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The structural dynamics of an iodide layer adsorbed on Au(111) were investigated using X-ray photon correlation spectroscopy (XPCS), electrochemical scanning tunneling microscopy (STM), and time-resolved X-ray diffraction. At the adsorption equilibrium of iodide at a constant electrode potential, the STM images captured at regular intervals show the migration of atomic vacancy sites in the ordered adsorbed iodide layer. The results indicate that reversible adsorption/desorption and site conversion continuously occur at the equilibrium state. Although the transitions occur at various time scales according to the STM images, the time decay of the autocorrelation function at the specular position is estimated to be 127 s according to the XPCS measurement. The dynamics observed using XPCS suggest that the vertical relaxation of the surface layers is associated with the adsorption of iodide.

Using in situ synchrotron X-ray reciprocal space mapping, this study investigates the evolution of lattice deformations in the InGaAs/GaAs(1 1 1)A structure with or without a thin InAs layer grown by molecular beam epitaxy. During the initial growth phase, InGaAs directly grown on GaAs(1 1 1)A showed an anomalous lattice shrinkage along the c-axis, with no change in the indium composition. Conversely, the InGaAs grown on InAs/GaAs(1 1 1)A showed no initial lattice distortion, but a variable indium composition. The evolution of the diffraction peak broadening was also monitored. The results confirmed that the thin InAs layer effectively improved the crystal quality during the initial growth of InGaAs.

The beamline for angle-resolved photoemission spectroscopy (ARPES) with a nano-focused beam (nano-ARPES) is planned as one of the public beamlines in NanoTerasu, the 3-GeV next-generation synchrotron radiation facility at Tohoku, Japan, which is scheduled to start operation in 2024. A 4 m long APPLE-II type undulator provides brilliant soft X-rays with various polarizations (linear horizontal and vertical, and left and right circular) in the energy range of 50-1,000 eV. A collimated plane grating monochromator is adopted as a soft X-ray monochromator because we can select the demagnification factor of grating cf f = cosα/cosβ between the high energy-resolution (HR) mode for HR-ARPES experiments and the low divergence mode for high-flux nano-ARPES measurements. This beamline aims to produce the high flux nano-focused beam by using ultrahigh precision reflective mirror optics, not a Fresnel zone plate used as a focusing optics in the previous nano-ARPES station at other synchrotron facilities.

A synchrotron radiation beamline in the soft- and tender-X ray energy range of 180-3000 eV with versatile polarization control has been designed for NanoTerasu, the 3-GeV next-generation synchrotron radiation facility at Tohoku, Japan. A series of four APPLE-II type undulators is adopted as a photon source to realize the required beam properties with high-speed polarization switching. The beamline optics is designed for a highly efficient and precise use of x-ray magnetic circular/linear dichroism (XMCD/XMLD) technique balancing high photon flux and energy resolution. The simulated performance of the segmented undulator together with the monochromator optics achieved the sufficiently high flux and energy resolution (E/ΔE) in whole target energy range. Two endstations with the different re-focus optics, one for marginal spot size with high flux and the other for ultimate focus down to ∼10 nm are also designed. The simulated performance of the beamline encourages the future researches of high-throughput and nm-focused spintronic measurements.

The optical design of the ultrahigh-resolution RIXS beamline, which is currently developed at NanoTerasu in Japan, is described. The main goal of this beamline is to perform ultrahigh-resolution RIXS measurements with a total energy resolution of E/ΔE>150,000 for both beamline and RIXS spectrometer. To achieve the ultra-high resolution, a 2D-RIXS spectrometer using energy-dispersive X-ray is employed to compensate for lower throughput at higher energy resolution, and the optics of the beamline is optimized for the 2D-RIXS spectrometer. A vertically dispersing in-focus variable-included-angle varied-line-spacing plane grating monochromator is employed for the beamline, with an entrance slit to ensure the ultrahigh resolution. First and second mirrors focus X-ray on entrance slits vertically and horizontally, respectively, and the divergent X-ray is irradiated onto the grating. For the 2D-RIXS spectrometer, there is no exit slit, and the vertically energy-dispersed X-ray is irradiated directly onto a sample. In front of the sample, X-ray is horizontally refocused by a Wolter type-I mirror. The expected horizontal focus size at the sample is ~0.7 μm. The expected photon flux is ~1×1011 photons/s at 500–1000 eV with a virtual slit width of 2 μm required for E/ΔE>150,000. The height of the dispersed X-ray available in the 2D-RIXS spectrometer is ~120 μm, which allows the use of a remarkably high flux of ~6×1012 photons/s, and the beamline will serve as an ultrahigh-resolution and high-efficiency RIXS facility.

In this study, we analyzed the influence of indium supply on the growth dynamics of gold-catalyzed InGaAs nanowires by in situ synchrotron X-ray diffraction. A high In/Ga supply ratio results in strong size inhomogeneity of Au particles and interrupts the nanowire growth at a certain point of time. Based on the experimental results, we discussed the state of Au catalysts with high indium content during the nanowire growth. We found that a growth temperature below the eutectic temperature is essential to avoid the growth interruption and maintain the nanowire growth. The high In/Ga ratio necessitates accurate size control of Au particles before growth for further improvement of the nanowire growth.

Strain relaxation of InxGa1−xAs/GaAs(001) with systematically changed In content between x=0.23 and x=0.80 has been studied using in situ synchrotron X-ray diffraction during molecular beam epitaxy growth. Correlation between the In composition and the degree of relaxation in the InGaAs films was derived from the reciprocal space maps. While InGaAs with a uniform composition was grown in the regime of the two-dimensional growth, a separation of the In composition was observed for the InGaAs films grown in the Stranski-Krastanov mode.

In this work, in situ synchrotron X-ray diffraction reciprocal space mapping (RSM) measurements were carried out for the radio-frequency plasma-assisted molecular beam epitaxy (RF-MBE) growth of GaInN on GaN and InN layers, which were also grown by RF-MBE on commercialized GaN/c-sapphire templates. In situ XRD RSM measurements were performed using an MBE apparatus directly coupled to an X-ray diffractometer at the beamline of the synchrotron radiation facility SPring-8. It was observed in situ that both lattice relaxation and compositional pulling occurred during the initial growth stage, reducing the strain of GaInN on GaN and InN. Different initial growth behaviors of GaInN on GaN and InN were also observed from the results of the evolution of GaInN integrated peak intensities.

In situ synchrotron X-ray reciprocal space mapping was carried out to investigate the evolution of lattice strain and crystal structure of InGaN/GaN heterostructure nanowires grown by molecular beam epitaxy. At the beginning of the growth, the InGaN lattice was compressively strained to that of GaN, resulting in the pseudomorphic growth. This strain started to relax at a thickness of 3 nm and fully relaxed at 9 nm. Concomitantly, polytypes consisting of the zinc-blende and wurtzite phases were formed in InGaN., Compound Semiconductor Week 2019

The molecular beam epitaxial (MBE) growth of twenty-period InGaN/GaN multi-quantum-well (MQW) nanowires was investigated by in situ X-ray reciprocal space mapping (in situ RSM). The evolution of strain, composition, and their inhomogeneities during the growth significantly varied with increasing number of QWs. After the growth of the ninth QWs, InGaN was tensilely strained with poor crystalline quality as inferred from the diffraction peak position and shape. At the same time, another peak emerged at the higher indium composition, suggesting the segregation of InN in the MQW nanowires., Compound Semiconductor Week 2019

In recent years, graphene growth technology has been greatly progressed, and it is possible to grow graphene with millimeter-size single crystals using metal-catalysis CVD. However, the transfer process is unavoidably which largely deteriorates the graphene. We have proposed direct precipitation method of graphene using a W capping layer. The method does not only require a transfer process, but also the introduction of wrinkles will be suppressed by optimizing the cooling rate at the graphene precipitation. The growth conditions such as thickness of amorphous carbon, annealing temperature, cooling rate and crystallinity of Ni catalyst were systematically changed to study the mechanism of the precipitation method using the W cap layer. By the optimization of the conditions, wrinkle-free multilayer graphene with D/G ratio of less than 0.1 were successfully obtained directly on a sapphire substrate.

In situ X-ray diffraction measurement was performed to study the precipitation mechanism of graphene from Ni catalyst with and without Ti capping layer using X-ray beam from a synchrotron radiation facility. The graphene precipitated on the surface of the catalyst in the case without the Ti capping layer while it did at the interface between the catalyst and the sapphire substrate in the case with the Ti capping layer. Each process, such as graphene nucleation and precipitation was successfully monitored even though graphene precipitated under the metal catalyst. The detailed mechanisms for both cases were discussed using the experimental results. Consequently, the crystallization of the catalyst is found to effectively suppress the precipitation at low temperature, which is useful to improve the quality of the precipitated graphene. The adjustment of the amount of the carbons is another important factor to precisely control the precipitation because graphene also precipitates after the carbons saturate the catalyst.

In-situ X-ray diffraction was used to investigate initial stages of GaN growth on graphene-covered SiO2 substrates with or without AlN buffer layers by plasma-assisted molecular beam epitaxy. The in-plane lattice parameter of GaN remained almost constant during growth without AlN buffer layers, confirming weak interactions between GaN and graphene. On the substrate with AlN buffer layers, the GaN lattice parameter continuously changed from AlN value to GaN value, indicating that the AlN islands act as seeds for GaN growth. Besides, GaN has preferential orientations epitaxial to graphene. Graphene can be used as a template of GaN growth on amorphous substrates.

We carry out real-time in situ synchrotron X-ray diffraction on the growth of GaN and AlN on SiC(0001) substrate by molecular beam epitaxy. At the initial growth stage of GaN/SiC or AlN/SiC heterostructure, the epitaxial overlayer develops affected by defects with the strain interaction between SiC, eventually showing characteristic lattice deformations. GaN was almost relaxed at the initial stage, showing the transition of the growth mode from 3D to 2D at around 4 nm. In contrast, AlN coherently grow on SiC(0001) at the initial stage for 13 nm concomitantly showing lattice deformation with the beneath SiC, subsequently showing gradual lattice relaxation.

The evolution of polytypism during GaAs nanowire growth was investigated by in situ X-ray diffraction. The growth of nanowires was found to start with the formation of zincblende structure, followed by the growth of wurtzite structure. The growth process was well reproduced by a simulation based on a layer-by-layer nucleation model. The good agreement between the measured and simulated results confirms that nucleation costs higher energy for the stackings changing the crystal structure than for those conserving the preceding structure. The transition in prevalent structure can be accounted for by the change of local growth conditions related to the shape of a triple phase line rather than by the change in supersaturation level, which quickly reaches steady state after starting growth.

In situ three-dimensional X-ray reciprocal space mapping ( in situ 3D-RSM) was employed for studying molecular beam epitaxial (MBE) growth of InGaAs multilayer structures on GaAs(0 0 1). Measuring the symmetric 004 diffraction allowed us to separately obtain film properties of individual layers and to track the real-time evolution of both residual strain and lattice tilting. In two-layer growth of InGaAs, significant plastic relaxation was observed during the upper layer growth, and its critical thickness was experimentally determined. At the same thickness, it was found that the direction of lattice tilting drastically changed. We discuss these features based on the Dunstan model and confirm that strain relaxation in the multilayer structure is induced by two kinds of dislocation motion (dislocation multiplication and the generation of dislocation half-loops).

Multilayer structures comprised of a central layer of the binary transition metal pnictide MnSb and outer layers of standard semiconductors have been grown using molecular beam epitaxy (MBE). The growth of the GaAs overlayers was characterized using a combination of reflection high energy electron diffraction (RHEED) and in situ surface x-ray diffraction (SXRD). It was found that a GaAs overlayer can be grown via MBE onto a MnSb(1 101)/GaAs(001) virtual substrate. For both GaAs(111)A and InGaAs(111)A starting substrates, it was found that the GaAs overlayer altered the final strain state of the central MnSb layer causing a change from tensile strain to compressive strain in the out of plane direction.

In situ synchrotron X-ray diffraction studies during the growth of arsenide and nitride semiconductors are presented. The large penetration depth of X-rays was exploited for revealing structural changes at buried interfaces as well as near the surface. Experiments were performed at a synchrotron beamline, BL11XU, SPring-8, using a molecular-beam epitaxy chamber integrated with a high-precision X-ray diffractometer. A high-speed X-ray reciprocal space mapping technique was applied to a variety of heteroepitaxial systems including InGaAs on GaAs(001), InGaAs on GaAs(111)A and GaN on SiC(0001). Results showed that even layers as thick as 200 nm were not necessarily stable even after being buried under an overlayer but could undergo significant structural changes during growth.

The effect of substrate orientation on strain relaxation mechanisms of an InGaAs layer grown on vicinal GaAs substrates was investigated by in situ X-ray diffraction (XRD). The crystallographic tilt and indium segregation in the InGaAs layer were altered depending on the miscut direction and angle. In the case of the substrate tilted 6° toward the [110] direction, one type of misfit dislocations was formed preferentially rather than other types, especially in the rapid relaxation phase. While in the case of the substrate tilted 6° toward the direction, no anisotropies during relaxation were observed. The present finding indicates that the appropriate use of vicinal substrates may lead to a novel method of improving the crystal quality of heterolayers.

We have investigated the growth by molecular beam epitaxy (MBE) of GaAs on MnSb. MnSb epilayers on GaAs(111), GaAs(001) and In0.5Ga0.5As(111) of thickness ∼ 50 nm were used as substrates for GaAs films. The MBE growth of GaAs was monitored in situ using synchrotron X-ray diffraction and reflection high energy electron diffraction. We show data on strain relaxation and growth mode, and discuss the epitaxial relationship between GaAs(001) and MnSb(11‾01). Schematic of the molecular beam epitaxy/X-ray diffraction in situ experiment and typical 2D detector data, with GaAs(111) and MnSb(0001) diffraction features.

A molecular beam epitaxy (MBE) chamber dedicated to nitride growth was developed at the synchrotron radiation facility SPring-8. This chamber has two beryllium windows for incident and outgoing X-rays, and is directly connected to an X-ray diffractometer, enabling in situ synchrotron X-ray measurements during the nitride growth. Experimental results on initial growth dynamics in GaN/SiC, AlN/SiC, and InN/GaN heteroepitaxy were presented. We achieved high-speed and high-sensitivity reciprocal space mapping with a thickness resolution of atomic-layer scale. This in situ measurement using the high-brilliance synchrotron light source will be useful for evaluating structural variations in the initial growth stage of nitride semiconductors.

The polytypism of GaAs nanowires was investigated by in situ X-ray diffraction under different growth conditions. The growth of nanowires was found to start with the formation of the zincblende structure, followed by the growth of the wurtzite structure. The observed growth process of nanowires was well reproduced by simulations based on a layer-by-layer nucleation model. At a low growth temperature and a high growth rate, stacking faults were found to be frequently introduced owing to the reduction in energy barrier. As a result, the zincblend and wurtzite segments in nanowires were highly fragmented and the wurtzite structure was formed in the early stage of growth.

We report an anomalous lattice deformation of GaN layers grown on SiC(0001) by molecular beam epitaxy. The evolution of the lattice parameters during the growth of the GaN layers was measured by in situ synchrotron X-ray diffraction. The lattice parameters in the directions parallel and normal to the surface showed significant deviation from the elastic strains expected for lattice-mismatched films on substrates up to a thickness of 10 nm. The observed lattice deformation was well explained by the incorporation of hydrostatic strains due to point defects. The results indicate that the control of point defects in the initial stage of growth is important for fabricating GaN-based optoelectronic devices.

Direct measurements on the growth of InAs quantum dots (QDs) and various cap layers during molecular beam epitaxy are performed by in situ X-ray diffraction (XRD). The evolution of strain induced both in the QDs and cap layers during capping is discussed based on the XRD intensity transients obtained at various lattice constants. Transients with different features are observed from those obtained during InGaAs and GaAs capping. The difference observed is attributed to In-Ga intermixing between the QDs and the cap layer under limited supply of In. Photoluminescence (PL) wavelength can be tuned by controlling the intermixing, which affects both the strain induced in the QDs and the barrier heights. The PL wavelength also varies with the cap layer thickness. A large redshift occurs by reducing the cap thickness. The in situ XRD observation reveals that this is a result of reduced strain. We demonstrate how such information about strain can be applied for designing and preparing novel device structures.

To evaluate local atomic structures around Co in high temperature diluted ferromagnetic semiconductor Co-doped TiO2, x-ray fluorescence holography and x-ray absorption fine structure experiments were carried out on rutile paramagnetic Ti0.99Co0.01O2 and ferromagnetic Ti0.95Co0.05O2 films. The Co atoms in the Ti0.99Co0.01O2 simply substituted for Ti sites in the rutile structure, whereas a suboxidic arrangement of CoO2Ti4 formed around Co in the Ti0.95Co0.05O2 films. A theoretical investigation based on a series of first-principles calculations indicated the stability of the aggregated suboxidic clusters in the rutile TiO2, supporting our hypothesis for the formation of suboxidic coordination in the highly Co-doped sample. The suboxidic coordination may be the source of strong exchange interaction, resulting in the high Curie temperature in Co-doped TiO2.