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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 7666

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Prof. Dr. Guanying Chen

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School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
Interests: lanthanide; crystals and nanocrystals; nonlinear; biophotonics; solar cells
Special Issues, Collections and Topics in MDPI journals

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

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
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

Open AccessArticle

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 682

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 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

Open AccessArticle

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 1080

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 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

Open AccessEditor’s ChoiceArticle

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 1426

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 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): η_s = 75.7%, τ_w = 11 s, M/# = 19.52, S = 2.85 cmJ⁻¹, Γ = 31.8 cm⁻¹ and ∆n_max = 6.66 × 10⁻⁵. The photorefractive properties of five systems (η_s, M/#, S, Γ and ∆n_max) under 476 nm wavelength from RF1 to RF4 continually increased the response time, while τ_w 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), η_s increased by a factor of 1.9, V_w (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 ∆n_max 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 (η_S, τ_w, M/#, S, ∆n_max) 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

Open AccessArticle

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 2775

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 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 EuGdCuSe_3, two (T_α_↔_β = 1494 K, ΔH_α_↔_β = 14.8 kJ/mol, T_β_↔_γ = 1530 K, ΔH_β_↔_γ = 4.8 kJ/mol) and for EuErCuSe₃ three polymorphic transitions (T_α_↔_β = 1561 K, ΔH_α_↔_β = 30.3 kJ/mol, T_β_↔_γ = 1579 K, ΔH_β_↔_γ = 4.4 kJ/mol, and T_γ_↔_δ = 1600 K, ΔH_γ_↔_δ = 10.1 kJ/mol). The compounds melt incongruently at the temperature of 1588 K, ΔH_melt = 17.9 ± 1.8 kJ/mol and 1664 K, ΔH_melt = 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

Open AccessReview

Pure and Yb-Doped La_xY_ySc_4-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 1101

Abstract

This paper reviews the progress in developing the La_xY_ySc_4-x-y(BO₃)₄-LYSB and Yb-doped La_xY_ySc_4-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 La_0.78Y_0.32Sc_2.90(BO₃)₄ and La_0.78Y_0.32Yb_0.04Sc_2.86(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 (La_1-xY_x)_1.25Sc_2.75(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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