掠入射X射线衍射在表面,界面和薄膜材料结构研究中的应用

掠入射Ｘ射线衍射是８０年代以来发展的一种新的结构分析技术．其贯穿深度小，信噪比高，分析深度可以控制，因而适用于对表面或界面重构、多层膜和超晶格结构分析．简要介绍掠入射Ｘ射线衍射有关理论和方法及其应用．     

簿膜结构分析中的低角X射线衍射方法

利用带折射修正的布喇格衍射定律和薄膜光学理论分析了低角Ｘ射线衍射谱中出现的一系列现象，导出了多层膜周期厚度和周期中不同材料间的配比率的计算公式，对多层膜的低角Ｘ射线衍射谱中主峰间的次峰现象作出了解释，并对低角Ｘ射线衍射测量单层膜厚度进行分析，给出了精确的测厚公式。     

薄膜结构分析中的低角X射线衍射方法

利用带折射修正的布喇格衍射定律和薄膜光学理论分析了低角Ｘ射线衍射谱中出现的一系列现象，导出了多层膜周期厚度和周期中不同材料间的配比率的计算公式，对多层膜的低角射线衍射谱中主峰间的次峰现象作出了解释，并对低角Ｘ射线衍射测量单层膜厚度进行了分析，给出了精确的测厚公式。     

纳米尺度HfO_2薄膜不同厚度对光学性质的影响

Hf O_2薄膜厚度达到纳米级别时,其光学性质会发生变化。光谱椭偏仪能够同时得到纳米尺度薄膜的厚度和光学常数,但是由于测量参数的关联性,光学常数的结果不准确可靠。本文采用溯源至SI单位的掠入射X射线反射技术对纳米尺度Hf O_2薄膜厚度进行准确测量,再以该量值为准确薄膜厚度参考值。利用光谱椭偏仪测量Hf O_2膜厚和光学常数时,参考膜厚量值,从而得到对应相关膜厚的薄膜准确光学参数。研究了以Al2O_3作为薄膜缓冲层的名义值厚度分别为2,5,10 nm的超薄Hf O_2薄膜厚度对光学性质的影响。实验结果表明,随着Hf O_2薄膜厚度的增加,折射率也逐渐增大,在激光波长632.8 nm下其折射率分别为1.901,2.042,2.121,并且接近于体材料,而消光系数始终为0,表明纳米尺度Hf O_2薄膜在较宽的光谱范围内具有较好的增透作用,对光没有吸收。     

薄膜、多层膜和一维超点阵材料的X射线分析新进展

Ｘ射线散射和衍射对于厚度为几个原子层到几十微米的薄膜材料是灵敏的。一般而言,Ｘ射线方法是非破坏性的,其中不要求样品制备,它们提供恰如其分的技术路线,以获得薄膜材料的结构等信息;分析能对从完整单晶膜和多晶膜到非晶膜的所有材料进行。本文评述了用Ｘ射线方法表征和研究这类薄膜材料的新进展。全文包括引论、常用的Ｘ射线方法、原子尺度薄膜的研究、工程薄膜和多层膜的研究、一维超点阵结构研究、超点阵界面粗糙度的Ｘ射线散射理论、不完整性和应变的衍射空间图或倒易空间图研究七个部分     

掠入射一维空间分辨光栅谱仪的特性及应用

描述了可在ＸＵＶ光谱区获得消像散光谱的掠入射一维空间分辨光栅光谱仪的原理，特别是作为光谱仪前置集及及像散补偿的掠入射反射光学系统的特性，并给出了成像光谱仪的空间分辨能力的实测方法和测量结果，实验值与用光线追踪模拟的结果相符，语言中还简述了该一维空间分辨光栅谱仪在激光等离子体诊断和Ｘ射线激光研究中的具体应用。     

薄膜、多层膜和一维超点阵材料的X射线分析新进展

Ｘ射线散射和衍射对于厚度为几个原子层到几十微米的薄膜材料是灵敏的。一般而言,Ｘ射线方法是非破坏性的,其中不要求样品制备,它们提供恰如其分的技术路线,以获得薄膜材料的结构等信息;分析能对从完整单晶膜和多晶膜到非晶膜的所有材料进行。本文评述了用Ｘ射线方法表征和研究这类薄膜材料的新进展。全文包括引论、常用的Ｘ射线方法、原子尺度薄膜的研究、工程薄膜和多层膜的研究、一维超点阵结构研究、超点阵界面粗糙度的Ｘ射线散射理论、不完整性和应变的衍射空间图或倒易空间图研究七个部分     

磁控溅射方法制备直径120mm高均匀性Mo/Si多层膜

为满足极紫外、软X射线和X射线大口径多层膜反射镜的需求,采用基板扫掠过矩形靶材表面的镀膜方法,在直径120 mm的平面基板上镀制了Mo/Si周期多层膜。通过调整基板扫掠过矩形靶材表面的速率修正了薄膜的沉积速率,极大地提高了薄膜厚度的均匀性。采用X射线衍射仪对反射镜不同位置多层膜周期厚度进行了测量,结果表明,在直径120 mm范围内,Mo/Si多层膜周期厚度的均匀性达到了0.26%。同步辐射测量多层膜样品不同位置处的反射率,结果表明,在直径120 mm范围内,多层膜的膜层厚度均匀,在入射角10°时13.75 nm波长处平均反射率为66.82%。     

一种可溯源的光谱椭偏仪标定方法

提出了一种用X射线反射术标定光谱椭偏仪的方法.作为一种间接测量方法,光谱椭偏术测得的薄膜厚度依赖于其光学常数,不具有可溯源性.在掠入射条件下,X射线反射术能测得薄膜的物理厚度,测量结果具有亚纳米量级的精密度且与薄膜光学常数无关.在单晶硅基底上制备了厚度分别为2nm,18nm,34nm,61nm及170nm的SiO2薄膜标样,并用强制过零点的直线拟合了两种方法的标样测量结果,拟合直线的斜率为1.013±0.013,表明该方法可在薄膜厚度测量中标定光谱椭偏仪.     

沉积速率对直流脉冲溅射钼薄膜微结构与光学性能的影响

用脉冲直流磁控溅射方法在硅片衬底上制备了厚度相同的单层钼薄膜,结合台阶仪、X射线衍射仪、场发射扫描电镜、原子力学显微镜和紫外-可见分光光度计分别研究了不同沉积速率对钼薄膜微结构、表面形貌和光学性能的影响。掠入射X射线反射谱拟合的钼薄膜厚度与设计厚度一致,说明当前钼薄膜制备工艺成熟稳定。沉积速率通过改变薄膜生长模式与薄膜形核率影响钼薄膜表面形貌演化。随着沉积速率的增大,薄膜越来越致密,钼(110)面的衍射峰强度逐渐增大,平均晶粒尺寸增大,表面粗糙度先降低后增加。     

磁控溅射制备极紫外高反射率多层膜应力研究

为制备硼边附近6.7 nm波长的极紫外高反射率多层膜反射镜,研究了Mo_2C/B_4C,Mo/B_4C周期多层膜,重点解决薄膜应力难题。采用直流磁控溅射技术制备了膜层厚度为30 nm的Mo,Mo_2C,B_4C,单层膜,周期厚度为3.5 nm,30对的Mo_2C/B_4C,Mo/B_4C周期多层膜。利用台阶仪测试了镀膜前后基底面形,计算并比较了不同薄膜样品的应力值。结果表明Mo_2C/B_4C多层膜压应力要远小于Mo/B_4C多层膜,且成膜质量与Mo/B_4C相当。因此Mo_2C/B_4C是应用于6.7 nm反射镜较好的多层膜材料组合。     

Application of kinoform lens for X‐ray reflectivity analysis

In this paper the first practical application of kinoform lenses for the X‐ray reflectivity characterization of thin layered materials is demonstrated. The focused X‐ray beam generated from a kinoform lens, a line of nominal size ～50 µm × 2 µm, provides a unique possibility to measure the X‐ray reflectivities of thin layered materials in sample scanning mode. Moreover, the small footprint of the X‐ray beam, generated on the sample surface at grazing incidence angles, enables one to measure the absolute X‐ray reflectivities. This approach has been tested by analyzing a few thin multilayer structures. The advantages achieved over the conventional X‐ray reflectivity technique are discussed and demonstrated by measurements.     

A theoretical practice on grazing‐exit energy dispersive X‐ray spectroscopy as a surface analysis strategy to investigate BiVO4 nano‐films

In the current work, a thin film of bismuth vanadate was defined over a silicon substrate, and a calculative Monte Carlo approach was followed to achieve the best grazing‐exit angle to acquire compositional data from top few nanometers of surface. This strategy is very beneficial in order to increase X‐ray signals originated from surface and diminish the background X‐ray signals started off from the substrate. In this regard, grazing‐exit energy dispersive X‐ray spectroscopy can be considered as an accessible and economical analytical tool to investigate thin films and nano‐layers. The major advantage of this method is that just by applying a re‐arrangement in a scanning electron microscope, it can be used to study compositional properties of thin layers. In this contribution, a theoretical approach using Monte Carlo models was used to simulate the behavior of electron beams impinging onto BiVO₄ nano‐layers with thickness of 50 nm and electron trajectories inside the film. Characteristic X‐rays and spatial energy distribution of the backscattered electrons were also calculated. Under grazing‐exit angle of around 0.5°, the best surface signal/background noise ratio was achieved. Copyright © 2014 John Wiley & Sons, Ltd.     

Internal reflection ellipsometry in air and water ambient

We measured a multilayer sample in air and water ambient below the critical angle of incidence based on internal reflection ellipsometry (IRE). Measurements with varying incident angle and varying wavelength both provided values by the fitting for refractive indices and thicknesses of layers consistent with design or theoretical ones. This verified that IRE is useful in measurement and analysis of thin films on transparent substrates and especially effective to study thin films at transparent substrate-liquid interfaces.     

ZnO薄膜的分子束外延生长及性能

利用分子束外延(MBE)和氧等离子体源辅助MBE方法分别在Si(100)、GaAs(100)和蓝宝石Al2O3(0001)衬底上用Zn、ZnS或以一定Zn-O化学计量比作缓冲层,改变衬底生长温度和氧压,并在氧气氛下,进行原位退火处理,得到ZnO薄膜。依据X射线衍射(XRD)图,表明样品的结晶性能尚好,且呈c轴择优取向;实验结果表明在不同衬底上生长的ZnO薄膜,由于晶格失配度不同,其衍射峰也有区别。用原子力显微镜(AFM)观测薄膜的表面形貌,为晶粒尺寸约几十纳米的ZnO纳米晶,且ZnO晶粒呈六边形柱状垂直于衬底的表面。采用掠入射X射线反射率法测膜厚。在360nm激发下,样品的发光光谱是峰值为410,510nm的双峰谱,是与样品表面氧缺陷有关的深能级发光。     

"包络法"在Ba(ZrTi)O3铁电薄膜中的应用

采用溶胶一凝胶法在石英衬底上制备Ba(ZrTi)O3铁电薄膜,U-3010紫外光谱仪测量BZT薄膜的透射光谱,光谱表明制备的BZT薄膜样品厚度均匀,利用“包络法”计算出薄膜的厚度约为301.3nm,并得到薄膜的复折射率随入射光频率的变化曲线,进一步拟和出BZT薄膜的透射谱。研究表明在紫外光区到近红外光区“包络法”计算精度高。     

铌酸锶钡薄膜的微结构与电光性能的研究

本文叙述了使用溶胶凝胶法在MgO(0 0 1)的衬底上制备铌酸锶钡薄膜的过程 ,膜层厚度可达 5 μm。通过X射线衍射、摇摆曲线、扫描、拉曼散射光谱等方法研究了薄膜的微结构性能 ,实验发现 ,铌酸锶钡薄膜具有了较好的 (0 0 1)方向的优先取向性能 ,并且随着薄膜厚度的增加 ,其晶体取向性也会随之不断改进。熔石英的透明衬底上生长的SBN薄膜具有较大的电致双折射效应 ,其有效电光系数能够高达 6 6 2× 10 -11m/V。     

掠射技术与X射线荧光分析

掠射技术引入Ｘ射线荧光分析成为一种新的材料及薄膜分析技术。运用此技术命同材料表面及薄膜的密度、厚度、界面粗糙度、成分的深度和剖面分布等各种信息，本文介绍了掠射技术在Ｘ射线荧光分析中的应用及近年来的发展和前景。     

4.48 nm正入射软X射线激光用Cr/C多层膜高反射镜的研制

针对4.48nm类镍钽软X射线激光及其应用实验,设计制备了工作于这一波长的近正入射多层膜高反射镜。选择Cr/C为制备4.48nm高反射多层膜的材料对,通过优化设计,确定了多层膜的周期、周期数以及两种材料的厚度比。模拟了多层膜非理想界面对高反射多层膜性能的影响。采用直流磁控溅射方法在超光滑硅基片上实现了200周期Cr/C多层膜高反射镜的制备。利用X射线衍射仪测量了多层膜结构,在德国BessyⅡ同步辐射上测量了在工作波长处多层膜反射率,测量的峰值反射率达7.5%。对衍射仪测量的掠入射反射曲线和同步辐射测量的反射率曲线分别进行拟合,得到的粗糙度和厚度比的结果相近。测试结果表明,所制备的Cr/C多层膜样品结构良好,在指定工作波长处有较高的反射峰,达到了设计要求。     

Validation and traceability of XRF and SEM‐EDS elemental analysis results for solder in high‐reliability applications

A procedure and calibration samples were developed for X‐ray fluorescence spectrometry and scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS) analysis methods for Sn and Pb amounts in solder and coatings. Test methods are needed by laboratories that perform destructive physical analysis of high‐reliability electronics for MIL‐STD‐1580B. Calibrants are prepared by evaporative deposition of multiple, alternating quantities of pure Sn and pure Pb having mass per unit area proportional to mass fractions of Sn and Pb in a solder being mimicked. Validation reference materials are prepared by evaporative deposition of thin films of SRM 1729 Tin Alloy (97Sn–3Pb). Films are created on high‐purity Ni foil to mimic some actual electronics structures and prevent charging during SEM‐EDS measurements. Maximum thickness of films prepared this way must be kept below approximately 1 µm to ensure that the entire thickness is probed by the primary X‐ray or electron beam and that measured X‐rays come from the entire thickness of all films. Detailed procedures are presented, and method performance was characterized. The primary purpose is to create calibrations for Sn and Pb that are simple to implement and establish traceability to the international system of units. The secondary purpose is to validate calibrations using a certified reference material to prove that, for simpler structures of thin solder coatings on metal, both X‐ray fluorescence and SEM‐EDS provide accurate results. Keeping films thin may be unrealistic in comparison with some, if not many, electronic structures, but this approach enables a laboratory to demonstrate competence in a controlled manner. Copyright © 2014 John Wiley & Sons, Ltd.