Crystal Growth of Multifunctional Borates and Related Materials

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

Deadline for manuscript submissions: closed (20 December 2018) | Viewed by 25745

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Department of Crystallography and Crystal Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia
Interests: crystal growth; crystallography; crystal chemistry; crystal morphology; liquid phase epitaxy; micro- and nanocrystallization; inorganic compounds
* Passed away in May 2020
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Dear Colleagues,

Most borate materials have attracted considerable attention, owing to their remarkable characteristics and potential applications. For instance, they demonstrate nonlinear optical and piezoelectric effects (CsB3O5, LiB3O5, CsLiB6O10, KBe2BO3F2, Sr2Be2BO7, K2Al2B2O7, Ca4GdO(BO3)3, b-BaB2O4, R2CaB10O19 (R = rare earth metals), RM3(BO3)4 (М = Аl, Cr, Ga, Fe, Sc), luminescent (RBO3) and magneto-electrical properties (RFe3(BO3)4, RСr3(BO3)4, HoAl3(BO3)4, TbAl3(BO3)4), etc.

Nowadays, more than 1000 representatives of the anhydrous borate family are listed in the Inorganic Crystal Structure Database. These compounds are characterized by the great variety in their crystal structures, caused in the linkage of planar BO3–triangles and BO4–tetrahedra as fundamental structural units, and this leads to glass formation in viscous borate-based melts. Investigations of “conditions–composition–structure-properties” relationships can help to develop growth in technology of single crystal components for high performance electronic and optical devices for industrial, medical and entertainment applications.

The structural stability of many silicates, phosphates and germanates also depends on the delocalization of formal charges of the AnOm (A=Si,Ge,P) anions as a result of their polymerization. The regular variations in their structural motifs makes it possible to forecast (optimistically, more or less) new phase systems for the synthesis of advanced materials as well, because currently most of these single crystals are not available in good size or quality. A further analysis of these inorganic polymer structures will set forth the judicious ways towards better understanding the growth mechanisms of multifunctional crystals, and this Special Issue is intended to fill this gap in the field.

Prof. Dr. Nikolay I Leonyuk
Guest Editor

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Keywords

  • Crystal Growth
  • Crystallography
  • Crystal Chemistry
  • Borates
  • Multifunctional Materials

Published Papers (7 papers)

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Editorial

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4 pages, 156 KiB  
Editorial
Crystal Growth of Multifunctional Borates and Related Materials
by Nikolay I Leonyuk
Crystals 2019, 9(3), 164; https://doi.org/10.3390/cryst9030164 - 21 Mar 2019
Cited by 7 | Viewed by 2289
Abstract
Crystalline materials play an important role in modern physics and electronics [...] Full article
(This article belongs to the Special Issue Crystal Growth of Multifunctional Borates and Related Materials)

Research

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9 pages, 3228 KiB  
Article
Liquid-Phase Epitaxial Growth and Characterization of Nd:YAl3(BO3)4 Optical Waveguides
by Yi Lu, Peter Dekker and Judith M. Dawes
Crystals 2019, 9(2), 79; https://doi.org/10.3390/cryst9020079 - 01 Feb 2019
Cited by 4 | Viewed by 3370
Abstract
We investigated the fabrication of neodymium doped thin film optical waveguide-based devices as potential active sources for planar integrated optics. Liquid-phase epitaxial growth was used to fabricate neodymium-doped yttrium aluminum borate films on compatible lattice-matched, un-doped yttrium aluminum borate substrates. We observed the [...] Read more.
We investigated the fabrication of neodymium doped thin film optical waveguide-based devices as potential active sources for planar integrated optics. Liquid-phase epitaxial growth was used to fabricate neodymium-doped yttrium aluminum borate films on compatible lattice-matched, un-doped yttrium aluminum borate substrates. We observed the refractive index contrast of the doped and un-doped crystal layers via differential interference contrast microscopy. In addition, characterization by X-ray powder diffraction, optical absorption and luminescence spectra demonstrated the crystal quality, uniformity and optical guiding of the resulting thin films. Full article
(This article belongs to the Special Issue Crystal Growth of Multifunctional Borates and Related Materials)
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10 pages, 4394 KiB  
Article
Investigation of Piezoelectric Ringing Frequency Response of Beta Barium Borate Crystals
by Giedrius Sinkevicius and Algirdas Baskys
Crystals 2019, 9(1), 49; https://doi.org/10.3390/cryst9010049 - 17 Jan 2019
Cited by 10 | Viewed by 4505
Abstract
The piezoelectric ringing phenomenon in Pockels cells based on the beta barium borate crystals was analyzed in this work. The investigation results show that piezoelectric ringing is caused by multiple high voltage pulses with a frequency in the range from 10 kHz up [...] Read more.
The piezoelectric ringing phenomenon in Pockels cells based on the beta barium borate crystals was analyzed in this work. The investigation results show that piezoelectric ringing is caused by multiple high voltage pulses with a frequency in the range from 10 kHz up to 1 MHz. Experimental investigation of frequency response and Discrete Fourier transformation was used for analysis. The method of piezoelectric ringing investigation based on the analysis of difference of real and simulated optical signals spectrums was proposed. The investigations were performed for crystals with 3 × 3 × 25 mm, 4 × 4 × 25 mm and 4 × 4 × 20 mm dimensions. It was estimated that piezoelectric ringing in the beta barium borate crystal with dimensions of 3 × 3 mm × 25 mm occurred at the 150, 205, 445, 600 and 750 kHz frequencies of high voltage pulses. Full article
(This article belongs to the Special Issue Crystal Growth of Multifunctional Borates and Related Materials)
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11 pages, 3273 KiB  
Article
Comparative Investigation on the Emission Properties of RAl3(BO3)4 (R = Pr, Eu, Tb, Dy, Tm, Yb) Crystals with the Huntite Structure
by Enrico Cavalli and Nikolay I. Leonyuk
Crystals 2019, 9(1), 44; https://doi.org/10.3390/cryst9010044 - 16 Jan 2019
Cited by 7 | Viewed by 3416
Abstract
The luminescence properties of RAl3(BO3)4 (RAB, with R = Pr, Eu, Tb, Dy, Tm, Yb) huntite crystals grown from K2Mo3O10 flux were systematically characterized in order to investigate their excitation dynamics, with particular [...] Read more.
The luminescence properties of RAl3(BO3)4 (RAB, with R = Pr, Eu, Tb, Dy, Tm, Yb) huntite crystals grown from K2Mo3O10 flux were systematically characterized in order to investigate their excitation dynamics, with particular reference to the concentration quenching that in these systems is incomplete. To this purpose, selected excitation, emission, and decay profile measurements on diluted R:YAB crystals were carried out and compared with those of the concentrated compounds. The effects of the energy transfer processes and of the lattice defects, as well as the ion-lattice interactions, have been taken into consideration in order to account for the experimental results. Full article
(This article belongs to the Special Issue Crystal Growth of Multifunctional Borates and Related Materials)
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10 pages, 3502 KiB  
Article
Bismuth-Based Oxyborate Piezoelectric Crystals: Growth and Electro-Elastic Properties
by Feifei Chen, Xiufeng Cheng, Fapeng Yu, Chunlei Wang and Xian Zhao
Crystals 2019, 9(1), 29; https://doi.org/10.3390/cryst9010029 - 06 Jan 2019
Cited by 8 | Viewed by 3506
Abstract
The non-centrosymmetric bismuth-based oxyborate crystals have been extensively studied for non-linear optical, opto-electric and piezoelectric applications. In this work, single crystal growth and electro-elastic properties of α-BiB3O6 (α-BIBO) and Bi2ZnB2O7 (BZBO) crystals are reported. Centimeter-sized [...] Read more.
The non-centrosymmetric bismuth-based oxyborate crystals have been extensively studied for non-linear optical, opto-electric and piezoelectric applications. In this work, single crystal growth and electro-elastic properties of α-BiB3O6 (α-BIBO) and Bi2ZnB2O7 (BZBO) crystals are reported. Centimeter-sized α-BIBO and BZBO crystals were grown by using the Kyropoulos method. High resolution X-ray diffraction tests were performed to assess the crystal quality. The full-width at half-maximum values (FWHM) of the rocking curves were evaluated to be 35.35 arcsec and 47.85 arcsec for α-BIBO and BZBO samples, respectively. Moreover, the electro-elastic properties of α-BIBO and BZBO crystals are discussed and summarized, based on which the radial extensional and the face shear vibration modes were studied for potential acoustic device applications. The radial extensional mode electro-mechanical coupling factors kp were evaluated and found to be 32.0% and 5.5% for α-BIBO and BZBO crystals, respectively. The optimal crystal cuts with face shear mode were designed and found to be (YZt)/−53° (or (YZt)/37° cut) for α-BIBO crystal, and (ZXt)/±45° cut for BZBO crystal, with the largest effective piezoelectric coefficients being in the order of 14.8 pC/N and 8.9 pC/N, respectively. Full article
(This article belongs to the Special Issue Crystal Growth of Multifunctional Borates and Related Materials)
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13 pages, 9841 KiB  
Article
Twins in YAl3(BO3)4 and K2Al2B2O7 Crystals as Revealed by Changes in Optical Activity
by Johannes Buchen, Volker Wesemann, Steffen Dehmelt, Andreas Gross and Daniel Rytz
Crystals 2019, 9(1), 8; https://doi.org/10.3390/cryst9010008 - 22 Dec 2018
Cited by 4 | Viewed by 3356
Abstract
Many borate crystals feature nonlinear optical properties that allow for efficient frequency conversion of common lasers down into the ultraviolet spectrum. Twinning may degrade crystal quality and affect nonlinear optical properties, in particular if crystals are composed of twin domains with opposing polarities. [...] Read more.
Many borate crystals feature nonlinear optical properties that allow for efficient frequency conversion of common lasers down into the ultraviolet spectrum. Twinning may degrade crystal quality and affect nonlinear optical properties, in particular if crystals are composed of twin domains with opposing polarities. Here, we use measurements of optical activity to demonstrate the existence of inversion twins within single crystals of YAl 3 (BO 3 ) 4 (YAB) and K 2 Al 2 B 2 O 7 (KABO). We determine the optical rotatory dispersion of YAB and KABO throughout the visible spectrum using a spectrophotometer with rotatable polarizers. Space-resolved measurements of the optical rotation can be related to the twin structure and give estimates on the extent of twinning. The reported dispersion relations for the rotatory power of YAB and KABO may be used to assess crystal quality and to select twin-free specimens. Full article
(This article belongs to the Special Issue Crystal Growth of Multifunctional Borates and Related Materials)
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Review

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49 pages, 9954 KiB  
Review
Crystallochemical Design of Huntite-Family Compounds
by Galina M. Kuz’micheva, Irina A. Kaurova, Victor B. Rybakov and Vadim V. Podbel’skiy
Crystals 2019, 9(2), 100; https://doi.org/10.3390/cryst9020100 - 15 Feb 2019
Cited by 23 | Viewed by 4778
Abstract
Huntite-family nominally-pure and activated/co-activated LnM3(BO3)4 (Ln = La–Lu, Y; M = Al, Fe, Cr, Ga, Sc) compounds and their-based solid solutions are promising materials for lasers, nonlinear optics, spintronics, and photonics, which are characterized by multifunctional properties [...] Read more.
Huntite-family nominally-pure and activated/co-activated LnM3(BO3)4 (Ln = La–Lu, Y; M = Al, Fe, Cr, Ga, Sc) compounds and their-based solid solutions are promising materials for lasers, nonlinear optics, spintronics, and photonics, which are characterized by multifunctional properties depending on a composition and crystal structure. The purpose of the work is to establish stability regions for the rare-earth orthoborates in crystallochemical coordinates (sizes of Ln and M ions) based on their real compositions and space symmetry depending on thermodynamic, kinetic, and crystallochemical factors. The use of diffraction structural techniques to study single crystals with a detailed analysis of diffraction patterns, refinement of crystallographic site occupancies (real composition), and determination of structure–composition correlations is the most efficient and effective option to achieve the purpose. This approach is applied and shown primarily for the rare-earth scandium borates having interesting structural features compared with the other orthoborates. Visualization of structures allowed to establish features of formation of phases with different compositions, to classify and systematize huntite-family compounds using crystallochemical concepts (structure and superstructure, ordering and disordering, isostructural and isotype compounds) and phenomena (isomorphism, morphotropism, polymorphism, polytypism). Particular attention is paid to methods and conditions for crystal growth, affecting a crystal real composition and symmetry. A critical analysis of literature data made it possible to formulate unsolved problems in materials science of rare-earth orthoborates, mainly scandium borates, which are distinguished by an ability to form internal and substitutional (Ln and Sc atoms), unlimited and limited solid solutions depending on the geometric factor. Full article
(This article belongs to the Special Issue Crystal Growth of Multifunctional Borates and Related Materials)
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