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The contrasts in backscattered electron (BSE) images were studied from the cross section of a heat-treated steel sheet using a scanning electron microscope (SEM) equipped with a conventional annular BSE detector. BSE images were taken at various primary electron energies (Ep) and take-off angles (θ; measured from the specimen surface) of the detector. Low Ep and low θ improved surface information and channeling contrast, whereas high Ep and high θ enhanced bulk information and reduced channeling contrast, resulting in improved material (Z) contrast. These results regarding channeling contrast and Z contrast can be understood by the ratio of low-loss electrons (LLEs) to the inelastic BSE components detected; LLEs contribute to channeling contrast, and their ratio increases with decreasing Ep and θ. The systematic results obtained in this study are helpful for controlling SEM conditions in order to select Z and crystallographic information separately in BSE images for practical materials of interest. Copyright © 2014 John Wiley & Sons, Ltd.

Energy dispersive X-ray spectroscopy (EDS) has been applied to thin Cr films on Fe and Fe–Ni alloys with the primary electron energy (EP) of scanning electron microscopy (SEM) as low as 1.5 keV. The detection depth of SEM-EDS with an EP of 1.5 keV is estimated to be less than 20 nm for the L emission of Fe in Cr. Linear relationships were obtained between Fe–Ni alloy compositions determined by chemical analysis and those derived by a quantitative calculation from the Fe-L and Ni-L peaks measured with the EP from 1.5 to 15 keV. SEM-EDS can be a quantitative analysis technique with high spatial resolution for material surfaces when combined with low EP's. Copyright © 2014 John Wiley & Sons, Ltd.

In the HCCH molecule, H2+ ions have been produced only at the 1s→π* excitation, suggesting that the H2+ ion formation is mediated by the core excitation. The nuclear motion in the C 1s−1π* core-excited state is probed using a multiple-ion-coincidence imaging technique and the enhanced cis bending motion is found by examining the H–H correlation angle distributions. The H2+ formation is thus attributed to the cis bending motion caused in the C 1s−1π* state.

Photoelectron–photoion–photoion coincidence momentum imaging was applied to study 2p photoemission from Ar dimers. We present measurements of the kinetic energy released in fragmentation of Ar++2, angular distributions of energetic fragments, angular distributions of photoelectrons in the laboratory frame and in the molecular frame. The mean kinetic energy of fragment Ar+ ions, 2.2 eV, is larger than the value estimated from the Coulomb explosion model with the equilibrium Ar–Ar distance. No significant differences between the photoelectron angular distributions of monomers and dimers can be found in the laboratory frame. The photoelectron angular distributions of dimers in the molecular frame show a minimum for electron emission along the dimer axis at low energies (1.2 and 3.4 eV) and become isotropic at higher kinetic energies.

Reconstruction of an InP(001) surface structure upon H2S adsorption has been studied by low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), high-resolution electron energy loss (HREELS), and x-ray photoelectron spectroscopies (XPS). The HREELS result indicates that H2S is dissociated on the surface even at RT, leading to evolution of hydrogen from the surface. LEED patterns show (2×4) and (2×1) structures for the surface with sulfur coverages, 0 and 0.5–1 ML, respectively. A complex pattern appears at 0.25 ML. We find in STM images that the (2×1) structure starts to form even at 0.1 ML sulfur coverage at 350 °C. The (2×1) structure is almost established at 0.5 ML although the protrusions of about two atoms in size exist on the surface. The new (2×1) structure begins to grow from protrusions above 0.5 ML on the (2×1) surface found at 0.5 ML and it is established at about 1 ML where the c(2×2) structure with small domain is found. XPS result shows one chemical state of sulfur at 0.5...

The charge distribution inPb 2 Sr 2 YCu 3 O 8+δ and PbBaSrY 1− x Ca x Cu 3 O 7+δ has been studied by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES). The Cu 2p core-level and the Pb M 3 XANES show that the valences of Cu and Pb in the blocking layers are + 1 and + 2, respectively, for the oxides synthesized in a reducing atmosphere (δ = 0). The valences of Cu and Pb increase after oxidation by annealing in O 2 gas. On the other hand, the substitution of Ca for Y ( x = 0.2) hardly changes the valences of Cu and Pb. The core-levels of Ba, Sr and Y are not changed in the binding energy by the oxidation, but are shifted to the lower-binding-energy side by the substitution. These results will be discussed in terms of charge distributions in the crystal structures before and after the oxidation and substitution.

The electronic structures of Cr(PO 4 )·6H 2 O and Zn 3 (PO 4 ) 2 ·4H 2 O have been studied by using total-electron-yield X-ray absorption near-edge structure (TEY-XANES) and resonant Auger electron spectroscopy (AES). In P K edge XANES spectra. which are associated with the electron transition from P 1 s to P3 p -dominant states, a pre-edge peak followed by a main peak is observed for Cr(PO 4 )·6H 2 O but not for Zn 3 (PO 4 ) 2 ·4H 2 O. The main peaks have different energies. The energy differences between P KL 2,3 L 2,3 normal and spectator Auger peaks at specific photon energies are larger for Zn 3 (PO 4 ) 2 ·4H 2 O than for Cr(PO 4 )·6H 2 O. These are associated with differences between the hybridization of P3 p -dominant states and the3 d and4 s states of the cations. The sampling depth of TEY-XANES has also been estimated on the basis of simple specimen current measurements. The sampling depth measured by using silicon substrates covered with aluminium overlayers exceeds 100 nm. This value is determined by the penetration length of Auger electrons excited by the X-rays and the inelastic mean free path of secondary electrons excited by inelastically scattered Auger electrons.

We have developed an ultra-fast multi-hit TDC to improve the momentum resolution in the multiple coincidence momentum imaging spectroscopy. The TDC consists of 12 bit/100 MHz crystal oscillator counters and seven time-to-amplitude converters. The TDC receives signals up to 6 as start pulses and one signal as a stop signal. The time resolution of the TDC is about 120 ps under the time span of 40 μ s. Using the present TDC, we have obtained the vibrational-resolved core-level photoelectron momentum distribution of CO molecules in coincidence with two fragment ions.

The Pb 1201 phases, Pb 0.5 Cu 0.5 Sr 2− x La x CuO y , with x = 1.0–1.2 and Pb 0.6 Cu 0.4 Sr 2− x La x CuO y , with x = 0.9–1.2 have been prepared at 1010–1015°C for 1.7–2.0 hours in flowing oxygen. To evaluate the Cu valence in the CuO 2 sheet, the Pb valence is separately determined by K 2 Cr 2 O 7 titration, in addition to the oxygen content determination by iodometry. The T c (onset) rises as the oxygen content decreases due to release of the overdoping, but was not affected by La 3+ substitution for Sr 2+ and by the Pb content in the (Pb,Cu)O layer. The explanation is that the Cu valence in the CuO 2 sheet decreases as the oxygen content decreases, while the Pb valence is reduced by La 3+ substitution or the Pb content increases.

The binding energies of Sr 3 d 5 2 , Ba 3 d 5 2 , Ca 2 p 3 2 and Y 3 d 5 2 can be a measure of hole concentration in the CuO2 planes for the cuprates. We applied this to Bi2Sr2CaCu2Oy by a combination with the investigation the Bi 4 f 7 2 core level in order to elucidate the charge distribution in the crystal structure. Changes of the hole concentration in the CuO2 planes and charge redistribution caused by reducing oxygen content and by substituting Y for Ca are compared and discussed.

Measurements of superconducting properties, X-ray photoelectron and inverse-photoemission spectroscopy have been performed on Bi 2 Sr 2 Ca 1− x Gd x Cu 2 O y (0 ≤ x ≤ 1.0) ceramics, where the metal-insulator transition is observed at x ∼ 0.6. The density of states at the Fermi level is reduced with increasing Gd ion contents at Ca sites. Annealing the samples in vacuo increases the critical temperature even at optimum hole concentration ( x = 0.1). Changes in the electronic states are discussed in terms of the hole concentration.

Polycrystalline AgI-intercalated Bi 2 Sr 2 CaCu 2 O z is prepared and the structure and physical properties studied. The lattice parameters a and c are determined to be 5.40 and 22.8 A, respectively. The expansion of the lattice parameter c is 7.4 A, compared with that of a Bi 2 Sr 2 CaCu 2 O z (Bi2212) specimen ( c/2: 15.4 A ). This expansion is more than twice as large as that of iodine-intercalation (3.6 A). The EPMA measurement shows that the I/Ag ratio in the AgI-intercalated specimen is greater than 1.0. The T c is 69 K, which is lower than that of Bi2212 (75 K) and almost the same as that of IBi 2 Sr 2 CaCu 2 O z (IBi2212, 67 K). The effect of AgI-intercalation on the superconductivity is discussed.

The relation between the superconductivity and the Cu valence of TlSr 2 Ca 1− x Y x Cu 2 O y is investigated. The facts that the Cu valence of the optimum-doped specimen, if Tl 3+ is assumed, is rather low and that even the specimen with a Cu valence as low as 2.02 shows superconductivity suggest a small charge transfer from the TlO-layer to the CuO 2 -sheets. The binding energy shift of the Tl 4f core level measured by XPS lends support to the slight decrease in Tl valence.

The superconductivity of Tl 0.5 Pb 0.5 Sr 2− x Nd x CuO 5−δ was observed for x ≥ 0.3, although the calculated Cu valence assuming Tl 3+ and Pb 4+ is slightly above or below 2.0. The binding energy of the Tl and Pb 4f core levels measured by XPS shifted to higher energy than those of Tl 3+ and Pb 4+ in the reference materials, showing that the Tl and Pb valences are lower than 3 + and 4 +, respectively. These observations strongly suggest that holes in the CuO 2 sheet are created by charge transfer from the (Tl,Pb)O layer, similar to the double-layered TlBa cuprates. In contrast, the temperature variation of electrical conductivity of Tl 0.5 Pb 0.5 Sr 2 CuO 5−δ changed from metallic to semiconducting with increasing oxygen deficiency, δ, and no superconductivity was observed through any control of δ. Although XPS measurement also suggested that Tl and Pb valences lowered with increasing oxygen deficiency, δ, the reason why the system did not show superconductivity can be understood by the depletion of oxygen from the CuO 2 plane during deoxygenation.

We find a universal relationship between core-level binding energies of the Ba 3${\mathit{d}}_{5/2}$, Sr 3${\mathit{d}}_{5/2}$, Ca 2${\mathit{p}}_{3/2}$, and Y 3${\mathit{d}}_{5/2}$ levels and ${\mathit{T}}_{\mathit{c}}$ among several hole-type high-${\mathit{T}}_{\mathit{c}}$ and related oxides (the Y, Bi, and Pb systems) with two Cu-${\mathrm{O}}_{2}$ planes in a unit structure. The binding-energy dependence of ${\mathit{T}}_{\mathit{c}}$ is very similar to the hole-concentration dependence of ${\mathit{T}}_{\mathit{c}}$. This suggests that the local electronic states around Ba, Sr, Ca, and Y should be common and the core-level binding energies of these elements can be a measure of the hole concentration for these oxides.

Bi[sub 2+[ital x]]Sr[sub 2[minus][ital x]]CuO[sub [ital y]] (0.10[le][ital x][le]0.40) polycrystalline samples have been studied by x-ray diffraction, resistivity and Hall-coefficient measurements, x-ray and ultraviolet photoemission spectroscopy, and inverse-photoemission spectroscopy (IPES). The lattice constant of the [ital c] axis decreases and that of the [ital a]([ital b]) axis increases as a function of [ital x]. The results of Hall-coefficient measurements indicate that hole concentration is reduced as a function of [ital x], which is consistent with the results of oxygen-concentration measurements. We find no energy shifts of the core levels, valence bands, and conduction bands for the samples, which is completely different from the results for the Bi[sub 2]Sr[sub 2]Ca[sub 1[minus][ital x]]Y[sub [ital x]]Cu[sub 2]O[sub [ital y]] system. The results of IPES and resistivity measurements show that the metal-semiconductor transition occurs at about [ital x]=0.35. The states created by hole doping move to the Fermi level. The change in the electronic states is discussed.

This paper reviews valence states of rare-earth elements studied by photoelectron and X-ray absorption spectroscopies for the high- T c and related oxides, focussing on the rare-earth valences in the 1:2:3 and the 2:1:4 systems. Topics related to Pr in the 1:2:3 system and some rare earths in the 2:1:4 system are described.

The structure and superconductivity of Tl 0.5 Pb 0.5 Sr 2 CuO y were studied by controlling the oxygen content or partially substituting lanthanide ions for Sr(II). The crystal structure greatly changed with the oxygen content. The samples with nearly full oxygen content ( y ∼5.0) had tetragonal symmetry, while those with the lowest oxygen content ( y ∼4.3) showed orthrhombic symmetry. The c -dimension increased for y >4.8 and then decreased with decreasing oxygen content, while the a -dimension was almost independent of composition. On the other hand, in the case of lanthanide substitution, the a - and c -dimensions were increased and decreased respectively with increasing lanthanide content. Superconductivity appeared with the substitution of a small amount of lanthanide ions for Sr(II), but was never achieved by controlling the oxygen content.

The procedure of quantitative XPS analysis involving the relative sensitivity factors is most convenient to apply to high T c superconductor surfaces because this procedure does not require standards. However, a considerable limitation of such an approach is its relatively low accuracy. In the present work, a proposition is made to use for this purpose a modification of the relative sensitivity factor approach accounting for the matrix and the instrumental effects. The accuracy of this modification when applied to the binary metal alloys is 2% or better. A quantitative XPS analysis was made for surfaces of the compounds Bi 2 Sr 2 CuO 6 , Bi 2 Sr 2 CaCu 2 O 8 , and YBa 2 Cu 3 O Y . The surface composition determined for the polycrystalline samples corresponds reasonably well to the bulk stoichiometry. Slight deficiency of oxygen was found for the Bi-based compounds. The surface exposed on cleavage of the Bi 2 Sr 2 CaCu 2 O 8 single crystal was found to be enriched with bismuth, which indicates that the cleavage occurs along the BiO planes. This result is in agreement with the STM studies published in the literature.

Interfaces of titanium films (100 nm) formed by vacuum deposition and by ion plating onto austenitic stainless steels (type 304 stainless steel) were investigated using Auger electron spectroscopy (AES). Although AES depth profiles showed that ion plating produced a much deeper graded interface area than vacuum deposition, AES images of Ti proved that the AES depth profile of the ion-plated film was significantly influenced by preferential sputtering. Electron channelling patterns showed that the grains of the substrate whereTi remained during Ar ion sputtering have orientations close to the (110) of the λ-Fe structure. Transmission electron microscopy (TEM) observation showed an interface layer several nanometres thick on a (31 1 ) plane of type 304 stainless steel.

The International Prototype of the Kilogram, which is the only artificial material defining one of the fundamental constants, has been reported to gain mass as time elapses after it is cleaned. The surface of a Pt-Ir alloy that has been used for the newer Kilogram prototypes was analysed by XPS and thermal desorption spectroscopy (TDS) to investigate the cause of mass gain, its time dependence and the effect of the cleaning method. The main cause of the mass gain was found to be adsorption of carbon (in the form of hydrocarbons) and oxygen (as water) from the atmosphere. The amounts of the two contaminant elements were almost saturated 6 months after sample cleaning. Cleaning methods do not make a large difference to adsorption behaviour. Although surface iridium is slightly oxidized, this effect is negligibly small.

Valence bands and core levels of BaBi 1-x Pb x O 3-δ have been investigated over a full compositional range between x=0 and 1 using x-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). With the substitution of Pb for Bi, the valence band centered at about 4 eV shifts toward the Fermi level (E F ). A clear Fermi edge is observed in both XPS and UPS valence-band spectra for 0.7≤x≤0.9 and change of the density of states at E F is found to correspond to the T c of this system

The O1s core level spectra recorded for the Bi2Sr2Can−1CunO2n+2+δ (n = 1, 2, and 3) oxides are investigated by taking into account the layered structures, the well developed cleavage between double Bi-O layers, and the surface sensitivity of photoelectron spectroscopy. The results show that the O1s core lines with binding energies of 527.9, 528.7, and 529.4 eV can be attributed to oxygen atoms in the Cu-O2, Bi-O, and Sr-O layers, respectively. In the Bi2Sr2Ca1−xYxCu2Oy system, the O1s line corresponding to oxygen atoms in the Cu-O2 planes shifts significantly to the high binding energy side with the substitution of Y for Ca. These results are discussed in terms of hole concentrations of metal-oxygen bonds.

Core-level electronic states of the ${\mathrm{YBa}}_{2}$${\mathrm{Cu}}_{3}$${\mathrm{O}}_{\mathit{y}}$${\mathrm{Br}}_{\mathit{x}}$ superconductor, tetragonal, and orthorhombic ${\mathrm{YBa}}_{2}$${\mathrm{Cu}}_{3}$${\mathrm{O}}_{\mathit{z}}$, and ${\mathrm{BaBr}}_{2}$ have been studied with use of x-ray photoelectron spectroscopy. The intensity ratio of the satellite to Cu 2${\mathit{p}}_{3/2}$ line increases from 0.31 for the nonsuperconducting tetragonal phase to 0.46 for the brominated superconductor sample. The latter value is close to that for the superconducting orthorhombic phase (0.51), which strongly suggests that holes are doped by bromination into the tetragonal phase. Comparison of the binding energies of Ba 3${\mathit{d}}_{5/2}$ and Br 3d for the brominated sample with those of ${\mathrm{BaBr}}_{2}$ shows that bromine in the former sample is strongly interacting with barium. The mechanism for the recovery of the superconductivity is discussed in terms of hole doping.

To examine the stability of prototypes of the kilogram after cleaning, surface analysis techniques, including X-ray photoelectron spectroscopy (XPS), were applied to specimens cut from prototype material of Pt-10% Ir alloy. Traditional steam-jet cleaning (SJC) was compared with ultrasonic cleaning with solvents (UCS) in terms of cleaning effects and the progress of contamination. The results show that mass changes due to metallic factors such as oxidation, reduction and dissolution were negligibly small. In terms of carbon decrease and adsorption of water, UCS was superior to SJC. From analyses of peak area ratio by XPS, it was shown that the cleaner the surfaces, the higher the rate of contamination. But the contamination levels converged to a common value after a six-month exposure to air, irrespective of the cleaning method used. This finding is of great importance for the preservation of prototypes. The contaminating substances were found to be hydrocarbons from the ambient air. The mass gain for the surfaces of a prototype due to hydrocarbons after a six-month exposure to ambient air is estimated to be 4,3 μg for SJC and 16 μg for UCS.

Iodine-intercalated Bi 2 Sr 2 CaCu 2 O y (Bi-2212) single crystal has been studied by x-ray and ultra-violet photoemission spectroscopy (XPS and UPS). We find a strong I 3d 5 2 line at 618.4 eV and small one at 623 eV which correspond to I (−1) and I (+7) , respectively, which suggests that the former bonds to bismuth and the latter to oxygen. The intensity ratio of satellite to Cu 2p 3 2 main line is increased by iodine intercalation, which implies increase of Cu (+2) with 3 d 9 configuration. It is found that all XPS lines are shifted by about 0.1 eV to low-binding-energy-side with the intercalation. Above results are discussed in terms of hole-doping.

Intercalation of iodine into the Bi 2 Sr 2 Ca n -1 Cu n O y ( n =1,2,3) superconductors has been studied. A variety of measurements indicate charge transfer is associated with the intercalation process, both directly to the BiO layers and also to the superconducting CuO 2 sheets. Changes in T c on intercalation can be understood in terms of hole doping to the CuO 2 planes. Hall coefficient measurements on a single crystal n =2 sample supported an increase in hole concentration, and an XPS study clearly showed the ionic character for the intercalated iodine, accompanied by changes in the Fermi level. Investigation of the c -axis resistivity, also on n =2 single crystals, indicated a change from the semiconductive behaviour of the parent crystal to an apparently metallic character, though the c -axis resistivity remained high.

Changes in the electronic states for Ba1-xKxBiO3- delta ( delta =0 and 0.5) due to various surface treatments (fracturing, scraping and ion sputtering) have been studied by X-ray photoelectron spectroscopy. It is found that marked spectral changes occur as a result of scraping and sputtering; the core levels are broadened and the intensity at the top of the valence bands is reduced. These results are discussed in terms of the reduction of elements and damage in the surface region. The above results cause the authors to conclude that fracturing these samples is suitable as a cleaning procedure for this system. The Bi 4f, Ba 4d and O 1s core levels have very low binding energies and are shifted by 0.2-0.4 eV to lower binding energies on 50% substitution of K for Ba. The Bi 4f line seems to contain a single chemical state for BaBiO3- delta , and more than one chemical state for Ba0.5K0.5BiO3- delta . The top of the valence band is found to be 0.5 eV below the Fermi level for BaBiO3- delta , while a clear Fermi edge appears for the K-doped material in the valence band spectra from both X-ray and ultraviolet photoelectron spectroscopy. The electronic states of BaBiO3- delta and K doping effects are discussed and compared with band calculations.

Summary Fifty-four cases of undifferentiated neuroblastoma (stroma-poor neuroblastoma with undifferentiated histology) were studied immunohistochemically for the presence ofS-100 protein-positive cells and extracellular matrix proteins (laminin, type IV collagen and fibronectin). In 30 of the 54 patients, the tumor had S-100 protein-positive cells in the peculiar stroma observed as thick fibrocellular septa (trabecular pattern) or delicate fibrovascular mesh work surrounding small nests of tumor cells (reticular pattern). The tumors were divided into four subgroups according to the stromal patterns: type A showing a predominant "reticular" pattern (14 cases); type B showing a predominant "trabecular" pattern (6 cases); type C showing both "reticular" and "trabecular" patterns (14 cases), and type D lacking either pattern but rich in vascular channels (20 cases). Clinicopathologically, the patients with S-100 protein-positive cells had a more favorable outcome (86.7% 2-year survival rate) than patients without these cells (12.0% 2-year survival rate). It is concluded that the existence of peculiar fibrovascular stroma containing S-l 00 protein-positive cells and extracellular matrix proteins is correlated with a favorable prognosis in undifferentiated neuroblastomas.

Pb 2 Sr 2 (Ln,Ce) n Cu 3 O 6+2n+δ (Pb32 n 2) and Pb(Ba,Sr) 2 (Ln,Ce) n Cu 3 O 5+2n+δ (Pb22 n 2) (Ln=Y, n=3, 4, … and 0⩽δ⩽2.0) were synthesized and investigated by XPD, HREM, TGA and SEM-EDX. Almost-single phase of Pb 2 Sr 2 YCe 2 Cu 3 O 12+δ (Pb3232) was prepared using a gel-citric acid method, although it was not obtained through a solid state reaction. The crystal structure of Pb32 n 2 and Pb22 n 2, which was studied by XPD analysis and HREM, was found to be layered constructed by stacking of (Pb, Cu) triple or double layers and (Ln, Ce) multiple fluorite layers. These compounds showed a phase transition accompanied with oxygen absorption and desorption, similar to Pb3212 and Pb3222. SEM observation and EDX analysis of sintered surface indicated that homogeneous dispersion of CeO 2 led the products to intergrowth structure of Pb32 n 2 and Pb22 n 2 ( n = 3, 4, …) with multiple fluorite layers.

Electronic states of K 2p and C 1s core levels and valence bands for K χ C 60 ( χ =0≈6.3) have been studied by X-ray photoelectron spectroscopy (XPS). We find two different chemical states of potassium with binding energy 293.8 and 294.9 eV. The K 2p 3 2 line becomes a single peak at χ = 6.3. These results are discussed in terms of the sites occupied by K in K χ C 60 . The C 1s line (285.1 eV) for C 60 is shifted by 0.3 eV to the side of higher binding energy by a very small amount of K, which is consistent with the shift of the valence band. The other line at 284.4 eV appears at 10 min evaporation (χ = 0.8). The intensity of the former is reduced and that of the latter increases with the evaporation time.

The properties of Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub {ital y}} annealed at 200--650 {degree}C in vacuum (10{sup {minus}4}Pa) are studied by x-ray powder diffraction, ac magnetization, and Hall measurement. The amount of oxygen loss, {Delta}{ital y}, was obtained by an integration of the oxygen partial pressure measured by a quadrupole mass spectrometer. The {ital T}{sub {ital c}} increases from 65 to 92 K, which is accompanied by a small amount of oxygen loss (on the order of 10{sup {minus}3}). The {ital a} and {ital c} axes are extended by the oxygen loss. The change of the hole concentration estimated by Hall measurement is of the same order of magnitude as that for the other superconducting oxides against the change of {ital T}{sub {ital c}}, however, it is larger by about two orders of magnitude than that expected from the oxygen loss. This discrepancy suggests charge redistribution in the structure.

Pb(Ba, Sr) 2 (Ln, Ce) 2 Cu 3 O y (Ln: lanthanoid, y =9.0–10.4) with (Pb, Cu) double layers and (Ln, Ce) fluorite layers was designed and obtained as a single phase. The structure of Pb(Ba, Sr) 2 (Ln, Ce) 2 Cu 3 O y , which was derived from Pb(Ba, Sr) 2 YCu 3 O y by replacing oxygen-defect Y layers with (Ln, Ce) 2 O 2 layers, was confirmed by high-resolution electron microscopy. The microstructure of (Pb, Cu) double layers of a quenched specimen was examined by means of high-resolution image with an imaging plate. A slowly cooled specimen with an oxygen content of y =10.2 lost 1.2 oxygen atoms above 580°C with an abrupt and reversible transition. The nature of this phase transition was similar to that of PbBaSrYCu 3 O y described in our previous paper. No superconductivity was found in Pb(Ba, Sr) 2 (Ln, Ce) 2 Cu 3 O y in spite of the CuO 2 doublet sheets, similar to Pb 2 Sr 2 LnCe Cu 3 O y with (Ln, Ce) fluorite layers.

Superconductivity and composition analysis of PbBaSr(Y, Ca)Cu 3 O y with fixed ratio of Sr/Ba = 1 were studied. Synthesis condition and superconductivity of Pb(Ba, Sr) 2 (Y, Ca)Cu 3 O y with various ratio of Sr/Ba and Ca/Y were also studied. It was found that T c increased with increasing Ca concentration, and that Sr-rich specimens allowed to contain more Ca. PbBa 0.8 Sr 1.2 Y 0.6 Ca 0.4 Cu 3 O 7 showed superconductivity with zero-resistance temperature of 42 K, which was higher than PbBaSrY 0.7 Ca 0.3 Cu 3 O 7 with maximum Ca content for Sr/Ba = 1. Decrease in averaged ionic radii of Ba and Sr in Sr-rich compositions would be favorable for the contraction of Cu-O bonds by hole-doping via Ca substitution for Y.

The effects of Ce substitution and reduction on the core levels and valence electronic states of Nd{sub 2{minus}{ital x}}Ce{sub {ital x}}CuO{sub 4{minus}{ital y}} have been investigated using x-ray photoelectron spectroscopy (XPS). It is found that the surfaces could be tremendously degraded by scraping, leading to changes in the electronic structures of Cu, O, and the Fermi edge. The changes in the Cu 2{ital p} spectra imply that the Ce substitution and the reduction donate electrons to Cu sites to show the appearance of monovalent Cu. The fraction of monovalent Cu derived from the Cu 2{ital p} spectra is less than the amount of Ce, which suggests that Ce is in the mixed-valence state. The XPS valence spectra show the Fermi edge formed by the electrons injected into the electronic state with the Cu 3{ital d}{sup 10} configuration. The nature of the Fermi edge is discussed in terms of photoionization cross section.

We have studied the grain boundaries of the YBa2Cu307 superconductor using micro-focused X-ray photoelectron spectroscopy. It is found that barium carbonate, barium hydroxide, and barium species with a low binding energy (777.8 eV) are more predominant on the grain boundary surfaces than on scraped surfaces. The Ba 3d5/2 line at 777.8 eV is more intense for the orthorhombic superconducting oxide than for the tetragonal insulator. The origin of this line is discussed

Superconducting PbBaSrY 1− x Ca x Cu 3 O 7 with a maximum T c onset at 65 K was synthesized. Single-phase materials were obtained for 0 ⩽ x ⩽ 0.25 by sintering in a 1% O 2 -N 2 gas at 750–830°C and quenching from 785°C. Superconductivity appeared for x ⩾ 0.15 and T c increased with increasing Ca content. PbBaSrY 0.7 Ca 0.3 O 7 was confirmed to achieve zero resistance at 37 K with about 45% bulk superconductivity. Superconductivity was considered to occur by hole introduction in CuO 2 sheets by substituting Y 3+ with Ca 2+ , the same mechanism as in Pb 2 Sr 2 Y 1− x Ca x Cu 3 O 8 .

We present a joint theoretical and experimental investigation of the N 1s photoionization of NO{sub 2} in the shape resonance region. The theoretical calculations, based on a single-channel relaxed-core Hartree-Fock approximation, predict that the shape resonance appears only in the A{sub 1}{yields}B{sub 2} transition and that the shape resonance energy of the N 1s{sup -1} {sup 1}A{sub 1} channel is about 2.6 eV lower in kinetic energy than that of the N 1s{sup -1} {sup 3}A{sub 1} channel, suggesting that the potential for the {sup 1}A{sub 1} channel is much more attractive than that for the {sup 3}A{sub 1} channel. Symmetry-selected cross sections measured by means of a multiple-ion coincidence imaging prove that the shape resonance appears only in the A{sub 1}{yields}B{sub 2} transition, as predicted by the calculation. The experimental partial cross sections for the N 1s{sup -1} {sup 1}A{sub 1} and {sup 3}A{sub 1} channels measured by means of conventional electron spectroscopy exhibit the shape-resonance maxima at photon energies of 416.3 and 415.9 eV, respectively, at corresponding kinetic energies of 3.0 and 3.3 eV, respectively, implying that the attractive potential for the {sup 1}A{sub 1} channel is overestimated in the single-channel approximation. The possible role played by correlationmore » effects on the K-shell ionization of NO{sub 2} is discussed in terms of interchannel coupling between the main-line channels and, possibly, with additional excited target states.« less

The doubly degenerate core-excitedΠ state of N2O splits into two due to the static Renner–Teller effect. The lower state, A1, has a bent stable geometry and the molecule excited to this state starts to deform itself toward this bent geometry. To probe the effect of the potential energy surfaces of the core-excited A1 states on the nuclear motion, we measure the momenta of the three atomic ions in coincidence by means of the ion momentum imaging technique. We find that the potential energy surface affects the molecular deformation significantly. N2O in the terminal N 1s[–1]3πA1 excited state is observed to be bent more than that in the central N 1s[–1]3πA1 excited state. This means that N2O in the terminal N 1s[–1]3πA1 excited state bends faster than that in the central N 1s[–1]3πA1 excited state. When the excitation energy is decreased within the 1s[–1]3π resonances, the nuclear motion in the A1 states becomes faster. This is interpreted by the notion that the excitation occurs onto the steeper slope part of the potential energy surface of the excited state for the lower excitation energy. The branching ratio of the A1 excitation increases with the decrease in the excitation energy. ©2004 American Institute of Physics.

A Doppler‐free electron spectroscopy apparatus that consists of a high‐resolution electron spectrometer and a molecular beam source has been installed on beamline 27SU at SPring‐8 in Japan. The apparatus is described and the Auger resonant Raman spectra of neon atoms recorded at the 1s ‐> 3p excitation and those of water molecules recorded at the O 1s ‐> 2b2 excitation are presented to demonstrate the performance.

Core-level electronic states for TlBa2Ca1-xYxCu2O7- delta (x=0, 0.1, 0.8 and 1.0) are investigated by X-ray photoelectron spectroscopy (XPS). As an effect of yttrium substitution, the Tl core-level shifts toward the higher binding energy side. This implies that electrons donated do not only fill the hole state in Cu-O, but also are partially transferred to the Tl site.

Clean and H2S‐adsorbed GaP(001) surfaces have been studied by inverse and ultraviolet photoemission spectroscopy (IPES) and (UPS) and by high‐resolution electron energy loss spectroscopy. H2S is found to be dissociated on the surface, leaving only sulfur on it, which is consistent with UPS results. IPES spectra show strong reduction in intensity at 1.5 and 4.5 eV above the Fermi level upon sulfur adsorption. The reduction in the former indicates tremendous decrease of unoccupied states, which correspond to dangling bonds of surface gallium atoms, in the band gap by H2S passivation.

A soluble beta-galactoside-binding lectin, galectin-3 has been shown to be involved in cell adhesion and activation of immune cells. Although galectin-3 is known to be expressed in various types of cells, it has not been shown whether galectin-3 is expressed in T lymphocytes. We present evidence here that galectin-3 is expressed in activated murine T lymphocytes including CD4+ and CD8+ T cells but not in resting T cells. Galectin-3 expression was induced by anti-CD3 mAb or mitogen and enhanced by common gamma-chain signaling cytokines, IL-2, IL-4, and IL-7, in activated T lymphocytes, whereas the inflammatory cytokines including TNF-alpha and IFN-gamma did not. Galectin-3 expression and proliferation were down-regulated by withdrawal of IL-2 and gamma irradiation. Antisense but not sense phosphorothioated oligonucleotides for galectin-3 inhibited galectin-3 expression and blocked proliferation of T cells significantly. This study suggests that up-regulation of galectin-3 plays an important role in proliferation of activated T lymphocytes.

In an attempt to refine the diagnosis and surgical treatment system for spontaneous shoulder pain in supine position (SPSP) in long-term hemodialysis (LTHD) patients we reviewed shoulders of patients during a 4-year period.Clinical findings, imaging findings and operative results (average duration of follow-up was 39 months) on both shoulders of 110 patients (Shigei Hospital, Okayama, Japan) were analyzed to identify the cause of SPSP in order to accurately differentiate it from other shoulder pains, and to select the proper treatment method.As the hemodialysis period lengthened, increase in the incidence and severity of bone and soft tissue changes (radiolucency, joint destruction, increase of thickness of subacromial bursa and rotator cuff, and synovial proliferation) in the shoulder induced by dialysis-related amyloidosis were noted in roentgenography, ultrasonography and magnetic resonance imaging. SPSP occurred in the LTHD patients. An increase in subacromial bursa and rotator cuff thickness correlated with SPSP. A decrease in subacromial space correlated with change in position and SPSP. An increase of subacromial pressure was judged to be the cause of SPSP, and subacromial decompression by coraco-acromial ligament release was effective for relieving SPSP. When massive synovial proliferation or invasion of granulation tissues was observed in the glenohumeral joint, arthroscopic debridement was necessary.SPSP is a sensitive indicator of a distinct subacromial lesion frequently found in LTHD patients. These lesions can be treated by minimally invasive endoscopic coraco-acromial ligament release, resulting in marked pain relief.

Seventy-nine shoulders suspected of rotator cuff tears were examined by ultrasonography (US) and forty-three received surgery. Long and short axis scans were performed and findings of each were separately classified according to a five-grade system, and the results were correlated with the actual extent of tear observed during surgery. Internal echogenicity and subacromial impingement were analyzed before and after surgery. A accuracy of US in detecting rotator cuff tears was analyzed. In addition, the correlation between cuff shape observed by US before surgery and actual shape observed during surgery was assessed. It was noted that cuff thinning and abnormalities in shape did not recover to normal after surgery. However, in the cases of discontinuities observed by US before surgery, US findings indicated that the torn cuff was anchored to the greater tuberosity and functional during active motion. Although post-operative US findings were not normal, clinical results were good in most cases. Sensitivity of US for detecting rotator cuff tear was 100% and specificity 94%. US is non-invasive, cost effective and allows the physician to examine the joint while it is in motion. Therefore, at this time, we use US as a screening method for detecting rotator cuff tears. Furthermore, US allows us to check for re-tears while the joint is in motion, which is essential for accurate diagnosis.

Forty-one hands of 37 patients with idiopathic carpal tunnel syndrome treated by endoscopic carpal tunnel release (ECTR) were followed up for more than one year after surgery. Surgical results were evaluated using Kelly's criteria, the Semmes-Weinstein test, the static and moving 2-point discrimination tests, tip-pinch strength, and motor and sensory nerve conduction studies. Clinical results, according to Kelly's criteria three months after surgery, were excellent or good in 36 hands, and fair or poor in five hands. No recovery was evident at six months and 12 months after surgery in fair and poor hands. Based on these findings, we conclude that a neurolysis of the median nerve and release of constriction of the thenar muscle branch should be performed using the conventional open technique for patients with poor results three months after ECTR if the patients are dissatisfied with ECTR results.

We recently reported that tumor eradication induced by immunotherapy (IT) in a congenic mouse model using tumor infiltrating lymphocytes (TIL) + recombinant interleukin-2 (rIL-2) is dependent on recruitment of naive host immune cells at the tumor sites. The recruitment of host immune cells was induced mainly through a local secretion of interferon-gamma (IFN-gamma) produced by donor T cells. We now further investigated how a non-specific inflammatory response progresses to a host T-cell-mediated tumor-specific response. In cross-over experiments using MCA-105 and MCA-205 sarcoma tumors, pulmonary metastatic disease was eradicated only in mice treated with tumor-matched TIL + rIL-2. In vitro, TIL stimulated with the tumor of origin secreted relatively high levels of IFN-gamma and granulocyte-macrophage colony stimulating factor (GM-CSF) compared to TIL stimulated with mismatched tumor cells. In lungs of tumor-bearing mice treated with matched TIL + rIL-2, significant increases in the percentages of IFN-gamma, GM-CSF and tumor necrosis factor-alpha (TNF-alpha) positive cells were detected, as well as of macrophages, natural killer (NK) cells and dendritic cells. Depletion of macrophages or NK cells did not inhibit the efficacy. In contrast, depletion of dendritic cells partially inhibited the efficacy of the treatment. Combined depletion of dendritic cells and macrophages abrogated more than 80% of the efficacy. Our data suggest that successful IT may require 3 steps: (1) release of inflammatory cytokines by donor TIL after restimulation by tumor cells; (2) infiltration of host immune cells in response to local cytokine production; and (3) activation of tumor-specific host immune cells by dendritic cells and to a lesser extent by macrophages.

We describe a female infant with obstructive jaundice due to inflammatory stenosis of the choledochus. It was surrounded and narrowed by a xanthogranulomatous lesion, extending from xanthogranulomatous cholecystitis (XGC). The obstructive jaundice was released by a cholecystectomy, resection of the choledochus, and hepaticojejunostomy. This is the first reported case of infantile XGC associated with obstructive jaundice.

Chemical analysis by K2Cr2O7 titration and the binding energy measurement of Pb 4f7/2 by XPS were applied for the evaluation of valence state of Pb in (Pb,Cu)Sr2(Ca,Y)Cu2Oy and (Pb,Cu)(Sr,La)2CuOy. Correlation between the binding energy of Pb 4f7/2 and analytical valence of Pb was observed, showing that the present chemical analysis was reliable.