Ran Liu

AMn₇O₁₂ perovskites (with A = divalent elements) show complex structural and magnetic transitions including incommensurate orbital density waves and coupled/decoupled modulated spin helicity originating from charge-ordered Mn³⁺/Mn⁴⁺ cations with the 3:1 ratio at the B perovskite sites and unusual apically compressed Jahn–Teller distortions of MnO₆ octahedra. The same Mn³⁺:Mn⁴⁺ ratio can be achieved in RCuMn₆O₁₂ compositions, where R is a trivalent rare-earth cation. Therefore, the comparison in behavior of AMn₇O₁₂ and RCuMn₆O₁₂ is of interest. In this work, the A-site-ordered quadruple perovskite NdCuMn₆O₁₂ was prepared by a high-pressure high-temperature method. Its structural properties were investigated by synchrotron powder X-ray diffraction between 100 K and 350 K and laboratory powder X-ray diffraction between 5 K and 300 K. It shows a first-order structural phase transition from Im-3 symmetry (at high temperatures) to R-3 symmetry near 292 K. The structural transition is accompanied by charge (Mn³⁺/Mn⁴⁺) and unusual orbital (on the Jahn–Teller active Mn³⁺ cations located in MnO₆ octahedra) orders. However, no additional structural/orbital modulations were found at lower temperatures in comparison with AMn₇O₁₂. Magnetic properties were investigated by temperature- and field-dependent magnetization and specific heat measurements, where a ferrimagnetic transition was found near 120 K. In addition, low-temperature magnetic anomalies were observed near 20 K, probably originating from the Nd sublattice.

A-site-ordered quadruple perovskite manganites, AMn₇O₁₂, show many interesting physical phenomena, including orbital and spin modulations, spin-induced multiferroic properties, and competitions between different magnetic ground states. Doping with Cu²⁺ can result in colossal magnetoresistance properties, ferrimagnetism, and additional structural modulations producing electric–dipole helicoidal textures. Many previous works have focused on large-concentration doping, reaching ACu₃Mn₄O₁₂ compositions. Small-concentration doping has been investigated in a limited number of systems, e.g., in BiCu_xMn_7−xO₁₂. In this work, we investigated solid solutions of NdCu_xMn_7−xO₁₂ with x = 0.1, 0.2, and 0.3, prepared at 6 GPa and 1500 K. Specific heat measurements detected three magnetic transitions at x = 0 (at T_N3 = 9 K, T_N2 = 12 K, and T_N1 = 84 K) and two transitions at x = 0.1 (at T_N2 = 10 K and T_N1 = 78 K), while only one transition was found at x = 0.2 (T_N1 = 72 K) and x = 0.3 (T_N1 = 65 K). Differential scanning calorimetry (DSC) measurements showed sharp and strong peaks near T_OO = 664 K at x = 0, corresponding to an orbital-order (OO) structural transition from I2/m to Im-3 symmetry. DSC anomalies were significantly broadened and their intensities were significantly reduced at x = 0.1–0.3, and structural transitions were observed near T_OO = 630 K at x = 0.1, T_OO = 600 K at x = 0.2, and T_OO = 570 K at x = 0.3. The x = 0.1 sample clearly showed double-peak features on the DSC curves near T_OO because of the presence of two close phases. High-resolution synchrotron powder X-ray diffraction studies gave strong evidence that phase separation phenomena took place in the x = 0.1–0.3 samples, where two I2/m phases with an approximate ratio of 1:1 were present (e.g., a = 7.47143 Å, b = 7.36828 Å, c = 7.46210 Å, and β = 90.9929° for one phase and a = 7.46596 Å, b = 7.37257 Å, c = 7.45756 Å, and β = 90.9328° for the second phase at x = 0.3). The Curie–Weiss temperature changed from negative (for x = 0, 0.1, and 0.2) to positive (for x = 0.3). T_OO, T_N1, the Curie–Weiss temperature, and magnetization (at 5 K and 70 kOe) changed almost linearly with x.

The appearance of spin-induced ferroelectric polarization in the so-called type-II multiferroic materials has received a lot of attention. The nature and mechanisms of such polarization were intensively studied using perovskite rare-earth manganites, RMnO₃, as model systems. Later, multiferroic properties were discovered in some RFeO₃ perovskites and possibly in some RCrO₃ perovskites. However, R₂NiMnO₆ double perovskites have ferromagnetic structures that do not break the inversion symmetry. It was found recently that more complex magnetic structures are realized in A-site-ordered quadruple perovskites, RMn₃Ni₂Mn₂O₁₂. Therefore, they have the potential to be multiferroics. In this work, dielectric properties in magnetic fields up to 9 T were investigated for such perovskites as RMn₃Ni₂Mn₂O₁₂ with R = Ce to Ho and for BiMn₃Ni₂Mn₂O₁₂. The samples with R = Bi, Ce, and Nd showed no dielectric anomalies at all magnetic fields, and the dielectric constant decreases with decreasing temperature. The samples with R = Sm to Ho showed qualitatively different behavior when the dielectric constant started increasing with decreasing temperature below certain temperatures close to the magnetic ordering temperatures, T_N. This difference could suggest different magnetic ground states. The samples with R = Eu, Dy, and Ho still showed no anomalies on the dielectric constant. On the other hand, peaks emerged at T_N on the dielectric constant in the R = Sm sample from about 2 T up to the maximum available field of 9 T. The Gd sample showed peaks on dielectric constant at T_N between about 1 T and 7 T. Transition temperatures increase with increasing magnetic fields for R = Sm and decrease for R = Gd. These findings suggest the presence of magnetic-field-induced multiferroic states in the R = Sm and Gd samples with intermediate ionic radii. Dielectric properties at different magnetic fields are also reported for Lu₂NiMnO₆ for comparison.

ABO₃ perovskite materials with small cations at the A site, especially with ordered cation arrangements, have attracted a lot of interest because they show unusual physical properties and deviations from general perovskite tendencies. In this work, A-site-ordered quadruple perovskites, RMn₃Ni₂Mn₂O₁₂ with R = Nd, Sm, Gd, and Dy, were synthesized by a high-pressure, high-temperature method at about 6 GPa. Annealing at about 1500 K produced samples with additional (partial) B-site ordering of Ni²⁺ and Mn⁴⁺ cations, crystallizing in space group Pn–3. Annealing at about 1700 K produced samples with disordering of Ni²⁺ and Mn⁴⁺ cations, crystallizing in space group Im–3. However, magnetic properties were nearly identical for the Pn–3 and Im–3 modifications in comparison with ferromagnetic double perovskites R₂NiMnO₆, where the degree of Ni²⁺ and Mn⁴⁺ ordering has significant effects on magnetic properties. In RMn₃Ni₂Mn₂O₁₂, one magnetic transition was found at 26 K (for R = Nd), 23 K (for R = Sm), and 22 K (for R = Gd), and two transitions were found at 10 K and 36 K for R = Dy. Curie–Weiss temperatures were close to zero in all compounds, suggesting that antiferromagnetic and ferromagnetic interactions are of the same magnitude.

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).

Ag sinter paste joining as a proven die bonding technology have been used in the electric vehicle. However, for the Ag sinter paste joining, metallization layers on substrate are usually necessary such as Ni-P/Au or Ni-P/Ag to get a good bonding quality. The direct bonding on DBC (direct bonded copper) or DBA (Direct Bonded Aluminum) substrates without metallization layers are very attractive. In this study, we investigated the direct bonding on an aluminum (Al) substrate by Ag sinter paste and propose an abrasive blasting processes to treat the Al surface to increase the initial bonding quality. The result show that the shear strength of SiC/Al joint structure by Ag sinter paste can be improved by treating the Al surface. The shear strength of joint structure without surface treatment increased from 26.9 MPa to 32.2 MPa for a strong blasting treatment on Al surface. In addition, the results of thermal shock test (-40 ℃~150℃) also show that the blasting treatment on Al surface can improve the shear strength and reliability of SiC/Al joint structure.

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.