arXiv subjects

Tyrel M. McQueen

Publications and source records attributed to Tyrel M. McQueen.

At least 19 recordsLinked to original sources

arXiv2026

Scandium diboride: a semi-metallic, lattice, thermally matched substrate for vertical AlGaN power electronics

We report the properties of hexagonal (space group P6/mmm) scandium diboride ($\mathrm{ScB}_2$) single crystals grown by a laser diode floating zone method at growth rates of ~1mm/hr under B-rich conditions with (002) rocking curve widths $Δω$=38'' approaching the quality of commercial SiC/GaN substrates. Lattice expansion measurements reveal matching to $\mathrm{Al_{0.55}Ga_{0.45}N}$ with a coefficient of thermal expansion ~5ppm/K at typical AlGaN growth temperatures, enabling thick AlGaN layers for ultra-wide bandgap (UWBG) power electronics >1kV. We measure semi-metallic room temperature resistivity ~15$μΩ$ cm, climbing to ~93$μΩ$ cm at 773K with a $T^2$ dependence effectively eliminating substrate parasitic resistance, the limiting factor in exploiting the full potential of UWBG. The Debye temperature $θ_{D,ScB_2}$ from heat capacity and lattice expansion is ~850K well matched to $θ_{D,ScB_2}$, but lower than the 1100K measured for Sc-rich growth conditions. We discuss Debye matching as a key substrate codesign criterion providing significant overlap in phonon modes for heat removal and thermal matching during AlGaN growth. The competitive thermal conductivity at room temperature 53W/mK is half that from full first principles calculations, a discrepancy we attribute to the presence of Sc-vacancies generated by B-rich growth. while the resistivity is ~2x the theoretical value, indicating that both electrons and phonons play equal role in thermal transport. The smooth ~2.5nm rms roughness surface enables advanced heat removal modalities through engineered phonon bridges and phonon polaritons in $\mathrm{ScB}_2$/AlGaN interfacial heterostructures, potentially allowing ~10-100x increase in power handling over state-of-the-art GaN/SiC.

cond-mat.mtrl-sci↗

arXiv2026

Hysteresis without coexistence: disorder-rounded first-order transitions in a van der Waals magnet

Quenched disorder can profoundly modify phase transitions. In low-dimensional systems, theory predicts that even weak quenched disorder can round the thermodynamic discontinuities associated with a first-order phase transition. Here, we employ time-domain terahertz spectroscopy to investigate the quasi-two-dimensional trimerized kagome van der Waals magnet family Nb$_3$Cl$_{8-x}$Br$_x$ ($x=0$, 1 and 8). We observe the emergence of an additional phonon branch upon Br substitution, whose spectral weight increases and frequency softens with increasing Br concentration. The temperature evolution of the phonon frequencies reveals a clean first-order transition in Nb$_3$Cl$_8$ characterized by macroscopic phase coexistence and thermal hysteresis. In contrast, the transition in the substitutionally disordered compound Nb$_3$Cl$_7$Br retains its hysteresis while exhibiting a substantially broadened transition with no resolvable macroscopic phase coexistence. These observations reveal disorder-induced fragmentation of the transition into locally favored domains instead of well-defined bulk phases separated by stable phase boundaries. The behavior is consistent with the Imry-Wortis and the Aizenman-Wehr scenarios for the effect of quenched disorder in low-dimensional systems, which destabilizes macroscopic phase coexistence and rounds the thermodynamic discontinuities associated with first-order transitions. Thermal hysteresis persists in the disordered compound despite the lack of resolvable coexistence, indicating that the two features often treated as a single hallmark of first-order character arise distinctly and can be separated by disorder. Moreover, our results establish Nb$_3$Cl$_{8-x}$Br$_x$ as a promising platform for investigating the effects of disorder on first-order transitions in low-dimensional systems.

cond-mat.str-el↗

arXiv2026

Human and LLM Collaboration for Accelerated Materials Synthesis and Discovery

Although Large Language Models (LLM) and Artificial Intelligence (AI) tools have enabled a rapid increase in the generation rate of predicted materials, the rate of new materials discovery has lagged behind. This is due to the challenges associated with designing a sequence of chemical reactions to predictably produce new materials, especially in new structure types. Here, we report a study of human and LLM generated recipes for the synthesis of known and new materials. The success of the recipes is determined through in-lab experimentation, and the results are passed back to the humans and LLMs in a closed-loop process to study the effects of their collaboration. The Ruddlesden-Popper homologous series was selected for all material candidates to provide a materials phase space that is simultaneously well studied and likely to host undiscovered materials. We find that humans (H) and LLM (L) have similar success rates: 83(8)% (H) and 75(9)% (L) [known materials, round one], 17(9)% (H) and 22(10)% (L) [unknown materials, round one], 79(8)% (H) and 71(9)% (L) [known materials, round two], and 22(7)% (H) and 14(6)% (L) [unknown materials, round two]. Through this collaborative human-LLM effort, we discovered Ba3PtO5, a material with a new structural prototype that constitutes the missing 1D member of the herein reported dimensionally tunable Rock-Salt Perovskite (RSP) homologous series of the form (AX)m(ABX3)p, of which the Ruddlesden-Popper series is a subset.

cond-mat.mtrl-sci↗

arXiv2026

Crystal growth and characterization of the ultra-high temperature substrate $\mathrm{Ta_{1-x}Hf_{x}C_{0.5}}$

Incorporation of $\mathrm{Al_{y}Ga_{1-y}N}$ (AGN) semiconductors into high power electronics offers efficiency improvements in power transmission, generation, and use, if approaches to eliminate the defects arising from film-lattice mismatch can be established. Here, we report the optical floating zone crystal growth of $\mathrm{Ta_{1-x}Hf_{x}C_{0.5}}$ (x = 0.2), a new metallic substrate material family lattice matched to the ultra-wide-band-gap, Al-rich side (y = 0.91) of the AGN solid solution. Laue diffraction demonstrates large single crystal domains in the as-grown boule. Single crystal x-ray diffraction at T = 213 K in conjunction with first principles calculations shows that the material adopts a layered crystal structure with AA-type stacking of (Ta/Hf)-C-(Ta/Hf) trilayers described in the trigonal space group P-3m1 (#164), with a = 3.1168(4) Å, c = 4.9644(4) Å, and $β$ = 120.0°. X-ray photoelectron spectroscopy (XPS) measurements show the Hf:Ta ratio to be close to the nominal value of 0.8:0.2 in the grown crystal. Density Functional Theory calculations reveal that this structure is stabilized by the low energy of carbon-vacancy formation of a hypothetical $\mathrm{(Ta/Hf)_{1}C_{1}}$ anti-NiAs structure type, and imply flexibility in interface structure with an overlayer nitride film. A surface preparation/polishing procedure is developed that reduces root mean square (RMS) surface roughness from as-cut 130 nm to 7 nm as measured by atomic force microscopy. Scanning electron microscopy shows the presence of a native surface oxide, removed by polishing, along with carbon-rich pits. Time-domain thermoreflectance measurements show a room temperature thermal conductivity of $κ$ = 18.1(4) W m-1 K-1. These results provide key first steps for utilizing metallic, lattice matched, substrates for the growth of Al-rich AGN semiconductors.

cond-mat.mtrl-sci↗

arXiv2026

Stripping Symmetry: Electrochemical Oxidation to a Superconducting Polar Metal in Au2Pb0.914P2

Polar metals and noncentrosymmetric superconductors are exceptionally rare, yet their broken inversion symmetry can give rise to emergent electronic phenomena including mixed singlet-triplet superconducting pairing. As only a few such materials have been found among known compounds, accessing new examples requires synthetic strategies that go beyond conventional crystal growth. Here, we use electrochemical topotactic deintercalation to remove Pb from the centrosymmetric parent compound Au$_2$PbP$_2$, producing the polar metal Au$_2$Pb$_{0.914}$P$_2$. Unlike conventional chemical doping, this transformation actively drives structural symmetry-breaking: the partial removal of Pb triggers a cooperative electronic and geometric rearrangement, mediated by a second-order Jahn-Teller effect and stereochemically active lone pairs, that locks the product into a polar, noncentrosymmetric superspace group Ama2(01g)ss0. We solve the complete (3+1)D modulated structure by synchrotron single-crystal X-ray diffraction and confirm the polar assignment through nonlinear electronic transport. Below T$_c$ = 1.52 K, Au$_2$Pb$_{0.914}$P$_2$ becomes a type-II superconductor whose heat capacity and AC susceptibility both exhibit power-law behavior, suggestive of a gap structure governed by the broken inversion symmetry of the host lattice. This work establishes electrochemical oxidation as a rational route to metastable noncentrosymmetric superconductors through chemically directed symmetry-breaking.

cond-mat.supr-con↗

arXiv2026

K$_2$Co$_2$(TeO$_{3}$)$_{3}$ $\cdot$ 2.5 H$_2$O : A mineral-inspired pseudo-honeycomb cobalt dimer antiferromagnet

In recent years, magnetically-frustrated triangular and honeycomb lattice cobaltates have seen extensive study in the pursuit of a quantum spin liquid (QSL) state in a real material. In this work, we describe the hydroflux synthesis of K$_2$Co$_2$(TeO$_{3}$)$_{3}$ $\cdot$ 2.5 H$_2$O (KCoTOH), a novel zemannite-type antiferromagnet (AFM) possessing structural elements of both triangular dimer and honeycomb structural motifs. Bulk magnetometry and specific heat data support the onset of long-range AFM order below $T_\text{N}$ = 7.6(1) K, with neutron diffraction and muon spin relaxation ($μ$SR) measurements placing the majority of the ordered moment within the pseudo-honeycomb plane. We resolve three unique oscillation frequencies from the zero-field $μ$SR spectra, additionally suggesting a remarkably low level of structural disorder in as-grown KCoTOH crystals. Whereas interactions between dimerized chains of Co$^{2+}$ cations are typically observed to be negligible or ferromagnetic in nature, the largely planar ordering motif observed in KCoTOH is instead stabilized by net antiferromagnetic interactions through bridging tellurite groups. This work highlights the potential of hydroflux synthesis methods in the stabilization of magnetic materials possessing novel and potentially more frustrated lattice geometries.

cond-mat.str-el↗

arXiv2026

Hydroflux Crystal Growth of Alkali Tellurate Oxide-Hydroxides

This study investigates the synthesis of novel magnetic materials via hydroflux synthesis, a method that combines flux-based and hydrothermal techniques. Single crystals of three novel alkali tellurate oxide hydroxides were synthesized. One, CsTeO3(OH), is nonmagnetic and a new member of the series ATeO3(OH) (A = alkali). The other two phases contain magnetic Cu-Te substructures, one of which, KCu2Te3O8(OH), is structurally three-dimensional and undergoes several magnetic ordering transitions. The other, Cs2Cu3Te2O10, is structurally two-dimensional and remains paramagnetic above T = 2 K. These exploratory investigations of novel phase spaces reveal key factors, including hydroxide concentration, precursor solubility, and oxidizing power of the solution, in the formation and composition of alkali tellurate oxide hydroxides.

cond-mat.mtrl-sci↗

arXiv2025

Driving the field-free Josephson diode effect using Kagome Mott insulator barriers

Josephson junctions (JJs), devices consisting of two superconductors separated by a barrier, are of great technological importance, being a cornerstone of quantum information processing. Classical understanding of superconductor-insulator-superconductor JJs is that conventional insulator's properties, other than magnetism, do not significantly influence the junction's behavior. However, recent work on quantum material (QM) JJs - using Mott insulator Nb3Br8 - resulted in magnetic field-free non-reciprocal superconductivity, termed the Josephson diode effect (JDE), implying the QM's intrinsic properties can modulate superconductivity in non-trivial ways. To date, the underlying mechanism and dependence of the JDE on correlation strength (U/t) has not been elucidated. Here we fabricate QMJJs using correlated Kagome insulators with varying U/t, Nb3X8 (X=Cl, Br, I), observing a decreasing trend of the field-free JDE with Nb3Cl8 reaching ~48% efficiency, Nb3Br8 ~6%, and Nb3I8 having no discernible JDE, matching the trend of decreasing U/t from Cl to I and suggesting correlation in insulators drives the field-free JDE.

cond-mat.supr-con↗

arXiv2025

The superconducting diode effect in Josephson junctions fabricated from structurally chiral Mo$_3$Al$_2$C

The superconducting diode effect occurs in superconducting materials in which both spin and inversion symmetry are broken. The recently observed chirality-induced spin selectivity effect demonstrates that chiral materials break both symmetries. Thus a Josephson junction interface with the left-handed structure on one side of the junction and the right-handed structure on the other should exhibit a diode effect. Here, we report the electrical transport properties of right-handed/left-handed and right-handed/right-handed devices fabricated from single crystals of the structurally chiral superconductor Mo$_3$Al$_2$C. Fraunhofer-like magnetic diffraction patterns confirm the presence of Josephson effect in all but one of our devices. A magnetic field-induced superconducting diode effect is demonstrated in the right-handed/left-handed devices by a statistically significant difference in $I_{c+}$ and $I_{c-}$, with a maximum asymmetry of 5\%. The intrinsic superconducting diode effect is not observed in the right-handed/right-handed devices. We provide an explanation for the presence of the superconducting diode effect in the right-handed/left-handed devices.

cond-mat.supr-con↗

arXiv2025

Atomically Modulating Competing Exchange Interactions in Centrosymmetric Skyrmion Hosts GdRu2X2 (X = Si, Ge)

Magnetic skyrmions are topologically protected spin states enabling high-density, low-power spin electronics. Despite growing efforts to find new skyrmion host systems, the microscopic mechanisms leading to skyrmion phase transitions at specific temperatures and magnetic fields remain elusive. Here, we systematically study the isostructural centrosymmetric magnets- GdRu2X2 (X = Si and Ge), and the role of X-p orbitals in modifying magnetic exchange interactions. GdRu2Ge2 single crystals, synthesized by arc melting, exhibit two high-entropy pockets associated with skyrmion phases at 0.9 T < H < 1.2 T and 1.3 T < H < 1.7 T, 2 K < T < 30 K-more accessible condition at lower fields and higher temperatures than that in the Si counterpart. Entropy estimations from heat capacity measurements align with magnetization data, and transport studies confirm a topological Hall effect, highlighting the system's nontrivial spin textures and Berry curvature. Compared to GdRu2Si2, electronic structure and exchange interaction evaluations reveal the more extended Ge-4p orbitals enhance competing exchange interactions in GdRu2Ge2, thereby manifesting the rich skyrmion behavior. This work demonstrates how modifying exchange interactions at the atomic level enables the tunability of topologically nontrivial electronic states while advancing our understanding of skyrmion formation mechanisms for future spintronics.

cond-mat.mtrl-sci↗

arXiv2025

A Crystallographic Metric for Continuous Quantification of Unit Cell Deformation

Describing the deviation of a real structure from a hypothetical higher-symmetry ideal can be a powerful tool to understand and interpret phase transitions. Here we introduce a simple yet effective metric that quantifies the degree of unit cell distortion relative to a cube, called the cubic deviation metric. This enables continuous comparisons between unit cells of different geometries. We demonstrate the potential of this tool with four separate case study applications to real material systems: 1) discontinuous structural phase transitions in pseudobrookites; 2) homological structure classification; 3) structure-correlated piezoelectricity in hexagonal materials; and 4) superconducting materials design in the cuprate family. Although this metric does not replace detailed structural or group theory analysis, it enables comparison across different compositional and structural compound variants, even in the presence of disorder or absence of group-subgroup correlation.

cond-mat.mtrl-sci↗

arXiv2025

Real-space orbital tiling approach for the design of novel superconductors

Despite substantial advances in the field, we still lack a predictive framework capable of guiding the discovery of new families of superconductors. While momentum-space approaches have advanced the microscopic understanding of superconductivity, they offer limited guidance for materials design based on atomic building blocks. Here, we propose a real-space framework which conceptualizes Cooper pairs as confined standing waves resulting from coherent tilings of atomic orbitals. We call this model the Real-space Orbital Superconducting Pathway (ROSP). Using a tight-binding toy model, we show that the energetics of electron pairing depend on the configuration and overlap of real-space orbitals, which motivates \textit{a priori} design of superconducting families from orbital tiling. We connect the ROSP model to Roald Hoffmann's isolobal analogy to classify families of superconductors based on shared orbital tilings, rather than structure or electron count. As an example, we suggest that superconductivity in La$_{3}$Ni$_{2}$O$_{7}$ and LaNiO$_{2}$, despite differing structures and electron counts, may arise from a common ROSP. We introduce a new notation to classify two-dimensional square-net ROSPs and further propose several new families of superconductors on the anti-cuprate lattice. This framework provides a new model for predicting and designing families of high-T$_c$ superconductors from real-space orbital architecture, even without microscopic knowledge of the attractive pairing interaction.

cond-mat.supr-con↗

arXiv2025

Growth of hexagonal BN crystals by traveling-solvent floating zone

Large, high-purity single-crystals of hexagonal BN (h-BN) are essential for exploiting its many desirable and interesting properties. Here, we demonstrate via X-ray tomography, X-ray diffraction and scanning electron microscopy that h-BN crystals can be grown by traveling-solvent floating-zone (TSFZ). The diameters of grown boules range from 3 - 5 mm with lengths from 2 - 10 mm. Tomography indicates variable grain sizes within the boules, with the largest having areas of $\approx$ 1 mm $\times$ 2 mm and thickness $\approx$ 0.5 mm. Although the boules contain macroscale flux inclusions, the h-BN lattice itself is of high quality for samples grown under optimized conditions. The currently optimized growth procedure employs an Fe flux, moderate N$_2$ pressure ($P_{N2} \approx$ 6 bar), and a growth rate of 0.1 mm/h. Raman spectroscopy for an optimized sample gives an average linewidth of 7.7(2) cm$^{-1}$ for the E$_{\mathrm{2g}}$ intralayer mode at 1365.46(4) cm$^{-1}$ and 1.0(1) cm$^{-1}$ for the E$_{\mathrm{2g}}$ interlayer shear mode at 51.78(9) cm$^{-1}$. The corresponding photoluminescence spectrum shows sharp phonon-assisted free exciton peaks and minimal signal in the energy range corresponding to carbon-related defects ($E$ = 3.9 4.1 eV). Our work demonstrates the viability of growing h-BN by the TSFZ technique, thereby opening a new route towards larger, high-quality crystals and advancing the state of h-BN related research.

cond-mat.mtrl-sci↗

arXiv2025

Symmetry-mediated quantum coherence of $W^{5+}$ spins in an oxygen-deficient double perovskite

Elucidating the factors limiting quantum coherence in real materials is essential to the development of quantum technologies. Here we report a strategic approach to determine the effect of lattice dynamics on spin coherence lifetimes using oxygen deficient double perovskites as host materials. In addition to obtaining millisecond $T_1$ spin-lattice lifetimes at T ~ 10 K, measurable quantum superpositions were observed up to room temperature. We determine that $T_2$ enhancement in $Sr_2CaWO_{6-δ}$ over previously studied $Ba_2CaWO_{6-δ}$ is caused by a dynamically-driven increase in effective site symmetry around the dominant paramagnetic site, assigned as $W^{5+}$ via electron paramagnetic resonance spectroscopy. Further, a combination of experimental and computational techniques enabled quantification of the relative strength of spin-phonon coupling of each phonon mode. This analysis demonstrates the effect of thermodynamics and site symmetry on the spin lifetimes of $W^{5+}$ paramagnetic defects, an important step in the process of reducing decoherence to produce longer-lived qubits.

cond-mat.mtrl-sci↗

arXiv2024

Bonding Interactions Can Drive Topological Phase Transitions in a Zintl Antiferromagnetic Insulator

While $\sim$30% of materials are reported to be topological, topological insulators are rare. Magnetic topological insulators (MTI) are even harder to find. Identifying crystallographic features that can host the coexistence of a topological insulating phase with magnetic order is vital for finding intrinsic MTI materials. Thus far, most materials that are investigated for the determination of an MTI are some combination of known topological insulators with a magnetic ion such as MnBi$_2$Te$_4$. Motivated by the recent success of EuIn$_{2}$As$_{2}$, we investigate the role of chemical pressure on topologically trivial insulator, Eu$_5$In$_2$Sb$_6$ via Ga substitution. Eu$_5$Ga$_2$Sb$_6$ is predicted to be topological but is synthetically difficult to stabilize. We look into the intermediate compositions between Eu$_5$In$_2$Sb$_6$ and Eu$_5$Ga$_2$Sb$_6$ through theoretical works to explore a topological phase transition and band inversion mechanism. We attribute the band inversion mechanism to changes in Eu-Sb hybridization as Ga is substituted for In due to chemical pressure. We also synthesize Eu$_{5}$In$_{4/3}$Ga$_{2/3}$Sb$_{6}$, the highest Ga concentration in Eu$_{5}$In$_{2-x}$Ga$_{x}$Sb$_{6}$, and report the thermodynamic, magnetic, transport, and Hall properties. Overall, our work paints a picture of a possible MTI via band engineering and explains why Eu-based Zintl compounds are suitable for the co-existence of magnetism and topology.

cond-mat.mtrl-sci↗

arXiv2024

Anomalous electronic energy relaxation and soft phonons in the Dirac semimetal Cd$_3$As$_2$

We have used a combination of linear response time-domain THz spectroscopy (TDTS) and high-field non-linear THz spectroscopy to separately probe the electronic momentum and energy relaxation rates respectively of the Dirac semimetal Cd$_3$As$_2$. We find, consistent with prior measurements, that Cd$_3$As$_2$ has an enormous nonlinearities in the THz frequency range. We extract the momentum relaxation rate of Cd$_3$As$_2$ using Drude fits to the optical conductivity. We also conduct THz range 2D coherent spectroscopy. The dominant response is a pump-probe signal, which allow us to separately extract the energy relaxation rate. We find that the rate of energy relaxation decreases down to the lowest measured temperatures. We connect this to Cd$_3$As$_2$ anomalous lattice dynamics, evidence for which is found in its low thermal conductivity and soft phonons in Raman scattering. The lack of a peak in the energy relaxation rate as a function of T can be connected to the linear in T dependence of the current relaxation e.g. the phonon scattering is elastic down to the lowest measured temperatures approximately 120 K.

cond-mat.str-el↗

arXiv2024

SiO$_2$-mediated facile hydrothermal synthesis of spiroffite-type Co$_2$Te$_3$O$_8$

The hydrothermal synthesis of novel materials typically relies on both knowledge of the redox activities of all cations present in the reaction solution and a small toolset of so-called mineralizers to tune the solution's overall chemical potential. Upon the use of a less conventional mineralizer species, SiO$_2$, we show the stabilization of spiroffite-type Co$_2$Te$_3$O$_8$ under less forceful hydrothermal conditions than in previous reports. When synthesized in the presence of both SiO$_2$ and each respective alkali carbonate as a secondary mineralizer, silicon substitution in place of tellurium in the host structure becomes apparent, and the corresponding introduced disorder gives rise to enhanced low-temperature ferromagnetism. Our results highlight the complexities of underutilized and combined mineralizer species in the stabilization and tuning of complex magnetic ground states via hydrothermal synthesis techniques.

cond-mat.mtrl-sci↗

arXiv2024

Unmasking charge transfer in the Misfits: ARPES and ab initio prediction of electronic structure in layered incommensurate systems without artificial strain

Common belief is that the large band shifts observed in incommensurate misfit compounds, e.g. (LaSe)1.14(NbSe2)2, are due to interlayer charge transfer. In contrast, our analysis, based on both ARPES measurements and a specialized ab initio framework employing only quantities well defined in incommensurate materials, demonstrates that the large band shifts instead reflect changes in valence band hybridization and interlayer bonding. The strong alignment of our ab initio predictions and ARPES measurements confirms our understanding of the incommensurate electronic structure and charge transfer.

cond-mat.mtrl-sci↗