arXiv subjects

Daniel R. Gamelin

Publications and source records attributed to Daniel R. Gamelin.

At least 19 recordsLinked to original sources

arXiv2026

Synthesis of the Elusive Bulk Iodide Double-Perovskite Semiconductor, Cs2AgBiI6: Microcrystals and Photoconductive Films

Three-dimensional (3D) iodide double-perovskite (elpasolite) semiconductors have attracted interest as potential lead-free metal-halide absorber layers for solar applications. Although studied extensively by computational methods, they have remained largely inaccessible synthetically, consistent with their predicted thermodynamic instability. Here, we report the first synthesis of bulk Cs2AgBiI6, demonstrating both microcrystalline and thin-film forms. Microcrystalline powders of Cs2AgBiI6 were prepared via anion exchange from phase-pure Cs2AgBiBr6 microcrystals. The resulting iodide elpasolite shows broad absorption throughout the visible with a 1.70 +/- 0.05 eV optical bandgap and near-infrared photoluminescence centered at 1.03 eV. We identify the elimination of trace moisture in bulk Cs2AgBiBr6 as the critical factor enabling complete halide exchange and isolation of bulk Cs2AgBiI6 with phase purity. In inert atmosphere, microcrystalline Cs2AgBiI6 shows no decomposition when stored for months at room temperature or heated to ~70 °C, and it appears equally stable in dry air. Building upon these insights, we then demonstrate the preparation of phase-pure Cs2AgBiI6 films by flash thermal evaporation of Cs2AgBiBr6 followed by anion exchange. Photoconductivity measurements on such Cs2AgBiI6 films demonstrate photocarrier generation and transport, marking the first optoelectronic measurement on this elusive 3D iodide double perovskite.

cond-mat.mtrl-sci↗

arXiv2026

Photon Statistics from Yb3+-Doped CsPbCl3 are Inconsistent with Quantum Cutting

CsPb(Cl1-xBrx)3:Yb3+ has been widely reported as a broadband quantum-cutting material with a photoluminescence quantum yield exceeding 100%, making it a promising candidate for enhancing the blue-green spectral response of silicon photovoltaics. Many groups have reproduced absolute photoluminescence quantum yields over 100%, but others have struggled to obtain such high values. Here, we test the quantum-cutting capabilities of CsPbCl3:Yb3+ nanocrystals and bulk material using photon-correlation analysis. A quantum-cutting material is expected to exhibit photon bunching, but our experiments on CsPbCl3:Yb3+ show no such behavior. In fact, we observe the opposite -- anti-bunching -- under focused-excitation conditions. This observation can be explained with the previously established Auger-quenching pathway in CsPbCl3:Yb3+. Our results thus confirm high-power Auger quenching but question earlier descriptions of quantum cutting in CsPb(Cl1-xBrx)3:Yb3+.

cond-mat.mtrl-sci↗

arXiv2026

The Impact of Magnons, Defects, and Rapid Energy Migration on the Optical Properties of the 2D Magnet CrPS4

Strong coupling between optical and magnetic excitations could enable contactless, spatially resolved, or ultrafast interrogation and control of magnetism in two-dimensional (2D) materials and devices. The layered 2D A-type antiferromagnet CrPS4 stands out among van der Waals (vdW) magnets for its rich optical fine structure, but its spectroscopy is not yet understood and has so far been interpreted without consideration of magnetic exchange. Here, we show that this fine structure comes primarily from exchange-mediated coupling between on-site optical "spin-flip" transitions of Cr3+ and low-energy spin transitions involving the surrounding lattice. Well-resolved magnon sidebands to optical 4A2 <--> 2E transitions are observed in photoluminescence (PL) and PL excitation spectra, as well as a pronounced PL sideband due to short-range exchange splitting. Energy migration is probed using Yb3+ dopants as traps, revealing sub-picosecond inter-site excitation hopping. Formation of dispersive Frenkel excitons of coupled on-site d-d transitions due to inter-site exchange is discussed. In addition to impacting how optical fine structure is interpreted in this and potentially other vdW magnets, these findings may have ramifications for future applications of layered 2D magnets by revealing new opportunities to drive mode-specific spin-wave excitations using light.

cond-mat.mtrl-sci↗

arXiv2025

Hydrothermal Synthesis of Ultra-high Aspect Ratio $β$-NaYF Disks via Methyliminodiacetic Acid (MIDA)

The hexagonal $β$-phase of sodium yttrium fluoride (NaYF) is a leading host material for lanthanide upconversion and anti-Stokes fluorescence laser refrigeration based on its low phonon energies and high upconversion efficiency. Recently experiments have been proposed to use this material as an optically-levitated sensor of high-frequency gravitational waves. In order to maximize signal-to-noise in this experiment, the NaYF sensor must have both a two-dimensional, disk-like morphology and also a large mass. Here we report a novel hydrothermal process based on the chelation ligand methylimidodiacetic acid (MIDA) to realize hexagonal $β$-NaYF prisms with corner-to-corner diameters up to 44 $\mathrm{μm}$ while keeping the height around 1 $\mathrm{μm}$. The surface quality is comparable to particles synthesized with EDTA based on atomic force microscopy (AFM) measurements. Unlike particles synthesized with EDTA the $β$-NaYF particles show no lensing based on curvature of the hexagonal basal plane. Single crystal X-ray diffraction data were refined to the P-62c (#190) space group which to the best of our knowledge has not been reported in the literature. One of six 44 $\mathrm{μm}$ $β$-NaYF disks doped with 10% ytterbium showed laser refrigeration of ($-4.9 \pm 1.0$) K suggesting future applications in both levitated optomechanics and microoptics.

cond-mat.mtrl-sci↗

arXiv2025

Optical Spin Sensing and Metamagnetic Phase Control in the 2D Van der Waals Magnet Yb3+-Doped CrPS4

The emergence of two-dimensional magnets within the van der Waals toolkit has introduced unprecedented opportunities to develop ultrathin spintronic technologies. Strong coupling between spin and optical properties in such materials can further enable novel spin-photonic capabilities of both fundamental and technological interest. Here, we investigate the optical and spin properties of the air-stable, layered A-type antiferromagnet chromium thiophosphate (CrPS4) when doped with Yb3+. We show that the collective spin properties of CrPS4 are encoded in the sharp f-f luminescence of isolated Yb3+ dopants via strong magnetic superexchange coupling between the two, and that spontaneous magnetic ordering in CrPS4 induces large exchange splittings in the narrow Yb3+ f-f photoluminescence features below TN. Spin reorientation in CrPS4 via a "spin-flop" metamagnetic transition modulates the Yb3+ f-f luminescence energies and exchange splittings. This pronounced link between spin and optical properties enables the demonstration of optically driven spin-flop transitions in CrPS4.

cond-mat.mtrl-sci↗

arXiv2025

Exciton Annihilation by Lanthanide Dopants: An Atomic Probe of Sub-Diffraction Exciton Diffusion in Ferromagnetic CrI3

Excitons in two-dimensional (2D) magnetic van der Waals (vdW) materials offer unique windows into the properties of strongly correlated electrons. Their generation can be used to drive magnetic phase transitions, manipulate spins coherently, or access novel non-equilibrium regimes. Despite extensive investigation into the spin physics of CrI3, exciton dynamics in this archetypal magnetic 2D material remain underexplored. Here, we report the use of Yb3+ impurity point defects as exciton annihilators to probe exciton diffusion in CrI3. Variable-temperature photoluminescence (PL) measurements for a series of x% Yb3+:CrI3 samples reveal thermally activated Dexter-type site-to-site hopping of excitons, with low exciton diffusivity associated with strong electron-nuclear coupling. Using Monte Carlo modeling calibrated by the experimental data, diffusivities are found to be orders of magnitudes lower than in 2D vdW semiconductors. Exciton diffusion lengths (LD) are below ~3 nm at all temperatures, and thus well below the optical diffraction limit. These results have basic implications for the use of excitons to probe and manipulate their surroundings in this and related magnetic CrX3 materials.

cond-mat.mtrl-sci↗

arXiv2024

Optically Resolved Exchange Splittings in the Doped Van der Waals Ferromagnet CrBr3:Yb3+

The chromium-trihalides (CrX3; X = Cl, Br, I) have long served as model systems for understanding magnetism and magneto-optics in ionic crystals, and they have recently also emerged as archetypes of magnetic two-dimensional (2D) Van der Waals materials. Although the physical properties of CrX3 compounds have now been explored in great depth, the use of impurity doping to generate new properties remains surprisingly underexplored. Here we report on the magnetic and magneto-optical properties of lanthanide-doped CrBr3, in which Yb3+ is introduced as a spin-bearing optical point defect. Narrow-line near-infrared dopant photoluminescence is efficiently sensitized by CrBr3-to-Yb3+ energy transfer. Magneto-optical measurements show facile spin manipulation of the paramagnetic Yb3+ impurities by the surrounding CrBr3 lattice. Photoluminescence data reveal that the Kramers spin degeneracies of the ground- and excited-state Yb3+ doublets are spontaneously lifted by strong magnetic exchange with neighboring Cr3+ ions, such that individual Yb3+ spin transitions are easily resolved even at zero external magnetic field. The temperature and field dependence of these splittings can be used to probe both local and long-range spin correlations. These results highlight the use of extrinsic optical impurities to add new spin-photonic functionality to this classic 2D Van der Waals magnet.

cond-mat.mtrl-sci↗

arXiv2023

Structure and Stability of the Iodide Elpasolite, Cs2AgBiI6

Iodide elpasolites (or double perovskites, A2B'B"I6, B' = M+, B" = M3+) are predicted to be promising alternatives to lead-based perovskite semiconductors for photovoltaic and optoelectronic applications, but no iodide elpasolite has ever been definitively prepared or structurally characterized. Iodide elpasolites are widely predicted to be unstable due to favorable decomposition to the competing A3B2I9 (B = M3+) phase. Here, we report the results of synchrotron XRD and X-ray total scattering measurements on putative Cs2AgBiI6 nanocrystals made via anion exchange from parent Cs2AgBiBr6 nanocrystals. Rietveld refinement of XRD and PDF data shows that these nanocrystals indeed exhibit a tetragonal (I4-m) elpasolite structure, making them the first example of a structurally characterized iodide elpasolite. A series of experiments probing structural relaxation and the effects of surface ligation or grain size all point to the critical role of surface free energy in stabilizing the iodide elpasolite phase in these nanocrystals.

cond-mat.mtrl-sci↗

arXiv2023

Magnetic Amplification at Yb3+ "Designer Defects" in the van der Waals Ferromagnet, CrI3

The two-dimensional (2D) van der Waals ferromagnet CrI3 has been doped with the magnetic optical impurity Yb3+ to yield materials that display sharp multi-line Yb3+ photoluminescence (PL) controlled by the magnetism of CrI3. Magneto-PL shows that Yb3+ magnetization is pinned to the magnetization of CrI3. An effective internal field of ~10 T at Yb3+ is estimated, attributed to strong in-plane Yb3+-Cr3+ superexchange coupling. The anomalously low energy of Yb3+ PL in CrI3 reflects relatively high Yb3+-I- covalency, contributing to Yb3+-Cr3+ superexchange coupling. The Yb3+ PL energy and linewidth both reveal the effects of spontaneous zero-field CrI3 magnetic ordering within 2D layers below TC, despite the absence of net magnetization in multilayer samples. These results illustrate the use of optical impurities as "designer defects" to introduce unique functionality to 2D magnets.

cond-mat.mtrl-sci↗

arXiv2022

Intercell Moiré Exciton Complexes in Electron Lattices

Excitons, Coulomb-bound electron-hole pairs, play a fundamental role in both optical excitation and correlated phenomena in solids. When an exciton interacts with other quasi-particles, few- and many-body excited states, such as trions, exciton Fermi-polarons, Mahan excitons can appear. Here, we report a new interaction between exciton and charges enabled by unusual quantum confinement in 2D moiré superlattices, which results in novel exciton many-body ground states composed of moiré excitons and correlated electron lattices. Unique to H-stacked (or 60o-twisted) WS2/WSe2 heterobilayer, we found that the interlayer atomic registry and moiré structural reconstruction leads to an interlayer moiré exciton (IME) whose hole in one layer is surrounded by its partner electron's wavefunction spread among three adjacent moiré traps in the other layer. This 3D excitonic structure can enable large in-plane electrical quadrupole moments in addition to the vertical dipole. Upon doping, the electric quadrupole facilitates the binding of IME to the charges in neighboring moiré cells, forming an intercell charged exciton complex. The exciton complex is unveiled by the IME photoluminescence energy jumps when the electron lattices form at both fractional and integer-filled moiré minibands, with replica-like spectral features between successive integer moiré fillings. Our work provides the framework in understanding and engineering emergent exciton many-body states in correlated moiré charge orders.

cond-mat.mes-hall↗

arXiv2022

Light-Induced Ferromagnetism in Moiré Superlattices

Many-body interactions between carriers lie at the heart of correlated physics. The ability to tune such interactions would open the possibility to access and control complex electronic phase diagrams on demand. Recently, moiré superlattices formed by two-dimensional materials have emerged as a promising platform for quantum engineering such phenomena. The power of the moiré system lies in the high tunability of its physical parameters by tweaking layer twist angle, electrical field, moiré carrier filling, and interlayer coupling. Here, we report that optical excitation can drastically tune the spin-spin interactions between moiré trapped carriers, resulting in ferromagnetic order in WS2/WSe2 moiré superlattices over a small range of doping at elevated temperatures. Near the filling factor v = -1/3 (i.e., one hole per three moiré unit cells), as the excitation power at the exciton resonance increases, a well-developed hysteresis loop emerges in the reflective magnetic circular dichroism (RMCD) signal as a function of magnetic field, a hallmark of ferromagnetism. The hysteresis loop persists down to charge neutrality, and its shape evolves as the moiré superlattice is gradually filled, indicating changes of magnetic ground state properties. The observed phenomenon points to a mechanism in which itinerant photo-excited excitons mediate exchange coupling between moiré trapped holes. This exciton-mediated interaction can be of longer range than direct coupling between moiré trapped holes, and thus magnetic order can arise even in the dilute hole regime under optical excitation. This discovery adds a new and dynamic tuning knob to the rich many-body Hamiltonian of moiré quantum matter.

cond-mat.mes-hall↗

arXiv2021

Spin-Orbit Coupled Exciton-Polariton Condensates in Lead Halide Perovskites

Spin-orbit coupling (SOC) is responsible for a range of spintronic and topological processes in condensed matter. Here we show photonic analogs of SOCs in exciton-polaritons and their condensates in microcavities composed of birefringent lead halide perovskite single crystals. The presence of crystalline anisotropy coupled with splitting in the optical cavity of the transverse electric (TE) and transverse magnetic (TM) modes gives rise to a non-Abelian gauge field, which can be described by the Rashba-Dresselhaus Hamiltonian near the degenerate points of the two polarization modes. With increasing density, the exciton polaritons with pseudospin textures undergo phase transitions to competing condensates with orthogonal polarizations. Unlike their pure photonic counterparts, these exciton polaritons and condensates inherit nonlinearity from their excitonic components and may serve as quantum simulators of many-body SOC processes.

cond-mat.quant-gas↗

arXiv2021

Unraveling intrinsic flexoelectricity in twisted double bilayer graphene

Moiré superlattices of two-dimensional (2D) materials with a small twist angle are thought to exhibit appreciable flexoelectric effect, though unambiguous confirmation of their flexoelectricity is challenging due to artifacts associated with commonly used piezoresponse force microscopy (PFM). For example, unexpectedly small phase contrast ($\sim$$8^{\circ}$) between opposite flexoelectric polarizations was reported in twisted bilayer graphene (tBG), though theoretically predicted value is $180^{\circ}$. Here we developed a methodology to extract intrinsic moiré flexoelectricity using twisted double bilayer graphene (tDBG) as a model system, probed by lateral PFM. For small twist angle samples, we found that a vectorial decomposition is essential to recover the small intrinsic flexoelectric response at domain walls from a large background signal. The obtained three-fold symmetry of commensurate domains with significant flexoelectric response at domain walls is fully consistent with our theoretical calculations. Incommensurate domains in tDBG with relatively large twist angles can also be observed by this technique. Our work provides a general strategy for unraveling intrinsic flexoelectricity in van der Waals moiré superlattices while providing insights into engineered symmetry breaking in centrosymmetric materials.

cond-mat.mtrl-sci↗

arXiv2021

Highly Anisotropic Excitons and Multiple Phonon Bound States in a Van der Waals Antiferromagnetic Insulator

Two-dimensional semiconducting systems, such as quantum wells and transition metal dichalcogenides, are the foundations to investigate low dimensional light-matter interactions. To date, the study of elementary photoexcitation, namely the exciton, in 2D semiconductors with intrinsic magnetic order remains a challenge due to the lack of suitable material platforms. Here, we report an observation of excitons coupled to zigzag antiferromagnetic order in the layered antiferromagnetic insulator NiPS3 using both photoluminescence (PL) and optical reflection spectroscopy. The exciton exhibits a linewidth as narrow as ~350 ueV with near unity linear polarization in the PL spectrum. As the thicknesses of samples is reduced from five layers to bilayers, the PL intensity is drastically suppressed and eventually vanishes in monolayers, consistent with the calculated bandgap being highly indirect for both bilayer and monolayer. We observed strong linear dichroism (LD) over a broad spectra range, which shares the same optical anisotropy axis, being locked to the zigzag direction, as the exciton PL. Both LD and the degree of linear polarization in the exciton PL decrease as the temperature increases and become negligible above the Neel temperature. These observations suggest both optical quantities are probes of the symmetry breaking magnetic order parameter. In addition, a sharp resonance in the LD spectrum is observed with an energy near the exciton PL. There exist over ten exciton-A1g phonon bound states on its high energy side, which likely result from the strong modulation of the ligand-to-metal charge transfer energy by strong electron-lattice interactions. Our work establishes NiPS3 as a new 2D platform for exploring magneto-exciton physics with strong correlations, as well as a building block for 2D heterostructures for engineering physical phenomena with time reversal symmetry breaking.

cond-mat.mes-hall↗

arXiv2020

Coherent Spin Precession and Lifetime-Limited Spin Dephasing in CsPbBr3 Perovskite Nanocrystals

Carrier spins in semiconductor nanocrystals are promising candidates for quantum information processing. Using a combination of time-resolved Faraday rotation and photoluminescence spectroscopies, we demonstrate optical spin polarization and coherent spin precession in colloidal CsPbBr3 nanocrystals that persists up to room temperature. By suppressing the influence of inhomogeneous hyperfine fields with a small applied magnetic field, we demonstrate inhomogeneous hole transverse spin-dephasing times (T2*) that approach the nanocrystal photoluminescence lifetime, such that nearly all emitted photons derive from coherent hole spins. Thermally activated LO phonons drive additional spin dephasing at elevated temperatures, but coherent spin precession is still observed at room temperature. These data reveal several major distinctions between spins in nanocrystalline and bulk CsPbBr3 and open the door for using metal-halide perovskite nanocrystals in spin-based quantum technologies.

cond-mat.mtrl-sci↗

arXiv2020

Yb3+ speciation and energy-transfer dynamics in quantum-cutting Yb3+-doped CsPbCl3 perovskite nanocrystals and single crystals

Yb3+-doped inorganic metal-halide perovskites (Yb3+:CsPbX3, X = Cl, Br) have recently been discovered to display highly efficient quantum cutting, in which the energy from individual blue or UV photons absorbed by the material is re-emitted in the form of pairs of near-infrared photons by Yb3+ dopants. Experimental photoluminescence quantum yields approaching 200{%} have been reported. As the first quantum-cutting materials that combine such high photoluminescence quantum yields with strong, broadband absorption in the visible, these materials offer unique opportunities for enhancing the efficiencies of solar technologies. Little is known about the fundamental origins of this quantum cutting, however. Here, we describe variable-temperature and time-resolved photoluminescence studies of Yb3+:CsPbCl3 in two disparate forms - colloidal nanocrystals and macroscopic single crystals. Both forms show very similar spectroscopic properties, demonstrating that quantum cutting is an intrinsic property of the Yb3+:CsPbX3 composition itself. Diverse Yb3+ speciation is observed in both forms by low-temperature photoluminescence spectroscopy, but remarkably, quantum cutting is dominated by the same specific Yb3+ species in both cases. Time-resolved photoluminescence measurements provide direct evidence of the previously hypothesized intermediate state in the quantum-cutting mechanism. This intermediate state mediates relaxation from the photogenerated excited state of the perovskite to the emissive excited state of Yb3+, and hence is of critical mechanistic importance. At room temperature, this intermediate state is populated within a few picoseconds and has a decay time of only ~ 7 ns in both nanocrystalline and single-crystal Yb3+:CsPbCl3. The mechanistic implications of these observations are discussed.

cond-mat.mtrl-sci↗

arXiv2020

2D van der Waals Nanoplatelets with Robust Ferromagnetism

We have synthesized unique colloidal nanoplatelets of the ferromagnetic two-dimensional (2D) van der Waals material CrI3 and have characterized these nanoplatelets structurally, magnetically, and by magnetic circular dichroism spectroscopy. The isolated CrI3 nanoplatelets have lateral dimensions of ~25 nm and ensemble thicknesses of only ~4 nm, corresponding to just a few CrI3 monolayers. Magnetic and magneto-optical measurements demonstrate robust 2D ferromagnetic ordering in these nanoplatelets with Curie temperatures similar to those observed in bulk CrI3, despite the strong spatial confinement. These data also show magnetization steps akin to those observed in micron-sized few-layer 2D sheets and associated with concerted spin-reversal of individual CrI3 layers within few-layer van der Waals stacks. Similar data have also been obtained for CrBr3 and anion-alloyed Cr(I1-xBrx)3 nanoplatelets. These results represent the first example of laterally confined 2D van der Waals ferromagnets of any composition. The demonstration of robust ferromagnetism at nanometer lateral dimensions opens new doors for miniaturization in spintronics devices based on van der Waals ferromagnets.

cond-mat.mtrl-sci↗

arXiv2017

Excitonic Zeeman Splittings in Colloidal CdSe Quantum Dots Doped with Single Magnetic Impurities

Doping a semiconductor quantum dot with just a single impurity atom can completely transform its physical properties. Here, we report and analyze the magnetic circular dichroism (MCD) spectra of colloidal CdSe quantum dot samples containing on average fewer than one Mn2+ per quantum dot. Even at this sub-single-dopant level, the low-temperature low-field data are dominated by impurity-induced Zeeman splittings caused by dopant-carrier sp-d exchange. Unlike in more heavily doped quantum dots, however, the MCD intensity at the first CdSe exciton shows a field-induced sign flip as the field strength is increased, reflecting competition between sp-d exchange and the intrinsic Zeeman splittings of comparable magnitude. Most unusually, the competition between these two effects leads to a large apparent shift in the first MCD peak maximum, which we show is attributable to a difference in sign of the intrinsic excitonic g factor between the first and second excitons. Finally, the sp-d and intrinsic contributions to the excitonic Zeeman splittings each exhibit unique magnetic-field and temperature dependencies, allowing the MCD spectra of undoped, singly doped, and bi-doped quantum dot sub-ensembles to be analyzed.

cond-mat.mes-hall↗