Radioluminescence, thermoluminescence and dosimetric properties of ZnO ceramics

Larisa Grigorjeva, Aleksejs Zolotarjovs, Sergej Yu Sokovnin, Donats Millers, Krisjanis Smits, Vladislav G. Il`ves

Two types of ZnO ceramics were fabricated and characterized by XRD, SEM methods. The radioluminescence spectra were measured within the 300–550 K range. The defect luminescence band peaking at ~2.35 eV is the dominant one in radioluminescence spectra in both of the fabricated ceramics. The thermostimulated luminescence (TSL) glow-curves were measured after X-ray irradiation at 300 K. It was concluded that the complex overlapping peak within the 320–450 K temperature range consists of two components (~360–375 K and 400–420 K). The ratio of component intensities differs in both ceramics. The positions of high temperature TSL components (480–520 K) also differ in both samples; therefore not only sintering conditions but also the properties of the initial powder are very important for characteristics of TSL. A linear dependence of peak intensity on irradiation dose was observed up to ~3 kGy for ceramic 1 and up to 9 kGy for ceramic 2.


Ceramics International

DOI: 10.1016/j.ceramint.2017.02.016

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Unexpected Epitaxial Growth of a Few WS2 Layers on 1100 Facets of ZnO Nanowires

Boris Polyakov, Alexei Kuzmin, Krisjanis Smits, Janis Zideluns, Edgars Butanovs,
Jelena Butikova, Sergei Vlassov, Sergei Piskunov, and Yuri F. Zhukovskii


Core-shell nanowires is an interesting and perspective class of radially heterostructured nanomaterials where epitaxial growth of the shell can be realized even at signi ficant core-shell lattice mismatch. In this study epitaxial hexagonally-shaped shell consisting of WS2 nanolayers was grown on f1100g facets of prismatic wurtzite-structured
[0001]-oriented ZnO nanowires for the first time. A synthesis was performed by annealing in a sulfur atmosphere of ZnO/WO3 core-shell structures, produced by reactive
DC magnetron sputtering of amorphous a-WO3 layer on top of ZnO nanowire array.
The morphology and phase composition of synthesized ZnO/WS2 core-shell nanowires were con firmed by scanning and transmission electron microscopy (SEM and TEM),micro-Raman and photoluminescence spectroscopy. Epitaxial growth of WS2(0001) layer(s) on f1100g facets of ZnO nanowire is unexpected due to incompatibility of their symmetry and structure parameters. To relax the interfacial incoherence, we propose a model of ZnO/WS2 interface containing WS2 bridging groups inside and use first-principles simulations to support its feasibility.

J. Phys. Chem. C

DOI: 10.1021/acs.jpcc.6b06139

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Complex tribomechanical characterization of ZnO nanowires: nanomanipulations supported by FEM simulations

Sergei Vlassov, Boris Polyakov, Sven Oras, Mikk Vahtrus,
Mikk Antsov, Andris Šutka Krisjanis Smits, Leonid M Dorogin and
Rünno Lõhmus

In the present work, we demonstrate a novel approach to nanotribological measurements based
on the bending manipulation of hexagonal ZnO nanowires (NWs) in an adjustable halfsuspended
configuration inside a scanning electron microscope. A pick-and-place manipulation
technique was used to control the length of the adhered part of each suspended NW. Static and
kinetic friction were found by a ‘self-sensing’ approach based on the strain profile of the
elastically bent NW during manipulation and its Young’s modulus, which was separately
measured in a three-point bending test with an atomic force microscope. The calculation of static
friction from the most bent state was completely reconsidered and a novel more realistic crackbased
model was proposed. It was demonstrated that, in contrast to assumptions made in
previously published models, interfacial stresses in statically bent NW are highly localized and
interfacial strength is comparable to the bending strength of NW measured in respective bending

Nanotechnology 27 (2016) 335701 (10pp)


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Effect of Point Defects on Luminescence Characteristics of ZnO Ceramics

P. A. Rodnyi, K. A. Chernenko, A. Zolotarjovs, L. Grigorjeva,
E. I. Gorokhova, and I. D. Venevtsev

Abstract—Photo- and thermally stimulated luminescence of ZnO ceramics are produced by uniaxial hot pressing. The luminescence spectra of ceramics contain a wide band with a maximum at 500 nm, for which oxygen vacancies VO are responsible, and a narrow band with a maximum at 385 nm, which is of exciton nature. It follows from luminescence excitation spectra that the exciton energy is transferred to luminescence centers in ZnO. An analysis of the thermally stimulated luminescence curves allowed detection of a set of discrete levels of point defects with activation energies of 25, 45, 510, 590 meV, and defects with continuous energy distributions in the range of 50–100 meV. The parameters of some of the detected defects are characteristic of a lithium impurity and hydrogen centers. The photoluminescence kinetics are studied in a wide temperature range.
DOI: 10.1134/S1063783416100309

ISSN 1063-7834,

Physics of the Solid State, 2016, Vol. 58, No. 10, pp. 2055–2061.

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Gas sensitive luminescence of ZnO coatings obtained by plazmaelectrolytic oxidation

L. Grigorjeva, D. Millers, K. Smits, A. Zolotarjovs

The ZnO coatings on Zn substrate were obtained using plasma electrolytic oxidation method. The XRDand SEM methods were used for structural and morphological characterization of obtained coatings. Theluminescence of ZnO coatings were studied and compared with luminescence characteristics of ZnO sin-gle crystal. It is shown that luminescence intensity in ZnO defect band depends on oxygen concentrationin ambient atmosphere. The effect is of interest for oxygen sensing based on ZnO coating luminescence

Sensors and Actuators A 234 (2015) 290–293


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Photocatalytic Properties of TiO2 and ZnO Nanopowders

L. Grigorjeva, J. Rikveilis, J. Grabis, Dz. Jankovica,
C. Monty, D. Millers, K. Smits

Photocatalytic activity of TiO2 and ZnO nanopowders is studied
depending on the morphology, grain sizes and method of synthesizing.
Photocatalysis of the prepared powders was evaluated by degradation of the
methylene blue aqueous solution. Absorbance spectra (190–100 nm) were
measured during exposure of the solution to UV light. The relationships
between the photocatalytic activity and the particle size, crystal polymorph
phases and grain morphology were analyzed. The photocatalytic activity of
prepared TiO2 nanopowders has been found to depend of the anatase-to-rutile
phase ratio. Comparison is given for the photocatalytic activity of ZnO
nanopowders prepared by sol-gel and solar physical vapour deposition
(SPVD) methods

Latvian Journal of Physics and Technical Sciences 2013, N 4

DOI: 10.2478/lpts-2013-0025

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The luminescence of ZnO ceramics

L. Grigorjeva , D.Millers , K.Smits , J.Grabis , J.Fidelus , W. qojkowski , T.Chudoba , K.Bienkowski 

The luminescence properties of ZnO ceramics with grains 100-5000 nm sintered by different techniques from nanopowders were studied. The luminescence decay times were compared with that obtained for ZnO singlecrystal. The temperature dependence of non-exponential decay of defect luminescence (2.0-2.6 eV) was measured in wide time, intensity and temperature range.The luminescence decay kinetic at T=20 K shows the decay close to I(t) w t1 dependence. At temperature region 50-250 K the decay kinetics is more complicated since the TSL was observed in this temperature region. It is shown that the luminescence properties of NP and ceramics strongly depend on defect distribution on grains surface
and the volume/surface ratio determine the luminescence decay in ZnO nanostructures and ceramics.

Radiation Measurements


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Time-resolved cathodoluminescence and photoluminescence of nanoscale oxides

L. Grigorjeva, D. Millers, A. Kalinko, V. Pankratov, K. Smits

The nanostructured oxide materials such as ZnO, ZrO2, and Y3Al5O12 (YAG) are perspective materials for transparent scintillating and/or
laser ceramics. The luminescence properties of single crystals, nanopowders and ceramic were compared. Nominally pure and rare-earth doped
nanopowders and ceramics have been studied by means of time-resolved luminescence spectroscopy.
The fast blue luminescence band was studied in ZnO ceramics sintering from different raw materials.
The luminescence centres of ZrO2:Y were compared in a single crystal, ceramic and nanopowder.
It is shown that ceramic sintering parameters have a strong influence on time-resolved luminescence characteristics in cerium-doped YAG.

Journal of The European Ceramic Society


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Excitonic luminescence in ZnO nanopowders and ceramics

L. Grigorjeva , D. Millers , K. Smits , V. Pankratov , W. Łojkowski, J. Fidelus , T. Chudoba , K. Bienkowski , C. Monty 

Fast photoluminescence spectra in the spectral region of 3.1–3.45 eV in ZnO and ZnO:Al ceramics were
studied at 14 and 300 K. Ceramics with grains smaller than 100 nm were sintered from nanopowders
by high pressure (8 GPa) and low temperature (350 C). Ceramics with grain sizes 1–5 lm were sintered
at 1400 C. It is shown that excitonic luminescence spectra depend on the ceramics grain size, post preparing
annealing and doping. The excitonic luminescence decay time was faster than 2 ns and the afterglow
at 30 ns was 0.05%.

Optical Materials 2009


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Time-resolved absorption and luminescence following electron-hole pair creation in ZnO

R. Andrew Wall, Kyle C. Lipke, K. B. Ucer, R. T. Williams, D. Millers, K. Smits, and L. Grigorjeva

We report transient absorption induced by electron-hole excitation
in undoped ZnO. A laser pump/continuum probe
method covers 2–300 ps, and an electron pulse with lamp
transmission covers 8–300 ns. The broad absorption spectrum
increases monotonically with wavelength from 900 to 1600
nm. Following a reasonable hypothesis that the free-carrierlike
induced infrared absorption is proportional to the total
number of free carriers, excitons, and shallow-trapped carriers
in the sample, these data allow setting an upper limit on
the quantum efficiency of a specified lifetime component of
luminescence. For the undoped commercial ZnO studied in
this report, the quantum efficiency of room temperature excitonic
luminescence is less than 5%. This means that there is
significant room for improvement in applications aiming to
use room-temperature excitonic blue luminescence of ZnO
for fast scintillators and light sources. Direct observation that
a large majority of excitations are tied up for more than 100
nanoseconds in shallow traps confirms the premise for studies
undertaken at Oak Ridge National Laboratory to improve the
excitonic luminescence yield and decay rate of ZnO by donor
doping. The preliminary results presented here on undoped
ZnO suggest that induced absorption measurements should be
a useful diagnostic of quantum efficiency while studying such
dopant effects.

Physica Status Solidi (C) Current Topics in Solid State Physics

DOI 10.1002/pssc.200879896

phys. stat. sol. (c) 6, No. 1, 323–326 (2009)

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Luminescence Properties of ZnO Nanocrystals and Ceramics

Larisa Grigorjeva, Donats Millers, Janis Grabis, Claude Monty, Aleksandr Kalinko, Krishjanis Smits,
Vladimir Pankratov, and Witold Łojkowski

Abstract—The luminescence excitation spectra, luminescence
spectra and the nanosecond-scale decay kinetics were studied.
The ZnO and ZnO:Al nanopowders were prepared by vaporization-
condensation in a solar furnace using different raw powders:
commercial, hydrothermal and those obtained by plasma synthesis.
Exciton-phonon as well as exciton-exciton interaction
processes in nanopowders, a bulk crystal and ZnO ceramics were
studied and compared. The fast decay and low afterglow intensity
of ZnO nanopowders and ceramics support these materials for

IEEE Transactions on Nuclear Science, VOL. 55, NO. 3, JUNE 2008

Digital Object Identifier 10.1109/TNS.2008.921931

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The Luminescence Properties of ZnO nanopowders

Aleksandr Kalinko, Janusz D. Fidelus, Larisa Grigorjeva, Donats Millers, Claude J. Monty, Adam Presz and Krisjanis Smits

Abstract. Pure and Al3+ doped ZnO nanopowders were studied by means of time-resolved
luminescence spectroscopy. The powders were synthesized by hydrothermal and plasma
methods. These powders were used as a raw material for vaporization-condensation process
inside the Solar reactor. The commercially available ZnO nanopowder was studied for a
comparison. Exciton to defect band luminescence intensity ratio was estimated in different
types of ZnO nanopowders. It was found that nanopowders with whiskers morphology show
superlinear luminescence intensity depending on excitation density. The observed effect
depends on the average nanoparticle size and on the powder morphology.

IOP Publishing
Journal of Physics: Conference Series 93 (2007) 012044


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