.　AES的应用系统组成 扫描俄歇纳米探针可分析原材料（粉末颗粒，片材等）表面组成，晶粒观察，金相分布，晶间晶界偏析，又可以分析材料表面缺陷如纳米尺度的颗粒物、磨痕、污染、腐蚀、掺杂、吸附等，还具备深度剖析功能表征钝化层，包覆层，掺杂深度，纳米级多层膜层结构等。AES的分析深度4-50 Å，二次电子成像的空间分辨可达 3纳米，成分分布像可达8纳米，分析材料表面元素组成 （Li ~ U），是真正的纳米级表面成分分析设备。可满足合金、催化、半导体、能源电池材料、电子器件等材料和产品的分析需求。   AES 应用的几种例子，从左到右为半导体FIB-cut，锂电阴极向陶瓷断面分析   小结 本文小编粗浅的介绍了俄歇电子能谱AES的一些基础知识，后续我们还会提供更有价值的知识和信息，希望大家持续关注“表面分析家”！

(This page is in Chinese only.  For details, please kindly contact our representative.)   1.　概述 固态电池作为一个全新的技术方案，引起了广泛的研究兴趣，并得到了诸多探索。众所周知，固态电池的电解质和电极材料均是固态的，两者间界面材料相容，才能有效地传导离子，从而降低电池内部阻抗。   化学组成与电子能带结构分析能够帮助了解电解质与电极之间的界面性质，这对于半导体材料、纳米材料以及电池器件的研究十分重要。可利用TOF-SIMS、XPS、AES和UPS/LEIPS等技术来表征固态电池LiPON电解质和LiCoO2正极之间的界面，以获得相应成分、化学态和能带的信息。XPS和TOF-SIMS实验结果表明，在LiPON/LiCoO2 界面附近存在一个具有特定化学态的界面层，在该界面层发现了LiCoO2被还原的现象。为进一步了解界面上所发生的化学反应机制，可以利用UPS（紫外光电子能谱）和LEIPS (低能量反光电子能谱)来分析能带电子结构，为优化电池制备工艺提供指导。   2.　紫外光电子能谱和低能量反光电子能谱 如图1所示，紫外光电子能谱（UPS），基于光电效应，利用紫外光（hν=21.22 eV）激发价带电子, 可以获取样品价带位置（VB/HOMO）、功函数（Ф）和电离势（IE）信息。低能量反光电子能谱（LEIPS）是采用低能量电子（小于5 eV）入射到样品表面，与未占据态（导带）耦合释放出光子，然后通过光子探测器对发射光子进行检测，从而获取样品导带（CB/LUMO）和电子亲和势（EA）的信息。将UPS与LEIPS结合，可以完整地表征出样品的能带电子结构。 图1 UPS和LEIPS的基本原理   PHI XPS系统采用低能量电子（小于5 eV）作为LEIPS入射电子源，可以减弱电子束照射引起的样品损伤，提供更加可靠的导带信息。如图2所示，PHI XPS 系统在分析腔体上集成了XPS、UPS和LEIPS，可以原位对样品完成组分、化学态、价带和导带等完整电子结构的测试，结合Ar离子枪和团簇离子枪（GCIB/C60）可以进一步完成深度方向上电子结构的探测。 图2 PHI XPS系统功能示意图   3.　应用 从固态电池材料中制备了的LiPON和LiCoO2两种薄膜，然后利用UPS和LEIPS（如图2所示）分别对两种薄膜进行测试，全面获取两种材料相对于真空能级的电子能带结构。   图3 LEIPS和UPS测试的示意图   我们知道费米能级表征了电子填充能级的强弱。图4结果显示LiCoO2 的费米能级比LiPON的低，因此当LiPON电解质层沉积到LiCoO2电极界面时，电子倾向于从LiPON扩散到LiCoO2中，从而引起LiCoO2的还原。由此可见，通过UPS和LEIPS获取能带结构，能帮助解释XPS, TOF-SIMS以及AES的实验结果，进一步探究界面化学反应机制。 图4 LiPON和LiCoO2能带结构   4.　结论 PHI XPS 系统采用低能量反光电子能谱（LEIPS），可以避免电子束对样品的辐照损伤。同时，PHI XPS 分析腔体集成的XPS、UPS和LEIPS，可以对样品原位获取完整的电子结构探测。在这项研究中，准确的能级排列图有助于深入理解电解质/电极界面特性。

(This page is in Chinese only.  For details, please kindly contact our representative.)   1.　概述 锂离子电池 (LIB)具有工作电压高、能量密度大、循环寿命长、无记忆效应等优点，被广泛用于智能手机等便携电子设备，同时大容量锂离子电池已经成为电动汽车的主要动力电源。但是，现有的锂电池存在一些安全隐患。近日国家应急管理部公布的新能源汽车火灾数据显示，在2022年的第一季度，电动车发生自燃的事故有640起，平均每日有7例事故。这是因为在传统的锂离子电池中使用的是有机液态电解质，这些有机物分解电压较低、易燃易爆，即使是轻微的损坏也可能导致爆炸或引起火灾。   图1. 电动汽车着火安全问题   全固态电池（ASSBs）是一种使用固体电极和固体电解质的电池，由于采用了固态电解质替代传统的有机液态电解质，有望从根本上解决电池的安全性问题，还能进一步提升锂电池的能量密度和循环寿命，符合未来高安全性高能量密度锂电池发展的方向。然而，固体电解质（SE）和电极界面处的内阻是固态电池实际应用的最大障碍之一，因为该界面处的内阻限制了锂离子在充电/放电循环期间的传输效率。   2.　扫描俄歇电子能谱 扫描俄歇电子能谱（AES）是研究固体电解质材料和界面的显微结构和组分的重要方法，但是AES仪器的入射电子束照射容易引起样品损伤。例如LiPON电解质在电子束的照射下，易产生还原现象。使用AES设备的低电流模式可以减少对样品的损伤，同时性能优异的能量分析器可以提供重要组分Li的化学态信息。   图2 PHI VersaProbe系列XPS设备的扫描俄歇电子能谱配件   3.　应用 本案例样品采用多层结构，如图3样品截面的俄歇电子能谱SEM所示，多层结构分别为LiPON电解质，LiCoO2正极，Pt/Ti集流体和玻璃基底。为准确获取固态电池的化学性质及组成，采用AES低电流模式进行检测。图4结果表明，俄歇谱图中32 eV和40 eV处的信号分别对应LiPON和LiCoO2中的不同Li化学状态。此外，LiPON和LiCoO2的Li化学态分布图与SEM影像一一对应（见图3）。Li KVV俄歇谱证明了使用低电流AES检测，可以避免LiPON电解质的还原，从而得到Li准确化学态的分析结果。   图3 俄歇电子能谱的SEM影像与锂化学状态图的叠加   图4 锂的KVV型俄歇跃迁能谱   4.　结论 PHI VersaProbe系列XPS可搭载高空间分辨率和高灵敏度的扫描俄歇电子能谱配件，通过采用低电流且短时间的电子照射，在确保没有引起样品损伤的情况下，可以快速获得高能量分辨的AES化学状态图像。总而言之，pA-AES能够保证不同材料的真实性并提供可靠的分析结果。  

(This page is in Chinese only.  For details, please kindly contact our representative.)   　　X射线光电子能谱（X-ray Photoelectron Spectroscopy，简称XPS），是一种基于光电效应的电子能谱，是测量电子能量的谱学技术，最初是被用来进行化学分析，因此也被称为化学分析电子能谱 （Electron Spectroscopy for Chemical Analysis，简称ESCA）。   　　表面是指物体最表层的几层原子和覆盖在其上面的一些外来原子和分子所形成的的表面层。表面的厚度一般在零点几纳米到几个纳米之间，表面层具有独特的性质，与内层性质有很大差异甚至完全不同。由于表面在现代科学技术中的作用日益重要，所以科学家们把表面称为物质第四态，叫做“表面态”。表面态指表面的局域电子能级，是一些在与固体体相离域电子能带交换电子或共享电子方面具有活性的能级。 　　XPS是一种重要的常规表面成分分析技术，其分析深度约为0~100埃，也就是10nm以内（目前ULVAC-PHI的HAXPES具有双阳极靶、双单色器，已经具备30nm深度的无损分析能力）。它不但可以提供分子结构和原子价态方面的信息，还能提供各种化合物的元素组成和含量、化学状态、分子结构、化学键方面的信息，可以给出表面、微小区域和深度分布等方面的信息。XPS可用于定性和半定量分析除H、He以外所有表面元素，因而广泛地应用于材料研究的各个领域。   Resource from XPS International – XPS Periodic Table   发展简史 　　1887年，海因里希·鲁道夫·赫兹发现了光电效应；1895年伦琴发现X射线；1905年，爱因斯坦解释了该现象（并为此获得了1921年的诺贝尔物理学奖）。两年后的1907年，P.D. Innes用伦琴管、亥姆霍兹线圈、磁场半球（电子能量分析仪）和照像平版做实验来记录宽带发射电子和速度的函数关系，他的实验事实上记录了人类第一条X射线光电子能谱。其他研究者如亨利·莫塞莱、罗林逊和罗宾逊等人则分别独立进行了多项实验，试图研究这些宽带所包含的细节内容。XPS的研究由于战争而中止，第二次世界大战后瑞典物理学家凯·西格巴恩和他在乌普萨拉的研究小组在研发XPS设备中获得了多项重大进展，并于1954年获得了氯化钠的首条高能高分辨X射线光电子能谱，显示了XPS技术的强大潜力。1967年之后的几年间，西格巴恩就XPS技术发表了一系列学术成果，使XPS的应用被世人所公认。在与西格巴恩的合作下，美国惠普公司于1969年制造了世界上首台商业单色X射线光电子能谱仪。1981年西格巴恩获得诺贝尔物理学奖，以表彰他将XPS发展为一个重要分析技术所作出的杰出贡献。   基本原理     　　XPS的原理是用X射线去辐射样品，使原子或分子的内层电子或价电子受激发射出来。被光子激发出来的电子称为光电子，通过测量光电子的能量，可以得到丰富的信息。以光电子的动能/束缚能（binding energy，Eb=hv光能量-Ek动能-w功函数）为横坐标，相对强度（脉冲/s）为纵坐标可做出光电子能谱图。光电子的结合能具有指纹效应，可用于鉴别元素及其化学态，并可以对其进行定性和半定量分析。通过结合能的识别得到的谱图可以鉴别元素的组成、化学态的解析（如下谱图所示）。     系统组成 　　一台商业化的XPS系统通常包括以下部分：单色化X射线源系统、真空系统、样品观察和操控系统、光电子探测器、能量分析器、能量传输透镜、电荷中和系统、Ar离子枪、能谱仪控制和数据处理系统、烘烤加热系统、循环水冷却系统、电气控制柜等。随着技术的不断发展，在大面积XPS分析、小面积微区XPS分析、SXI二次电子成像及精准定位、变角XPS分析、深度剖析、低能双束荷电中和等基本功能上，更多的功能可以在XPS系统的基础上得以实现，其中比较常见的功能包括：紫外光电子能谱（UPS）、反光电子能谱（IPES）、离子刻蚀技术（C60、Ar团簇离子枪）、SAM 扫描俄歇能谱、反射式电子能量损失谱（REELS）、样品加热冷却、真空互联等等……   XPS的应用 　　XPS几乎应用于所有表面问题的研究，可定性半定量分析固体材料表面成分信息（包括元素组成、化学态等），并且通过X射线可以进行选区分析从而表征成分的分布情况（ULVAC-PHI扫描聚焦式X射线可小于7.5微米）；所以XPS可被广泛应用于合金、矿物、半导体、高分子聚合物，催化剂、硅酸盐陶瓷、生物医药、能源材料等分析领域。           XPS可以应对从大面积到微区的分析需求，既可以表征表面成分，表面多层薄膜等，又可以对环境颗粒物、表面缺陷（腐蚀，异物，污染，分布不均等）进行微区定位分析，因此对于各种材料开发，材料剖析与失效机理的分析和研究具有不可替代的作用。   小结 　　本文小编粗浅的介绍了X射线光电子能谱仪的一些基础知识，后续我们还会提供更有价值的知识和信息，希望大家持续关注“表面分析家”！   请扫上方二维码关注“表面分析家”公众号     Acknowledgment Thank you XPS International for providing XPS Periodic Table

Hello everyone. We are happy to inform you of the establishment of the Surface Analysis Family.    Please scan the QR code above and follow Surface Analysis Family The formation of this family is based on the goodwill to bring information about surface analysis in terms of the newest technologies, applications, education, publication journal and even market the latest trend. In working in the surface analysis field for tens of years, we feel we have an obligation to make a contribution to try to bring everyone’s knowledge to a higher level. And this is the ultimate will for establishing this platform of the Surface Analysis Family.   The Surface Analysis Family – Target for passing and sharing the related knowledge   The surface analysis had been greatly utilised in the technology and the research field including material properties, organic & inorganic chemicals, metal, polymer, photo-voltaic, battery, environment, semiconductor and many more. From research to actual products, surface analysis has been a critical portion of helping modern technologies to grow. Hence as the final outcome of bringing a better life for humans in the world.   Surface Science can be applied in many different categories, as illustrated in the above picture     Let’s start with the Surface! To start off, let’s start by discussing what is a surface?   A surface, by definition, is an INTERFACE, a marked discontinuity from one material to another. Since no change is ever instantaneous, there is a finite depth for any real surface. In surface analysis, the surface depth is defined by the technique used to characterize it. This depth may vary from an atomic layer, approximately 3-5 Angstrom to as much as 1um.   Surface is like the skin of a person, making all the “first” interactions with others. The above picture had shown such an illustration with also listing the practical importance of the surface of a given solid   In theory, indeed we usually have to start like above the so-called “definition”. However, sometimes it could be easier if we can use some real-life example to express such “definition” for our easy understanding. So if we were to describe the “surface” of some matters in some casual expressions, maybe we can compare it to the skin of a person. Our skin is always the first “interface” to interact with other things or other persons. With such, it could be easy to understand how important is the surface of any matter to play a very important factor. (Well, there is always an advantage for a good looking person)     Let’s look at an example of Surface Analysis Since the surface is so much critical, it makes being able to analyze and characterize it to be an important goal to reach. Below listed some commonly used techniques in surface analysis: Topography     • Visual, Optical Microscopy, SEM… etc.    Elemental/Chemistry     • X-ray Photoelectron Spectroscopy (XPS)     • Auger Electron Spectroscopy (AES)     • Secondary Ion Mass Spectrometry (SIMS)     • EDS, RBS, XRF, FTIR, EELS, RAMAN…. etc.   Take an example from the Auger Electron Spectroscopy, which combined also the SEM function. Below shows an example of how we can characterize a steel sample. The top-middle is the SEM image of the sample surface at 10,000X magnification. The grain structure can be observed. Then a multi-point analysis, shown as point #1~#4, is carried out with the respective Auger analysis spectrum shown. From the spectrum data, it can be easily observed the detecting elements on the 4 selected points are very different. The Auger analysis tool can go 1-step further to perform so-called Auger mapping to show the elemental distribution in a 2-D dimension shown in the bottom-centre image.   The above picture shows an example of Surface Analysis in the case of Auger Electron Spectroscopy (AES) It started from the top-centre SEM image > multi-points analysis with the 4’s Auger energy spectrum and concluded the elemental distribution over a surface by the Auger mapping data     Now we see evidence of how useful is Surface Analysis~ As above mentioned, surface analysis is a proven subject to make a critical contribution to our modern day's technologies as well as a tool for bringing a better life to the world. Certainly, it is impossible to get all information with just one single technique. Rather, there is a number of Surface Analysis techniques which could help in the characterization of the material surface. Below the figure is the very famous SMART chart from EAG, a well-known Analysis company in the world.   A famous and popular Analysis Technique SMART Chart, summarizing various techniques to their detection limit, sampling depth, analytical spot size and so on     Summary Surface Analysis Family on this kicking start will continue to bring more information sharing to everyone. And we are also so much welcome if anyone is/are interested in sharing their knowledge and information with us. Or even if there is a topic you are in question, we will be very happy to hear it from you. Eventually, by building a common Surface Analysis platform here, we vision for all of us that it will benefit all and ultimately continue to make step-up for our Surface Analysis Family.     Background The Surface Analysis Family is initiated by PHI CHINA, a company established in China since 2010. PHI CHINA is the representative for ULVAC-PHI in China. We specialize in surface analysis techniques & instrumentation including XPS, AES, Tof-SIMS and Dynamic SIMS. Members of PHI CHINA are capable of building up a surface analysis instrument to well-utilizing it for producing good data for various applications.   Contact person：张伟 William.Zhang Tel no.: 18500084171 Email：william.zhang@coretechint.com   Surface Analysis Family

Application of X-ray Photoelectron Spectroscopy has seen growth in literary every field of science and technology in recent years due to its unique capabilities of being surface sensitive and providing quantitative elemental and chemical composition.   If we look at which area of applications are using XPS, in particular PHI USA instrumentation, the most are electronics, catalysts, environmental science, polymers, and energy storage. PHI USA instruments provide high throughput needed for metrological measurements of semiconductors, efficient charge neutralization, and spectral resolution required for analysis of polymeric materials, and unique solutions such as controlled atmosphere transfer, in situ cooling and heating, and electrochemical applications needed for a catalytic, battery, and organic electronic materials.   Four areas have the highest percentage growth in XPS application in the last five years – electrocatalysts 1-2 used in alternative fuel cell technologies, perovskites used in organic electronics 3-4 and battery materials5, textiles used as novel materials in stretchable diodes6 and supercapacitors7-8 and pharmaceuticals9.   Figure highlights figures for electocatalyst 1 perovksites3, textile10 and pharmaceuticals9 applications.   References: Morales-Guio, et al.  Nat Catal 1, 764–771 (2018). https://doi.org/10.1038/s41929-018-0139-9 Kim, JY., et al.  Nat Commun 12, 3765 (2021). https://doi.org/10.1038/s41467-021-24105-9 Liu, C., et al.  Nat Commun 12, 6394 (2021). https://doi.org/10.1038/s41467-021-26754-2 Zhang, H., et al.  Nat Commun 12, 3383 (2021). https://doi.org/10.1038/s41467-021-23566-2 Nowroozi, M.A., et al.  Commun Mater 1, 27 (2020). https://doi.org/10.1038/s43246-020-0030-5 Matsuhisa, N., et al. Nature 600, 246–252 (2021). https://doi.org/10.1038/s41586-021-04053-6 Ko, WY., et al.  Sci Rep 6, 18887 (2016). https://doi.org/10.1038/srep18887 Cheng, S., et al.  Sci Rep 7, 6681 (2017). https://doi.org/10.1038/s41598-017-07102-1 Wang, LS., et al. Sci Rep 11, 12410 (2021). https://doi.org/10.1038/s41598-021-91925-6 Deng, X., et al.  Sci Rep 5, 10138 (2015). https://doi.org/10.1038/srep10138        

Since the introduction of PHI XPS, the series of VersaProbe has become the most popular XPS instrument in the world. Last year, PHI had launched the latest fourth-generation XPS: "PHI VersaProbe 4".       The PHI VersaProbe 4 features a newly designed analyzer that enables high sensitivity analysis from tiny to large areas. The unique microfocus scanning X-ray and SXI images can be used as sample navigation through SEM-like SXI images to achieve a 100% accurate definition of the micro-analysis position.   The world's first PHI VersaProbe 4 arrived in China on 21 December 2021. This system also included multiple optional functions on the base XPS. Due to the epidemic and the Chinese New Year holiday, the installation schedule was delayed. The installation ended up to start from early February and the acceptance eventually completed on 14 February this year, taking 2 weeks for the full instrument setup and hand-over training to the customers.   Completion of Installation   The upgrades and highlights of PHI VersaProbe 4: 1. Brand new appearance design   2. Greater sensitivity and resolution for large area analysis   3. Extremely high detection limits   4. Imaging large-area stitching   5. Upgrade of software automation function  

High-quality research publications are at the cornerstone of scientific advancement, understanding, and communication. Here, we review the year 2021 and the impact that the PHI Auger Electron Spectroscopy (AES) instrument has had in supporting scientific breakthroughs.   Over 1300 scholar publications, including peer-reviewed articles and book chapters, have been published in 2021 using PHI AES instruments, many of which were published in high-impact journals (Nature and Science group).   PHI AES instruments were used to study a large range of materials for applications of high technological and research importance - solar cells based on perovskites1, gallium arsenide2, and silicon3 ;  prosthesis and medical implants4-6; 2D materials for quantum electronic devices7; novel catalysts for fuel cells, water splitting, energy storage8-9, and the removal of organic micropollutants10; light emitting diodes11-12; thermoelectric materials13; deep-sea tribocorrosion of metal alloys14; low carbon steels for nuclear power plants and water-cooled reactors15; steel pitting corrosion16; additive manufacturing17; lithium-ion batteries18-19; and all solid-state batteries20.   One paper published this year in Nature Communications as a collaborative study led by the National Engineering Laboratory for Industrial Wastewater Treatment at the East China University of Science and Technology is of impressive scientific merit. This work demonstrates the viability of a naturally abundant Fe/Mn-based catalyst to boost the future development of biomass products such as biofuel and enhance plastics degradation and wastewater treatment. Using the PHI 710 Scanning Auger Nanoprobe, Wang and coworkers21 mapped the fresh and used Mn-based catalyst with a sub-micron spatial resolution to elucidate the mechanism of catalyst oxidation (Figure 1). High spatial resolution (<8 nm) elemental mapping using the PHI 710 instrument enabled superior visualization of this highly topographic material.   Fig. 1: Scanning Auger mapping of Mn of fresh (bottom) and used (top) MnO2/Goe catalyst   Another esteemed paper published this year in NPG Asia Materials by Haindl and coworkers22 at the Tokyo Institute of Technology and the University of Glasgow utilizes the PHI 710 Auger instrument to study Fe-based superconductors. In this work, the interface chemistries of Fe-pnictide heterostructure layered materials were probed via Auger depth profiling. The Auger depth profiles reveal smooth and clean interfaces in undoped and Co2+ substituted cases, and an interface layer formation present in the case of excess O2- during deposition (Figure 2). The ability to precisely depth profile these extremely thin layers highlights the capabilities of the monoatomic Ar+ ion gun equipped on the PHI 710 and demonstrates minimal sputter mixing and enhanced depth resolution.   Fig. 2: STEM images of a. clean, undoped Sm-1111/Ba-122 interface, b. clean, Co2+-substituted La-1111/Ba-122interface; c. interface layer (IFL) formation in Sm-1111/Ba-122 with excess O2–.  AES depth profiles across the interface for d. undoped Sm-1111/Ba-122, e. Co2+-substituted La-1111/Ba-122, and f. Sm-1111/Ba-122 with excess O2–   A third high-impact publication this year in Electrochemica Acta by Zhao and coworkers23 uses the PHI 710 Scanning Auger Nanoprobe to study Na-ion battery materials. In this work, the stability and performance of Na-ion battery technology was enhanced via surface modification of sodium manganese hexacyanoferrate (NaMnHCF) as a cathode material. Auger spectroscopy was used to analyze the in-depth chemical composition of the modified surface. The spectra reveal an increase in Cu composition and a decrease in Mn composition after sputtering ~20 nm into the material. This modification significantly improves the long-term stability of the electrode.   Fig. 3: In-depth AES spectra of Mn and Cu on a microscale grain of NaMnHCF after the ion-exchange modification   PHI CHINA is proud of the role the PHI 710 Scanning Auger Nanoprobe has played in achieving such prestigious scientific advancements over this past year. Please visit the citations below for more details regarding the studies mentioned in this article. https://doi.org/10.1021/acsomega.1c05002 https://doi.org/10.1016/j.apsusc.2021.149205 https://doi.org/10.1016/j.optmat.2021.111291 https://doi.org/10.1116/6.0001233 https://doi.org/10.1016/j.cej.2021.133940 https://doi.org/10.1002/jbm.b.34781 https://doi.org/10.1126/sciadv.abk1892 https://doi.org/10.1002/adfm.202107058 https://doi.org/10.1016/j.electacta.2021.139266 https://doi.org/10.1016/j.ceja.2021.100214 https://iopscience.iop.org/article/10.1088/2053-1591/ac3fdd/meta https://doi.org/10.1039/d1nr04220c https://doi.org/10.2320/matertrans.E-M2021812 https://doi.org/10.1016/j.corsci.2020.109185 https://doi.org/10.3103/S0967091221070068 https://doi.org/10.3390/met11030428 https://doi.org/10.1117/12.2601291 https://doi.org/10.1016/j.jpowsour.2021.229573 https://doi.org/10.3390/batteries7040065 https://doi.org/10.1002/aenm.202101370 https://doi.org/10.1038/s41467-021-27240-5 https://doi.org/10.1038/s41427-021-00336-6 https://doi.org/10.1016/j.electacta.2021.138842

We are looking back at the impact of PHI TOF-SIMS instruments in supporting scientific publications in the year 2021. Over 900 scholar publications, including peer-reviewed articles and book chapters, have been published in 2021 using PHI nanoTOF instruments. PHI TOF-SIMS instruments were used to study a large range of materials for applications of high technological and research importance - solar cells based on perovskites1-3, 2D materials4, biological materials5,6, and batteries.7-9   Here we would like to highlight a few papers that demonstrate the unique capabilities of PHI nanoTOF instruments.   In the first paper published in Nature (cited 6 times in the first year), our customers from New York University Tandon School of Engineering used a PHI nanoTOF II instrument as well as a PHI VersaProbe to study perovskite based solar cells1. They conducted TOF-SIMS depth profiling to demonstrate how reducing the content of lithium ions in the hole-transporting layers (HTL) lowered the overall content in the vertical device direction. “Lithium ions intercalating into the perovskite active layer can result in decomposition of the perovskite and formation of metallic lead, creating recombination sites. The lithium ions were concentrated in particular in the bottom contact layers (Figure 1a), which has been shown to result in device failure.” Authors demonstrated that carbon dioxide doping results in a device in which lithium-ion signal is much lower with a minimum accumulation of lithium ions in the bottom contact layers (Fig. 1b)   Fig. 1 TOF-SIMS depth profile of pristine solar cell (a) and CO2-treated layer (b)   Another paper published in Advanced Electronic Materials is focused on functionalization of 2D materials, such as MoS2 and WSe2.4 Authors from the University of Bundeswehr combined atomic force microscopy-infrared (AFM-IR) spectroscopy and monolayer sensitive TOF-SIMS, to “overcome the limitations of classical surface analysis and prove the highly selective functionalization of the 2D material surface, which is preferred over the substrate.” In Figure 2, the elemental maps of negative secondary ions 32S−, 28Si−, O−, C−, CH−, and CH2− were collected from a single, clearly distinguishable, PBI functionalized, and CVD-grown MoS2 flake on a SiO2/Si substrate. This paper highlighted the great potential of unconventional techniques such as TOF-SIMS in the field of 2D materials and organic SAMs.   Fig. 2 High resolution TOF-SIMS maps of 32S−, 28Si−, O−, C−, CH−, and CH2− secondary ions   Fig. 3 ToF-SIMS results of bare and hydroxyapatite coated cathode powders, (d) positive fragments: LiOH+, LiOH2+, LiCO2+, (e) negative fragments: CaPOH3−, LiCaPO−, LiCaPOH− fragments (top: bare; bottom: coated) (f) Schematic illustration for the detailed modification process   The third paper we would like to highlight is published by authors from Small Engineering & Sejong Battery Institute and focuses on improving stability of Ni-rich cathodes for lithium-ion batteries. The authors used hydroxyapatite as a coating material, which showed excellent chemical and mechanical properties that provide a suitable coating medium for Ni-rich cathode materials. LiOH+ (m/z = 24.01), LiOH2+ (m/z = 25.01), and LiCO2+(m/z = 51.00) fragments, corresponding to the residual lithium compounds, emerged to be significantly high for the bare material relative to the coated materials (Figure 3d). Fragments from lithium-doped hydroxyapatite were also detected (Figure 3e). These fragments were not observed for the uncoated cathode. In addition, TOF-SIMS was used to study the surface of the coating after electrochemical reaction for 500 and 1000 cycles. The formation of fluorinated Ca4.67Li0.33(PO4)3F and CaF2 layers was found to be related to morphological stability.   Read more about these and other discoveries in the papers cited below. https://doi.org/10.1021/acsami.1c15505 https://www.nature.com/articles/s41586-021-03518-y#Sec26 https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202101454 https://doi.org/10.1038/s41566-021-00857-0 https://doi.org/10.1002/aelm.202000564 https://doi.org/10.1038/s41598-021-92044-y https://doi.org/10.1038/s41598-020-78416-w https://doi.org/10.1002/smll.202104532 https://doi.org/10.1116/6.0001044 https://doi.org/10.1016/j.ensm.2021.11.017