Emerging Rare-Earth Doped Materials

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

Deadline for manuscript submissions: closed (28 February 2023) | Viewed by 7591

Special Issue Editor


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Guest Editor
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
Interests: lanthanide; crystals and nanocrystals; nonlinear; biophotonics; solar cells
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Special Issue Information

Dear Colleagues,

Impurity doping is a common strategy that can be used to develop novel functional materials. In past decades, rare-earth (RE) elements have been widely used as dopants in host materials to impart new properties or modify their properties, significantly expanding their applications. Here, we are pleased to announce a Special Issue entitled “Emerging Rare-Earth Doped Materials” in Crystals. We intend to publish high-quality articles to present the latest discoveries and/or an overview of the field.

In light of recent advances, research articles, short communications, and review articles that are related but not limited to the following topics are encouraged to be submitted to this Special Issue:

  • Novel rare-earth doped materials with different compositions and/or architectures;
  • Various strategies for doping host materials with rare-earth elements;
  • Characterization methods for rare-earth doped materials and analysis of physical/chemical properties;
  • Application of computational methods and data science in the research of rare-earth doped materials, such as density functional theory (DFT), and machine learning;
  • Practical applications of rare-earth-doped materials, especially in new areas such as lasers, bioimaging, catalysis, etc.

Prof. Dr. Guanying Chen
Guest Editor

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Keywords

  • rare earth
  • single crystals
  • bulk materials
  • nanocrystals
  • phosphors
  • rare earth luminescent materials
  • semiconductors
  • insulators

Published Papers (5 papers)

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Research

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19 pages, 7595 KiB  
Article
Structural Evolution in a Series of Isomorphous Rare Earth Compounds as Response of Lanthanide Contraction
by Hans Reuter, Marcel Böltken, Maik Horstmann and Markus Haase
Crystals 2023, 13(7), 1043; https://doi.org/10.3390/cryst13071043 - 30 Jun 2023
Cited by 1 | Viewed by 671
Abstract
The structural parameters of the rare-earth diacetate halide trihydrates, RE(OAc)2Hal·3H2O with RE = Ce − (Pm) − Lu and Hal = Cl, Br, have been determined by low temperature, high-resolution SCXRD in order to examine the effect of lanthanide [...] Read more.
The structural parameters of the rare-earth diacetate halide trihydrates, RE(OAc)2Hal·3H2O with RE = Ce − (Pm) − Lu and Hal = Cl, Br, have been determined by low temperature, high-resolution SCXRD in order to examine the effect of lanthanide contraction on the coordination geometry in this series of isomorphous compounds consisting of cationic, acetate-bridged, non-linear, one-dimensional coordination polymers of composition [RE(H2O)3(OAc)2]+ and laterally hydrogen bonded halide ions, Hal. Although the shrinkage of the unit cell volume follows lanthanide contraction very well over the complete range of investigated RE elements, many other parameters (i.e., lattice constants, angles and distances in the RE··· RE alignment, RE-O bond lengths, etc.) exhibit a more complex response on lanthanide contraction often expressed by sigmoid curves that can be ascribed to a continuous transition from CN9 (RE = Ce) to CN8 (RE = Lu) as one acetate group loses the chelate function, an effect accompanied by significant structural changes of the carboxylate group. Therefore, data are best analyzed by use of two subsets represented by the two different structure types of Ce and Lu, the structural features of which change with decreasing/increasing the size of RE3+, up to the borderline between both subsets. Full article
(This article belongs to the Special Issue Emerging Rare-Earth Doped Materials)
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10 pages, 3163 KiB  
Article
Study on Growth Interface of Large Nd:YAG Crystals
by Jiliang Quan, Guanzhen Ke, Yali Zhang, Jian Liu and Jinqiang Huang
Crystals 2023, 13(6), 970; https://doi.org/10.3390/cryst13060970 - 19 Jun 2023
Cited by 1 | Viewed by 1056
Abstract
A study was performed on the growth interface of a large-diameter 1 at% neodymium-doped yttrium aluminum garnet (Nd:YAG) single crystal grown using the Czochralski method. Red parallel light and an orthogonal polarizing system were used to observe the distribution of the central and [...] Read more.
A study was performed on the growth interface of a large-diameter 1 at% neodymium-doped yttrium aluminum garnet (Nd:YAG) single crystal grown using the Czochralski method. Red parallel light and an orthogonal polarizing system were used to observe the distribution of the central and lateral cores of the crystal at different growth interfaces. The solid–liquid interface of large-diameter Nd:YAG crystal growth was mainly determined via the interaction between natural and forced convection. The shape of the solid–liquid interface was mainly controlled via maintaining the crystal rotation rate and the temperature field. Interface inversion generally occurred during the shoulder-expanding stage and late stages of the growth of the cylindrical portion of the crystal. The occurrence of interface inversion is directly related to the temperature field, process parameters, and diameter of the crystal. The growth shape of the crystal interface determined the size and distribution of the central and lateral cores of the crystal. The area of the central and lateral cores was reduced via adjusting the temperature gradient of the solid–liquid interface and crystal rotation speed. Full article
(This article belongs to the Special Issue Emerging Rare-Earth Doped Materials)
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9 pages, 1008 KiB  
Article
Optimization of Blue Photorefractive Properties and Exponential Gain of Photorefraction in Sc-Doped Ru:Fe:LiNbO3 Crystals
by Lei Xu and Guanying Chen
Crystals 2022, 12(8), 1059; https://doi.org/10.3390/cryst12081059 - 29 Jul 2022
Cited by 2 | Viewed by 1416
Abstract
Sc:Ru:Fe:LiNbO3 crystals were grown from congruent melt by using the Czochralski method. A series of LiNbO3 crystals (Li/Nb = 48.6/51.4) with 0.1 wt% RuO2, 0.06 wt% Fe2O3 and various concentrations of Sc203 were [...] Read more.
Sc:Ru:Fe:LiNbO3 crystals were grown from congruent melt by using the Czochralski method. A series of LiNbO3 crystals (Li/Nb = 48.6/51.4) with 0.1 wt% RuO2, 0.06 wt% Fe2O3 and various concentrations of Sc203 were prepared. RF1 and RF4 refers to the samples containing 0 mol% Sc203 and 3 mol% Sc203, respectively. The photorefractive properties of RF4 were measured by Kr+ laser (λ = 476 nm blue light): ηs = 75.7%, τw = 11 s, M/# = 19.52, S = 2.85 cmJ−1, Γ = 31.8 cm−1 and ∆nmax = 6.66 × 10−5. The photorefractive properties of five systems (ηs, M/#, S, Γ and ∆nmax) under 476 nm wavelength from RF1 to RF4 continually increased the response time, while τw was continually shortened. Comparing the photorefractive properties of Sc (1 mol%):Ru (0.1 wt%):Fe (0.06 wt%): LiNbO3 measured by Kr+ laser (λ = 476 nm blue light) with Sc (1 mol%):Fe (0.06 wt%):LiNbO3 measured by He-Ne laser (633 nm red light), ηs increased by a factor of 1.9, Vw (response rate) increased by a factor of 13.9, M/# increased by a factor of 1.8 and S increased by a factor of 32. The ∆nmax improved by a factor of 1.4. A strong blue photorefraction was created by the two-center effect and the remarkable characteristic of being in phase between the two gratings recorded in shallow and deep trap centers. The photorefractive properties (ηS, τw, M/#, S, ∆nmax) were increased with an increase in Sc3+ ion concentration. Damage-resistant dopants such as Sc3+ ions were no longer resistant to damage, but they enhanced the photorefractive properties at the 476 nm wavelength. The experimental results clearly show that Sc-doped two-center Ru:Fe:LiNbO3 crystal is a promising candidate blue photorefraction material for volume holographic storage. Sc-doped LiNbO3 crystal can significantly enhance the blue photorefractive properties according to the experimental parameters. Therefore, the Sc:Ru:Fe:LiNbO3 crystal has better photorefractive properties than the Ru:Fe:LiNbO3 crystal. Full article
(This article belongs to the Special Issue Emerging Rare-Earth Doped Materials)
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16 pages, 5536 KiB  
Article
Synthesis, Structure, and Properties of EuLnCuSe3 (Ln = Nd, Sm, Gd, Er)
by Oleg V. Andreev, Victor V. Atuchin, Alexander S. Aleksandrovsky, Yuriy G. Denisenko, Boris A. Zakharov, Alexander P. Tyutyunnik, Navruzbek N. Habibullayev, Dmitriy A. Velikanov, Dmitriy A. Ulybin and Daniil D. Shpindyuk
Crystals 2022, 12(1), 17; https://doi.org/10.3390/cryst12010017 - 23 Dec 2021
Cited by 11 | Viewed by 2766
Abstract
EuLnCuSe3 (Ln = Nd, Sm, Gd, Er), due to their complex composition, should be considered new materials with the ability to purposefully change the properties. Samples of the EuLnCuSe3 were prepared using Cu, rare earth metal, Se (99.99%) by the ampoule [...] Read more.
EuLnCuSe3 (Ln = Nd, Sm, Gd, Er), due to their complex composition, should be considered new materials with the ability to purposefully change the properties. Samples of the EuLnCuSe3 were prepared using Cu, rare earth metal, Se (99.99%) by the ampoule method. The samples were obtained by the crystallization from a melt and annealed at temperatures 1073 and 1273 K. The EuErCuSe3 crystal structure was established using the single-crystal particle. EuErCuSe3 crystallizes in the orthorhombic system, space group Cmcm, KCuZrS3 structure type, with cell parameters a = 4.0555 (3), b = 13.3570 (9), and c = 10.4602 (7) Å, V = 566.62 (6) Å3. In structure EuErCuSe3, erbium ions are coordinated by selenium ions in the octahedral polyhedron, copper ions are in the tetrahedral coordination, europium ions are between copper and erbium polyhedra layers and are coordinated by selenium ions as two-cap trigonal prisms. The optical band gap is 1.79 eV. At 4.7 K, a transition from the ferrimagnetic state to the paramagnetic state was detected in EuErCuSe3. At 85 and 293 K, the compound is in a paramagnetic state. According to XRPD data, EuLnCuSe3 (Ln = Nd, Sm, Gd) compounds have a Pnma orthorhombic space group of the Eu2CuS3 structure type. For EuSmCuSe3, a = 10.75704 (15) Å, b = 4.11120 (5) Å, c = 13.37778 (22) Å. In the series of EuLnCuSe3 compounds, the optical band gap increases 1.58 eV (Nd), 1.58 eV (Sm), 1.72 eV (Gd), 1.79 eV (Er), the microhardness of the 205 (Nd), 210 (Sm), 225 (Gd) 235 ± 4 HV (Er) phases increases, and the thermal stability of the phases increases significantly. According to the measurement data of differential scanning calorimetry, the EuNdCuSe3 decomposes, according to the solid-phase reaction T = 1296 K, ΔH = 8.2 ± 0.8 kJ/mol. EuSmCuSe3 melts incongruently T = 1449 K, ΔH = 18.8 ± 1.9 kJ/mol. For the EuGdCuSe3, two (Tαβ = 1494 K, ΔHαβ = 14.8 kJ/mol, Tβγ = 1530 K, ΔHβγ = 4.8 kJ/mol) and for EuErCuSe3 three polymorphic transitions (Tαβ = 1561 K, ΔHαβ = 30.3 kJ/mol, Tβγ = 1579 K, ΔHβγ = 4.4 kJ/mol, and Tγδ = 1600 K, ΔHγδ = 10.1 kJ/mol). The compounds melt incongruently at the temperature of 1588 K, ΔHmelt = 17.9 ± 1.8 kJ/mol and 1664 K, ΔHmelt = 25.6 ± 2.5 kJ/mol, respectively. Incongruent melting of the phases proceeds with the formation of a solid solution of EuSe and a liquid phase. Full article
(This article belongs to the Special Issue Emerging Rare-Earth Doped Materials)
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Review

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25 pages, 9549 KiB  
Review
Pure and Yb-Doped LaxYySc4-x-y(BO3)4 Crystals: A Review of Recent Advances
by Alin Broasca, Madalin Greculeasa, Flavius Voicu, Cristina Gheorghe and Lucian Gheorghe
Crystals 2023, 13(2), 169; https://doi.org/10.3390/cryst13020169 - 18 Jan 2023
Viewed by 1092
Abstract
This paper reviews the progress in developing the LaxYySc4-x-y(BO3)4-LYSB and Yb-doped LaxYySc4-x-y(BO3)4-LYSB:Yb huntite-type crystals grown by the Czochralski method as new candidates for [...] Read more.
This paper reviews the progress in developing the LaxYySc4-x-y(BO3)4-LYSB and Yb-doped LaxYySc4-x-y(BO3)4-LYSB:Yb huntite-type crystals grown by the Czochralski method as new candidates for the next generation of nonlinear optical (NLO) and/or laser crystals. Considering the incongruent melting of these crystals, the initial compositions of the melt and the pulling and rotation rates were optimized. Additionally, a special thermal setup was engineered to grow LYSB-type crystals by the Czochralski crystal growth method. The chemical compositions of the LYSB and LYSB:Yb grown crystals were found to be La0.78Y0.32Sc2.90(BO3)4 and La0.78Y0.32Yb0.04Sc2.86(BO3)4, respectively. Therefore, for the LYSB:Yb crystal, the doping concentration of Yb3+ ions was considered to be 4 at.% with respect to the nonstoichiometric (La1-xYx)1.25Sc2.75(BO3)4 undoped compounds, i.e., LYSB:Yb (4 at.%). In terms of NLO properties, the obtained results demonstrate that LYSB and LYSB:Yb (4 at.%) crystals possess remarkable properties specific to huntite-type crystals. The main advantage of these crystals consists in the fact that they may be obtained with large dimensions and excellent optical quality by the Czochralski method, which recommends them as a new class of highly efficient crystals for different NLO applications, including second harmonic generation (SHG) of high-power or high-energy laser beams. The laser performances of the LYSB:Yb (4 at.%) crystal prove its favorable intrinsic properties to generate laser emissions in the 1 µm range with high efficiency. The efficient laser emission at ~1028 nm together with good NLO characteristics to convert its own emission into emission at ~514 nm via SHG make the LYSB:Yb (4 at.%) crystal a very promising active medium to be used in self-frequency doubling configuration. Full article
(This article belongs to the Special Issue Emerging Rare-Earth Doped Materials)
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