Rare Earths-Doped Materials (Volume II)

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Inorganic Crystalline Materials".

Deadline for manuscript submissions: closed (31 August 2023) | Viewed by 16434

Special Issue Editors


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Guest Editor
Faculty of Chemistry and Pharmacy, Sofia University, Sofia, Bulgaria
Interests: inorganic chemistry; material science; chemistry of rare earths; photocatalysis; environmental problems
Special Issues, Collections and Topics in MDPI journals

E-Mail Website
Guest Editor
Department of Inorganic Chemistry, Faculty of Chemistry and Pharmacy, University of Sofia “St. Kliment Ohridsky”, Sofia, Bulgaria
Interests: solid-state chemistry; material characterization; crystallography; heterogeneous catalysis and photocatalysis
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The articles included in the first volume of the Special Issue, “Rare Earths-Doped Materials”, published in Crystals 2020, 10; Crystals 2021, 11; and Crystals 2022, 12, as well as our personal experience, make it clear that the interest and research on the subject is continuing intensively. Therefore, with this letter, we announce the second volume of Rare Earths-Doped Materials and invite you to participate. The focus of the Issue is on the research and investigation of RE-doped materials: the methods for their synthesis and characterization, as well as the development of new properties (optical, magnetic, photocatalytic, biological, etc.). Topics of interest for the Special Issue include: (i) the development and application of different methods to obtain RE-doped materials; (ii) the application of different techniques for material characterization; (iii) RE-doped materials with specific structural and optical properties. 

We encourage the submission of high-quality manuscripts in the form of research articles, short communications, and reviews for contribution to the second release of this Special Issue.

Prof. Dr. Maria Milanova
Dr. Martin Tsvetkov
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Crystals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • rare earth elements
  • single crystals
  • bulk crystals
  • nanocrystals
  • phosphors
  • composite materials
  • semiconductors
  • insulators

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Published Papers (11 papers)

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Research

23 pages, 3154 KiB  
Article
Influence of Synthesis Conditions on the Crystal, Local Atomic, Electronic Structure, and Catalytic Properties of (Pr1−xYbx)2Zr2O7 (0 ≤ x ≤ 1) Powders
by Victor V. Popov, Ekaterina B. Markova, Yan V. Zubavichus, Alexey P. Menushenkov, Alexey A. Yastrebtsev, Bulat R. Gaynanov, Olga V. Chernysheva, Andrei A. Ivanov, Sergey G. Rudakov, Maria M. Berdnikova, Alexander A. Pisarev, Elizaveta S. Kulikova, Nickolay A. Kolyshkin, Evgeny V. Khramov, Victor N. Khrustalev, Igor V. Shchetinin, Nadezhda A. Tsarenko, Natalia V. Ognevskaya and Olga N. Seregina
Crystals 2023, 13(9), 1405; https://doi.org/10.3390/cryst13091405 - 21 Sep 2023
Cited by 1 | Viewed by 2756
Abstract
The influence of Yb3+ cations substitution for Pr3+ on the structure and catalytic activity of (Pr1−xYbx)2Zr2O7 powders synthesized via coprecipitation followed by calcination is studied using a combination of long- (s-XRD), [...] Read more.
The influence of Yb3+ cations substitution for Pr3+ on the structure and catalytic activity of (Pr1−xYbx)2Zr2O7 powders synthesized via coprecipitation followed by calcination is studied using a combination of long- (s-XRD), medium- (Raman, FT-IR, and SEM-EDS) and short-range (XAFS) sensitive methods, as well as adsorption and catalytic techniques. It is established that chemical composition and calcination temperature are the two major factors that govern the phase composition, crystallographic, and local-structure parameters of these polycrystalline materials. The crystallographic and local-structure parameters of (Pr1−xYbx)2Zr2O7 samples prepared at 1400 °C/3 h demonstrate a tight correlation with their catalytic activity towards propane cracking. The progressive replacement of Pr3+ with Yb3+ cations gives rise to an increase in the catalytic activity. A mechanism of the catalytic cracking of propane is proposed, which considers the geometrical match between the metal–oxygen (Pr–O, Yb–O, and Zr–O) bond lengths within the active sites and the size of adsorbed propane molecule to be the decisive factor governing the reaction route. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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12 pages, 3389 KiB  
Article
Highly Efficient Orange-Red Emission in Sm3+-Doped Yttrium Gallium Garnet Single Crystal
by Huiting Zhang, Zhonghua Zhu, Shengdi Ta, Ninghan Zeng, Limin Wu, Wenxia Wu, Peng Zhang, Shoulei Xu, Bernard Albert Goodman and Wen Deng
Crystals 2023, 13(8), 1273; https://doi.org/10.3390/cryst13081273 - 18 Aug 2023
Cited by 3 | Viewed by 991
Abstract
High-quality single crystals with empirical composition Y2.96Sm0.04Ga5O12 (YGG: Sm3+) were successfully prepared by the optical floating zone method for the first time and compared with related single crystals of Y [...] Read more.
High-quality single crystals with empirical composition Y2.96Sm0.04Ga5O12 (YGG: Sm3+) were successfully prepared by the optical floating zone method for the first time and compared with related single crystals of Y2.96Sm0.04Al5O12 (YAG: Sm3+). With both crystals, XRD showed that Sm3+ entered the cubic-phase structure. Optical absorption spectra produced a series of peaks from Sm3+ in the 250 nm to 550 nm range, and photoluminescence excitation (PLE) spectra detected at 613 nm showed strong excitation peaks at 407 nm and 468 nm. A strong emission peak at 611 nm (orange-red light) was observed in the photoluminescence (PL) spectra under excitations at both 407 and 468 nm, respectively, but it was much brighter under excitation at 407 nm. Furthermore, with both emission spectra, the peaks from the YGG: Sm3+ crystal were significantly more intense than those from the YAG: Sm3+ crystal, and both experienced a blue shift. In addition, under excitation at 407 nm, the color purity of the emitted orange-red light of YGG: Sm3+ was higher than that of the YAG: Sm3+ crystal, and the fluorescence lifetime for the 4G5/26H7/2 transition of YGG: Sm3+ was longer than that of the YAG: Sm3+ crystal. The optical properties of the YGG: Sm3+ crystal are better than those of the YAG: Sm3+ crystal. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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10 pages, 1351 KiB  
Article
Influence of Golden Nanoparticles on the Incorporation of Eu2+ into BaI2 and Defect Concentration
by Katarína Ridzoňová, Maksym Buryi, Vladimir Babin, David John, Jan Drahokoupil, Neda Neykova, Tatsiana Salamakha and Yauhen Tratsiak
Crystals 2023, 13(6), 902; https://doi.org/10.3390/cryst13060902 - 1 Jun 2023
Viewed by 914
Abstract
Conjugated BaI2:Eu (5 at.%) nanocrystalline particles were synthesized, decorated with golden nanoparticles (GNP). GNP demonstrated some hydrophilic effect, leading to the BaI2·H2O phase creation. The Eu2+ luminescence intensity was reduced according to the GNP content. This [...] Read more.
Conjugated BaI2:Eu (5 at.%) nanocrystalline particles were synthesized, decorated with golden nanoparticles (GNP). GNP demonstrated some hydrophilic effect, leading to the BaI2·H2O phase creation. The Eu2+ luminescence intensity was reduced according to the GNP content. This was due to the decreased number of Eu2+ ions in the BaI2, most probably, arising from the Au substitution for Ba competing with Eu. Moreover, the decay time of luminescence was decreased upon GNP content. This was explained by the moderation of negative charge in the GNP, leading to the repulsion with an electron in the excited Eu2+. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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16 pages, 4227 KiB  
Article
Mechanochemically Synthesized Solid Solutions La1−xCexFeO3+x/2 for Activation of Peroxydisulfate in Catalytical Reaction for Tetracycline Degradation
by Martin Tsvetkov, Elzhana Encheva, Stefani Petrova, Ivanka Spassova and Maria Milanova
Crystals 2023, 13(5), 769; https://doi.org/10.3390/cryst13050769 - 5 May 2023
Cited by 2 | Viewed by 1151
Abstract
The synthesis of orthoferrites of the type La1−xCexFeO3+x/2, x = 0.00, 0.01, 0.03, 0.05, and 0.07, by applying a simple and effective mechanochemical transformation from the constituent oxides is presented. Physicochemical methods such as powder X-ray diffraction [...] Read more.
The synthesis of orthoferrites of the type La1−xCexFeO3+x/2, x = 0.00, 0.01, 0.03, 0.05, and 0.07, by applying a simple and effective mechanochemical transformation from the constituent oxides is presented. Physicochemical methods such as powder X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–Vis spectroscopy, and Brunauer–Emmett–Teller (BET) adsorption were applied to gain information about the effect of Ce4+ content on the structural, textural, and optical properties of the samples. The catalytic activity of the samples for water decontamination was determined in a photo-Fenton-like activation of persulfate for removal of tetracycline hydrochloride as model pollutant. The presence of persulfate, PDS, considerably increased the removal efficiency under visible light illumination. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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14 pages, 5165 KiB  
Article
The Role of Er3+ Content in the Luminescence Properties of Y3Al5O12 Single Crystals: Incorporation into the Lattice and Defect State Creation
by Maksym Buryi, Amayès Médhi Gaston-Bellegarde, Jan Pejchal, Fedor Levchenko, Zdeněk Remeš, Katarína Ridzoňová, Vladimir Babin and Sergii Chertopalov
Crystals 2023, 13(4), 562; https://doi.org/10.3390/cryst13040562 - 25 Mar 2023
Cited by 2 | Viewed by 1109
Abstract
Erbium-doped Y3Al5O12 (YAG) single crystals grown using the micro-pulling-down technique were investigated. Three Er concentrations were chosen: 0.1, 0.3 and 1 at%. Er3+ electron paramagnetic resonance (EPR) spectra were measured in the ground and first excited states. [...] Read more.
Erbium-doped Y3Al5O12 (YAG) single crystals grown using the micro-pulling-down technique were investigated. Three Er concentrations were chosen: 0.1, 0.3 and 1 at%. Er3+ electron paramagnetic resonance (EPR) spectra were measured in the ground and first excited states. The corresponding g tensors and 167Er hyperfine interaction were changing upon Er content indicating moderation of the Er-O bond length and/or Er local surrounding. Photoluminescence (PL) and radioluminescence (RL) spectra were complex, consisting of strongly overlapped typical Er3+ transitions. In addition, there were other broad PL band (3.1 eV) and RL band (3.95 eV) attributed to the F+ center and yttrium substituting for aluminum (YAl), respectively. The X-ray excited decay kinetics exhibited a decrease of the decay time of the YAl from hundreds of nanoseconds to nanoseconds upon Er doping level. This is discussed and explained considering EPR data. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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13 pages, 6613 KiB  
Article
Impact of Erbium Doping in the Structural and Magnetic Properties of the Anisotropic and Frustrated SrYb2O4 Antiferromagnet
by Diana Lucia Quintero-Castro, Juanita Hincapie, Abhijit Bhat Kademane, Minki Jeong, Matthias Frontzek, Alexandra Franz, Amutha Ramachandran, Fabiano Yokaichiya, J Ross Stewart and Rasmus Toft-Petersen
Crystals 2023, 13(3), 529; https://doi.org/10.3390/cryst13030529 - 20 Mar 2023
Viewed by 1586
Abstract
We present a systematic study of the structural and magnetic properties of a series of powder samples of SrYb2xErxO4 with different Yb/Er concentrations. Magnetometry and neutron diffraction have been used to study the magnetic ground states [...] Read more.
We present a systematic study of the structural and magnetic properties of a series of powder samples of SrYb2xErxO4 with different Yb/Er concentrations. Magnetometry and neutron diffraction have been used to study the magnetic ground states of the compound series, while inelastic neutron scattering was used to investigate the crystal field excitations for a chosen concentration. These results show that the crystal structure remains the same for all compositions, while the lattice parameters increase linearly with the Er content. All compounds showed some type of magnetic transition below 1 K, however, both the magnetic structure and nature of the phase transition vary throughout the series. The samples present a non-collinear magnetic structure with the moments lying on the ab plane for low Er content. For high Er content, the magnetic structure is collinear with the moments aligned along the c-axis. A critical concentration is found where there is a bifurcation between zero-field and field-cooled magnetic susceptibility. This irreversible process could be due to the random mixture of single-ion magnetic anisotropies. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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12 pages, 4391 KiB  
Article
Up-Conversion Photoluminescence in Thulia and Ytterbia Co-Doped Yttria-Stabilized Zirconia Single Crystals
by Danni Huang, Tong Xiao, Beibei Fu, Shoulei Xu, Yuyang Huang, Wen Deng and Zhukun Zhou
Crystals 2023, 13(3), 460; https://doi.org/10.3390/cryst13030460 - 7 Mar 2023
Cited by 2 | Viewed by 1312
Abstract
ZrO2 is an attractive host matrix for luminescence material because of its excellent physical properties, such as low phonon energy and wide band gap. In this work, the highly transparent Tm2O3 and Yb2O3 co-doped yttria stabilized [...] Read more.
ZrO2 is an attractive host matrix for luminescence material because of its excellent physical properties, such as low phonon energy and wide band gap. In this work, the highly transparent Tm2O3 and Yb2O3 co-doped yttria stabilized zirconia (YSZ) (abbreviated as Yb/Tm: YSZ) single crystals were grown by the optical floating zone method. The Yb/Tm: YSZ samples were stabilized in the cubic phase at room temperature when Yb3+ and Tm3+ replaced Y3+. The influence of Yb3+ co-doping on the up-conversion luminescence properties of the crystals was systematically studied. A total of 0.5 mol% Tm2O3 and 2.0 mol% Yb2O3 co-activated YSZ single crystal (abbreviated as 2.0Yb/Tm: YSZ) has the maximum luminous intensity. There were seven absorption peaks located at around 358, 460, 679, 783.3, 850–1000, 1200, and 1721.5 nm that were observed in the absorption spectrum of the 2.0Yb/Tm: YSZ single crystal. There were three up-conversion peaks at around 488, 658 and 800 nm that were observed when the Yb/Tm: YSZ samples were excitated at 980 nm. The fluorescence lifetime of Tm3+ for the 1G43H6 transition of the 2.0Yb/Tm: YSZ sample is 7.716 ms as excited with a 980 nm laser. In addition, the oscillator strength parameters Ωλ (λ = 2, 4 and 6) of this sample were derived by the Judd–Ofelt theory to evaluate the laser performance of the host materials. The ratio Ω46 of this sample is 0.80, implying its excellent laser output. Therefore, the 2.0Yb/Tm: YSZ single crystal is a considerable potential material for laser and luminescence applications. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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15 pages, 4658 KiB  
Article
Structural and Spectroscopic Effects of Li+ Substitution for Na+ in LixNa1−xCaLa0.5Er0.05Yb0.45(MoO4)3 Upconversion Scheelite-Type Phosphors
by Chang Sung Lim, Aleksandr Aleksandrovsky, Maxim Molokeev, Aleksandr Oreshonkov and Victor Atuchin
Crystals 2023, 13(2), 362; https://doi.org/10.3390/cryst13020362 - 20 Feb 2023
Cited by 9 | Viewed by 1407
Abstract
New triple molybdates LixNa1−xCaLa0.5(MoO4)3:Er3+0.05/Yb3+0.45 (x = 0, 0.05, 0.1, 0.2, 0.3) were manufactured successfully using the microwave-assisted sol-gel-based technique (MAS). Their room-temperature crystal structures were determined in space group [...] Read more.
New triple molybdates LixNa1−xCaLa0.5(MoO4)3:Er3+0.05/Yb3+0.45 (x = 0, 0.05, 0.1, 0.2, 0.3) were manufactured successfully using the microwave-assisted sol-gel-based technique (MAS). Their room-temperature crystal structures were determined in space group I41/a by Rietveld analysis. The compounds were found to have a scheelite-type structure. In Li-substituted samples, the sites of big cations were occupied by a mixture of (Li, Na, La, Er, Yb) ions, which provided a linear cell volume decrease with the Li content increase. The increased upconversion (UC) efficiency and Raman spectroscopic properties of the phosphors were discussed in detail. The mechanism of optimization of upconversion luminescence upon Li content variation was shown to be due to the control of excitation/energy transfer channel, while the control of luminescence channels played a minor role. The UC luminescence maximized at lithium content x = 0.05. The mechanism of UC optimization was shown to be due to the control of excitation/energy transfer channel, while the control of luminescence channels played a minor role. Over the whole spectral range, the Raman spectra of LixNa1−xCaLa0.5(MoO4)3 doped with Er3+ and Yb3+ ions were totally superimposed with the luminescence signal of Er3+ ions, and increasing the Li+ content resulted in the difference of Er3+ multiple intensity. The density functional theory calculations with the account for the structural disorder in the system of Li, Na, Ca, La, Er and Yb ions revealed the bandgap variation from 3.99 to 4.137 eV due to the changing of Li content. It was found that the direct electronic transition energy was close to the indirect one for all compounds. The determined chromaticity points (ICP) of the LiNaCaLa(MoO4)3:Er3+,Yb3+ phosphors were in good relation to the equal-energy point in the standard CIE (Commission Internationale de L’Eclairage) coordinates. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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15 pages, 3451 KiB  
Article
Ultrathin Rare-Earth-Doped MoS2 Crystalline Films Prepared with Magnetron Sputtering and Ar + H2 Post-Annealing
by Chenglin Heng, Xuan Wang, Chaonan Zhao, Gang Wu, Yanhui Lv, Hanchun Wu, Ming Zhao and Terje G. Finstad
Crystals 2023, 13(2), 308; https://doi.org/10.3390/cryst13020308 - 13 Feb 2023
Cited by 2 | Viewed by 1633
Abstract
In this work, we propose a method to prepare large-area, crystalline ultrathin rare-earth (RE, i.e., Eu, Yb, Er and Tb)-doped MoS2 thin films, using magnetron sputtering and subsequent Ar + H2 annealing. The film thickness of as-deposited samples varied from 60 [...] Read more.
In this work, we propose a method to prepare large-area, crystalline ultrathin rare-earth (RE, i.e., Eu, Yb, Er and Tb)-doped MoS2 thin films, using magnetron sputtering and subsequent Ar + H2 annealing. The film thickness of as-deposited samples varied from 60 to 100 nm, and decreases to be below 10 nm after annealing at 550 °C for 30 min. X-ray diffraction and Raman spectra analysis revealed that the sample films were crystallized after the annealing, which resulted in a MoS2 crystallite size of about 4–5 nm. X-ray photoelectron spectroscopy indicated that most of the RE ions existed in the films in trivalent states. The optical bandgap of the RE-doped MoS2 samples decreased from 1.6 eV (undoped) to 1.3 eV (Eu-doped) in the UV-vis absorption spectra. Electrical measurements showed that the electrical resistance decreased from 9.13 MΩ (undoped) to 0.34 MΩ (Yb-doped), the carrier density increased by one to two orders of magnitude and the carrier mobility decreased from 5.4 cm2/V·s (undoped) to 0.65 cm2/V·s (Yb-doped). The sign of the Hall coefficients indicated that the undoped MoS2 and the Yb-, Tb- and Er-doped MoS2 samples were n-type semiconductors, while the Eu-doped sample showed p-type characteristics. This study may be helpful to broaden the photoelectronic applications of these two-dimensional materials. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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15 pages, 10501 KiB  
Article
The Effect of Ne+ Ion Implantation on the Crystal, Magnetic, and Domain Structures of Yttrium Iron Garnet Films
by Igor Fodchuk, Andrij Kotsyubynsky, Andrii Velychkovych, Ivan Hutsuliak, Volodymyra Boychuk, Volodymyr Kotsyubynsky and Liubomyr Ropyak
Crystals 2022, 12(10), 1485; https://doi.org/10.3390/cryst12101485 - 19 Oct 2022
Cited by 2 | Viewed by 1565
Abstract
The mechanism of the influence of crystal inhomogeneities on the magnetic and domain microstructures of functional materials based on yttrium iron garnet heterostructures is an important subject of investigation due to the aim to predict parameters for manufacturingpurposes. A study of the structural [...] Read more.
The mechanism of the influence of crystal inhomogeneities on the magnetic and domain microstructures of functional materials based on yttrium iron garnet heterostructures is an important subject of investigation due to the aim to predict parameters for manufacturingpurposes. A study of the structural and magnetic characteristics of a set of yttrium iron garnet films grown on gadolinium–gallium garnet substrate is presented. High-resolution X-ray diffractometry, Mössbauer spectroscopy, MFM, as well as ion implantation simulation and X-ray diffraction simulation were used together to determine the features of the effect of Ne+ ion implantation with different dose rates on the samples. The simulation of ion implantation with E = 82 keV showed energy loss profiles of Ne ions with subsequent defect formation up to amorphization of near-surface layers at high doses. Implantation creates two magnetically non-equivalent types of tetrahedrally located Fe3+ ions, which leads to a rotation of the total magnetic moment relative to the film surface and a change in the width of the magnetic domain stripes. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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8 pages, 3397 KiB  
Article
Synthesis and Upconversion Luminescence Properties of BaBiO2Cl:Yb3+,Er3+ Phosphor
by Zhuanzhuan Zhang and Yanjie Liang
Crystals 2022, 12(10), 1465; https://doi.org/10.3390/cryst12101465 - 17 Oct 2022
Cited by 1 | Viewed by 1300
Abstract
The interaction of near-infrared (NIR) light with matter that produces high-energy visible light emissions is known as photon upconversion, which has shown promising applications in different fields, including optoelectronics, biomedicine and photovoltaics. In this paper, a novel BaBiO2Cl:Yb3+,Er3+ [...] Read more.
The interaction of near-infrared (NIR) light with matter that produces high-energy visible light emissions is known as photon upconversion, which has shown promising applications in different fields, including optoelectronics, biomedicine and photovoltaics. In this paper, a novel BaBiO2Cl:Yb3+,Er3+ upconversion phosphor was successfully synthesized through a simple high-temperature solid-state reaction route. The crystal structure, phase purity, microstructure and upconversion luminescence properties of the as-prepared phosphor were characterized comprehensively. The XRD and SEM results clearly demonstrate the successful synthesis of the target phosphors with high purity. When excited by a 980 nm NIR laser, the as-prepared BaBiO2Cl:Yb3+,Er3+ phosphor exhibited intense red upconversion luminescence due to the Er3+ 4F9/24I15/2 transition, which enabled this phosphor to have high promise for important applications, such as anti-counterfeiting and advanced photonics. Full article
(This article belongs to the Special Issue Rare Earths-Doped Materials (Volume II))
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