Anomalous Kinetics of Diffusion-Controlled Defect Annealing in Irradiated Ionic Solids

The authors thanks A. Ch. Lushchik, M. Izerrouken, and V. Lisitsyn for stimulating discussions. This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euroatom research and training programme 2014-2018 under Grant Agreement No. 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission. R.V. acknowledges the financial support by the MEIC (Ministerio de Economa, Industria y Competitivad; Project ENE2015-70300-C3-1-R). The calculations were performed using facilities of the Stuttgart Supercomputer Center (Project DEFTD 12939).

F centre production in CsI and CsI–Tl crystals under Kr ion irradiation at 15 K

Abstract We present results of simultaneous in situ luminescence and optical absorption studies in scintillator CsI and CsI–Tl crystals, exposed to very dense electronic excitations induced by 86Kr ions (8.63 MeV/amu). Irradiation at 15 K leads to the formation of the prominent F absorption band. In addition, several other features of the broad absorption between exciton and F bands were ascribed to an anion vacancy, α centre (240 nm), self-trapped hole, Vk centre (410 nm) and interstitials, H centres (560 nm). We have found that low doping of thallium (∼1017 cm−3) causes the F centre formation to proceed more rapidly than in pure crystal. On the other hand, we were not able to create any a…

Small radius electron and hole polarons in PbX2 (X = F, Cl, Br) crystals: a computational study

First-principles hybrid density functional theory (DFT) calculations were performed for small radius polarons – self-trapped electrons (STELs) and holes (STHs) in PbX2 (X = F, Cl, Br) crystals, widely used as parent materials for inorganic halide perovskites (CsPbX3) and scintillators. The atomic and electronic structures, spin and charge distributions and formation energies for both types of polarons were predicted for orthorhombic PbF2 and STELs for cubic PbF2. The STH structure was identified in a controversial case of PbCl2. We also confirmed and analyzed in detail experimentally suggested configurations for other cases. It is shown how, due to a delicate balance of ionic and covalent c…

Quantum chemical calculations of the electron center diffusion in MgO crystals

Large-scale quantum chemical simulations of the diffusion hops of empty cation and anion vacancies, as well as F + and F centers in MgO crystals have been done. The atomic configurations for 224-site cluster and charge density distribution are analyzed for the equilibrium and saddle-point configurations during the defect hops. The relevant activation energy for diffusion increases monotonically in the series V a → F + → F center.

Luminescence and ultraviolet excitation spectroscopy of SrI2 and SrI2:Eu2+

Abstract We report measurements of luminescence and its ultraviolet excitation spectra in SrI2 and SrI2:Eu2+ at temperatures of 10 and 300 K. Attention is focused on determining the exciton energy and its temperature shift from features of the excitation spectra and limits placed by absorption spectroscopy on a 120 μm thin crystal, on observation of a broadened Eu emission band attributed to trace Eu associated with oxygen in nominally undoped crystals, and on adding observations concerning the 3.4 eV band at low temperature attributed by Pustovarov et al. to the self-trapped exciton.

Ab initio calculations for the polar (0 0 1) surfaces of YAlO3

Abstract The results of ab initio calculations of polar YAlO3 (0 0 1) surfaces by means of a hybrid B3LYP exchange-correlation functional as it is implemented in the CRYSTAL computer code are presented. Both polar YO and AlO2-terminations of the cubic YAlO3 (0 0 1) surface were considered. We performed relaxation of atoms on the upper three layers of both YO and AlO2-terminated YAlO3 (0 0 1) surfaces using in our calculations slabs containing 22 and 23 atoms as well as 9 layers, respectively. We predict a significant increase of the Al-O chemical bond covalency on the AlO2-terminated YAlO3 (0 0 1) surface with respect to the YAlO3 bulk. Our calculated YO and AlO2-terminated YAlO3 polar (0 0…

Polar nanoregions in Pb(Mg1/3Nb2/3)O3 (PMN): insights from a supercell approach

Abstract We report construction of a model of polar nanoregions in the PMN relaxor ferroelectric based on first-principles lattice dynamics for chemically ordered supercells [S.A. Prosandeev et al., Phys. Rev. B 70, 134110 (2004)], combined with invariance under permutations and dipole-dipole interaction as a source supporting randomly oriented residual polarization. Representative analytical estimates of polar nanore-gion — supercell mapping reproduce both nonzero local and zero macroscopic polarization of the structure, as well as the temperature change of the supercell anisotropy at cooling and field cooling.

Accumulation of radiation defects and modification of micromechanical properties under MgO crystal irradiation with swift 132Xe ions

This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014-2018 and 2019-2020 under grant agreement No. 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission. A.A. also acknowledges support via the project GF AP05134257 of Ministry of Education and Science of the Republic of Kazakhstan .

Positron Annihilation Lifetime Spectroscopy Insight on Free Volume Conversion of Nanostructured MgAl2O4 Ceramics

H.K. and A.I.P. are grateful for the support from the COST Action CA17126. H.K. was also supported by the Ministry of Education and Science of Ukraine (project for young researchers No. 0119U100435). In addition, I.K. and H.K. were also supported by the National Research Foundation of Ukraine via project 2020.02/0217, while the research of A.I.P. was funded by the Latvian research council via the Latvian National Research Program under the topic ?High-Energy Physics and Accelerator Technologies?, Agreement No: VPP-IZM-CERN-2020/1-0002. In addition, the research of A.I.P. has been supported by the Latvian-Ukrainian Grant LV-UA/2021/5. The Institute of Solid State Physics, University of Latvi…

Stabilization of primary mobile radiation defects in MgF2 crystals

Abstract Non-radiative decay of the electronic excitations (excitons) into point defects ( F – H pairs of Frenkel defects) is main radiation damage mechanism in many ionic (halide) solids. Typical time scale of the relaxation of the electronic excitation into a primary, short-lived defect pair is about 1–50 ps with the quantum yield up to 0.2–0.8. However, only a small fraction of these primary defects are spatially separated and survive after transformation into stable, long-lived defects. The survival probability (or stable defect accumulation efficiency) can differ by orders of magnitude, dependent on the material type; e.g. ∼10% in alkali halides with f.c.c. or b.c.c. structure, 0.1% in…

Quantum chemical simulations of the optical properties and diffusion of electron centres in mgo crystals

Semiempirical quantum chemical simulations have been undertaken to obtain the self-consistent atomic and electronic structure of the two basic electron defects in MgO crystals: F+ and F centres (one and two electrons trapped by an 0 vacancy, V,). The calculated absorption and luminescence energies agree well with the experimental data; the excited states of both defects are found to be essentially delocalised over nearest-neighbour cations. The activation energy for diffusion is found to increase monotonically in a series V, --f F+ --f F centre (2.50 eV, 2.72 eV and 3.13 eV, respectively).

The Kinetics of Correlated Annealing of F, I Centres in KBr Crystals

Computer Simulations of the Band Structure and Density of States of the Linear Chains of NaCl Ions

The authors thank Eugene Kotomin and V. Kuzovkov for fruitful discussions and valuable suggestions. A.I.P thanks A.Moskina for the technical assistance in preparation of the manuscript. A.I.P also gratefully acknowledges a project LZP-2018/1-0214 from the Latvian Council of Science for partial support.

Influence of F centres on structural and electronic properties of AlN single-walled nanotubes

We analyse the influence of uncharged N vacancies (neutral F centres), created either under conditions of AlN nanotube growth or by its soft irradiation, on the atomic and electronic structure. Periodic one-dimensional (1D) density functional theory (DFT) calculations on models of defective single-walled nanotubes (SW NTs) allow us to analyse how NT chirality and concentration of F centres change their properties compared to the corresponding defect-free nanotubes. We have simulated reconstruction around periodically repeated F centres on 1 nm AlN SW NTs with armchair- and zigzag-type chiralities. To achieve the limit of an isolated vacancy for both chiralities, we have considered different…

Tracks induced in TeO2 by heavy ions at low velocities

On the basis of its thermal properties, TeO2 crystal was selected as an insulator with low threshold electronic stopping power for track formation Set. The crystals were irradiated by S, Zn, Mo, Kr, Te and Pb ions and the optical absorption and track formation were studied. Comparison is made with the published results on LiNbO3 ,Y 3Fe5O12 and SiO2 quartz. Good quantitative agreement is found with the predictions of the thermal spike model of Szenes with respect to Set and the variation of the track size with the electronic stopping power Se. It is shown that TeO2 has a high eAciency g at low ion velocities, which is a characteristic feature of the damage cross-section velocity eAect. ” 200…

First Principles Calculations of Atomic and Electronic Structure of TiAl3+- and TiAl2+-Doped YAlO3

In this paper, the density functional theory accompanied with linear combination of atomic orbitals (LCAO) method is applied to study the atomic and electronic structure of the Ti3+ and Ti2+ ions substituted for the host Al atom in orthorhombic Pbnm bulk YAlO3 crystals. The disordered crystalline structure of YAlO3 was modelled in a large supercell containing 160 atoms, allowing simulation of a substitutional dopant with a concentration of about 3%. In the case of the Ti2+-doped YAlO3, compensated F-center (oxygen vacancy with two trapped electrons) is inserted close to the Ti to make the unit cell neutral. Changes of the interatomic distances and angles between the chemical bonds in the de…

Time-resolved pulsed OSL of ceramic YAP:Mn phosphors

The paper deals with the results of comparative study on time-resolved pulsed optically stimulated luminescence (TR-OSL) response of ceramic YAP:Mn materials prepared by different methods. In parti...

Computer modelling of radiation damage in cation sublattice of corundum

Results of quantum chemical computer simulations of close Frenkel defects in corundum crystals are presented and discussed. The conclusion is drawn that the energy barrier for a back recombination up to fourth nearest neighbours is less than 0.3 eV, i.e. such pairs should be unstable at temperatures above 40 K.

Photostimulated luminescence properties of neutron image plates

Abstract The luminescence properties of two commercial neutron-sensitive image-plates based on Gd 2 O 3 -doped BaFBr:Eu 2 + storage phosphors are examined. These are white Fuji plates and blue Fuji plates (BAS-ND) with Gd 2 O 3 content by weight of 34% and 50%, respectively. Both plates show two maxima in the photostimulation spectrum near 500 nm and 600 nm, with the ratio of the peak responses ( I 600 nm / I 500 nm ) 1.39 and 0.53 for the white and blue plates respectively. The optimum wavelengths for photostimulation for the two phosphors are therefore different. The response of the blue plate is only 25% that of the white plate, if each is stimulated at its optimum wavelength.

Radiation-induced defects in sapphire single crystals irradiated by a pulsed ion beam

Abstract The luminescence and thermal stability of defects formed in α-Al2O3 single crystals after powerful (300 keV) pulsed irradiation with C+/H+ ion beam were investigated. It was found by measuring of optical density, photoluminescence, and pulsed cathodoluminescence that ion irradiation induces both single F-, F+-centers and F2-type aggregate centers. An intense thermoluminescence band with a complex shape was observed in the broad temperature range of 350–700 K, its intensity decreases with increasing of the energy density of the ion beam. The thermal stability of the F-type defects produced in α-Al2O3 after irradiation with a pulsed ion beam is comparable to that in neutron-irradiate…

FTIR Studies of Silicon Carbide 1D-Nanostructures

Stable 1D silicon carbide nanostructures (nanowires) have been obtained via combustion synthesis route. Infrared absorption and reflection spectra for as-obtained and purified SiC nanowires were compared with the spectra of commercially available SiC nanomaterials. Principal vibrational modes have been identified. Reflectivity spectrum has been reconstructed by modeling of the dielectric function

Thermal annealing of radiation damage produced by swift 132Xe ions in MgO single crystals

Abstract The annealing kinetics of the electron-type F+ and F color centers in highly pure MgO single crystals irradiated by 0.23-GeV 132Xe ions with fluences covering three orders of magnitude (Φ = 5 × 1011 –3.3 × 1014 ions/cm2) are studied experimentally via dependence of the optical absorption on preheating temperature. The annealing data are analyzed in terms of the diffusion-controlled bimolecular reactions between F-type centers and complementary interstitial oxygen ions. The behavior of the main kinetic parameters – the migration energies and pre-exponential factors – for different irradiation fluences is discussed and compared with that for other wide-gap binary materials from previ…

First Principles Calculations of Atomic and Electronic Structure of Ti3+Al- and Ti2+Al-Doped YAlO3

M.G.B. appreciates support from the Chongqing Recruitment Program for 100 Overseas Innovative Talents (grant no. 2015013), the Program for the Foreign Experts (grant no. W2017011), Wenfeng High-end Talents Project (grant no. W2016-01) offered by the Chongqing University of Posts and Telecommunications (CQUPT), Estonian Research Council grant PUT PRG111, European Regional Development Fund (TK141), and NCN project 2018/31/B/ST4/00924. This study was supported by a grant from Latvian Research Council No. LZP-2018/1-0214 (for AIP). Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Program H202…

Modification of Polymer-Magnetic Nanoparticles by Luminescent and Conducting Substances

The polymer encapsulated magnetic nanoparticles were obtained by suspension polymerization of styrene in the aqueous dispersion of magnetite. Functionalization of capsules was carried out by adsorp...

Evidence for the formation of two types of oxygen interstitials in neutron-irradiated α-Al2O3 single crystals

Authors are indebted to R. Vila for stimulating discussions. Tis work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014–2018 and 2019–2020 under Grant agreement No 633053. The views and opinions expressed herein do not necessarily refect those of the European Commission. In addition, the research leading to these results has received funding from the Latvian grant LZP-2018/1-0147 (EV). Institute of Solid State Physics, University of Latvia as the Center of Excellence is supported through the Framework Program for European universities Union Horizon 2020, H2020-WIDESPREAD-01–2016–2017-TeamingP…

Temperature dependence of luminescence of LiF crystals doped with different metal oxides

Photoluminescence and cathodoluminescence of LiF crystals doped with different binary metal oxides were measured in the wide temperature range of 50-300 K and time interval of 10−8−10−1 s after the nanosecond electron excitation pulse. Both as-grown those and crystals irradiated by an electron beam in range of absorbed dose up to 103 Gy were studied. It is shown that spectral-kinetic characteristics of the luminescence depend on the absorbed dose (type of created/accumulated color centers), the irradiation temperature, the concentration of hydroxyl, which promotes incorporation of the MeO complex (Me: W, Ti, Fe, Li) into the crystal lattice, and the cation-dopants.

Ion track template technique for fabrication of ZnSe2O5 nanocrystals

The work was performed under the grant of the Ministry of Education and Science of the Republic of Kazakhstan AP05134367 and Latvian grant lzp

Optical absorption and Raman studies of neutron-irradiated Gd3Ga5O12 single crystals

Abstract In this work we have performed a comparative analysis of optical absorption and micro-Raman spectra for series of Gd3Ga5O12 (GGG) single crystals irradiated by fast neutrons with fluences from 1016 n/cm2 to 1018 n/cm2. It was found that the optical absorption spectra of non-irradiated Czochralski grown GGG consist of the relatively narrow lines in the UV spectral range related to the 4f–4f transitions in Gd3+. Transitions from the 6S7/2 ground state to the 6P, 6J and 6D states in a Gd3+ cation are clearly detected. For a GGG crystal containing Ca impurity ions, additional absorption band at 350 nm is observed, and it is tentatively ascribed to oxygen vacancies associated with Ca im…

Calculations of the geometry and optical properties ofFMgcenters and dimer (F2-type) centers in corundum crystals

CALCULATIONS OF THE GEOMETRY AND OPTICAL-PROPERTIES OF F-MG CENTERS AND DIMER (F-2-TYPE) CENTERS IN CORUNDUM CRYSTALS

The peculiarities of the radiation damage accumulation kinetics in the case of defect complex formation

Abstract The kinetics of radiation defect accumulation under irradiation by heavy particles is theoretically analysed under the assumption of defect complex genesis, particularly, the ones of anion and cation vacancies. The obtained analytical mathematical model and revealed peculiarities of radiation dose dependencies can be used for analysis of the experimental results for different crystalline materials for solid-state electronics and photonics.

Ab-Initio Calculations of Oxygen Vacancy in Ga2O3 Crystals

The research has been funded by the Science Committee of the Ministry of Education and Science of the Republic of Kazakhstan (Grant No. AP08856540). J. Purans and A.I.Popov acknowledge the ERAF project 1.1.1.1/20/A/057 “Functional Ultrawide Bandgap Gallium Oxide and Zinc Gallate Thin Films and Novel Deposition Technologies”. The Institute of Solid State Physics, University of Latvia (Latvia) as the Centre of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017-Teaming Phase2 under grant agreement No. 739508, project CAMART2.

Influence of complex impurity centres on radiation damage in wide-gap metal oxides

Different mechanisms of radiation damage of wide-gap metal oxides as well as a dual influence of impurity ions on the efficiency of radiation damage have been considered on the example of binary ionic MgO and complex ionic–covalent $Lu_{3}Al_{5}O_{12}$ single crystals. Particular emphasis has been placed on irradiation with $\sim$2 GeV heavy ions ($^{197}Au, ^{209}Bi, ^{238}U$, fluence of 10$^{12}$ ions/cm$^{2}$) providing extremely high density of electronic excitations within ion tracks. Besides knock-out mechanism for Frenkel pair formation, the additional mechanism through the collapse of mobile discrete breathers at certain lattice places (e.g., complex impurity centres) leads to the c…

Tendencies in ABO3 Perovskite and SrF2, BaF2 and CaF2 Bulk and Surface F-Center Ab Initio Computations at High Symmetry Cubic Structure

This research was partly funded by the Latvian Council of Science project No. LZP‐ 2020/2‐0009 (for R. Eglitis), as well as the ERAF Project No. 1.1.1.1/18/A/073. We express our gratitude for the financial support from Latvian–Ukraine cooperation Project No. Latvia–Ukraine LV‐ UA/2021/5. The Institute of Solid State Physics, University of Latvia (Latvia), as the Centre of Excellence has received funding from the European Unions Horizon 2020 Framework Pro‐ gramme H2020‐WIDESPREAD01‐2016‐2017‐Teaming Phase2 under Grant Agreement No. 739508, project CAMART2.

Comparative quantum chemistry study of the F-center in lanthanum trifluoride

Abstract In this study we report the results of first principle quantum chemical modeling of electronic structure and spatial configuration of LaF3 crystal containing the F-center. Theoretical predictions of atomic and electronic properties of LaF3 are given by means of density functional theory. From our modeling we predict that the F-center placed at fluorine ion position between the lanthanum planes at tysonite LaF3 is the most energetically stable. In order to interpret the structure of the optical absorption spectrum of X-irradiated LaF3 we performed calculations of excited and transition states of the F-center within the embedded cluster formalism using time dependent density function…

Peculiarities of the diffusion-controlled radiation defect accumulation kinetics under high fluencies

We are grateful to A. Lushchik and E. Shablonin for numerous and valuable discussions. This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014-2018 and 2019-2020 under grant agreement No 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission. The raw/processed data required to reproduce these findings cannot be shared at this time as the data also forms part of an ongoing study.

The Two Types of Oxygen Interstitials in Neutron‐Irradiated Corundum Single Crystals: Joint Experimental and Theoretical Study

About complexity of the 2.16-eV absorption band in MgO crystals irradiated with swift Xe ions

Abstract The precise study of the accumulation and subsequent thermal annealing of the defects responsible for the complex absorption band around 2.16 eV, being under discussion in the literature for a long time, has been performed in highly pure MgO single crystals exposed to 0.23-GeV 132Xe ions with a fluence of Φ = 5 × 1011 − 3.3 × 1014 ions/cm2. Three Gaussian components with the maxima at 2.16, 2.02 and 2.40 eV have been considered as a measure of so-called D1, D2 and D3 defects. Similar to the F and F+ centers, the concentration of these defects increases at high fluences without saturation marks, thus confirming their radiation-induced nature (involvement of novel Frenkel defects). T…

Impact of gadolinium on the structure and magnetic properties of nanocrystalline powders of iron oxides produced by the extraction-pyrolytic method

The work has been done in frame of the TransFerr project. It has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 778070. This research was also supported by Latvian Research Council project lzp-2018/1-0214. A.I.P. appreciates support from the Estonian Research Council grant (PUT PRG619).

Ab initio calculations of CaZrO3 (011) surfaces: systematic trends in polar (011) surface calculations of ABO3 perovskites

Financial support via Latvian-Ukrainian Joint Research Project No. LV-UA/2018/2 for A. I. Popov, Latvian Council of Science Project No. 2018/2-0083 “Theoretical prediction of hybrid nanostructured photocatalytic materials for efficient water splitting” for R. I. Eglitis and J. Kleperis as well as ERAF project No. 1.1.1.1/18/A/073 for R. I. Eglitis and J. Purans is greatly acknowledged.

Optical, infrared and electron-microscopy studies of metallic clusters in layered crystals

Abstract An influence of ( Cd i ) n metallic clusters on the optical absorption and phonon spectra of CdI 2 crystals was studied. Metallic clusters of spherical shape were formed during the growth of non-stoichiometric crystals. Radii of clusters are in range from 10 to 500 nm according to scanning electron microscopy (SEM) data. The density of clusters was estimated from fractal dimension calculations. The fractal dimension of ( Cd i ) n clusters has been found to be varied from 1.488 to 1.793. In the framework of Mie theory the spectral and size dependencies of extinction coefficients were calculated. From the experimentally obtained spectra it is evident that the metallic clusters are re…

Ab initio calculations of pure and Co+2-doped MgF2 crystals

This research was partly supported by the Kazakhstan Science Project № AP05134367«Synthesis of nanocrystals in track templates of SiO2/Si for sensory, nano- and optoelectronic applications», as well as by Latvian Research Council project lzp-2018/1-0214. Calculations were performed on Super Cluster (LASC) in the Institute of Solid State Physics (ISSP) of the University of Latvia. Authors are indebted to S. Piskunov for stimulating discussions.

Thermal annealing and transformation of dimer F centers in neutron-irradiated Al2O3 single crystals

This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014-2018 and 2019-2020 under grant agreement No 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission. In addition, the research leading to these results has received funding from the Estonian Research Council grant (PUT PRG619).

The Temperature Dependence of Scintillation Parameters in PbWO4 Crystals

The luminescence spectra, decay kinetics and yield of luminescence in undoped PbWO 3 crystals were studied after pulsed electron beam irradiation. The rise time of luminescence pulses shows that two mechanisms - excitonic and recombination - were involved in luminescence center excited state formation. It is proposed that excited states of WO 3 and WO 2- 4 luminescence centers were formed from some metastable state, possibly from Pb related excitation.

Texturing of Indium Phosphide for Improving the Characteristics of Space Solar Cells

This paper discusses and demonstrates the usefulness and prospects of using textured layers of indium phosphide as a material for space solar cells. Such designs improve the performance of the photovoltaic converter by increasing the effective area and surface roughness. Thus, it minimizes the background reflectivity of the surface. Textured layers on the InP surface were obtained by electrochemical etching using a bromous acid solution.

Long-term evolution of luminescent properties in CdI2 crystals

Fresh and aged melt-grown or gas-phase grown CdI2 crystals are studied by means of low-temperature photoluminescence spectroscopy. Noticeable transformations of emission spectra are observed after long-term aging. The formation of nanostructures containing cadmium oxide and cadmium hydroxide as well as the changes in local surrounding of iodine atoms and the possible growth of polytypic modifications of CdI2 are taken into account when considering the diversity of optical spectra.

Extraction–Pyrolytic Method for TiO2 Polymorphs Production

The authors thank V. Kuzovkov, A. Lushchik and M. Lushchik for many useful discussions. The research was (partly) performed in the Institute of Solid State Physics, University of Latvia ISSP UL. ISSP UL as the Center of Excellence is supported through the Framework Program for European universities Union Horizon 2020, H2020-WIDESPREAD-01–2016–2017-TeamingPhase2 under Grant Agreement No. 739508, CAMART2 project.

Nonlinear optical response of bulk ZnO crystals with different content of intrinsic defects

Abstract The nonlinear optical (NLO) properties of native defect-rich ZnO single crystals were studied in details within the excitation of the continuous wave (CW) and pulsed laser radiation at 532 nm (2.33 eV). Analysis of the experimental data of optical elastic scattering, Fourier transform infrared (FTIR), near infrared–visible–ultraviolet (NIR–Vis–UV) spectra recorded in reflection and absorption modes, and data of photoluminescence (PL) spectroscopy confirmed the contribution of both intrinsic defects and their clusters, being determined before by neutron diffraction and XRD analysis. It was shown that the high sensitivity of the NLO diagnostics via self-action of a laser beam is due …

Mechanism for energy transfer processes between Ce3+ and Tb3+ in LaPO4:Ce,Tb nanocrystals by time-resolved luminescence spectroscopy

The energy transfer mechanisms between Ce 3+ and Tb 3+ in LaPO 4 :Ce,Tb nanocrystals have been studied by means of time-resolved luminescence spectroscopy in a wide temperature range (10-300K). Special attention was paid to detailed comparative analysis of both rise and decay emission components of both Ce 3+ and Tb 3+ . Surprisingly, a relatively slow rise (several microseconds) of Tb 3+ emission under 266-nm laser excitation was detected, which corresponds to the 4f-5d transition of Ce 3+ in LaPO 4 . It was shown that this rise of Tb 3+ emission could not have arisen due to relaxation of Ce 3+ ions, whose excited state has a lifetime of about 20ns. It was demonstrated that the generally a…

Investigation of Critical Points of Pore Formation Voltage on the Surface of Semiconductors of A3B5 Group

In this work, critical values of pore-formation in electrochemical machining of semiconductors of A 3 B 5 group are studied. On the example of indium phosphide, the indicators of the series of dependence of current density on the voltage of anodization are studied. The rates of current density increase in the regime of gradual rise of anodization voltage are determined. According to these indicators, the intervals are established, within which the active pore-formation occurs on the surface of semiconductor.

Luminescence characteristics of magnesium aluminate spinel crystals of different stoichiometry

We are grateful to Drs E. Vasil’chenko and A. Maaroos for the help with experiments and useful discussions. This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014-2018 under grant agreement No 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission. In addition, the research leading to these results has received funding from the Estonian Research Council  Institutional Research Funding IUT02-26.

Surfactant-assisted synthesis of Cd1−xCoxS nanocluster alloys and their structural, optical and magnetic properties

We report the synthesis of Co-doped CdS nanoclusters (Cd1−xCoxS) for different doping concentrations (x = 0.10, 0.20 and 0.30) and characterization of their structural, optical, and magnetic properties. The structural properties studied by X-ray diffraction revealed hexagonal-greenockite structure and a decrease of the lattice parameters (a and c) with doping, showing incorporation of Co in the lattice. The morphology of the nanoclusters was studied by scanning electron microscopy. The optical absorption studies, using diffused reflectance spectroscopy, revealed that Co doping modifies the absorption band edge. Ferromagnetic phase was observed in the magnetization measurements at room-tempe…

Shallow and deep trap levels in X-ray irradiated β-Ga2O3: Mg

Abstract The results of the investigation of thermostimulated luminescence (TSL) and photoconductivity (PC) of the X-ray irradiated undoped and Mg2+ doped β-Ga2O3 single crystals are presented. Three low-temperature peaks at 116 K, 147 K and 165 K are observed on the TSL glow curves of undoped crystals. The high-temperature TSL peaks at 354 K and 385 K are dominant in Mg2+ doped crystals. The correlation between doping with Mg2+ ions and the local energy levels of the intrinsic structural defects of β-Ga2O3, which are responsible for the TSL peaks and PC, is established. The nature of TSL peaks and the appropriate photoconductivity excitation bands are discussed.

Radiation creation of cation defects in alkali halide crystals: Review and today's concept (Review Article)

Irradiation of alkali halide crystals creates pairs of Frenkel defects both in anion and cation sublattices. However, the particular nonimpact creation mechanisms (related to the decay of different electronic excitations) of cation Frenkel pairs are still unclear. At helium temperatures, there is yet no direct evidences of the creation of stable (long-lived) elemental cation defects. On the other hand, a number of complex structural defects containing cation vacancies and/or interstitials, were detected after irradiation of alkali halides at higher temperatures. Besides already proved mechanism related to the association of H and VK centers into trihalide molecules, the following possibilit…

Kinetics of nanocavity formation based onF-center aggregation in thermochemically reduced MgO single crystals

Division of Materials Science, Office of Basic Energy Sciences, SC 13, U.S. Department of Energy, Germantown, Maryland 20874-1290~Received 9 February 2001; published 19 July 2001!The dynamics of interacting F centers resulting in F aggregates and nanocavities is modeled in thermo-chemically reduced MgO single crystals. We have recently shown that thermal annealing of thermochemicallyreduced MgO with an exceptionally high F-center concentration (6310

Vacancy Defects in Ga2O3: First-Principles Calculations of Electronic Structure

This research was funded by the Science Committee of the Ministry of Education and Science of the Republic of Kazakhstan (Grant No. AP08856540) as well as by the Latvian research council via the Latvian National Research Program under the topic ?High-Energy Physics and Accelerator Technologies?, Agreement No: VPP-IZM-CERN-2020/1-0002 for A.I. Popov. In addition, J. Purans is grateful to the ERAF project 1.1.1.1/20/A/057 while A. Platonenko was supported by Latvian Research Council No. LZP-2018/1-0214. The authors thank A. Lushchik and M. Lushchik for many useful discussions. The research was (partly) performed in the Institute of Solid State Physics, University of Latvia ISSP UL. ISSP UL as…

First principles hybrid Hartree-Fock-DFT calculations of bulk and (001) surface F centers in oxide perovskites and alkaline-earth fluorides

Valuable discussions with E. A. Kotomin are gratefully acknowledged. Research contribution of R. E. and A. I. P. has been performed within the framework of the EUROfusion Enabling Research project: ENR-MFE19.ISSP-UL-02 “Advanced experimental and theoretical analysis of defect evolution and structural disordering in optical and dielectric materials for fusion applications.” The views and opinions expressed herein do not necessarily reflect those of the European Commission.

Theoretical simulations of I-center annealing in KCl crystals

Abstract This paper focus on theory of diffusion-controlled annealing of the most mobile radiation-induced defects—I centers—in KCl crystals. The kinetics of annealing of pairs of close oppositely charged defects—α-I centers (arising as a result of the tunnelling recombination of primary Frenkel defects—F and H centers) and F-I centers (when H center trap electrons) is calculated taking into account defect diffusion and Coulomb/elastic interaction. Special attention is paid to the conditions under which multi-stage annealing arises; theoretical results are compared with the relevant experimental data.

Ab initio calculations of the electronic structure for Mn2+-doped YAlO3 crystals

The electronic structure of Mn2+ ion substituted for the host Y atom in orthorhombic bulk YAlO3 crystals has been calculated by means of hybrid exchange-correlation functional HSE within density functional theory. The supercell approach has been used to simulate in Pbnm YAlO3 crystal the point defects, Mn-dopant and compensated the F+ center (oxygen vacancy with one trapped electron), to make unit cell neutral. Large 2 × 2 × 2 supercells of 160 atoms allow us to simulate substitutional point defect with concentration of about 3%. Mn2+ ions substituting for host Y form covalent Mn–O bonds, in opposite to the mostly ionic Y–O bond. The F center inserted to compensate the Mn2+ dopant in YAlO3 …

Synchrotron radiation studies on luminescence of Eu2+-doped LaCl3 microcrystals embedded in a NaCl matrix

Abstract LaCl3:Eu2+ microcrystals dispersed in the NaCl matrix have been obtained in the NaCl–LaCl3(1 mol.%)–EuCl3(0.1 mol.%) crystalline system. The low-temperature luminescent properties of these microcrystals have been studied upon the VUV and UV excitation by the synchrotron radiation. The spectroscopic parameters as well as decay time constants of Eu2+-doped LaCl3 host have been established. The excitation mechanism of divalent europium centers through energy transfer and reabsorption is discussed.

Kinetics of the electronic center annealing in Al2O3 crystals

Authors are greatly indebted to A. Ch. Lushchik, V. Kortov, M. Izerrouken and R.Vila for stimulating discussions. This work has been carried out within the framework of the Eurofusion Consortium and has received funding from the Euroatom research and training programme 2014–2018 under grant agreement No 633053 . The views and opinions expressed herein do not necessarily reflect those of the European Commission. The calculations were performed using facilities of the Stuttgart Supercomputer Center (project DEFTD 12939 ).

Photoconversion and dynamic hole recycling process in anion vacancies in neutron-irradiated MgO crystals

Optical spectroscopy and theory demonstrate that photon excitation of the positively charged anion vacancies (F{sup +} centers) at 5.0 eV in neutron-irradiated MgO crystals releases holes that are subsequently trapped at {ital V}-type centers, which are cation vacancies charge compensated by impurities, such as Al{sup 3+}, F{sup {minus}}, and OH{sup {minus}} ions. The concentration of trapped-hole centers was found to exceed that of available anion vacancies. The disproportionately large amount of holes produced is attributed to a dynamic recycling process, by which the F{sup +} center serves to release a hole to the {ital V}-type centers and subsequently trap a hole from an Fe{sup 3+} ion.…

Evolution of Free Volumes in Polycrystalline BaGa2O4 Ceramics Doped with Eu3+ Ions

H.K. and Y.K. would like to thank A. Ingram for assistance in PAL experiments. The authors thank E.A. Kotomin and M. Brik for the many useful discussions. The research was (partly) performed in the Institute of Solid State Physics, University of Latvia ISSP UL. ISSP UL as the Center of Excellence is supported through the Framework Program for European universities Union Horizon 2020, H2020-WIDESPREAD-01–2016–2017-TeamingPhase2 under Grant Agreement No. 739508, CAMART2 project.

Positron trapping defects in free-volume investigation of Ge–Ga–S–CsCl glasses

Abstract Evolution of free-volume positron trapping defects caused by crystallization process in (80GeS 2 –20Ga 2 S 3 ) 100−х (СsCl) x , 0 ≤ x ≤ 15 chalcogenide-chalcohalide glasses was studied by positron annihilation lifetime technique. It is established that CsCl additives in Ge–Ga–S glassy matrix transform defect-related component spectra, indicating that the agglomeration of free-volume voids occurs in initial and crystallized (80GeS 2 –20Ga 2 S 3 ) 100−х (СsCl) x , 0 ≤ x ≤ 10 glasses. Void fragmentation in (80GeS 2 –20Ga 2 S 3 ) 85 (СsCl) 15 glass can be associated with loosing of their inner structure. Full crystallization in each of these glasses corresponds to the formation of defe…

Electronic structure of MnAl3+- and MnAl2+-doped YAlO3: Prediction from the first principles

Abstract The atomic structure and electronic properties of Mn3+ and Mn2+ ions substituted for the host Al at YAlO3 have been studied from the first principles. The 2 × 2 × 2 supercell adopted for the bulk crystal phase of P b n m symmetry allows us to simulate substitutional point defect with concentration of about 3%. To perform ab initio modeling of Mn-doped YAlO3 we were using approach of hybrid exchange-correlation functional HSE within density functional theory. We predict a decrease of the Mn O bond covalency in the doped crystal with respect to the Al O bond of ideal orthorhombic YAlO3. Relatively large displacement of Y and Al atoms nearest to the F 0 -center inserted to stabilize t…

A simple analysis of the HA centre destruction temperatures for doped alkali halides

Abstract A simple relation for the destruction temperatures Td of the HA centres (H centres trapped by an impurity cation) as a function of the difference in the radii for a host cation and impurity in alkali halide crystals is presented and theoretically justified. This relation allows to predict Td for H centres trapped by other monovalent cation impurities.

Kinetics of correlated annealing of radiation defects in alkali halide crystals

Abstract Kinetics of the correlated annealing of pairs of neutral (F-H) Frenkel defects in the KBr crystal is treated theoretically, taking into account defect diffusion, and annihilation at short distances stimulated by an elastic interaction. It is shown that an elastic interaction affects the annealing kinetics and the survival probability of close geminate detects considerably. The widespread description of the correlated annealing in terms of a first-order reaction fails for close defects yielding effective energies which in fact differ essentially from an activation energy of diffusion. Ea, even if it is corrected by an interaction energy. The effect of the initial distribution of def…

Possible mechanism of energy storage in optically stimulable materials: doped alkali halides

Radiation-induced effects in doped alkali halides, mainly in KBr:In, are studied by the luminescence technique. The activator luminescence during a 10 s under UV-light or electron irradiation and, after it, the pulsed photostimulated luminescence on a phosphorescence background were investigated. The obtained results allow us to conclude that the main host lattice excitation relevant to both the luminescence processes mentioned above is a very mobile excitonic excitation including a photon phase and the self- trapped exciton in its composition. The photon phase, as we suppose, represents a free exciton luminescence at room temperature. In this phase, via multiple reabsorption in the low-ene…

Semi-empirical simulations of F-center diffusion in KCl crystals

Abstract The semi-empirical method and 224 atom quantum clusters were used for calculating the activation energy for diffusion of cation and anion vacancies and F-centers in KCl crystals. The relevant activation energies of 1.19 eV, 1.44 eV and 1.64 eV, respectively agree well with the experimental data.

Atomic, electronic and magnetic structure of an oxygen interstitial in neutron-irradiated Al2O3 single crystals

This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014-2018 and 2019-2020 under Grant Agreement No. 633053 and Enabling Research project: ENR-MFE19.ISSP-UL-02 “Advanced experimental and theoretical analysis of defect evolution and structural disordering in optical and dielectric materials for fusion application”. The views and opinions expressed herein do not necessarily reflect those of the European Commission. In addition, the research leading to these results has received funding from the Estonian Research Council grant (PUT PRG619).

Time-resolved cathodoluminescence spectroscopy of YAG and YAG:Ce3+ phosphors

Abstract The phosphor powders, both undoped and Ce3+ doped with different concentration Y3Al5O12 (YAG), were synthesized by the solid-state reaction method with addition of BaF2 flux. SEM and XRD characterization of the samples were performed. The spectral and luminescence decay kinetic characteristics under the electron beam irradiation with nano- and picoseconds pulse duration and the electron energies of 250 keV and 55 keV were studied, respectively. Two bands in the cathodoluminescence spectrum of YAG:Ce3+ phosphors were observed with maxima at 2.19 ± 0.05 and 2.4 eV. The intensity ratio of these two bands depends on the electron energy and the duration of the excitation pulse. Instead,…

EPR and optical spectroscopy of neutron-irradiated Gd3Ga5O12 single crystals

Abstract In this paper, we have performed comparative analysis of EPR, optical absorption (OA) and luminescence spectra for a series of Gd3Ga5O12 (GGG) single crystals irradiated with fast neutrons with fluencies varied from 1016 to 1020n/cm2. In a crystal irradiated with the maximum neutron fluence, the EPR spectra demonstrated the formation of several paramagnetic defects. In particular, EPR spectrum shows a strong resonance at (effective) g ≈ 1.4 with practically isotropic behavior in the crystal rotation around the [1 1 1] direction (magnetic field being perpendicular to [1 1 1]) and several weaker lines in the g ≈ 1.1–2.6 region, which show more pronounced angular dependences. While th…

Low temperature structural transformations on the (001) surface of SrTiO 3 single crystals

This work was supported by the Ministry of Education and Science of Ukraine under the contract M/51–2019 within the framework of the Program of Ukrainian–Latvian Scientific and Technical Cooperation and Latvian–Ukranian Grant LV-UA/2018/2. Authors are indebted to L.L. Rusevich, G. Zvejnieks, V.P. Gnezdilov and A. Glamazda for stimulating discussions.

Electronic excitations in ZnWO4 and ZnxNi1−x WO4 (x = 0.1 − 0.9) using VUV synchrotron radiation

The photoluminescence spectra and luminescence excitation spectra of pure microcrystalline and nano-sized ZnWO4 as well as the Zn x Ni1−x WO4 solid solutions were studied using vacuum ultraviolet (VUV) synchrotron radiation. The samples were also characterized by x-ray powder diffraction. We found that: (i) the shape of the photoluminescence band at 2.5 eV, being due to radiative electron transitions within the [WO6]6− anions, becomes modulated by the optical absorption of Ni2+ ions in the Zn x Ni1−x WO4 solid solutions; and (ii) no significant change in the excitation spectra of Zn0.9Ni0.1WO4 is observed compared to pure ZnWO4. At the same time, a shift of the excitonic bands to smaller en…

Structural and electronic properties of single-walled AlN nanotubes of different chiralities and sizes

Four models of single-walled AlN nanotubes (NTs), which possess (i) two different chiralities (armchair or zigzag type) and (ii) two different uniform diameters for both types of NTs (1 or 6 nm) have been constructed, in order to analyse the dependence of their properties on both morphology and thickness. Periodic one-dimensional (1D) DFT calculations performed on these models have allowed us to analyse how the chirality and curvature of the NT change its properties as compared to both AlN bulk with either wurtzite or zinc-blende structures and their densely packed surfaces. We have found that the larger the diameter of the AlN NT, the smaller the width of its bandgap, the strengths of its …

Photoconversion of F+ centers in neutron-irradiated MgO

Abstract In neutron-irradiated MgO crystals, experiments and theory demonstrate that photon excitation of the positively charged anion vacancies (F+ centers) at 5.0 eV releases holes that are subsequently trapped at V-type centers, which are cation vacancies charge-compensated by impurities, such as Al3+, F−, and OH− ions. A photoconversion mechanism occurs very likely via electron transfer to F+ centers from the quasi-local states which are induced in the valence band. INDO quantum chemical simulations of F+ centers confirmed the appearance of two induced quasi-local states located at 1.2 and 2.0 eV below the top of the valence band.

Ion-Track Template Synthesis and Characterization of ZnSeO3 Nanocrystals

A.I.P. thanks the Institute of Solid-State Physics, University of Latvia. ISSP UL as the Center of Excellence is supported through the Framework Program for European universities. The work was carried out within the framework of the grant AP05134367 of the Ministry Funding: The work was carried out within the framework of the grant AP05134367 of the Ministry of education and Science Science of of the Republic Republic of Kazakhstan.

Luminescence, vibrational and XANES studies of AlN nanomaterials

Abstract The paper reports comparative studies on synthesized aluminium nitride nanotubes, nanoparticles and commercially available micron-sized AlN powder using different spectroscopic techniques: cathodoluminescence measurements (CL), X-ray absorption near edge spectroscopy (XANES) and Fourier-transform infrared spectroscopy (FTIR). Crucial distinctions in CL spectra are observed for nano- and microsized aluminium nitride powders; systematic shift of the IR absorption maximum has been detected for nanostructured aluminium nitride as compared to commercial samples. Through XANES experiments on Al K-edge structural differences between nano- and bulk AlN are revealed, intensity of features i…

Cadmium clusters in CdI2layered crystals: the influence on the optical properties

The influence of overstoichiometric Cd i atoms on the optical properties of cadmium iodide layered crystals has been investigated. The results of optical absorption, luminescence, and luminescence excitation studies of CdI 2 crystals with controlled deviation from stoichiometric composition allow observing correlations between the Cd i concentration and features in absorption and emission spectra up to concentrations of 10 18 cm -3 . At higher concentrations the overstoichiometric cadmium atoms form clusters, which were observed using scanning electron microscopy. The extinction spectra of (CdI i ) n clusters are calculated in the frame of Mie theory and are found to correlate with the opti…

Theoretical simulations of regular and defective aluminium nitride nanotubes

For theoretical simulation on AlN nanotubes (NTs) of different chiralities (armchair-and zigzag-type) and uniform diameters, we have considered their single-walled (SW) 1D periodic models. For this aim, we have performed ab initio DFT calculations on AlN SW NTs using formalism of the localized Gaussian-type atomic functions as implemented in CRYSTAL-03 computer code. We have shown that the smaller the diameter of AlN single-walled nanotube is, the closer its electronic and structural properties to AlN bulk. We have analysed an influence of N vacancies (neutral F centres) created by either soft irradiation of nanotubes or under experimental conditions of their growth, on the atomic and elect…

Dynamics of F-center annihilation in thermochemically reduced MgO single crystals

Optical absorption measurements were used to monitor the thermal annihilation of oxygen vacancies (F-centers) in thermochemically reduced MgO crystals. The annihilation characteristics were sample-dependent and varied strongly with the F-center concentration. Different mechanisms for the destruction of F centers are suggested depending on their concentration.

Spectroscopic studies of Cr3+ ions in natural single crystal of magnesium aluminate spinel MgAl2O4

Abstract The natural spinel crystal MgAl2O4 containing the Cr3+ ions was studied experimentally and theoretically in this paper. The absorption and emission spectra at room and low temperatures were recorded. The experimental spectroscopic results were aided with the crystal field calculations, which returned the energy level schemes of the Cr3+ ions at the Al sites with the local D3d symmetry. Effects of the trigonal crystal field were clearly seen in the calculated results, which were compared with the experimental spectra to yield a good agreement between both data sets.

Diffusion-controlled annihilation and aggregation of F-centers in thermochemically reduced MgO crystals

Abstract The dynamics of F-center (an oxygen vacancy which has trapped two electrons) aggregation in thermochemically reduced MgO single crystals with an exceptionally high F-center concentration (6×1018 cm−3) is discussed. A theory of the Mg nanocavity formation process is developed based on diffusion-controlled aggregation of elastically interacting F centers and their annihilation at traps. We show that in contrast to the generally accepted viewpoint, the F centers in the bulk are not annealed out at the external sample surface but at internal defects, such as dislocations, subgrain boundaries and impurities. The mutual attraction of the F centers is a key factor controlling the aggregat…

Comparative study of the luminescence properties of macro- and nanocrystalline MgO using synchrotron radiation

MgO nano-powder with an average crystallite size of nanoparticles ranging 10-15 nm was synthesized using the extractive-pyrolytic method and was studied by room temperature VUV spectroscopy under synchrotron radiation excitation. Comparative analysis of their luminescent properties with that of mac- rocrystalline powder analogues and an MgO single crystal, grown by the arc-fusion method, has been per- formed under excitation by pulsed VUV synchrotron radiation. Special attention was paid to VUV spectral range, which is not reachable with commonly used lamp and laser sources. A considerable blue shift of about 0.3 eV in the excitation spectra of 2.95 eV emission band, was revealed in nanocry…

CdTe Nanocrystal Synthesis in SiO 2 /Si Ion‐Track Template: The Study of Electronic and Structural Properties

Morphology Study of the Porosity of the GaP Surface Layer Formed on the Surface of a Single Crystal by Electrochemical Etching

The article analyzes the morphological characteristics of a porous GaP surface layer formed on the surface of monocrystalline gallium phosphide by electrochemical etching. The correlations between the etching time and the appropriate size, shape and density of pores have been established and studied in detail.

Luminescence of nano- and macrosized LaPO4:Ce,Tb excited by synchrotron radiation

Abstract Comparing the luminescence properties of nanosized and macroscopic LaPO4:Ce,Tb powders are performed in wide spectral range using synchrotron radiation. In the present study, LaPO4:Ce,Tb nanopowder was produced by means of a microwave-induced synthesis in ionic liquids, whereas the bulk sample represents a commercial lamp phosphor. Emission and excitation of both, Ce3+ and Tb3+ luminescence, is observed to be different when comparing bulk and nanosized LaPO4:Ce,Tb. In particular, it was shown that the fine structure of the Ce3+ as well as the Tb3+ related emission is poorly resolved for the nanomaterial. It is suggested that the nanoparticles surface plays a key role regarding the …

Fast Luminescence Studies of NaLaF4: Pr3+ Glass Ceramics

Cathodoluminescence (CL) emission and photoluminescence (PL) emission and excitation spectra of $16\mathbf{Na}2\mathbf{O}-9\mathbf{NaF}-5\mathbf{LaF}_{3}-7\mathbf{Al}_{2}\mathbf{O}_{3}-63\mathbf{SiO}_{2}$ (mol%) activated with 3% $\mathbf{PrF}_{3}$ , hereinafter referred to as $\mathbf{NaLaF}_{4}:\mathbf{Pr}_{9}^{3+}$ have been investigated. In particular, CL spectra were measured with time resolution after excitation with a 120 keV electron beam. The characteristic Pr3+ ion emission with fast decay times $\tau_{1}=1.77$ ns and $\tau_{2}=52.97$ ns at peak intensity at 406 nm were observed, which correspond well to the emission bands of the $\mathbf{Pr}^{3+}$ ion in other luminescent materia…

Comparison of the F-type center thermal annealing in heavy-ion and neutron irradiated Al2O3 single crystals

Abstract The optical absorption and thermally stimulated luminescence of Al2O3 (sapphire) single crystals irradiated with swift heavy ions (SHI) 238U with energy 2.4 GeV is studied with the focus on the thermal annealing of the F-type centers in a wide temperature range of 400–1500 K. Its theoretical analysis allows us to obtain activation energies and pre-exponentials of the interstitial oxygen ion migration, which recombine with both types of immobile electron centers (F and F+ centers). A comparison of these kinetics parameters with literature data for a neutron-irradiated sapphire shows their similarity and thus supports the use of SHI-irradiation for modeling the neutron irradiation.

Excitation of different chromium centres by synchrotron radiation in MgO:Cr single crystals

The excitation spectra for the emissions of chromium-containing centres have been measured at 10 K using synchrotron radiation of 4–32 eV in MgO single crystals with different content of Cr$^{3+}$ (5–850 ppm) and Ca$^{2+}$ impurity ions. Both virgin crystals and the samples preliminarily irradiated with x-rays at 295 K have been studied. The role of complex chromium centres containing two Cr$^{3+}$ and a cation vacancy (sometimes nearby a Ca$^{2+}$ ion) on the luminescence processes and the transformation/creation of structural defects has been analysed. Such anharmonic complex centres could serve as the seeds for the creation of 3D defects that facilitate the cracking and brittle destructi…

Analysis of self-trapped hole mobility in alkali halides and metal halides

Support from Latvian National Research Program IMIS2 (2014–2017) and LZP Grant No. 237/2012 (2013–2016) is greatly appreciated.

Nanostructure Formation on ZnSe Crystal Surface by Electrochemical Etching

The article describes a simple method for nanostructuring the surface of monocrystalline zinc selenide. It is shown that the traditional electrochemical etching of n-ZnSe (111) samples in a concentrated solution of nitric acid leads to the appearance of massive etching pits and small pores on the surface. The dynamics of the process and stages of crystal dissolution has been studied. It is assumed that the porous zinc selenide obtained in this way can be used in optoelectronic structures, as well as as buffer layers for growing zinc oxide.

Numerical Evidences of Polarization Switching in PMN Type Relaxor Ferroelectrics

We present a conceptual and computational framework for chemically ordered Pb(Mg 1/3 Nb 2/3 O 3) (PMN) type supercells violating disorder of the host lattice. The effective Hamiltonian is specified by invariance under permutations of supercells and by the dipole-dipole interaction supporting both local nonzero and zero mean polarization of the structure. Statistics treated in canonical ensemble within the mean field approach reveals emergence of polar nanoregions as supported by interplay between the (random) initial state polarization of supercells and their interactions increased at cooling.

Optical investigation of the OH− groups in the LiNbO3 doped by copper

Doping ions and OH− groups absorption bands spatial profiles were investigated for the case of congruent LiNbO3 single crystal grown by Czochralski technique. Doping was performed after the crystal...

Ion track template technology for fabrication of CdTe and CdO nanocrystals

Abstract CdTe and CdO nanocrystals were synthesized by chemical deposition into a-SiO2/n-Si ion track template formed by 200 MeV Xe ion irradiation with the fluence of 108 ions/cm2. Depending on the temperature of the solution CdTe + CdO and single-phase CdO with a hexagonal crystal structure were obtained, respectively. The study of the current – voltage characteristics of the obtained structure with the single-phase CdO allows us to estimate the number of grain boundaries and the height of the potential barrier, as well as the n-type conductivity.

Efficiency of H center stabilization in alkali halide crystals at low-temperature uniaxial deformation

The efficiency of stabilization of H centers as well as its dependence on the degree of uniaxial deformation are considered within the framework of the modified geometric model of alkali halides. It is shown that stabilization of H centers is difficult in KI and RbI crystals, while in other NaCl-type crystals it becomes quite probable. Under uniaxial deformation, the interstitial space, in which the defect will be located, decreases, and the efficiency decrease. In the case of cesium halides, the orientation of the H centers takes place predominantly in the direction; therefore, the criteria for their stabilization differ from the NaCl-type alkali halide crystals. According to calculations,…

Luminescence Properties and Decay Kinetics of Mn2+ and Eu3+ Co-Dopant Ions In MgGa2O4 Ceramics

A. Luchechko gratefully acknowledges a grant from the Institute of Physics PAS for a research visit to the institute, while A.I. Popov has been supported by project LZP-2018/1-0214 from the Latvian Council of Science.

BiI3 nanoclusters in melt-grown CdI2 crystals studied by optical absorption spectroscopy

Optical absorption spectroscopy of CdI2–BiI3 layered crystals has been performed in the temperature range of 77–300 K. The main absorption, observed in these crystals at 2.59 eV is related to quantum confined exciton absorption of bimolecular BiI3 cluster. Low energy absorption peaks at 2.38 eV, 2.06 eV and 1.94 eV can be tentatively assigned to larger clusters composed of 4, 6 or more BiI3 molecules. In ultra-thin samples of CdI2–BiI3 several bands at 2.84 eV, 3.03 eV and 3.27 eV were observed which are ascribed to higher excited states of the excitons in bimolecular BiI3 cluster.

Effect of Poly(Titanium Oxide) on the Viscoelastic and Thermophysical Properties of Interpenetrating Polymer Networks

The authors thank V. Serga for many useful discussions. The research was (partly) performed in the Institute of Solid State Physics, University of Latvia ISSP UL. ISSP UL as the Center of Excellence is supported through the Framework Program for European universities Union Horizon 2020, H2020-WIDESPREAD-01–2016–2017-Teaming Phase 2 under Grant Agreement No. 739508, CAMART2 project.

Luminescence properties of KNbO3 crystals

Thermostimulated luminescence, X-ray-induced luminescence, photostimulated luminescence as well as the time-resolved luminescence and absorption after pulsed electron beam irradiation were studied in KNbO3 crystals at 80–400 K. A correlation between defects causing the luminescence and blue-light-induced IR absorption effects supressing the second harmonic generation efficiency in KNbO3 is discussed.

A Contradiction between Pulsed and Steady-State Studies in the Recombination Kinetics of Close Frenkel Defects in KBr and KCl Crystals

Theoretical study of the kinetics of the correlated annealing of pairs of close (geminate) F-H centers in KCl and KBr crystals controlled by their diffusion and elastic attraction shows that the multi-step (kink) decay in defect concentrations observed more than once in thermostimulated experiments takes place only for very close F-H center pairs which are no further than fourth nearest neighbors. On the other hand, it is demonstrated (both theoretically and experimentally) that such F-H center pairs should be destroyed by the tunneling recombination already at time ≤10 -4 s, i.e. much before beginning of the thermostimulated experiments. Possible explanations of this contradiction are sugg…

Time-resolved luminescence and induced absorption in PbWO4

Abstract Luminescence and short-lived induced absorption are studied for two undoped PbWO4 crystals. Luminescence decay at LNT is delayed relative to irradiation pulse. The delay observed is either due to reabsorption of luminescence or due to creation of luminescence center excited states via energy or/and charge transfer after irradiation pulse. Short-lived absorption is observed within 1.1–3.6 eV spectral region at LNT as well as at RT. It is proposed that the short-lived absorption band peaking at ~ 3.5 eV is intrinsic.

Multicolor photon emission from organic thin films on different substrates

Abstract Thin films of 1-pentyl-2 / ,3 / -difluoro-3 /// -methyl-4 //// -octyl- p -quinquephenyl and 9,10-Bis (4-pentylphenylethynyl)antracene organic molecules were grown on optical glass, silicon and porous silicon substrates. First optical and luminescent properties of such hybrid composites are thoroughly studied using spectroscopic techniques. The strong decrease of aggregation in thin films of 1-pentyl-2 / ,3 / -difluoro-3 /// -methyl-4 //// -octyl- p -quinquephenyl on porous silicon was observed. The possibility of simultaneous red, green and blue tunable photon emission from organic film/porous silicon hybrid structure is demonstrated.

Systematic trends in YAlO3, SrTiO3, BaTiO3, BaZrO3 (001) and (111) surface ab initio calculations

We greatly acknowledge the financial support via Latvian-Ukrainian Joint Research Project No. LV-UA/2018/2, Latvian Council of Science Grant No. 2018/2-0083 “Theoretical prediction of hybrid nanostructured photocatalytic materials for efficient water splitting”, Latvian Council of Science Grant No. 2018/1-0214 as well as ERAF Project No. 1.1.1.1/18/A/073.

Low-temperature studies of Cr 3+ ions in natural and neutron-irradiated g-Al spinel

This study was supported by a grant from Latvian Council of Science (agreement No. LZP-2018/1-0214).

Low-temperature luminescence of CdI2 under synchrotron radiation

Synchrotron radiation is applied to study visible and UV luminescence spectra and their excitation spectra of undoped as well as In and Sb doped cadmium iodide crystals at 10 K. The origin of principal luminescence bands and the role of impurities in the formation of emission centers are discussed. The luminescence properties have been explained based on the electronic structure of CdI2 crystals.

Microstructure of Ag2BI4(B = Ag, Cd) superionics studied by SEM, impedance spectroscopy and fractal dimension analysis

Two silver ion conducting solid electrolytes, Ag2HgI4 and Ag2CdI4, representing a wide class of AgI-based halogenide superionics have been the subjects of study by means of electrical impedance spectroscopy, SEM, porosity measurements and fractal dimension analysis. Even though both materials have been obtained by the same method under strictly identical conditions they were found to exhibit certain differences at the microstructural level. Thus, by the direct measurements of porosity and density it was found that the grain boundaries are better developed in silver mercuric iodide. On the assumption that pore geometry in the materials under study displays fractal character it was shown that…

Photostimulated emission of KBr—In previously exposed to UV- or X-radiation

Abstract We have performed a photostimulated luminescence (PSL) study of a KBr—In crystal previously irradiated in the exciton fundamental absorption band. It is shown that the PSL arises from three types of close defect pair. It is also shown that one of these three kinds of defect pairs is {F, In2+}, whereas the electron centre of the two other pairs has a more complex nature.

Time-resolved luminescence of YAG:Ce and YAGG:Ce ceramics prepared by electron beam assisted synthesis

Abstract The luminescence characteristics of YAG:Ce and YAGG:Ce ceramic phosphors produced by electron beam assisted synthesis have been investigated. The obtained emission and decay kinetics characteristics have been compared with those for commercial phosphors synthesized by conventional methods and showed good qualitative and quantitative correspondence. In our opinion, the used electron-beam-assisted synthesis method could be considered as a perspective production method of high refractory multicomponent oxide ceramics.

Nanoporous characterization of modified humidity-sensitive MgO-Al 2 O 3 ceramics by positron annihilation lifetime spectroscopy method

The work was supported by the Ukrainian Ministry of Education and Science. H. Klym thanks Prof. O. Shpotyuk for the fruitful discussion.

Time-resolved luminescence of CsITl crystals excited by pulsed electron beam

Abstract Results of the time-resolved measurements of CsITl crystal luminescence under electron pulse excitation at room temperature are reported. The rise and decay times of both 400 and 500 nm emission bands have been measured. The results obtained show that the main mechanism of the luminescence excitation is hole recombination luminescence which is due to self-trapped hole migration toward Tl 0 centres. Stimulation spectra of photostimulated luminescence of CsITl are also analyzed.

ESD of nonthermal halogen atoms from In-doped (001) KBr

Abstract We have measured the kinetic energy distributions of neutral halogen atoms emitted due to electron-stimulated desorption (ESD) from In-doped (001)KBr single crystals. The concentration of In+ in investigated samples varied between 1017 and 1020 particles/cm3. The measurements were performed at target temperature of 150°C. In all cases the energy spectra consist of two peaks. The distribution of low-energy particles can be described by the thermal (Maxwellian) energy spectrum. Particles contributing to the second peak have nonthermal kinetic energies. The emission of halogen atoms having nonthermal energies decreases with an increase in the concentration of In impurities. At the sam…

Distinctive features of diffusion-controlled radiation defect recombination in stoichiometric magnesium aluminate spinel single crystals and transparent polycrystalline ceramics

This work has been performed within the framework of the EUROfusion Enabling Research project: ENR-MFE19.ISSP-UL-02 “Advanced experimental and theoretical analysis of defect evolution and structural disordering in optical and dielectric materials for fusion application”. The views and opinions expressed herein do not necessarily reflect those of the European Commission. Research of A.L, E.F.,, V.S and E.S has been partly supported by the Estonian Research Council grant (PUT PRG619); has been also carried out within the framework of the EUROfusion Consortium and has received funding from the Euratom research and training programme 2014–2018 and 2019–2020 under grant agreement No 633053. The …

Intrinsic nanostructures on the (001) surface of strontium titanate at low temperatures

Atomically smooth (001) surfaces of SrTiO3 cut from the high-quality single crystals at two different miscut angles 0.9 and 7.0 deg between the real flat surfaces and crystallographic planes (001) were analyzed by means of the reflection high energy electron diffraction (RHEED) method from the room down to liquid helium temperatures. The diffraction patterns typical of the RHEED geometry close to ideal for a small miscut angle and those exhibiting distinct features of the specific periodicity associated with regular steps, which form due to the larger miscut angle, are presented. The surface symmetry and energetics were shown to impose differences in lattice parameters in parallel to a surf…

Computer Simulation of the Electric Transport Properties of the FeSe Monolayer

The research has been supported by the grant of the Ministry of Education and Science of the Republic of Kazakhstan AP08052562. In addition, the research of AIP has been supported by the Latvian- Ukrainian Grant LV-UA/2018/2.

Structural and electronic properties of β-NaYF4 and β-NaYF4:Ce3+

AP is indebted for a financial support provided by Scientific Research Project grant for Students and Young Researchers Nr. SJZ/2017/3 sponsored at the Institute of Solid State Physics, University of Latvia , while AIP is thankful for the financial support from Latvian Research Council lzp-2018/1-0214 .

Thermal annealing of radiation defects in MgF2 single crystals induced by neutrons at low temperatures

Abstract Primary radiation defects in ionic solids consist of Frenkel defects – pairs of defects - anion vacancies with trapped electrons (F-type centers) and interstitial ions. Upon temperature increase after irradiation, the electronic F-type centers are annealed due to recombination with mobile interstitials. Analysis of the recombination (annealing) kinetics allows us to obtain important information on the interstitial migration. At high radiation doses more complex dimer (F2-type) centers are observed in several charge states, which are well distinguished spectroscopically. We analysed here available experimental kinetics of the F2-type center annealing in MgF2 in a wide temperature ra…

Creation and thermal annealing of structural defects in neutron-irradiated MgAl 2 O 4 single crystals

Abstract Several novel hole-type defects (a hole localized at a regular oxygen ion near a negatively charged structural defect) have been revealed in fast neutron irradiated MgAl2O4 crystals using the EPR method. The pulse annealing of the EPR signal of these centers was compared to that of radiation induced optical absorption in the same crystals. Taking into account the determined models of V1, V2 and V22 paramagnetic centers, the tentative scenario of the thermal annealing process of neutron-induced defects (hole-type and complementary electron F-type ones) is proposed. In addition, one more paramagnetic hole center consisting of an Al|Mg as-grown antisite defect near an aluminum vacancy…

Low temperature X-ray luminescence of KNbO3 crystals

We have studied X-ray luminescence of KNbO3 single crystal. The 575 nm luminescence band has been studied in the temperature range of 15‐45 K. The quenching parameters were found to be Qa 12 3 meV and ma 4 10 11 s ˇ1 .N o luminescence has been observed under heavy ion excitation ( 86 Kr ions, 8.63 MeV/amu) even at 15 K. ” 2000 Elsevier

First-principles simulations of the electronic density of states for superionic Ag2CdI4 crystals

Abstract Energy band dispersion calculations have been performed for Ag 2 CdI 4 superionic within a framework of local density approximation (Perdew–Zunger parameterization) exploiting the first-principles CASTEP computer code. The ab-initio electronic structure simulations were performed for both ( I 4 and I 42 m ) types of e -Ag 2 CdI 4 crystalline structures. Principal optical functions as well as the density of electronic states in the spectral range of inter-band optical transitions (2.5 eV–20 eV) were determined. Theoretically calculated absorption coefficients derived from the obtained band structure are compared with appropriate experimental data.

CsPbCl3 nanocrystals dispersed in the Rb0,8Cs0,2Cl matrix studied by far-infrared spectroscopy

Abstract The comparative far-infrared spectroscopy studies of Rb0.8Cs0.2Cl and Rb0.8Cs0.2Cl containing CsPbCl3 nanocrystals between 170 and 320 K are reported. The effect of cesium lead chloride nanocrystals on the phonon modes of the host matrix, particularly manifested in different temperature behavior of LO–TO splitting and the temperature dependence of high frequency dielectric constant, are demonstrated.

Characterization of LiF and CaF2 surfaces using MIES and UPS (HeI)

Metastable impact electron spectroscopy (MIES) and UPS (HeI) in combination with ab initio calculations (CRYSTALcode) were applied to study surface and bulk defects in LiF and CaF2. The investigated stoichiometric, defective and doped surfaces are LiF, LiF doped with Mg, and CaF2. The experimental information obtained on the electronic structure of stoichiometric and defective surfaces of LiF (100), LiF on W (110) and CaF2 (111) is discussed on the basis of the ab initio calculations. MIES spectra show features from Li agglomerates on the surface of electron bombarded LiF. The electronic structure of the LiF:Mg single crystal shows additional features above the valence band maximum caused b…

Fast-neutron-induced and as-grown structural defects in magnesium aluminate spinel crystals with different stoichiometry

Abstract Several hole-type paramagnetic defects (a hole localized at a regular oxygen ion near charged structural defect/defects) have been revealed in fast-neutron-irradiated MgO⋅2.5Al2O3 single crystals using the EPR method. Three of them (a dominant V1 and small amount of V2 and V22) were recently revealed in a neutron-irradiated stoichiometric MgAl2O4, while a novel V4 center, ascribed to a hole in a form of O− ion nearby a complex of a magnesium vacancy and a positively charged antisite defect (V4 ≡ O–‑VMg‑Al|Mg), was created by fast neutrons only in a nonstoichiometric single crystal. The pulse annealing of the EPR signal of these centers was compared to that of radiation induced opti…

Effects of Mn doping on dielectric properties of ferroelectric relaxor PLZT ceramics

This work has been supported by Latvian state research program IMIS2 .

Raman spectra of vacancy-containing LiF: Predictions from first principles

Abstract The electronic structure and Raman scattering from face-centered cubic LiF with three types of vacancies — an F-center, an F ′ -center and a vacancy without electrons ( v F ) — has been calculated by means of hybrid exchange–correlation functional within density functional theory. Our modeling predicts the effective charge of 0.87 e , 1.50 e and 0.10 e on the defect, respectively. The F-center induces two in-gap energy levels for two spin states split by 3.4 eV, while the F ′ -center and the v F induce a single in-gap level 3.8 eV and 2.9 eV below the bottom of conduction band, respectively. The calculated Raman spectra are thoroughly discussed and are found to match well the earli…

Atomic structure of manganese-doped yttrium orthoaluminate

Abstract Using hybrid exchange-correlation functional within density functional theory we have performed first-principle total energy calculations of Mn-doped yttrium orthoaluminate (YAlO3). Its equilibrium atomic structure has been predicted through optimization of coordinates of all atoms using a supercell approach. In our research both Mn3+ and Mn2+ ions have been substituted for the host alumina atom at orthorhombic Pbnm unit cell of YAlO3. F-center has been implemented as charge-compensating defect in case, when Mn2+ dopant is under study. In this study we thoroughly analyze the atomic displacements in seven nearest to Mn ion coordination spheres. Insertion of isoelectronic substitutio…

Structural investigation of crystallized Ge-Ga-Se chalcogenide glasses

H. Klym thanks to the Ministry of Education and Science of Ukraine for support and Dr. P. Demchenko for the assistance in XRD experiments.

Ab initioand semiempirical calculations ofH−centers in MgO crystals

The atomic and electronic structure of ${\mathrm{H}}^{\ensuremath{-}}$ ions substituting for ${\mathrm{O}}^{2\ensuremath{-}}$ ions in regular sites in MgO crystals are calculated using an ab initio Hartree-Fock (HF) cluster approach and its semiempirical version, intermediate neglect of the differential overlap. The theoretical optical absorption energy is predicted to be 10 eV, which is supported by analysis of experimental data for the ${\mathrm{H}}^{\ensuremath{-}}$ centers in a series of ionic crystals. The HF simulations of ${\mathrm{H}}^{\ensuremath{-}}$ ion diffusion via direct interstitial hops along the [100] axis predict an activation energy of about 3 eV.

Synthesis of porous indium phosphide with nickel oxide crystallites on the surface

Y. Suchikova, S. Kovachov, I. Bohdanov, І. Bardus show their appreciation to the Ministry of Education and Science of Ukraine for its support, in particular: grant 0122U000129 “Search for Optimal Conditions for the Synthesis of Nanostructures on the Surface of Semiconductors A3B5, A2B6 and Silicon for Photonics and Solar Energy,” and grant 0121U109426 “Theoretical and Methodological Principles of Systemic Fundamentalization of Intended Specialist Training in the Field of Nanophase Materials Science for Productive Professional Activity”.

Computer Simulations of I-Center Annealing in KCl and KBr Crystals. Theoretical Interpretation of Thermostimulated Experiments

Results of computer simulations of the kinetics of correlated annealing of pairs of close α–I and F–I centers in KCI and KBr crystals, enhanced by I-center diffusion and Coulomb or elastic attractions, respectively, are presented. Special attention is paid to the conditions under which multi-stage annealing stages arise as it has been observed experimentally more than once. Our general conclusions are: (i) a weak elastic interaction affects the recombination kinetics and the survival probability even for relatively well-separated F–I pairs, the more so is true for the case of Coulomb attraction between charged α–I pairs; (ii) the multi-step (kink) structure arises only for close (typically,…