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At least 217 records · Page 12

Thermally induced formation of 2D hexagonal BN nanoplates with tunable characteristics

We have investigated a thermally induced combustion route for preparing 2D hexagonal BN nanoplates from B{sub 2}O{sub 3}+(3+0.5k)Mg+kNH{sub 4}Cl solid system, for k=1–4 interval. Temperature–time profiles recorded by thermocouples indicated the existence of two sequential exothermic processes in the combustion wave leading to the BN nanoplates formation. The resulting BN nanoplates were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy, PL spectrometry, and Brunauer–Emmett–Teller surface area analysis. It was found that B{sub 2}O{sub 3} was converted into BN completely (by XRD) at 1450–1930 °C within tens of seconds in a single-step synthesis process. The BN prepared at a k=1–4 interval comprised well-shaped nanoplates with an average edge length ranging from 50 nm to several micrometer and thickness from 5 to 100 nm. The specific surface area of BN nanoplates was 13.7 g/m{sup 2} for k=2 and 28.4 m{sup 2}/g for k=4. - Graphical abstract: 2D hexagonal BN nanoplates with an average edge length ranging from 50 nm to several micrometer and thickness from 5 to 100 nm were prepared by combustion of B{sub 2}O{sub 3}+(3+0.5k)Mg+kNH{sub 4}Cl solid mixture in nitrogen atmosphere. - Highlights: • Thermally induced combustion route was developed for synthesizing BN nanoplates from B{sub 2}O{sub 3}. • Mg was used as reductive agent and NH{sub 4}Cl as an effective nitrogen source. • Temperature–time profiles and the combustion parameters were recorded and discussed. • BN with an average edge length from 50 nm to several micrometer and thickness from 5 to 100 nm were prepared. • Our study clarifies the formation mechanism of BN in the combustion wave.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal growth of incommensurate members of 2H-hexagonal perovskite related oxides: Ba{sub 4}M{sub z}Pt{sub 3−z}O{sub 9} (M=Co, Ni, Cu, Zn, Mg, Pt)

Millimeter sized crystals of six oxides of approximate composition Ba{sub 4}M{sub z}Pt{sub 3-z}O{sub 9} (M=Co, Ni, Cu, Zn, Mg, Pt) were grown from molten K{sub 2}CO{sub 3} fluxes and found to crystallize in a 2H hexagonal perovskite-related structure type. The compositions of these incommensurate structures, which belong to the A{sub 3n+3m}A′{sub n}B{sub 3m+n}O{sub 9m+6n} family of 2H hexagonal perovskite related oxides, were characterized by X-ray diffraction, energy dispersive spectroscopy, and magnetic susceptibility measurements. The specific synthetic considerations, crystal growth conditions, and magnetic susceptibility measurements are discussed. - Graphical abstract: SEM image and average commensurate unit cell of Ba{sub 4}Pt{sub 3}O{sub 9.} - Highlights: • Single crystals of the series Ba{sub 4}A′{sub z}Pt{sub 3-z}O{sub 9} were grown via a molten carbonate flux. • Ba{sub 4}Pt{sub 3}O{sub 9} and all substitutional variants are incommensurate, composite structures. • All compounds have an approximate stoichiometry of Ba{sub 4}A′Pt{sub 2}O{sub 9.}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantitative description of microstructure defects in hexagonal boron nitrides using X-ray diffraction analysis

A routine for simultaneous quantification of turbostratic disorder, amount of puckering and the dislocation and stacking fault density in hexagonal materials was proposed and tested on boron nitride powder samples that were synthesised using different methods. The routine allows the individual microstructure defects to be recognised according to their effect on the anisotropy of the X-ray diffraction line broadening. For quantification of the microstructure defects, the total line broadening is regarded as a linear combination of the contributions from the particular defects. The total line broadening is obtained from the line profile fitting. As testing material, graphitic boron nitride (h-BN) was employed in the form of hot-isostatically pressed h-BN, pyrolytic h-BN or a h-BN, which was chemically vapour deposited at a low temperature. The kind of the dominant microstructure defects determined from the broadening of the X-ray diffraction lines was verified by high resolution transmission electron microscopy. Their amount was attempted to be verified by alternative methods. - Highlights: • Reliable method for quantification of microstructure defects in BN was suggested. • The method is based on the analysis of anisotropic XRD line broadening. • This XRD line broadening is unique and characteristic of the respective defect. • Thus, the quantification of coexistent microstructure defects is possible. • The method was tested on hexagonal BN, which was produced by different techniques.

36 MATERIALS SCIENCE↗

Nanoscale analysis of dispersive ferroelectric domains in bulk of hexagonal multiferroic ceramics

Highlights: • Aberration corrected STEM is used to link ferroelectric properties of vacancy doped multiferroic LuMnO3 ceramics to lattice defects. • Nano-scale perturbation in lattice or chemistry provokes polarization switching or phase shift of ferroelectric domains. • Partial edge dislocations modify rule of 6 in topologically protected 6-fold vortices in hexagonal RMnO3 ceramics. • Chemistry shift/lattice distortions modify ferroelectric properties, domain size and polarization switching in multiferroic. • Change in ferroelectric properties results in modification of magnetic properties in magnetoelectric h-RMnO3 multiferroic. - Abstract: The atomic nature of topologically protected ferroelectric (FE) walls in hexagonal ReMnO{sub 3} oxides (R: Sc, Y, Er, Ho, Yb, Lu) creates an interesting playground to study effects of defects on domain walls. The 6-fold FE vortices in this multiferroic family lose the ordering by the rule of 6 in the presence of partial edge dislocations (PED) besides it can be modified by chemical doping. Therefore, it is essential to comprehend the cross coupling of FE walls and defects or vacancies in the lattice of multiferroics. Atomic resolution STEM is used to explore the correlative response of electrical polarization of FE domains in the presence of defects in multiferroic ceramics. Such level of resolution also allows the study of switching of FE domains on encounter of lattice defects. The driving force behind appearance of dispersed, small FE domains in images of piezo force microscopy is revealed by observation of lattice defects and FE boundaries simultaneously at the nano-scale. Planar defects and FE domain walls play their role of internal interfaces consequently such interplaying duly modifies the magnetic and FE properties of multiferroic oxides.

36 MATERIALS SCIENCE↗

Synthesis and anomalous magnetic properties of hexagonal CoO nanoparticles

Highlights: {yields} The as-synthesized CoO nanoparticles are of pyramid configuration with hcp structure. {yields} The hexagonal CoO particles do not exhibit antiferromagnetic transition around 300 K. {yields} The CoO particles have relative large saturation magnetization and coercivity at 5 K. {yields} The shift of hysteresis loops is consistent with the result of multisublattice model. {yields} The particles contain intrinsic antiferromagnetic structure and uncompensated spins. -- Abstract: CoO nanoparticles in the 38-93 nm range have been prepared by thermal decomposition. The particles were characterized to be pyramid shape with a hexagonal close-packed structure. Their anomalous magnetic behavior includes: (i) vanishing of antiferromagnetic transition around 300 K; (ii) creation of hysteresis below a blocking temperature of 6-11 K; (iii) presence of relatively large moments and coercivities accompany with specific loop shifts at 5 K; and (iv) appearance of an additional small peak located in low field in the electron spin resonance spectrum. Further, the present results provide evidence for the existence of uncompensated surface spins. The coercivity and exchange bias decrease with increasing particle size, indicating a distinct size effect. These observations can be explained by the multisublattice model, in which the reduced coordination of surface spins causes a fundamental change in the magnetic order throughout the total CoO particle.

36 MATERIALS SCIENCE↗

Enhancement of photocatalytic H{sub 2} evolution on hexagonal CdS by a simple calcination method under visible light irradiation

Highlights: Black-Right-Pointing-Pointer A simple calcination treatment eliminated the trap energy levels of hexagonal CdS. Black-Right-Pointing-Pointer The rate of photocatalytic H{sub 2} evolution was dramatically enhanced by 55.8 times. Black-Right-Pointing-Pointer Further improved by 6.3 times to 749 {mu}mol h{sup -1} with 0.2 wt% Pt co-catalyst. -- Abstract: An easy-handling calcination method has been used to eliminate the trap energy levels of hexagonal cadmium sulfide (CdS). The treated CdS exhibited extremely high photocatalytic activity for H{sub 2} production under visible light irradiation. The rate of photocatalytic H{sub 2} evolution has been dramatically enhanced by 55.8 times to 118 {mu}mol h{sup -1} and further improved by 6.3 times to 749 {mu}mol h{sup -1} after loading with 0.2 wt% Pt co-catalyst.

36 MATERIALS SCIENCE↗

Rapid synthesis of ordered hexagonal mesoporous silica and their incorporation with Ag nanoparticles by solution plasma

Graphical abstract: Overall reactions of mesoporous silica and AgNPs-incorporated mesoporous silica syntheses by solution plasma process (SPP). Highlights: ► SPP for rapid synthesis of mesoporous silica. ► SPP for rapid synthesis of mesoporous silica and AgNPs incorporation. ► Higher surface area and larger pore diameter of mesoporous silica synthesized by SPP. -- Abstract: Rapid synthesis of silica with ordered hexagonal mesopore arrangement was obtained using solution plasma process (SPP) by discharging the mixture of P123 triblock copolymer/TEOS in acid solution. SPP, moreover, was utilized for Ag nanoparticles (AgNPs) incorporation in silica framework as one-batch process using silver nitrate (AgNO{sub 3}) solution as precursor. The turbid silicate gel was clearly observed after discharge for 1 min and the white precipitate formed at 3 min. The mesopore with hexagonal arrangement and AgNPs were observed in mesoporous silica. Two regions of X-ray diffraction patterns (2θ < 2° and 2θ = 35–90°) corresponded to the mesoporous silica and Ag nanocrystal characteristics. Comparing with mesoporous silica prepared by a conventional sol–gel route, surface area and pore diameter of mesoporous silica prepared by solution plasma were observed to be larger. In addition, the increase in Ag loading resulted in the decrease in surface area with insignificant variation in the pore diameter of mesoporous silica. SPP could be successfully utilized not only to enhance gelation time but also to increase surface area and pore diameter of mesoporous silica.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uniform NaYF{sub 4}:Yb, Tm hexagonal submicroplates: Controlled synthesis and enhanced UV and blue upconversion luminescence

Graphical abstract: Display Omitted Highlights: ► β-NaYF{sub 4} phosphors as an excellent upconversion materials. ► Oleic acid can promote the transformation of α → β phase NaYF{sub 4}. ► The shape and size of β-NaYF{sub 4} submicroplate can be tuned by reactant concentration. ► Enhanced UV and blue peaks can be obtained by varying Yb{sup 3+} and Tm{sup 3+} concentration. -- Abstract: We reported the preparation of cubic (α-) and hexagonal (β-) NaYF{sub 4} particles in high boiling organic solvents 1-octadecene (ODE) and oleic acid (OA), through a thermal decomposition synthesis route. The as-prepared products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), photoluminescence (PL) spectra. By tuning the OA/ODE volume ratio and reactant concentration, we could manipulate the morphology, size, and crystal structure of the products. Highly uniform β-NaYF{sub 4} submicroplates were obtained from α-NaYF{sub 4} nanoparticles by increasing the OA/ODE volume ratio, while the phase kept unchanged with the increasing of reactant concentration. Upconversion emissions from UV to NIR emissions were observed in β-NaYF{sub 4} hexagonal submicroplates under 980 nm laser diode excitation. In addition, the enhanced UV and blue upconversion emissions were obtained by varying Tm{sup 3+} and Yb{sup 3+} ion concentration.

36 MATERIALS SCIENCE↗

Transition behavior of asymmetric polystyrene-b-poly(2-vinylpyridine) films: A stable hexagonally modulated layer structure

The phase transitions in the films of an asymmetric polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) were investigated by grazing incidence small-angle X-ray scattering (GISAXS) and transmission electron microscopy (TEM). Compared with the sequential transitions in the bulk, hexagonally perforated layer (HPL) – gyroid (GYR) – disorder (DIS) upon heating, the transitions in film geometry were dramatically changed with decreasing thickness due to the growing preferential interactions from substrate, resulting in a thickness-dependent transition diagram including four different morphologies of hexagonally modulated layer (HML), coexisting (HML and GYR), GYR, and DIS. Particularly in the films ≤10Lo, where Lo is d-spacing at 150 °C, a stable HML structure was identified even above the order-to-disorder transition (ODT) temperature of the bulk, which was attributed to the suppressed compositional fluctuations by the enhanced substrate interactions.

block copolymer↗

Damage buildup in multilayer hexagonal boron nitride films under Ar ion bombardment

Ion irradiation can be used to modify properties of two-dimensional hexagonal boron nitride (2D-hBN). However, the behavior of multilayer 2D-hBN under ion bombardment remains essentially unexplored. Here, in this study, we systematically study the damage buildup in 40-nm-thick multilayer 2D-hBN films irradiated at room temperature with 500 keV Ar ions with doses up to 0.64 displacements per atom. Transmission electron microscopy, soft X-ray absorption spectroscopy, and Raman spectroscopy are employed to study effects of ion irradiation. Results reveal a monotonic buildup of damage that can be described by the phenomenological zero cascade overlap model. Compared to the behavior of other group-III nitride semiconductors, radiation damage in hBN is influenced by polymorphism, involving transitions between bonding configurations of hexagonal, cubic, and amorphous phases.

Seo, M. [Lawrence Livermore National Laboratory (L↗

Long-range magnetic order and relaxor ferroelectricity in a hexagonal high-entropy ferrite

Multiferroics that combine ferroelectricity and magnetic order are attractive for electronic and spintronic technologies, yet chemical disorder that promotes relaxor ferroelectricity usually suppresses long-range magnetic order. Here, we report entropy-stabilized relaxor multiferroicity in epitaxial hexagonal (Tb0.2Dy0.2Ho0.2Lu0.2Yb0.2)FeO3 thin films. Structural, magnetic, dielectric, and synchrotron spectroscopic measurements show the coexistence of relaxor ferroelectricity and long-range ferromagnetic order. We find that improper ferroelectricity remains robust against A-site configurational disorder, while the Fe sublattice preserves magnetic exchange. This separation of the microscopic origins of the polar and magnetic responses enables chemically disordered multiferroicity. Our results establish entropy engineering in hexagonal ferrites as a route toward multifunctional oxide thin films and provide a general design strategy for high-entropy multiferroics.

Miertschin, Duncan [Baylor University]↗

Chemically Tunable Aspect Ratio Control and Laser Refrigeration of Hexagonal Sodium Yttrium Fluoride Upconverting Materials

Hexagonal sodium yttrium fluoride with Na 3x Y 2-x F 6 stoichiometry (β-NaYF) is a promising material for luminescence upconversion applications due to the narrow crystal field splitting of the Yb(III) ion’s lower 2 F 7/2 manifold. However, growing single crystals of β-NaYF remains an outstanding challenge due to thermal expansion stresses that cause cracking during melt growth. Here, we demonstrate a novel hydrothermal synthesis of β-NaYF with the ability to tune the aspect ratio from microplatelets to microrods with aspect ratios that match computationally predicted cavity (Mie) resonances. These crystals have a root-mean-square roughness below 1 nm after calcination, which makes them ideal for optical cavities. The β-NaYF microcrystals are doped with 10% Yb(III) cations and are used to build optomechanical laser-refrigeration devices consisting of a hexagonal β-NaYF crystal located at the end of a cantilever. Laser refrigeration of these devices by >12.5 °C is observed using calibrated measurements of both the cantilever’s fundamental eigenfrequency and a Boltzmann fit to crystal field luminescence from the Yb(III) ions.

36 MATERIALS SCIENCE↗

Novel Class of Rhenium Borides Based on Hexagonal Boron Networks Interconnected by Short B 2 Dumbbells

Transition metal borides are known due to their attractive mechanical, electronic, refractive, and other properties. A new class of rhenium borides was identified by synchrotron single-crystal X-ray diffraction experiments in laser-heated diamond anvil cells between 26 and 75 GPa. Recoverable to ambient conditions, compounds rhenium triboride (ReB 3 ) and rhenium tetraboride (ReB 4 ) consist of close-packed single layers of rhenium atoms alternating with boron networks built from puckered hexagonal layers, which link short bonded (~ 1.7 angstrom) axially oriented B 2 dumbbells. The short and incompressible Re-B and B-B bonds oriented along the hexagonal c-axis contribute to low axial compressibility comparable with the linear compressibility of diamond. Sub-millimeter samples of ReB 3 and ReB 4 were synthesized in a large-volume press at pressures as low as 33 GPa and used for material characterization. Crystals of both compounds are metallic and hard (Vickers hardness, H V = 34(3) GPa). Geometrical, crystal-chemical, and theoretical analysis considerations suggest that potential ReB x compounds with x > 4 can be based on the same principle of structural organization as in ReB 3 and ReB 4 and possess similar mechanical and electronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonequivalent Spin Exchanges of the Hexagonal Spin Lattice Affecting the Low-Temperature Magnetic Properties of RInO 3 (R = Gd, Tb, Dy): Importance of Spin–Orbit Coupling for Spin Exchanges between Rare-Earth Cations with Nonzero Orbital Moments

Here, rare-earth indium oxides RInO 3 (R = Gd, Tb, Dy) consist of spin-frustrated hexagonal spin lattices made up of rare-earth ions R 3+ , where R 3+ = Gd 3+ (f 7 , L = 0), Tb 3+ (f 8 , L = 3), and Dy 3+ (f 9 , L = 5). We carried out DFT calculations for RInO 3 , including on-site repulsion U with/without spin–orbit coupling (SOC), to explore if their low-temperature magnetic properties are related to the two nonequivalent nearest-neighbor (NN) spin exchanges of their hexagonal spin lattices. Our DFT + U + SOC calculations predict that the orbital moments of the Tb 3+ and Dy 3+ ions are smaller than their free-ion values by ~2μ B while the Tb 3+ spins have an inplane magnetic anisotropy, in agreement with the experiments. This suggests that the f orbitals of each R 3+ (R = Tb, Dy) ion are engaged, though weakly, in bonding with the surrounding ligand atoms. The magnetic properties of GdInO 3 with the zero orbital moment are adequately described by the spin exchanges extracted by DFT + U calculations. In describing the magnetic properties of TbInO 3 and DyInO 3 with nonzero orbital moments, however, the spin exchanges extracted by DFT + U + SOC calculations are necessary.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Relevance of the Nuclear Quantum Effects on the Proton/Deuteron Transmission through Hexagonal Boron Nitride and Graphene Monolayers

According to recent experiments, atomically thin hexagonal boron nitride and graphene are permeable to protons and deuterons (and not to other atomic species), and the experimental estimates of the activation energy are lower than the theoretical values by about 0.5 eV for the isolated proton-membrane transfer model. Our analysis of the electronic potential energy surfaces along the normal to the transmission direction, obtained using correlated electronic structure methods, suggests that the aqueous environment is essential to stabilize the proton { as opposed to the hydrogenatom { transmission. Therefore, the process is examined within a molecular model of H 2 O { H(D) + { material { H 2 O. Exact quantum-mechanical scattering calculations are performed to assess the relevance of the nuclear quantum eects, such as tunneling factors and the kinetic isotope eect (KIE). Deuteration is found to aect the thermal reaction rate constants (KIE of 3-4 for hexagonal boron nitride and 20-30 for the graphene) and to eectively lower the barriers to the proton transfer by 0.2 and 0.4 eV for the two membranes, respectively. This lowering eect is reduced for the deuteron by approximately a factor of three. A more comprehensive description of the proton transmission is likely to require an extended explicit aqueous environment.

36 MATERIALS SCIENCE↗

Photocarrier Dynamics in TlGaS 2 Nanoflakes and van der Waals Heterostructures with Hexagonal Boron Nitride and WS 2 Nanoflakes: Implications for Optoelectronic Applications

We present an experimental investigation on photocarrier dynamics in a TlGaS 2 bulk crystal and its heterostructures with hexagonal BN and WS 2 . The samples were obtained by mechanical exfoliation and dry transfer techniques. The photocarrier dynamics was monitored by a transient absorption technique. We observed a direct optical transition of about 555 nm in the TlGaS 2 crystal. By utilizing transient absorption of that transition, we obtained a hot-carrier energy relaxation time of less than 1 ps and a carrier lifetime of about 300 ps in TlGaS 2 at room temperature. In the hexagonal-BN-TlGaS 2 heterostructure, the photocarrier dynamics was similar to that in TlGaS 2 , indicating the type-I band alignment of this structure with both band extremes located in TlGaS 2 . In the monolayer WS 2 -TlGaS 2 heterostructure, we observed charge transfer from TlGaS 2 to WS 2 and an extended lifetime of the transferred carriers in WS 2 . Here, these results introduce TlGaS 2 as a promising layered material for developing two-dimensional van der Waals materials that can be combined with other two-dimensional materials for various optoelectronic devices.

36 MATERIALS SCIENCE↗

Atomistic Insights into Nucleation and Formation of Hexagonal Boron Nitride on Nickel from First-Principles-Based Reactive Molecular Dynamics Simulations

Atomistic-scale insights into the growth of a continuous, atomically thin hexagonal boron nitride (hBN) lattice from elemental boron and nitrogen on Ni substrates were obtained from multiscale modeling combining density functional theory (DFT) and reactive molecular dynamics. The quantum mechanical calculations focused on the adsorption and reaction energetics for the hBN building-block species, i.e., atomic B, N, BxNy (x, y = 1, 2), on Ni(111) and Ni(211), and the diffusion pathways of elemental B and N on these slab model surfaces and in the sublayer. B can diffuse competitively on both the surface and in the sublayer, while N diffuses strictly on the substrate surface. The DFT data were then used to generate a classical description of the Ni–B and Ni–N pair interactions within the formulation of the reactive force field, ReaxFF. Using the potential developed from this work, the elementary nucleation and growth process of an hBN monolayer structure from elemental B and N is shown at the atomistic scale. The nucleation initiates from the growth of linear BN chains, which evolve into branched and then hexagonal lattices. Subsequent DFT calculations confirmed the structure evolution energetically and validate the self-consistency of this multiscale modeling framework. On the basis of this framework, the fundamental aspects regarding crystal quality and the role of temperature and substrates used during hBN growth can also be understood.

Liu, Song↗

Pb:Sn Ratio-Driven Polytypism and Band Modulation in Photoresponsive Hexagonal Perovskitoids

Three-dimensional (3D) perovskites of the formula AMX 3 are known for their excellent optoelectronic properties, but their design is limited by the narrow range of A-site cations that can template the 3D corner-sharing structure, and many of the viable options have already been explored. These materials also face structural instability under environmental conditions. In contrast, 3D hexagonal perovskitoids, with the same chemical formula, may offer enhanced stability and richer structural diversity through a range of corner- and face-sharing octahedral configuration options, providing greater opportunities for structural design; however, challenges such as synthesis complexity and wide band gaps have hindered optoelectronic performance achieved to date. Herein, we synthesized a structural homologous series of mixed-metal hexagonal perovskitoids with the formula APb 1-x Sn x I 3 (x = 0, 0.25, 0.50, 0.75, 1; A = ethylammonium, guanidinium) and identified three polytypes (9R, 12R, 6H) using single-crystal X-ray diffraction (SCXRD). These structures exhibited increasing corner-sharing connectivity with higher Sn content, revealing a previously unobserved relationship between metal composition and structural evolution in perovskitoid materials. The incorporation of Sn reduced the band gap (tunable from 2.51 eV to 1.87 eV) and drove structural transformations, a trend seen also in density functional theory (DFT) calculations, which suggest a thermodynamic preference for Pb at face-sharing sites and Sn at corner-sharing sites. DFT band structure calculations and optical spectroscopy also reveal an anomalous behavior in these materials, which we term polytypic band modulation. This phenomenon combines conventional band bowing with the structural transformations that occur as Sn content increases, as observed in the band gap and in photoluminescence spectra. Photodiodes fabricated from thin films of these materials exhibited stable and pronounced photoresponses across various light intensities over time. Furthermore, the combination of templating 3D perovskitoids with multiple cations and alloying Pb and Sn, suggests a vastly underexplored phase space that offers new parameters to tune perovskitoids.

Cations↗