Studying nanomagnets and magnetic heterostructures with X-ray PEEM at the Swiss Light Source

Polarization dependent X-ray absorption spectroscopy and microscopy enables the element selective investigation of magnetic systems at the nanoscale. At the Swiss Light Source a photoemission electron microscope is used for the study of a broad variety of systems. Here, a review of recent activities is presented with a focus on instrumental and analytical developments. A new procedure for the 3 dimensional determination of the magnetization vector has been developed, and is demonstrated for GdFeCo microstructures displaying in-plane and out-of-plane domains, and sub-20 nm Fe nanoparticles. The recent progress for measurements in applied magnetic fields is presented and a new set-up for time-resolved measurements employing femtosecond laser pulses is described.     

Element-selective mapping of magnetic moments in ultrathin magnetic films using a photoemission microscope

We combine X-ray magnetic circular dichroism (XMCD) and photoelectron emission microscopy to obtain locally resolved magnetic information on a microscopic scale. Scanning the photon energy across elemental absorption edges and recording microscopic images of the local secondary electron intensity for both photon helicities at each photon energy step allows to analyze local XMCD spectra at any position of the imaged area of the sample. With the help of magnetic sum-rules local quantitative information about magnetic moments can be extracted from such microspectroscopic measurements. The full power of XMCD as a spectroscopic tool is so maintained, while microscopic spatial resolution is added.     

High-precision sample stage for photoemission microscopy of organic films

A high-precision sample stage for photoemission microscopy has been constructed to translate the sample by ±3 mm with accuracy better than 100 nm. The stage is actuated by step motors settled outside the vacuum. The accuracies of the translations were measured by observing a standard patterned sample with a photoemission electron microscope (PEEM) of 50 nm resolution. The accuracy was nearly independent of the distance of each translation step and the error was not accumulated by repeated steps. After round-trip translations up to 0.2 mm, the sample came back to the original position with accuracy of ±50 nm. The performance of the stage was demonstrated by observing growth processes of lead phthalocyanine (PbPc) films formed on graphite.     

同步辐射X射线磁二色性在自旋电子学研究中的应用

文章对同步辐射X射线磁圆二色谱和X射线磁线二色谱的独特优点进行了综合分析,并通过一些典型应用实例说明同步辐射磁性测量技术具有元素分辨能力、高灵敏度、纳米量级空间分辨能力和皮秒量级时间分辨能力,并可用于测量铁磁性和反铁磁性,因而在自旋电子学材料和器件研究领域具有广泛的应用前景.     

Exploring nanomagnetism with soft X-ray microscopy

Magnetic soft X-ray microscopy images magnetism in nanoscale systems with a spatial resolution down to 15 nm provided by state-of-the-art Fresnel zone plate optics. X-ray magnetic circular dichroism (X-MCD) is used as the element-specific magnetic contrast mechanism similar to photoemission electron microscopy (PEEM), however, with volume sensitivity and the ability to record the images in varying applied magnetic fields which allows study of magnetization reversal processes at fundamental length scales. Utilizing a stroboscopic pump-probe scheme one can investigate fast spin dynamics with a time resolution down to 70 ps which gives access to precessional and relaxation phenomena as well as spin torque driven domain wall dynamics in nanoscale systems. Current developments in zone plate optics aim for a spatial resolution towards 10 nm and at next generation X-ray sources a time resolution in the fs regime can be envisioned.     

Micromagnetic analysis of unusual, V-shaped domain transitions in MnAs nanowires

V-shaped domain transitions in α‐MnAs nanowires were investigated by micromagnetic simulations. These rather unusual domain patterns are commonly observed experimentally by surface-sensitive magnetic imaging techniques. It has been speculated that the accompanying inclined domain walls in MnAs are the result of either an exchange biasing effect between ferromagnetic α‐MnAs wires and antiferromagnetic β‐MnAs wires or possibly due to competing exchange mechanisms in MnAs. Here we present evidence that these domain features are in fact transitions between three-dimensional flux-closure domains of opposite chirality and can therefore rule out the involvement of an antiferromagnetic biasing effect or anisotropic exchange. The formation of the energetically unfavorable V-shaped domain transitions is discussed in the context of the magneto-structural phase transition of the sample.     

Molecular orientation of thiol-derivatized tetraphenylporphyrin on gold studied by XPS and NEXAFS

Tetraphenylporphyrins bearing four linkers consisting of thioacetyl-functionalized carbon chains were immobilized on a gold surface via thiolate-gold bonds using two different preparation routes. The structure of these molecular layers was characterized in detail with synchrotron radiation based core-level spectroscopy, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results show that the geometry of the molecular layers and the number of linkers that bind to the gold surface depends on the preparation schemes. The deprotection of the linkers through removal of the terminal acetyl group before the molecular adsorption (deprotected systems) resulted in porphyrins bound to the gold surface with on the average three linkers, their normal axis being tilted ∼38° with respect to the surface normal. On the other hand, porphyrin layers prepared directly with the acetyl group still in place on the linkers (protected systems) are made of molecules bound to the gold surface via two linkers on the average. The resulting orientation is more upright, with the normal axis of the porphyrin plane tilted ∼50° with respect to the surface normal. Moreover, NEXAFS measurements revealed that the acetyl deprotected porphyrin layers have a higher degree of ordering than the protected systems.     

Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source

We present examples of the application of synchrotron-based spectroscopies and microscopies to environmentally relevant samples. The experiments were performed at the molecular environmental science beamline (11.0.2) at the Advanced Light Source, Lawrence Berkeley National Laboratory. Examples range from the study of water monolayers on Pt(1 1 1) single crystal surfaces using X-ray emission spectroscopy and the examination of alkali halide solution/water vapor interfaces using ambient pressure photoemission spectroscopy, to the investigation of actinides, river water biofilms, Al-containing colloids and mineral–bacteria suspensions using scanning transmission X-ray spectromicroscopy. The results of our experiments show that spectroscopy and microscopy in the soft X-ray energy range are excellent tools for the investigation of environmentally relevant samples under realistic conditions, i.e., with water or water vapor present at ambient temperature.     

Tuning the coercive field of Ni and CuNi thin films with the embedding of Co nanoparticles: An element-specific study

Cobalt nanoparticles have been embedded either within magnetic thin films of CuNi or Ni, or at their interface with an Al capping layer. Soft X-ray magnetic circular dichroism (XMCD) was used to measure element-specific hysteresis loops, allowing discrimination between the nanoparticles and the host film. The hysteresis shows coupling between the nanoparticles and the films and a reduction in coercivity is observed when positioning the nanoparticles within the film, as opposed to at its interface with the cap. Sum rule analysis of the XMCD spectra makes it possible to determine the orbital to spin moment ratios for Co and Ni in the samples. The difference in the calculated ratios is consistent with the differences in the coercivities, the films appearing more homogenous due to hybridization of the 3d bands of Co and Ni when the nanoparticles are embedded deeper within the films, creating less pinning sites and hence a lower coercivity.     

Thickness-dependent magnetic domain structures of Co ultra-thin film investigated by scanning transmission X-ray microscopy

Thickness-dependent magnetic domain structure of ultrathin Co wedge films (0.3 nm–1.0 nm) sandwiched by Pt layers was investigated by scanning transmission x-ray microscopy (STXM) employing X-ray magnetic circular dichroism (XMCD), utilizing elliptically polarized soft x-rays and electromagnetic fields, with a spatial resolution of 50 nm. The magnetic domain images measured at the Co L₃ edge showed the evolution of the magnetic domain structures from maze-like form to the bubble-like form as the perpendicular magnetic field was applied. The asymmetric domain expansion of a 500 nm-scale bubble domain was also measured when the in-plane and perpendicular external magnetic field were applied simultaneously.     

Geometrical characterization of adenine and guanine on Cu(1 1 0) by NEXAFS, XPS, and DFT calculation

Adsorption of purine DNA bases (guanine and adenine) on Cu(1 1 0) was studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine-structure spectroscopy (NEXAFS), and density-functional theory (DFT) calculation. At coverages near 0.2 monolayers, Angular-resolved NEXAFS analysis revealed that adenine adsorbates lie almost flat and that guanine adsorbates are tilted up on the surface with the purine ring parallel to the atom rows of Cu(1 1 0). Referring to the previous studies on pyrimidine DNA bases [M. Furukawa, H. Fujisawa, S. Katano, H. Ogasawara, Y. Kim, T. Komeda, A. Nilsson, M. Kawai, Surf. Sci. 532-535 (2003) 261], the isomerization of DNA bases on Cu(1 1 0) was found to play an important role in the adsorption geometry. Guanine, thymine and cytosine adsorption have an amine-type nitrogen next to a carbonyl group, which is dehydrogenated into imine nitrogen on Cu(1 1 0). These bases are bonded by the inherent portion of -NH-CO- altered by conversion into enolic form and dehydrogenation. Adenine contains no CO group and is bonded to Cu(1 1 0) by participation of the inherent amine parts, resulting in nearly flatly-lying position.     

Study of the local micro-structure and magnetic and transport properties of CrxGe1−x thin films

The local micro-structure as well as the magnetic and transport properties of Cr_xGe_1−x films prepared by means of magnetron sputtering have been investigated. Structural analysis shows that Cr atoms are situated in substitutional sites in the Ge lattice. Electrical transport properties indicate that Cr introduces a shallow acceptor level at 0.016 eV from the valence band implying Cr substituting for Ge. The low temperature ferromagnetism observed in the films is mediated mainly by ferromagnetic superexchange interactions between diluted Cr ions.     

利用X射线磁性圆二色吸收谱计算3d过渡族磁性原子的轨道和自旋磁矩

在4个方面研究了实验数据的预处理和应用加和定则中的问题.1)外磁场对样品电流法测量的吸收谱强度的影响.发现外磁场H<200×10^-4T时，信号强度正比于H^-β；当H>200×10^-4T时，尽管外磁场继续增加，但信号强度基本保持不变.2)不同方向的电磁铁剩磁会导致吸收谱的分离.这种分离与入射光的偏振态和样品的磁性无关，可以通过乘以一个常数很好地消除这种分离.3)通过XPSPEAK 4.1对实验数据拟合，写出了吸收谱的解析函数.利用解析函数的积分值，建立一种相对“客观"的标准，判断在一定的实验条件下，不同的数值积分方法的准确性.4)以误差函数作为吸收谱的背景函数，建立了一套完整的X射线磁性圆二色的数据处理方法.最后用Bode积分法计算出20nm厚Co膜的轨道和自旋磁矩分别为0.141μ_B和1.314μ_B. 关键词： X射线磁性圆二色 加和定则 台阶函数 吸收谱拟合     

The variation of Mn-dopant distribution state with x and its effect on the magnetic coupling mechanism in Znl-xMnxO nanocrystals

Zn1-xMnxO （x = 0.0005, 0.001, 0.005, 0.01, 0.02） nanocrystals are synthesized by using a wet chemical process. The coordination environment of Mn is characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, and its X-ray absorption fine structure. It is found that the solubility of substitutional Mn in a ZnO lattice is very low, which is less than 0.4%. Mn ions first dissolve into the substitutional sites in the ZnO lattice, thereby forming Mn2＋O4 tetrahedral coordination when x ≤ 0.001, then entering into the interstitial sites and forming Mn3＋O6 octahedral coordination when x ≥ 0.005. All the samples exhibit paramagnetic behaviors at room temperature, and antiferromagnetic coupling can be observed below 100 K.     

The variation of Mn-dopant distribution state with x and its effect on the magnetic coupling mechanism in Zn_(1-x) Mn_x O nanocrystals

Zn1-x Mn x O(x = 0.0005,0.001,0.005,0.01,0.02) nanocrystals are synthesized by using a wet chemical process.The coordination environment of Mn is characterized by X-ray photoelectron spectroscopy,Raman spectroscopy,and its X-ray absorption fine structure.It is found that the solubility of substitutional Mn in a ZnO lattice is very low,which is less than 0.4%.Mn ions first dissolve into the substitutional sites in the ZnO lattice,thereby forming Mn2+O4tetrahedral coordination when x ≤ 0.001,then entering into the interstitial sites and forming Mn3+O6octahedral coordination when x ≥ 0.005.All the samples exhibit paramagnetic behaviors at room temperature,and antiferromagnetic coupling can be observed below 100 K.     

The molecular orientation of DNA bases on H-passivated Si(1 1 1) surfaces investigated by means of near edge X-ray absorption fine structure spectroscopy

Layers of the DNA bases adenine, cytosine, and guanine were deposited onto hydrogen passivated Si(1 1 1) surfaces. The average tilt angles of these molecules with respect to the substrate surface were determined by the angular dependence of the Near Edge X-ray Absorption Fine Structure (NEXAFS) of the carbon K-edge. The interpretation of the NEXAFS spectra was assisted by a semi-empirical approach to the calculation of the π^∗-transition region which employs density functional theory calculations and core level photoemission data.     

Real-time observation on surface diffusion and molecular orientations for phthalocyanine thin films at nanometer spacial resolution

The morphology, electronic structure and ordering of the phthalocyanine thin films have been investigated at nanometer scale by photoelectron emission microscopy (PEEM) excited by polarized soft X-rays from synchrotron light source. The sample investigated was micropattern of silicon phthalocyanine deposited on gold surface. The incident angle dependences of the X-ray absorption near edge structure (XANES) spectra at the silicon K-edge revealed that the molecules of 5-layered films are lying nearly flat on the surface. Clear image of the micropattern was observed by PEEM, showing that the molecules are deposited via Volmer–Weber (VW) mode at room temperature. While, the surface diffusion was observed upon heating, and the micropattern image almost disappeared at 240 °C, representing the deposition mode changes from VW-mode to Frank–van der Merwe (FM)-one. On the basis of the photon-energy dependences of the brightnesses in the PEEM images, it was found that the molecules diffusing to the fresh gold surface rather stand-up at 240 °C. The observed changes in the molecular orientations at nanometer domains are discussed on the basis of the strengths of the molecule–molecule and molecule–surface interactions.     

Structural and magnetic properties of FIB-irradiated microstructures on a Pt/Co multilayer

We present a study of the structural and magnetic effects induced by focused 30 keV Ga⁺ ion beam irradiation on a Pt(2.8 nm)/[Pt(0.6 nm)/Co(0.3 nm)]₆/Pt(6.5 nm) ferromagnetic multilayer, using transmission electron microscopy, optical and magneto-optical microscopy. The work is of relevance to high-density data-storage applications, where media planarity is crucial for device reliability.     

单晶和孪晶的Zn0.96Co0.04O稀磁半导体薄膜的制备与研究

采用分子束外延技术分别在不同晶面的蓝宝石（sapphire Al₂O₃）基片上制备了沿c轴生长的Zn_0.96Co_0.04O稀磁半导体薄膜.发现在Al₂O₃（1120）晶面（a面）上薄膜是二维层状外延生长的高质量单晶薄膜,而在Al₂O₃（0001）晶面（c面）上薄膜却具有有趣的孪晶结构,部分区域相互之间有一个30°的面内转动来减少和基片之间的失配度.在孪晶薄膜中存在的这些相互旋转形成的区域界面上会引起载流子强烈的散射作用,导致载流子迁移率的下降和平均自由程的缩短.利用X射线吸收精细结构技术证明了无论单晶还是孪晶的Zn_0.96Co_0.04O薄膜中所有的Co都以+2价替代进入了ZnO的晶格,而没有形成任何杂相.而对其磁性研究发现,孪晶的薄膜样品比高质量的单晶薄膜样品具有大得多的饱和磁矩.这充分说明孪晶薄膜中的铁磁性来源与缺陷有关.我们还对铁磁性耦合机制进行了探讨. 关键词： Co掺杂ZnO 稀磁半导体 X射线吸收精细结构 单晶和孪晶薄膜