We have studied the absorption spectra of x-ray irradiation-induced Ce2+ and Pr2+ ions in crystals of alkaline-earth fluorides. We have calculated absorption spectra of divalent praseodymium ions in SrF2 crystals doped with Pr2+ for the first time. The calculated spectra agree rather well with the experimental data. In crystals containing induced Ce2+ ions we have found strong electron-phonon coupling. In BaF2, we do not observe bands corresponded to divalent Ce or Pr ions.
It was shown that the divalent rare earth ions (La, Ce, Gd, Tb, Lu, and Y) in cubic sites in alkaline earth fluorides are unstable with respect to electron autodetachment since its d1(eg) ground state is located in the conduction band which is consistent with the general tendency of these ions in various compounds. The localization of doubly degenerate d1(eg) level in the conduction band creates a configuration instability around the divalent rare earth ion that leading to the formation of anion vacancy in the nearest neighborhood, as was reported in the previous paper [Journal of Physics and …
We report data on the luminescence spectra associated with photochromic centers in X-ray irradiated calcium fluoride crystals doped with Lu ions. Irradiation in low energy photochromic centers absorption band excites emission, which can be identify with transitions into photochromic centers. Ab initio calculation of absorption spectrum of photochromic center agrees rather well with experimental data.
Absorption, excitation and emission spectra of cadmium fluoride crystals doped with rare-earth ions were investigated. In contrast to alkaline-earth fluorides the absorption spectra due to 4f - 5d transitions of Ce$^{3+}$, Pr$^{3+}$ and Tb$^{3+}$ ions are broadened. No 5d-4f emissions were observed. These prove that 5d(e$_g$) levels of rare earth ions lie in conduction band of CdF$_2$ crystal. Emission spectra of Tb$^{3+}$ show the group of 4f-4f $^5$D$_4$-$^7$F$_j$ lines in contrast to other alkaline-earth fluorides where emission due to $^5$D$_3$-$^7$F$_j$ transitions is also observed. The a…
Fluoride crystals doped with rare-earth ions (REI) and pair centers in diamond for fast ($10^{-9}\rm{s}$) quantum computers (FQC) are proposed. As specific systems for REI doping, we propose $Ca_{1-x}Sr_{x}F_{2}$ crystals and their analogues. The $^{4}f$-states with different total orbital angular moments of these ions serve as two-level systems (qubits). Suitable REIs are proposed as well. It is established that the pair $SiV$ and $GeV$ centers in diamond are promising systems for fast optical quantum computers operating at elevated temperatures.
Time-resolved emission, excitation as well as emission decay curves of CaF$_2$, SrF$_2$, BaF$_2$ doped with HoF$_3$ were investigated. Most intensive emission bands near 168 nm, having long decay time, belong to spin-forbidden transitions from 5d$^1$4f$^9$ high spin (HS) states to ground $^5$I$_8$ states of Ho$^{3+}$ ions. Weak spin allowed 5d$^1$4f$^9$(LS)-4f$^{10}$ emission band at 158 nm was observed only in CaF$_2$-Ho crystals. Spin allowed and spin-forbidden excitation bands were observed in all crystals near 166 and 155 nm respectively. Fast component of spin-forbidden emissions due to m…
Electron spin flip in atoms or ions can cause neutrino pair emission, which provides a method to explore still unknown important neutrino properties by measuring spectrum of emitted photon in association, when electroweak rates are amplified by a phase coherence among participating atoms. Two important remaining neutrino issues to be determined are the absolute neutrino mass (or the smallest neutrino mass in the three-flavor scheme) and the nature of neutrino masses, either of Dirac type or of Majorana type. Use of Raman scattered photon was recently proposed as a promising tool for this purpo…
On the basis of the first-principles evolutionary crystal structure prediction of stable compounds in the Cu-F system, we predict two experimentally unknown stable phases -- Cu2F5 and CuF3. Cu2F5 comprises two interacting magnetic subsystems with the Cu atoms in the oxidation states +2 and +3. CuF3 contains magnetic Cu 3+ ions forming a lattice with the antiferromagnetic coupling. We showed that some or all of Cu 3+ ions can be reduced to Cu 2+ by electron doping, as in the well known KCuF3. Significant similarities between the electronic structures calculated in the framework of DFT+U suggest…
We have studied the magnetic and transport behavior of doped La0.65 A0.35 Mn0.95Fe0.05 O3 (A= Ca, Sr, Pb, Ba) compounds. All the compositions show ferromagnetic/metal to paramagnetic/insulator transition except the Pb doped sample which is insulating and ferromagnetic in the entire temperature range. The simultaneous occurrence of ferromagnetism and insulating behavior in Pb doped compound is most likely due to the presence of FM clusters separated by Fe and Mn ions that are coupled AFM and hence prevent the current from crossing the inter-domain region. The magnetization and Tc are decreased …
Results of absolute light output measurements on strontium and barium fluoride doped with PrF$_3$ and CeF$_3$ are presented and compared with scintillators having well-known light output (NaI-Tl, CsI-Tl, BGO). For pure SrF$_2$ crystal we obtain a value of about 28600 photons/MeV.
Despite the interest in MXenes in the last decade, all of the MXenes reported have a random mixture of surface terminations (-O, -OH, -F). In addition, restacked films have turbostratic disorder and often contain ions, solvent, and other species in between their layers. Here we report Y2CF2, a layered crystal with a unit cell isostructural to a MXene, in which layers are capped only by fluoride anions. We directly synthesize the 3D crystal through a high-temperature solid-state reaction, which affords the 3D crystal in high yield and purity and ensures that only fluoride ions terminate the lay…
Over the last few years of the heyday of hybrid halide perovskites, so many metal cations additives have been tested to improve their optoelectronic properties that it is already difficult to find an element that has not yet been tried. In general, the variety of these approaches is united under the name "doping", however, there is currently no clear understanding of the mechanisms of the influence of the metal ion additives on the properties of the lead halide perovskite materials. For many ions there is even no consensus on the most fundamental questions: what lattice position does a given i…
By means of photoemission and x-ray absorption spectroscopy, we have studied the electronic structure of (Ni,Zn,Fe,Ti)$_{3}$O$_{4}$ thin films, which exhibits a cluster glass behavior with a spin-freezing temperature $T_f$ of $\sim 230$ K and photo-induced magnetization (PIM) below $T_f$. The Ni and Zn ions were found to be in the divalent states. Most of the Fe and Ti ions in the thin films were trivalent (Fe$^{3+}$) and tetravalent (Ti$^{4+}$), respectively. While Ti doping did not affect the valence states of the Ni and Zn ions, a small amount of Fe$^{2+}$ ions increased with Ti concentrati…
Electronic structures of Zn$_{1-x}$Co$_x$O have been investigated using photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS). The Co 3d states are found to lie near the top of the O $2p$ valence band, with a peak around $\sim 3$ eV binding energy. The Co $2p$ XAS spectrum provides evidence that the Co ions in Zn$_{1-x}$Co$_{x}$O are in the divalent Co$^{2+}$ ($d^7$) states under the tetrahedral symmetry. Our finding indicates that the properly substituted Co ions for Zn sites will not produce the diluted ferromagnetic semiconductor property.
Double-exchange mechanisms in RE$_{1-x}$AE$_{x}$MnO$_{3}$ manganites (where RE is a trivalent rare-earth ion and AE is a divalent alkali-earth ion) relies on the strong exchange interaction between two Mn$^{3+}$ and Mn$^{4+}$ ions through interfiling oxygen 2p states. Nevertheless, the role of RE and AE ions has ever been considered "silent" with respect to the DE conducting mechanisms. Here we show that a new path for DE-mechanism is indeed possible by partially replacing the RE-AE elements by Mn$^{2+}$-ions, in La-deficient La$_{x}$MnO$_{3-δ}$ thin films. X-ray absorption spectroscopy demons…
Divalent tin oxides have attracted considerable attention as novel p-type oxide semiconductors, which are essential for realizing future oxide electronic devices. Recently, p-type Sn2Nb2O7 and SnNb2O6 were developed; however, enhanced hole mobility by reducing defect concentrations is required for practical use. In this work, we investigate the correlation between the formation of oxygen vacancy which may reduce the hole-generation efficiency and hole mobility, and the crystal structure in Sn-Nb complex oxides. Extended X-ray absorption fine structure spectroscopy and Rietveld analysis of x-ra…
X-ray absorption spectroscopy was used to determine the valence state in La$_2$Co$_{1-x}$Mn$_{1+x}$O$_6$ ($x\approx 0.23$) thin films. We found that in spite of the non-stoichiometry, Co is in a divalent state while Mn ions show a mixed valence state. The relation of this finding with the magnetic properties of the films is discussed. X-ray magnetic circular dichroism measurements prove that magnetic anisotropy originates from Co spin-orbit coupling and it is strain-dependent: a strong increase of the angular contribution to the magnetic moment is found when in-plane (out-of-plane) and cell pa…
We have studied the electronic structure of the diluted magnetic semiconductor Ga$_{1-x}$Mn$_{x}$N ($x$ = 0.0, 0.02 and 0.042) grown on Sn-doped $n$-type GaN using photoemission and soft x-ray absorption spectroscopy. Mn $L$-edge x-ray absorption have indicated that the Mn ions are in the tetrahedral crystal field and that their valence is divalent. Upon Mn doping into GaN, new state were found to form within the band gap of GaN, and the Fermi level was shifted downward. Satellite structures in the Mn 2$p$ core level and the Mn 3$d$ partial density of states were analyzed using configuration-i…
Rare-earth (RE) doped GaN is of interest for optoelectronics and spintronics and potentially for quantum applications. A fundamental understanding of the interaction between RE dopants and the semiconductor host is key to realizing the material's full potential. This work reports an investigation of lanthanide ($Ln$) defects in GaN using hybrid density-functional defect calculations. We find that all the $Ln$ dopants incorporated at the Ga lattice site, $Ln_{\rm Ga}$ ($Ln$ = La--Lu), are stable as trivalent ions, but Eu and Yb can also be stabilized as divalent and Ce, Pr, and Tb as tetravalen…
