Luminescence and vacuum ultraviolet excitation spectroscopy of cerium doped Gd3Ga3Al2O12 single crystalline scintillators under synchrotron radiation excitations

Authors gratefully acknowledge the financial support from the Latvian Science Council grant LZP-2018/2-0358 . The research leading to this result has been supported by the project CALIPSO plus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON2020 . The work of A.P.K. was supported by the Ministry of Science and Higher Education of the Russian Federation , state contracts No. 11.6181.2017/ITR .Cerium doped Gd3Ga3Al2O12 (GGAG) single crystals as well as GGAG:Ce single crystals co-doped by divalent (Mg2+, Ca2+), trivalent (Sc3+) or tetravalent (Zr4+, Ti4+) ions have been studied by means of the excitation luminescence spectroscopy in vacuum ultraviolet spectral range. Synchrotron radiation from the undulator beam was utilized for the luminescence excitation in the energy range from 4.5 to 800 eV. The influence of the co-dopant ions on the excitonic transitions as well as on the intrinsic defects in GGAG was revealed examining the luminescence emission and excitation spectra of both Gd3+ and Ce3+ ions in all single crystals studied. Special attention was paid to the analysis of Ce3+ excitation spectra in VUV spectral range (4.5–45 eV) where multiplication of electronic excitation (MEE) processes occur. It was obtained that GGAG:Ce single crystals having different co-dopant ions reveal distinguished efficiency of MEE. The role of intrinsic defects in MEE processes in the co-doped GGAG:Ce single crystals was elucidated.Latvian Science Council LZP-2018/2-0358,730872; Ministry of Science and Higher Education of the Russian Federation 11.6181.2017/ITR; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART²https://www.sciencedirect.com/science/article/pii/S2211379719334527?via%3Dihu

Effect of post-growth anneals in oxygen-containing atmosphere on the microhardness of single crystal calcium molybdate CaMoO4

Single crystal calcium molybdate CaMoO4 is a well-known material. However the interest to CaMoO4 has recently grown due to a number of its important applications including as a working material in cryogenic scintillation bolometers. CaMoO4 single crystals acquire blue color during growth due to the presence of color-center type defect centers which are unacceptable for optical applications. Color can be eliminated through annealing in an oxygen containing atmosphere, following which required optical components can be produced from the single crystals by mechanical treatment (cutting, polishing etc.). Therefore assessment of the mechanical properties of these single crystal materials is an important task for the optimal solution of issues occurring in the fabrication of optical components and their further practical application. There are but scarce data on the mechanical properties of CaMoO4, and the available ones have been reported without allowance for anisotropy. There is a significant scatter of data on the Mohs hardness of the single crystals, ranging from 3.3 to 6 in different publications. In this work we present data on calcium molybdate single crystals in the initial state and after high-temperature anneals of different durations in an oxygen containing atmosphere. We show that long-term annealing leads to decolorization of the crystals. Calcium molybdate single crystals prove to be quite brittle: the brittleness index Zp of the crystals in the initial state is the highest and equals 5, while annealing reduces the brittleness index to 4. The Palmqvist toughness factors S have been calculated The limit indentation destruction loads Flim have been determined and annealing in an oxygen containing atmosphere has been shown to increase Flim by 2.5 times for the Z cut and by 10 times for the X cut. The microhardness of the crystals has been shown to exhibit a II type anisotropy: the microhardness of all the specimens was higher for the Z cut than for the X cut. The microhardness anisotropy coefficients KH of the specimens have been evaluated. The bond ionicity degree I has been calculated on the basis of the experimentally measured microhardness

Effect of doping on the optical properties of lanthanum-gallium tantalate

Nominally pure lanthanum-gallium tantalate La3Ga5.5Ta0.5O14 crystals doped with aluminum, silicon and gallium oxide to above stoichiometric content have been grown by the Czochralski technique in iridium crucibles in argon and in agron with addition of oxygen atmospheres. The transmittance spectra of the crystals have been measured on a Cary-5000 UV-Vis-NIR spectrophotometer in the 200–800 nm range. Absorption spectra α(λ) have been plotted on the basis of the experimental data. The absorption spectra of the undoped crystals grown in an oxygen-free atmosphere have one weak absorption band at λ ~ 290 nm. The absorption spectra of the crystals grown in an agron with addition of oxygen have absorption bands at λ ~ 290, 360 and 480 nm. We show that for the crystals grown in an oxygen-free atmosphere, gallium doping to above stoichiometric content reduces the intensity of its only λ ~ 290 nm absorption band. Aluminum doping of the La3Ga5.5Ta0.5O14 crystals grown in an oxygen-free atmosphere significantly reduces the intensity of the λ ~ 290 nm absorption band and increases the intensity of the λ ~ 360 and 480 nm bands. Aluminum doping of the La3Ga5.5Ta0.5O14 crystals grown in an oxygen-containing atmosphere reduces the intensity of the λ ~ 360 and 480 nm bands and increases the intensity of the λ ~ 290 nm absorption band. Silicon doping of these crystals significantly reduces the intensity of the λ ~ 480 nm band and also reduces the intensity of the λ ~ 290 and 360 nm bands

Effect of doping on the optical properties of lanthanum-gallium tantalate

Nominally pure lanthanum-gallium tantalate La3Ga5.5Ta0.5O14 crystals doped with aluminum, silicon and gallium oxide to above stoichiometric content have been grown by the Czochralski technique in iridium crucibles in argon and in agron with addition of oxygen atmospheres. The transmittance spectra of the crystals have been measured on a Cary-5000 UV-Vis-NIR spectrophotometer in the 200–800 nm range. Absorption spectra α(λ) have been plotted on the basis of the experimental data. The absorption spectra of the undoped crystals grown in an oxygen-free atmosphere have one weak absorption band at λ ~ 290 nm. The absorption spectra of the crystals grown in an agron with addition of oxygen have absorption bands at λ ~ 290, 360 and 480 nm. We show that for the crystals grown in an oxygen-free atmosphere, gallium doping to above stoichiometric content reduces the intensity of its only λ ~ 290 nm absorption band. Aluminum doping of the La3Ga5.5Ta0.5O14 crystals grown in an oxygen-free atmosphere significantly reduces the intensity of the λ ~ 290 nm absorption band and increases the intensity of the λ ~ 360 and 480 nm bands. Aluminum doping of the La3Ga5.5Ta0.5O14 crystals grown in an oxygen-containing atmosphere reduces the intensity of the λ ~ 360 and 480 nm bands and increases the intensity of the λ ~ 290 nm absorption band. Silicon doping of these crystals significantly reduces the intensity of the λ ~ 480 nm band and also reduces the intensity of the λ ~ 290 and 360 nm bands

Luminescence in lanthanum-gallium tantalate

The optical and luminescent properties of undoped La3Ga5.5Ta0.5O14 lanthanum- gallium tantalate crystals grown in different atmospheres of pure argon gas and argon gas with different oxygen percentages have been studied. The optical absorption α(λ) spectra that characterize integral absorption and reflection have been measured in the 250–700 nm region. The spectral absorption functions have been calculated from the measured α(λ) spectra using the Kubelka–Munk formula. Luminescence has been observed in all the test specimens over a wide spectral region (375 to 650 nm) at 95 and 300 K. The luminescence spectra of the test crystals have a fine dispersed pattern represented by low-intensity discrete luminescence peaks. The 95 K luminescence peak maxima are more pronounced and shifted towards shorter wavelengths by ~16 nm (~0.1 eV) relative to the respective room temperature peaks. The crystal growth atmosphere has been demonstrated to largely affect the luminescent properties of the crystals: the higher the oxygen concentration in the growth atmosphere, the lower the luminescence intensity due to concentration quenching, the luminescence peak maxima shifting towards longer wavelengths. The positions of discrete luminescence peaks have been shown to correlate with the main 420 and 480 nm absorption bands with the respective ~20 nm (~0.2 eV) Stokes shift for crystals grown in different atmospheres. The luminescence in lanthanum-gallium tantalate crystals is a complex process involving several luminescence mechanisms

Effect of Ca2+ and Zr4+ co-doping on the optical properties of Gd3Al2Ga3O12: Ce single crystals

Scintillation materials capable of transforming absorbed high-energy particles into visible radiation photons find multiple applications including advanced medical visualization methods. Gd3Al2Ga3O12 : Ce is a promising oxygen-containing sсintillator for fabrication of detecting crystals of positron emission tomographs due to its unique properties, e.g. high density, high light yield, radiation hardness etc. However its kinetic parameters currently restrict its use in this field. Attempts at improving the luminescence rise and decay time kinetics by introducing additional impurities have become a top priority task for many researchers. Analyzing literary data one can conclude that the optical parameters of co-doped crystals have been studied insufficiently or have not been studied at all. We have studied Ca2+ and Zr4+ co-doped Gd3Al2Ga3O12 : Ce single crystals by optical spectroscopy in the 200–2200 nm. We have taken the optical transmittance, absorption and reflection spectra and measured the refractive indices. Dispersion curves have been obtained by approximation of experimental refractive indices using the Brewster method and the Cauchy equation. Material constants of these equations have been estimated for each of the co-doped crystals

Impedance spectroscopy study of lanthanum-gallium tantalate single crystals grown under different conditions

The effect of the growth atmosphere and the type of deposited current conductive coatings on the impedance/admittance of La3Ta0.5Ga5.5O14 lanthanum-gallium tantalate has been revealed. The lanthanum-gallium tantalate single crystals have been grown in argon and argon with admixture of oxygen gas atmospheres. Current conductive coatings of iridium, gold with a titanium sublayer, and silver with a chromium sublayer have been deposited onto the single crystals. The tests have been carried out taking into account the polarity of the specimens. The temperature and frequency dependences of the admittance of lanthanum-gallium tantalate have been measured in an alternating electric field at frequencies in the 5 Hz to 500 kHz range and temperatures from 20 to 450 °C. The specimens with gold current conductive coating have the lowest admittance. Analysis of the temperature and frequency functions of the dielectric permeability has shown the absence of any frequency dependence in the entire test range. Equivalent electric circuits have been constructed. Graphic-analytic and numeric analysis of the equivalent electric circuits of the electrode/langatate/electrode cells has shown that the admittance of the metal/langatate/metal cells is controlled by the electrochemical processes at the electrode/electrolyte/electrode interface. The absolute values of the impedance components depend on the langatate growth conditions and the type of the electrodes. Our measurements suggest that the material of the current conductive coating has a greater effect on the absolute values of the measured parameters than the growth atmosphere

Impedance spectroscopy study of lanthanum-gallium tantalate single crystals grown under different conditions

The effect of the growth atmosphere and the type of deposited current conductive coatings on the impedance/admittance of La3Ta0.5Ga5.5O14 lanthanum-gallium tantalate has been revealed. The lanthanum-gallium tantalate single crystals have been grown in argon and argon with admixture of oxygen gas atmospheres. Current conductive coatings of iridium, gold with a titanium sublayer, and silver with a chromium sublayer have been deposited onto the single crystals. The tests have been carried out taking into account the polarity of the specimens. The temperature and frequency dependences of the admittance of lanthanum-gallium tantalate have been measured in an alternating electric field at frequencies in the 5 Hz to 500 kHz range and temperatures from 20 to 450 °C. The specimens with gold current conductive coating have the lowest admittance. Analysis of the temperature and frequency functions of the dielectric permeability has shown the absence of any frequency dependence in the entire test range. Equivalent electric circuits have been constructed. Graphic-analytic and numeric analysis of the equivalent electric circuits of the electrode/langatate/electrode cells has shown that the admittance of the metal/langatate/metal cells is controlled by the electrochemical processes at the electrode/electrolyte/electrode interface. The absolute values of the impedance components depend on the langatate growth conditions and the type of the electrodes. Our measurements suggest that the material of the current conductive coating has a greater effect on the absolute values of the measured parameters than the growth atmosphere

Optical characteristics of single crystal Gd3Al2Ga3O12 : Ce

New emerging high-energy radiation detection techniques are based on the use of rare-earth ion doped materials. There is a great demand for new inorganic scintillators for medical applications, including X-ray and g radiation detection. In these applications, the new scintillating materials must comply with the main requirements such as high optical quality, high light yield, short response time etc. Materials satisfying these requirements include Gd3Al2Ga3O12 : Ce (GAGG : Ce) scintillating single crystals. By now the optical characteristics of GAGG : Ce have been studied insufficiently. We have therefore measured the spectral reflectance and transmittance characteristics of these crystals using optical spectroscopy in the 200–750 nm range. We have also measured the absorbance and refractive indices and the extinction coefficients, and assessed the optical band gap for GAGG : Ce crystals. For measuring the refractive indices, we have used two spectrophotometric methods, i.e. by the measured Brewster angle and by the reflectance for low incidence angles, i.e., close to the normal. Based on the results we have drawn up the dispersion functions of the refractive indices

Time-resolved luminescence and excitation spectroscopy of Co-doped Gd3Ga3Al2O12 scintillating crystals

The work of Viktorija Pankratova was supported by the Latvian Science Council grant LZP-2018/2-0358. Vladimir Pankratov gratefully acknowledges the financial support from the Ministry of Education and Science of the Russian Federation in the framework of Increase Competitiveness Program of NUST «MISiS» (Grant No. К3-2018-021). The research leading to this result has also been supported by the project CALIPSO plus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART 2. The optical absorption spectrum at low temperature reported in this paper were measured on the equipment of the Central of Collective Use “Isotope-geochemical studies” of the Institute of Geochemistry, Siberian Branch, Russian Academy of Sciences. Authors are grateful to A.I. Popov for the fruitful discussions.Cerium doped Gd3Ga3Al2O12 (GGAG) single crystals as well as GGAG:Ce single crystals co-doped by divalent (Mg2+, Ca2+) and tetravalent (Zr4+, Ti4+) ions have been studied by means of time-resolved luminescence as well as the excitation luminescence spectroscopy in vacuum ultraviolet (VUV) and soft X-ray (XUV) spectral range. Tunable laser excitation was applied for time-resolved experiments in order to obtain luminescence decay curves under excitations in Ce3+, Gd3+ and excitonic absorption bands. The influence of the co-dopant ions on the Ce3+ luminescence decay kinetics is elucidated. The fastest luminescence decay was observed for the Mg2+ co-doped crystals under any excitation below bandgap energy indicating the perturbation of the 5d states of Ce3+ by Mg2+ ions. Synchrotron radiation was utilized for the luminescence excitation in the energy range from 4.5 to 800 eV. Special attention was paid to the analysis of Ce3+ excitation spectra in VUV and XUV spectral range where multiplication of electronic excitation (MEE) processes occur. Our results demonstrated that GGAG:Ce single crystals co-doped by Mg2+ ions as well as the GGAG:Ce crystal annealed in vacuum reveal the most efficient excitation of Ce3+ emission in VUV-XUV excitation range. The role of intrinsic defects in MEE processes in the co-doped as well as in the annealed GGAG:Ce single crystals is discussed.Horizon 2020 Framework Programme CALIPSO Plus under the Grant Agreement 730872; Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement 739508; Science Council of Latvia LZP-2018/2-0358; Horizon 2020 Framework Programme project CAMART², Ministry of Science and Higher Education of the Russian Federation К3-2018-021