Origins of electronic band gap reduction in Cr/N codoped TiO2.

Recent studies indicated that noncompensated cation-anion codoping of wide-band-gap oxide semiconductors such as anatase TiO2 significantly reduces the optical band gap and thus strongly enhances the absorption of visible light [W. Zhu et al., Phys. Rev. Lett. 103, 226401 (2009)]. We used soft x-ray spectroscopy to fully determine the location and nature of the impurity levels responsible for the extraordinarily large (∼1 eV) band gap reduction of noncompensated codoped rutile TiO2. It is shown that Cr/N codoping strongly enhances the substitutional N content, compared to single element doping. The band gap reduction is due to the formation of Cr 3d3 levels in the lower half of the gap while the conduction band minimum is comprised of localized Cr 3d and delocalized N 2p states. Band gap reduction and carrier delocalization are critical elements for efficient light-to-current conversion in oxide semiconductors. These findings thus raise the prospect of using codoped oxide semiconductors with specifically engineered electronic properties in a variety of photovoltaic and photocatalytic applications.

Clustering of impurity atoms in Co-doped anatase TiO(2) thin films probed with soft x-ray fluorescence.

The electronic structure of Co-doped anatase TiO(2) epitaxial thin films grown at different partial oxygen pressures is investigated using soft x-ray emission spectroscopy. The resonantly excited Co L(2,3) x-ray emission spectra of ferromagnetic Ti(0.96)Co(0.04)O(2) samples for the oxygen-deficient regime show that the ratio of integral intensities for Co L(2) and L(3) emission lines significantly decreases with respect to nonmagnetic samples in the oxygen-rich regime. This is due to L(2)L(3)M(4,5) Coster-Kronig transitions and suggests that ferromagnetic Ti(0.96)Co(0.04)O(2) samples have n-type charge carriers and Co-Co bonds between substitutional and interstitial Co atoms are present while Co-O bonds are dominant in nonmagnetic Ti(0.96)Co(0.04)O(2) samples in the oxygen-rich regime. Electronic structure calculations show that the presence of free charge carriers and Co segregation play a crucial role in strong ferromagnetism at room temperature in Co-doped TiO(2).

Electron correlation effects in resonant inelastic X-ray scattering of NaV2O5.

Element- and site-specific resonant inelastic x-ray scattering spectroscopy (RIXS) is employed to investigate electron correlation effects in NaV2O5. In contrast to single photon techniques, RIXS at the vanadium L3 edge is able to probe d-d* transitions between V d-bands. A sharp energy loss feature is observed at -1.56 eV, which is well reproduced by a model calculation including correlation effects. The calculation identifies the loss feature as excitation between the lower and upper Hubbard bands and permits an accurate determination of the Hubbard interaction term U = 3.0 +/- 0.2 eV.

The organic aerosols of Titan.

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan tholin prepared by continuous D.C. discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mb is determined from x-ray to microwave frequencies. Values of n (approximately equal to 1.65) and k (approximately equal to 0.004 to 0.08) in the visible are consistent with deductions made by ground-based and spaceborne observations of Titan. Many infrared absorption features are present in k (lambda), including the 4.6 micrometers nitrile band. Molecular analysis of the volatile component of this tholin was performed by sequential and non-sequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition, acid hydrolysis produces a racemic mixture of biological and non-biological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.

Extreme ultraviolet transmission grating monochromator.

A compact monochromator has been designed to utilize recently developed free-standing XUV transmission gratings. Tests using a condensed spark source of far UV radiation show that this monochromator, with 20-microm slits, is capable of 0.08-nm resolution at 30 nm in the first order. A physical description of the system and test results are presented.

Soft x-ray emission from li-mg and li-Al alloys and comparisons with kkr-cpa calculations.

The K emission band of Li and L(23) emission bands of Mg and Al have been measured for Li-Mg and Li-Al prepared in a range of concentrations either by coevaporation or by evaporating thin films of Li on Mg(Al) substrates or Mg(Al) on Li substrates. The Li K spectrum is nearly unchanged at all alloy concentrations in the Li-Mg system but broadens and develops a low energy shoulder for large Al concentrations in the Li-Al system. Both Mg and Al L(23) spectra are narrower and more peaked at low energy in the equilibrium alloys than in the pure metals. The many-body threshold peaks on the Al and Mg L(23) spectra are generally suppressed by alloying with Li, except for low temperature coevaporated Li-Al samples where the peak persists to very Li-rich alloys. Data for a Li(80)Mg(20) alloy are compared with KKR-CPA calculations, and good agreement is found for both the Li K spectrum and the Mg L spectrum.

In situ preparation of thin sodium films as an expendable filter in the vacuum ultraviolet.

The use of a sodium film as a filter for wavelengths between 40 and 80 nm is discussed, and a technique to prepare these films is described. Sodium films of 230 nm thickness were demonstrated to have a transmission of 55% at 100 degrees K at a wavelength 41 nm. The transmission decreased to 40% after 18 h in a vacuum of 5x10(-8) Torr. Films of this thickness were shown to attenuate 20.5-nm radiation appearing in second order at 41 nm by at least a factor of 50.