The temperature-sensitive property of polyhydroxylated metallofullerene film of Gd@C82(OH)x with special hydroxyl number was studied using synchrotron radiation ultraviolet photoelectron spectroscopy (UPS) and TEM techniques. From room temperature (RT) to 4 degrees C the photoelectron onset energy of the spectra of Gd@C82(OH)12 shifted from 1.9 to 0.2 eV, indicating that Gd@C82(OH)12 automatically shifted from insulator at RT to semiconductor at 4 degrees C. However, this could not be observed for Gd@C82(OH)20. TEM experiments show that the variation of conductivity can be ascribed to formation of a microcrystal under low temperature. The dipole moment induced unique intermolecular interactions and self-assembled microcrystalline structures for Gd@C82(OH)12. This may cause reconstruction of the upper valence band formed by pi-like electrons as well as the density of states (DOS) around the Fermi level (EF) and reconstruct the deeper valence band formed by sigma-like electrons, eventually resulting in a shift to a semiconducting nature. These findings revealed a novel nature for polyhydroxylated Gd@C82(OH)x materials: Their insulating properties can be controllably tuned into semiconducting ones as a function of temperature.

The valence band structures of Al–N-codoped [ZnO:(Al, N)] and N-doped (ZnO:N) ZnO films were studied by normal and soft x-ray photoelectron spectroscopy. The valence-band maximum of ZnO:(Al, N) shifts up to Fermi energy level by about 300 meV compared with that of ZnO:N. Such a shift can be attributed to the existence of a kind of Al–N in ZnO:(Al, N), as supported by core level XPS spectra and comparison of modified Auger parameters. Al–N increased the relative quantity of Zn–N in ZnO:(Al, N), while N–N decreased that of Zn–N in ZnO:N.

Polyhydroxylation of metallofullerenes can control the direction and intensity of electron transfer between the innermost Gd and the outer carbon cage. The synergistic effect efficiently modulates the strong exchange interactions or coupling between the different electron levels of the innermost metallic atoms, leading to a periodical occurrence of energy level splitting and novel electronic properties in the 4f atom (see figure).

Pyrite FeS2 films have been prepared by thermally sulfurizing iron films deposited by magnetron sputtering.The electronic structures were studies by X-ray absorption near edge structure and X-ray photoemission spectrum. The results show that an S 3p valence band with relatively higher intensity compared to the calculation exists in 2—10eV range and a high density below the Fermi level of Fe 3d states were detected.A second gap of 2.8eV in the unoccupied density of states was found above the conduction band which was 2.4eV by experimentally calculation.The difference between t2g and eg which were formed in an octahedral crystal field was computed to be 2.1eV.

Valence-band type Auger lines in Al doped and undoped ZnO were comparatively studied with the corresponding core level x-ray photoelectron spectrography (XPS) spectra as references. Then the shift trend of energy levels in the valence band was that p and p-s-d states move upwards but e and p-d states downwards with increasing Al concentration. The decreased energy of the Zn 3d state is larger than the increased energy of the 0 2p state, indicating the lowering of total energy. This may indicate that Al doping could induce the enhancement of p-d coupling in ZnO, which originates from stronger Al-O hybridization. The shifts of these states and the mechanism were confirmed by valence band XPS spectra and 0 K-edge x-ray absorption spectrography (XAS) spectra. Finally, some previously reported phenomena are explained based on the Al doping induced enhancement of p-d coupling.

We have investigated the C1s X-ray absorption spectra of graphite, diamond and diamond-like car- bon ( DLC ) film using total electron yield mode of the surface sensitive photoelectron spectroscopy. After cleaning the surface in an ultra high vacuum system, we found the feature peaks of the sp3 and sp2 hybridized bonding on the C1s X-ray absorption spectra of DLC, which means that DLC is an amorphous carbon of sp2 mixed with sp3 bonding. And we have measured the C1s photoelectron spectra of a series of DLC films, and calculated the ratios of sp2/sp3.

对于 Pr1- SrxMnO3 体系 x = 0 和 0.3 以及 MnO2 在 O K 边进行了 X 射线吸收谱实验研究。在 x = 0 的 xPrMnO3 端点化合物进行空穴掺杂使 x = 0.3,当体系成为 Pr0.7Sr0.3MnO3 时,实验结果显示其在 Mn 3d 轨道上的电子数目并不随空穴掺杂减少,反而有增加的趋势。对该结果基于 O 2p 与 Mn 3d 轨道的杂化和共价键特性进行了探讨。

The valence band evolution Of C-60 film upon Yb intercalation is investigated by the synchrotron radiation photoemission spectroscopy (SR-PES) technique. The results show that only Yb2.75C60 forms at lower intercalation stages and imply that other phases of YbxC60 (x > 2.75) form with more Yb atoms intercalated into the Yb2.75C60 sample. No Fermi edge is observed for all the spectral lines in this work, which reveals that the superconducting Yb fulleride, whether it is Yb2.75C60 or other phase, has semiconducting property at room temperature. To extract the intrinsic density of state of the valence band from the Yb 4f-superposed experimental data, the SR-PE spectra were measured for the well-defined phase of Yb2,75C60 with varying photon energies (18.0-45.0 eV). The results show that the spectral data can drastically depart from the density of states of the valence band due to the photoemission of Yb 4f core levels. However, the valence band can, still be quantitatively extracted from the experimental data by the least-square simulation.

The Yb275C60 thin film was prepared and studied by using the synchrotron radiation ultraviolet photoemission spectroscopy(PES) in an ultrahighvacuum system. The spectral line obtained in the range between the Fermi level and ～5 eV binding energy consists of those lines from the valence band (the molecular orbital LUMO, HOMO and HOMO1 derived energy bands of C60) and core levels(Yb 4f7/2 and 4f5/2). Taking into account the variations of the photoinization cross sections of C 2p and Yb 4f with different photon energies, we have measured the photoemission spectra under the condition of varying photon energies, and carried out simulations to deduce the component contributions. The peak positions, widths and intensities for the components are obtained quantitatively. The results reveals that the photoemission of 4f electrons has a significant intensity with the photon energies larger than ～300 eV, and that the measured spectra depart drastically from the density of states of the valence band. To observe the valence band structure, one should carry out the PES measurements by using photons with energies less than 300 eV. The photoionization crosssection oscillation is also observed in Yb275C60 with almost the same oscillation period as that for pure C60 However, the oscillation amplitude is obviously smaller than that for pure C60, which reveals that the chemical environment of C60 in compounds has nonnegligible effects on the photoionization crosssection oscillation phenomenon.

The Yb275C60 thin film was prepared and studied by using the synchrotron radiation ultraviolet photoemission spectroscopy(PES) in an ultrahighvacuum system. The spectral line obtained in the range between the Fermi level and ～5 eV binding energy consists of those lines from the valence band (the molecular orbital LUMO, HOMO and HOMO1 derived energy bands of C60) and core levels(Yb 4f7/2 and 4f5/2). Taking into account the variations of the photoinization cross sections of C 2p and Yb 4f with different photon energies, we have measured the photoemission spectra under the condition of varying photon energies, and carried out simulations to deduce the component contributions. The peak positions, widths and intensities for the components are obtained quantitatively. The results reveals that the photoemission of 4f electrons has a significant intensity with the photon energies larger than ～300 eV, and that the measured spectra depart drastically from the density of states of the valence band. To observe the valence band structure, one should carry out the PES measurements by using photons with energies less than 300 eV. The photoionization crosssection oscillation is also observed in Yb275C60 with almost the same oscillation period as that for pure C60 However, the oscillation amplitude is obviously smaller than that for pure C60, which reveals that the chemical environment of C60 in compounds has nonnegligible effects on the photoionization crosssection oscillation phenomenon.

C60 monolayer was prepared on Ag(111) surface in ultra-high vacuum environment. The electronic state was investigated by the synchrotron radiation photoemission technique. The results reveal the remarkable covalent component to the C60–Ag bonding, which was not observed in previously reported works. The bonding in the interface is primarily covalent with some ionic contribution. Two covalent bonding features were observed distinctly at ∼4.1 and ∼4.7eV binding energy. These features are ascribed to the hybridization between the next highest occupied molecular orbital (HOMO-1) of C60 and the Ag 4d state. The work function of the C60 monolayer on Ag(111) is determined to be 4.63±0.10eV that is larger than that of the clean Ag(111) surface by 0.13±0.02eV. Yb intercalation was carried out to investigate the valence evolution of the monolayer system. The spectral weight at the Fermi level increases substantially at low intercalation stage. After the filling of the lowest unoccupied molecular orbital (LUMO) band, the sample exhibits the semiconducting property for all the rest intercalation levels, and the electronic state departs from the simple band-filling scheme. The electrons may occupy either the hybridizing state or the Madelung-derived state. The above observations are drastically different from that for bulk Yb fullerides, indicating novel properties of rare-earth-metal intercalated C60 monolayer.

The possibility of modulating the electronic configurations of the innermost atoms inside a nanospace, nano sheath with chemical modification was investigated using synchrotron X-ray photoelectron spectroscopy. Systems of definite nanostructures were chosen for this study. Systematic variations in energy, intensity, and width of pi and sigma O 1s core level spectra, in absorption characteristics of C 1s-->pi transition, in photoabsorption of pre-edge and resonance regions of the Gd 4d-->4f transition, were observed for Gd@C(82) (an isolated nanospace for Gd), Gd@C(82)(OH)(12) (a modified nanospace for Gd), and Gd@C(82)(OH)(22) (a differently modified nanospace for Gd), and the reference materials Gd-DTPA (a semi-closed space for Gd) and Gd(2)O(3). A sandwich-type electronic interaction along [outer modification group]-[nano sheaths]-[inner metallic atom] was observed in the molecules of modifications. This makes it possible to control electron-donation directions, either from the innermost metallic atom toward the outer nano sheaths or the reverse. The results suggest that one may effectively tune the fine structures of electronic configurations of such a metallic atom being astricted into nanostructures through changing the number or category of outer groups of chemical modifications. This may open a door to realizing the desired designs for electronic and magnetic properties of functionalized nanomaterials.

We studied the electronic structure of SrTi1-xRuxO3 using synchrotron radiation. The Experimental used in the study were photoemission (PES) and 0 1s X-ray absorption (XAS) spectroscopy. The PES and XAS spectra of SrTi1-xRuxO3 showed the Ru 4d bands changed with the change of X. Compared with the results of LIDA calculation, we analysis explain the experiment data.

Different photoelectron analyzer has different detectable area and acceptance angle, the experimental count rate is up to the photon flux density in the detected area, so the size of the X-ray source used for the analyzer is very important to get the best experimental result. Due to the experimental resolution and count rate of the analyzers is not so ideal, their relation to the beam spot of the beamline is studied. Result shows the size of beam spot at the sample position is too large, which helped to decide the upgrade project for beamline 4B9B and make the beam size much more smaller. A new design for high photon energy branch of the beamline upgrade with new post-focusing mirror is finished, meanwhile the focusing of low photon energy branch is also better designed.

We have performed an experimental investigation of X-ray absorption at O K -edge on both Pr1- SrxMnO3 x for x=0, x=0.3 and MnO2. Experimental results show that the electron number in Mn 3d orbitals of the end-point compound would increase, instead of decrease, with the increase of the hole-doping dose(x value). This phenomenon has been discussed in terms of orbital hybridization and covalent characters between O 2p and Mn 3d orbitals.

Experimental results, by x-ray absorption (XAS) at the oxygen K-edge and photon-energy dependence of the O 1s2p2p Auger line at the O K threshold, below Mn L-2,L-3 as well as well above the Mn L-2,L-3 edge of colossal magnetoresistance (CMR) manganites Pr1-xSrxMnO3 (PSMO) with x=0.0 and x=0.3 compositions, demonstrate the existence of an oxygen 2p hole state and show its importance in the electronic processes. Both XAS and Auger spectra self-consistently manifest that the oxygen 2p holes density of state (DOS) increases with hole doping in the PSMO system, hinting at a hole state transfer from e(g) symmetry orbitals of Mn 3d valence bands to oxygen 2p with a Mn4+ ion increase through Sr2+ doping. These are discussed in terms of the possible interatomic hybridization of Mn 3d with O 2p orbitals and a different O 2p valence band DOS for different PSMO compositions in the frame of a covalent picture.

The shape and variation rule of the three-phase boundary of the porous electrode used in batteries and fuel cells are studied. The traditional porous electrode is always partly immersed into the electrolyte, which is difficult to observe the shape and variation of the three-phase boundary. This work changes the traditional usage mode of the electrode to make the observation of the three-phase boundary be easy. The longitudinal height of the electrode can be enlarged and modulated andomly by this new usage mode: The establishment and the variation rule of the three-phase boundary shape as the reaction goes on are summarized by the experiment of the zinc-air battery. This paper theoretically analyses that the variation of the boundary can cause the variation of the electrical conduction of the electrolyte in the porous electrode and affect the internal resistance. It is also illustrated how the wetting property and pore structure of the porous electrode affect the three-phase boundary shape through the experiment.

Influences of structural properties on the stability of fullerenols are studied using experimental techniques including laser-induced dissociation associated with a time-of-flight measurement, synchrotron radiation XPS, and FT-IR spectroscopy. Stabilities of a family of fullerenols (C60(OH)42, C60(OH)44, C60(OH)30, C60(OH)30, C60(OH)32, and C60(OH)36) as functions of structural parameters—the hydroxyl number, intensity of the impure group, and the ratio of the carbonyl to hydroxyl groups—are investigated. It is found that the molecular stability largely depends on the quantity of impure groups, especially the highly oxygenated carbons in fullerenols, but less on the hydroxyl number. This is different from the previous consideration that the stability of fullerenols largely depends on the hydroxyl number. Previously, to gain the larger solubility required by practical applications, it was suggested to increase the number of the hydroxyl groups. This idea needs to be restudied, because in highly hydroxylated fullerenol molecules, the coinstantaneous formation of a large amount of impure groups is observed. The use of C60(OH) n >36 in practical applications should proceed with caution, since these could lead to unstable open-cage structures. The results reveal a way of controlling the formation of impure groups to gain fullerenols of high stability.

We have measured the photon energy dependence of the O 1s2p2p Auger line at the O K threshold, below Mn L2,3 as well as well above the Mn L2,3-edge of colossal magnetoresistance (CMR) manganites Pr1−xSrxMnO3 (PSMO) with x=0.0 and x=0.3 compositions. Experimental results show that the O 1s2p2p Auger peak splits and it can be best fitted to three component peaks. The relative intensity of the three peaks feature retain essentially similar values, in an experiment allowable error range of several percents, for both composition PSMO at O K threshold and below Mn L2,3 excitation, but the total intensity fluctuates that reflecting the final state effect characteristic feature. This situation further changes drastically at above Mn L2,3 excitation energy by increasing the total intensity of x=0.3 system by a factor of four to that of x=0.0. These are discussed in terms of possible interatomic response and different valence band DOS for different PSMO compositions in the frame of covalent picture.