Jacob P. C. Ruff

Emergence of coherence in the charge-density wave state of 2H-NbSe2

A charge-density wave (CDW) state has a broken symmetry described by a complex order parameter with an amplitude and a phase. The conventional view, based on clean, weak-coupling systems, is that a finite amplitude and long-range phase coherence set in simultaneously at the CDW transition temperature Tcdw. Here we investigate, using photoemission, X-ray scattering and scanning tunnelling microscopy, the canonical CDW compound 2H-NbSe2 intercalated with Mn and Co, and show that the conventional view is untenable. We find that, either at high temperature or at large intercalation, CDW order becomes short-ranged with a well-defined amplitude, which has impacts on the electronic dispersion, giving rise to an energy gap. The phase transition at Tcdw marks the onset of long-range order with global phase coherence, leading to sharp electronic excitations. Our observations emphasize the importance of phase fluctuations in strongly coupled CDW systems and provide insights into the significance of phase incoherence in ‘pseudogap’ states.

Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite

In a photovoltaic perovskite, entropy-driven structural transition enables kinetic trapping of a desired photovoltaic phase. A challenge of hybrid perovskite solar cells is device instability, which calls for an understanding of the perovskite structural stability and phase transitions. Using neutron diffraction and first-principles calculations on formamidinium lead iodide (FAPbI3), we show that the entropy contribution to the Gibbs free energy caused by isotropic rotations of the FA+ cation plays a crucial role in the cubic-to-hexagonal structural phase transition. Furthermore, we observe that the cubic-to-hexagonal phase transition exhibits a large thermal hysteresis. Our first-principles calculations confirm the existence of a potential barrier between the cubic and hexagonal structures, which provides an explanation for the observed thermal hysteresis. By exploiting the potential barrier, we demonstrate kinetic trapping of the cubic phase, desirable for solar cells, even at 8.2 K by thermal quenching.

Chiral phase transition in charge ordered 1T-TiSe2

It was recently discovered that the low-temperature, charge-ordered phase of 1T-TiSe(2) has a chiral character. This unexpected chirality in a system described by a scalar order parameter could be explained in a model where the emergence of relative phase shifts between three charge density wave components breaks the inversion symmetry of the lattice. Here, we present experimental evidence for the sequence of phase transitions predicted by that theory, going from disorder to nonchiral and finally to chiral charge order. Employing x-ray diffraction, specific heat, and electrical transport measurements, we find that a novel phase transition occurs ~7 K below the main charge ordering transition in TiSe(2), in agreement with the predicted hierarchy of charge-ordered phases.

Origin of long lifetime of band-edge charge carriers in organic–inorganic lead iodide perovskites

Significance Hybrid organic–inorganic perovskites (HOIPs) are among the most promising materials for next-generation solar cells that combine high efficiency and low cost. The record efficiency of HOIP-based solar cells has reached above 22%, which is comparable to that of silicon solar cells. HOIP solar cells can be manufactured using simple solution processing methods that can be drastically cheaper than the current commercial solar cell technologies. Despite the progress so far, the microscopic mechanism for the high solar cell efficiency in HOIPs is yet to be understood. Our study shows that rotation of organic molecules in HOIPs extends the lifetime of photoexcited charge carriers, leading to the high efficiency. This insight can guide the progress toward improved solar cell performance. Long carrier lifetime is what makes hybrid organic–inorganic perovskites high-performance photovoltaic materials. Several microscopic mechanisms behind the unusually long carrier lifetime have been proposed, such as formation of large polarons, Rashba effect, ferroelectric domains, and photon recycling. Here, we show that the screening of band-edge charge carriers by rotation of organic cation molecules can be a major contribution to the prolonged carrier lifetime. Our results reveal that the band-edge carrier lifetime increases when the system enters from a phase with lower rotational entropy to another phase with higher entropy. These results imply that the recombination of the photoexcited electrons and holes is suppressed by the screening, leading to the formation of polarons and thereby extending the lifetime. Thus, searching for organic–inorganic perovskites with high rotational entropy over a wide range of temperature may be a key to achieve superior solar cell performance.

Unidirectional spin density wave state in metallic (Sr1−xLax)2IrO4

Materials that exhibit both strong spin–orbit coupling and electron correlation effects are predicted to host numerous new electronic states. One prominent example is the Jeff = 1/2 Mott state in Sr2IrO4, where introducing carriers is predicted to manifest high temperature superconductivity analogous to the S = 1/2 Mott state of La2CuO4. While bulk superconductivity currently remains elusive, anomalous quasiparticle behaviors paralleling those in the cuprates such as pseudogap formation and the formation of a d-wave gap are observed upon electron-doping Sr2IrO4. Here we establish a magnetic parallel between electron-doped Sr2IrO4 and hole-doped La2CuO4 by unveiling a spin density wave state in electron-doped Sr2IrO4. Our magnetic resonant X-ray scattering data reveal the presence of an incommensurate magnetic state reminiscent of the diagonal spin density wave state observed in the monolayer cuprate (La1−xSrx)2CuO4. This link supports the conjecture that the quenched Mott phases in electron-doped Sr2IrO4 and hole-doped La2CuO4 support common competing electronic phases.Electron-doped Sr2IrO4 is an intriguing material for searching for an unconventional superconducting state. Here the authors demonstrate that a spin density wave state exists in the metallic phase of electron-doped Sr2IrO4 which provides a link between the electronic phase diagrams of the hole-doped cuprates and the electron-doped iridates.

Characterization of CdTe Sensors with Schottky Contacts Coupled to Charge-Integrating Pixel Array Detectors for X-Ray Science

Pixel Array Detectors (PADs) consist of an x-ray sensor layer bonded pixel-by-pixel to an underlying readout chip. This approach allows both the sensor and the custom pixel electronics to be tailored independently to best match the x-ray imaging requirements. Here we present characterizations of CdTe sensors hybridized with two different charge-integrating readout chips, the Keck PAD and the Mixed-Mode PAD (MM-PAD), both developed previously in our laboratory. The charge-integrating architecture of each of these PADs extends the instantaneous counting rate by many orders of magnitude beyond that obtainable with photon counting architectures. The Keck PAD chip consists of rapid, 8-frame, in-pixel storage elements with framing periods < 150 ns. The second detector, the MM-PAD, has an extended dynamic range by utilizing an in-pixel overflow counter coupled with charge removal circuitry activated at each overflow. This allows the recording of signals from the single-photon level to tens of millions of x-rays/pixel/frame while framing at 1 kHz. Both detector chips consist of a 128 × 128 pixel array with (150 μm)2 pixels.

Charge Density Wave in the New Polymorphs of RE2Ru3Ge5 (RE = Pr, Sm, Dy)

A new polymorph of the RE2Ru3Ge5 (RE = Pr, Sm, Dy) compounds has been grown as single crystals via an indium flux. These compounds crystallize in tetragonal space group P4/mnc with the Sc2Fe3Si5-type structure, having lattice parameters a = 11.020(2) Å and c = 5.853(1) Å for RE = Pr, a = 10.982(2) Å and c = 5.777(1) Å for RE = Sm, and a = 10.927(2) Å and c = 5.697(1) Å for RE = Dy. These materials exhibit a structural transition at low temperature, which is attributed to an apparent charge density wave (CDW). Both the high-temperature average crystal structure and the low-temperature incommensurately modulated crystal structure (for Sm2Ru3Ge5 as a representative) have been solved. The charge density wave order is manifested by periodic distortions of the one-dimensional zigzag Ge chains. From X-ray diffraction, charge transport (electrical resistivity, Hall effect, magnetoresistance), magnetic measurements, and heat capacity, the ordering temperatures (TCDW) observed in the Pr and Sm analogues are ∼200 and ∼175 K, respectively. The charge transport measurement results indicate an electronic state transition happening simultaneously with the CDW transition. X-ray absorption near-edge spectroscopy (XANES) and electronic band structure results are also reported.

The relation of local order to material properties in relaxor ferroelectrics

Correlating electromechanical and dielectric properties with nanometre-scale order is the defining challenge for the development of piezoelectric oxides. Current lead (Pb)-based relaxor ferroelectrics can serve as model systems with which to unravel these correlations, but the nature of the local order and its relation to material properties remains controversial. Here we employ recent advances in diffuse scattering instrumentation to investigate crystals that span the phase diagram of PbMg1/3Nb2/3O3-xPbTiO3 (PMN-xPT) and identify four forms of local order. From the compositional dependence, we resolve the coupling of each form to the dielectric and electromechanical properties observed. We show that relaxor behaviour does not correlate simply with ferroic diffuse scattering; instead, it results from a competition between local antiferroelectric correlations, seeded by chemical short-range order, and local ferroic order. The ferroic diffuse scattering is strongest where piezoelectricity is maximal and displays previously unrecognized modulations caused by anion displacements. Our observations provide new guidelines for evaluating displacive models and hence the piezoelectric properties of environmentally friendly next-generation materials.How local order affects the excellent piezoelectric properties of Pb-based relaxor ferroelectrics is unclear, but neutron diffuse scattering shows that non-relaxor distortions are implicated, indicating the important role of oxygen atoms.

Demystifying the growth of superconducting Sr2RuO4 thin films

We report the growth of superconducting Sr2RuO4 thin films by molecular-beam epitaxy on (110) NdGaO3 substrates with transition temperatures of up to 1.8 K. We calculate and experimentally validate a thermodynamic growth window for the adsorption-controlled growth of superconducting Sr2RuO4 epitaxial thin films. The growth window for achieving superconducting Sr2RuO4 thin films is narrow in growth temperature, oxidant pressure, and ruthenium-to-strontium flux ratio.We report the growth of superconducting Sr2RuO4 thin films by molecular-beam epitaxy on (110) NdGaO3 substrates with transition temperatures of up to 1.8 K. We calculate and experimentally validate a thermodynamic growth window for the adsorption-controlled growth of superconducting Sr2RuO4 epitaxial thin films. The growth window for achieving superconducting Sr2RuO4 thin films is narrow in growth temperature, oxidant pressure, and ruthenium-to-strontium flux ratio.

InSitμ@CHESS, a Resource for Studying Structural Materials

High-energy X-ray diffraction (HEXD) experiments, which include real-time measurements of micromechanical material response using in-situ loading and the non-destructive creation of three-dimensional maps of polycrystalline microstructure, are very rapidly replacing traditional macroscopic mechanical tests and forensic metallurgical characterization methods for structural materials. The center for Integrated Simulation and X-ray Interrogation Tools and Training for Micromechanics at the Cornell High Energy Synchrotron Source (InSitμ@CHESS) was created to facilitate the use of HEXD experiments on structural materials; more notably, metallic alloys such as steel, titanium, aluminum, and nickel. The Office of Naval Research (ONR) has financially supported InSitμ, specifically enabling enhanced industrial user support. This article describes the experimental considerations associated with using HEXD on structural materials and, through a set of examples, illustrates how InSitμ addresses these considerations.