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Synthesis, Structure and Properties of Metal Oxides

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Metals and Alloys".

Deadline for manuscript submissions: closed (20 October 2023) | Viewed by 10887

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Dr. Dmitry A. Shulyatev

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Materials Modeling and Development Laboratory, National University of Science and Technology MISIS, 119049 Moscow, Russia
Interests: crystal growth and characterization; floating zone melting; perovskites; high Tc superconductivity; magnetoresistivity; quasicrystals
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Dear Colleagues,

Metal oxides (MOs) constitute one of the most interesting and promising materials thanks to their diversified crystal structures and various physical properties. Many unique phenomena, for example, high-temperature superconductivity (HTSC) or colossal magnetoresistance (CMR), were first discovered in MOs.

Among the wide variety of MOs systems, specific families, such as transition metal oxides, can be distinguished. Metal oxides can also be classified by structural type. For example, extensive research is devoted to compounds with a perovskite-type structure. This issue aims to bring together papers on specific metal oxide compounds and reviews of various MOs families and structural types.

A great challenge in solid state physics is to obtain novel MOs and investigate their structure and properties. Papers related to the synthesis and study of novel MOs are very welcome and strongly encouraged.

MO single crystal growth is of particular interest. A specific feature of the multicomponent MO single crystals grown by different techniques is that many of them demonstrate a strong deviation from stoichiometry due to cationic or oxygen vacancies and compositional inhomogeneity along the growth direction. The study of defects in MOs and their influence on the properties of the studied compounds is one of the topics of this issue.

Both reviews and original research articles on MOs are also welcome. We are looking forward to your contributions to this Special Issue!

Dr. Dmitry A. Shulyatev
Guest Editor

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Keywords

metal monoxides
multicomponent MOs
transition metal oxides
perovskites and other metal oxide structures
synthesis of MOs and single crystals grown
cationic and oxygen vacancies and compositional inhomogeneity in MOs
novel metal oxides
application of MOs

Published Papers (7 papers)

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Research

15 pages, 5824 KiB

Open AccessArticle

Effect of the Deposit Temperature of ZnO Doped with Ni by HFCVD

by Delfino R. Gutiérrez, Godofredo García-Salgado, Antonio Coyopol, Enrique Rosendo-Andrés, Román Romano, Crisóforo Morales, Alfredo Benítez, Francisco Severiano, Ana María Herrera and Francisco Ramírez-González

Materials 2023, 16(4), 1526; https://doi.org/10.3390/ma16041526 - 11 Feb 2023

Cited by 2 | Viewed by 1355

Abstract

The effect of the deposit temperature of zinc oxide (ZnO) doped with nickel (Ni) by hot filament chemical vapor deposition (HFCVD) technique is reported in this work. The technique allows depositing ZnO:Ni in short intervals (1 min). A deposit of undoped ZnO is used as a reference sample. The reference sample was deposited at 500 °C. The ZnO:Ni samples were deposited at 500 °C, 400 °C, 350 °C, and 300 °C. The samples were studied using structural, morphological, and optical characterization techniques. The Ni incorporation to the ZnO lattice was verified by the shift of the X-ray diffraction peaks, the Raman peaks, the band gap, and the photoluminescence measurements. It was found that the deposit temperature affects the structural, morphological, and optical properties of the ZnO:Ni samples too. The structure of the ZnO:Ni samples corresponds to the hexagonal structure. Different microstructures shapes such as spheres, sea urchins, and agglomerate were found in samples; their change is attributed to the deposit temperature variation. The intensity of the photoluminescence of the ZnO:Ni improves concerning the ZnO due to the Ni incorporation, but it decreases as the deposit temperature decreases. Full article

(This article belongs to the Special Issue Synthesis, Structure and Properties of Metal Oxides)

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15 pages, 5841 KiB

Open AccessArticle

Ferrimagnetic Ordering and Spin-Glass State in Diluted GdFeO₃-Type Perovskites (Lu_0.5Mn_0.5)(Mn_1−xTi_x)O₃ with x = 0.25, 0.50, and 0.75

by Alexei A. Belik, Ran Liu, Andreas Dönni, Masahiko Tanaka and Kazunari Yamaura

Materials 2023, 16(4), 1506; https://doi.org/10.3390/ma16041506 - 10 Feb 2023

Viewed by 1175

Abstract

ABO₃ perovskite materials with small cations at the A site, especially those with ordered cation arrangements, have attracted a great deal of interest because they show unusual physical properties and deviations from the general characteristics of perovskites. In this work, perovskite solid solutions (Lu_0.5Mn_0.5)(Mn_1−xTi_x)O₃ with x = 0.25, 0.50, and 0.75 were synthesized by means of a high-pressure, high-temperature method at approximately 6 GPa and approximately 1550 K. All the samples crystallize in the GdFeO₃-type perovskite structure (space group Pnma) and have random distributions of the small Lu³⁺ and Mn²⁺ cations at the A site and Mn^4+/3+/2+ and Ti⁴⁺ cations at the B site, as determined by Rietveld analysis of high-quality synchrotron X-ray powder diffraction data. Lattice parameters are a = 5.4431 Å, b = 7.4358 Å, c = 5.1872 Å (for x = 0.25); a = 5.4872 Å, b = 7.4863 Å, c = 5.2027 Å (for x = 0.50); and a = 5.4772 Å, b = 7.6027 Å, c = 5.2340 Å (for x = 0.75). Despite a significant dilution of the A and B sublattices by non-magnetic Ti⁴⁺ cations, the x = 0.25 and 0.50 samples show long-range ferrimagnetic order below T_C = 89 K and 36 K, respectively. Mn cations at both A and B sublattices are involved in the long-range magnetic order. The x = 0.75 sample shows a spin-glass transition at T_SG = 6 K and a large frustration index of approximately 22. A temperature-independent dielectric constant was observed for x = 0.50 (approximately 32 between 5 and 150 K) and for x = 0.75 (approximately 50 between 5 and 250 K). Full article

(This article belongs to the Special Issue Synthesis, Structure and Properties of Metal Oxides)

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14 pages, 4088 KiB

Open AccessArticle

Dielectric and Spin-Glass Magnetic Properties of the A-Site Columnar-Ordered Quadruple Perovskite Sm₂CuMn(MnTi₃)O₁₂

by Alexei A. Belik, Ran Liu and Kazunari Yamaura

Materials 2022, 15(23), 8306; https://doi.org/10.3390/ma15238306 - 23 Nov 2022

Cited by 3 | Viewed by 1161

Abstract

Perovskite-type ABO₃ oxides show a number of cation-ordered structures, which have significant effects on their properties. The rock-salt-type order is dominant for B cations, and the layered order for A cations. In this work, we prepared a new perovskite-type oxide, Sm₂CuMn(MnTi₃)O₁₂, with a rare columnar A-site order using a high-pressure, high-temperature method at about 6 GPa and about 1700 K. Its crystal structure was studied with synchrotron powder X-ray diffraction. The compound crystallizes in space group P4₂/nmc (No. 137) at room temperature with a = 7.53477 Å and c = 7.69788 Å. The magnetic properties of the compound were studied with dc and ac magnetic susceptibility measurements and specific heat. Spin-glass (SG) magnetic properties were found with T_SG = 7 K, while specific heat, in the form of C_p/T, showed a strong, very broad anomaly developing below 20 K and peaking at 4 K. The dielectric constant of Sm₂CuMn(MnTi₃)O₁₂ was nearly frequency and temperature independent between 8 K and 200 K, with a value of about 50. Cu²⁺ doping drastically modified the magnetic and dielectric properties of Sm₂CuMn(MnTi₃)O₁₂ in comparison with the parent compound Sm₂MnMn(MnTi₃)O₁₂, which showed a long-range ferrimagnetic order at 34–40 K. The antisite disorder of Cu²⁺ and Mn²⁺ cations between square-planar and octahedral sites was responsible for the SG magnetic properties of Sm₂CuMn(MnTi₃)O₁₂. Full article

(This article belongs to the Special Issue Synthesis, Structure and Properties of Metal Oxides)

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14 pages, 3998 KiB

Open AccessArticle

VO_x Phase Mixture of Reduced Single Crystalline V₂O₅: VO₂ Resistive Switching

by Brian Walls, Oisín Murtagh, Sergey I. Bozhko, Andrei Ionov, Andrey A. Mazilkin, Daragh Mullarkey, Ainur Zhussupbekova, Dmitry A. Shulyatev, Kuanysh Zhussupbekov, Nikolai Andreev, Nataliya Tabachkova and Igor V. Shvets

Materials 2022, 15(21), 7652; https://doi.org/10.3390/ma15217652 - 31 Oct 2022

Cited by 1 | Viewed by 1535

Abstract

The strongly correlated electron material, vanadium dioxide (VO

_{2}

), has seen considerable attention and research application in metal-oxide electronics due to its metal-to-insulator transition close to room temperature. Vacuum annealing a V

_{2}

_{5}

(010) single crystal results in Wadsley phases [...] Read more.

The strongly correlated electron material, vanadium dioxide (VO

_{2}

), has seen considerable attention and research application in metal-oxide electronics due to its metal-to-insulator transition close to room temperature. Vacuum annealing a V

_{2}

_{5}

(010) single crystal results in Wadsley phases (V

_{n}

_{2 n + 1}

, n > 1) and VO

_{2}

. The resistance changes by a factor of 20 at 342 K, corresponding to the metal-to-insulator phase transition of VO

_{2}

. Macroscopic voltage-current measurements with a probe separation on the millimetre scale result in Joule heating-induced resistive switching at extremely low voltages of under a volt. This can reduce the hysteresis and facilitate low temperature operation of VO

_{2}

devices, of potential benefit for switching speed and device stability. This is correlated to the low resistance of the system at temperatures below the transition. High-resolution transmission electron microscopy measurements reveal a complex structural relationship between V

_{2}

_{5}

, VO

_{2}

and V

_{6}

_{13}

crystallites. Percolation paths incorporating both VO

_{2}

and metallic V

_{6}

_{13}

are revealed, which can reduce the resistance below the transition and result in exceptionally low voltage resistive switching. Full article

(This article belongs to the Special Issue Synthesis, Structure and Properties of Metal Oxides)

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10 pages, 3579 KiB

Open AccessArticle

A Novel Mineral-like Copper Phosphate Chloride with a Disordered Guest Structure: Crystal Chemistry and Magnetic Properties

by Galina Kiriukhina, Olga Yakubovich, Larisa Shvanskaya, Anatoly Volkov, Olga Dimitrova, Sergey Simonov, Olga Volkova and Alexander Vasiliev

Materials 2022, 15(4), 1411; https://doi.org/10.3390/ma15041411 - 14 Feb 2022

Cited by 4 | Viewed by 1533

Abstract

Novel copper phosphate chloride has been obtained under middle-temperature hydrothermal conditions. Its crystal structure was established based on the low-temperature X-ray diffraction data: Na₂Li_0.75(Cs,K)_0.5[Cu₅(PO₄)₄Cl]·3.5(H₂O,OH), sp. gr. C2/m, a = 19.3951(8) Å, b = 9.7627(3) Å, c = 9.7383(4) Å, β = 99.329(4)°, T = 150 K, MoK_α (λ = 0.71073 Å), R = 0.049. The crystal structure includes tetrameric copper clusters as the main building blocks, which are built of four CuO₄Cl pyramids sharing apical Cl vertices. The clusters are combined through phosphate groups and additional copper-centered polyhedra to form two mostly ordered periodic layers. Between the layers and inside the framework channels, alkali ions, H₂O molecules, or OH groups are statistically distributed. Na₂Li_0.75(Cs,K)_0.5[Cu₅(PO₄)₄Cl]·3.5(H₂O,OH) is a synthetic modification of a sampleite-polymorph of the lavendulan mineral group and represents a new member in a mero-plesiotype series of copper phosphates and arsenates, for which the crystal structures contain two-periodic [Cu₄X(TO₄)₄]_∞ modules (T = As, P; X = Cl, O). Magnetically, this phase exhibits the phase transition at T_C = 6.5 K, below which it possesses a weak ferromagnetic moment. Full article

(This article belongs to the Special Issue Synthesis, Structure and Properties of Metal Oxides)

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17 pages, 6138 KiB

Open AccessArticle

Effects of Non-Stoichiometry on the Ground State of the Frustrated System Li_0.8Ni_0.6Sb_0.4O₂

by Evgeniya Vavilova, Timur Salikhov, Margarita Iakovleva, Tatyana Vasilchikova, Elena Zvereva, Igor Shukaev, Vladimir Nalbandyan and Alexander Vasiliev

Materials 2021, 14(22), 6785; https://doi.org/10.3390/ma14226785 - 10 Nov 2021

Cited by 1 | Viewed by 1323

Abstract

The non-stoichiometric system Li_0.8Ni_0.6Sb_0.4O₂ is a Li-deficient derivative of the zigzag honeycomb antiferromagnet Li₃Ni₂SbO₆. Structural and magnetic properties of Li_0.8Ni_0.6Sb_0.4O₂ were studied by means of X-ray diffraction, magnetic susceptibility, specific heat, and nuclear magnetic resonance measurements. Powder X-ray diffraction data shows the formation of a new phase, which is Sb-enriched and Li-deficient with respect to the structurally honeycomb-ordered Li₃Ni₂SbO₆. This structural modification manifests in a drastic change of the magnetic properties in comparison to the stoichiometric partner. Bulk static (dc) magnetic susceptibility measurements show an overall antiferromagnetic interaction (Θ = −4 K) between Ni²⁺ spins (S = 1), while dynamic (ac) susceptibility reveals a transition into a spin glass state at a freezing temperature T_SG ~ 8 K. These results were supported by the absence of the λ-anomaly in the specific heat C_p(T) down to 2 K. Moreover, combination of the bulk static susceptibility, heat capacity and ⁷Li NMR studies indicates a complicated temperature transformation of the magnetic system. We observe a development of a cluster spin glass, where the Ising-like Ni²⁺ magnetic moments demonstrate a 2D correlated slow short-range dynamics already at 12 K, whereas the formation of 3D short range static ordered clusters occurs far below the spin-glass freezing temperature at T ~ 4 K as it can be seen from the ⁷Li NMR spectrum. Full article

(This article belongs to the Special Issue Synthesis, Structure and Properties of Metal Oxides)

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11 pages, 2440 KiB

Open AccessArticle

Chirality and Magnetocaloricity in GdFeTeO₆ as Compared to GdGaTeO₆

by Elena Zvereva, Tatyana Vasilchikova, Maria Evstigneeva, Angelica Tyureva, Vladimir Nalbandyan, João Gonçalves, Paolo Barone, Alessandro Stroppa and Alexander Vasiliev

Materials 2021, 14(20), 5954; https://doi.org/10.3390/ma14205954 - 10 Oct 2021

Cited by 2 | Viewed by 1732

Abstract

GdFeTeO₆ and GdGaTeO₆ have been prepared and their structures refined by the Rietveld method. Both are superstructures of the rosiaite type (space group

P \bar{3} 1 c

). Their thermodynamic properties have been investigated by means of magnetization M and [...] Read more.

GdFeTeO₆ and GdGaTeO₆ have been prepared and their structures refined by the Rietveld method. Both are superstructures of the rosiaite type (space group

P \bar{3} 1 c

). Their thermodynamic properties have been investigated by means of magnetization M and specific heat C_p measurements, evidencing the formation of the long-range antiferromagnetic order at T_N = 2.4 K in the former compound and paramagnetic behavior down to 2 K in the latter compound. Large magnetocaloric effect allows considering GdFeTeO₆ for the magnetic refrigeration at liquid hydrogen stage. Density functional theory calculations produce estimations of leading Gd–Gd, Gd–Fe and Fe–Fe interactions suggesting unique chiral 120° magnetic structure of Fe³⁺ (S = 5/2) moments and Gd³⁺ (J = 7/2) moments rotating in opposite directions (clockwise/anticlockwise) within weakly coupled layers of the rosiaite type crystal structure. Full article

(This article belongs to the Special Issue Synthesis, Structure and Properties of Metal Oxides)

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