Large and Persistent Photoconductivity due to Hole-Hole Correlation in CdS

Large and persistent photoconductivity (LPPC) in semiconductors is due to the trapping of photo-generated minority carriers at crystal defects. Theory has suggested that anion vacancies in II-VI semiconductors are responsible for LPPC due to negative-U behavior, whereby two minority carriers become kinetically trapped by lattice relaxation following photo-excitation. By performing a detailed analysis of photoconductivity in CdS, we provide experimental support for this negative-U model of LPPC. We also show that LPPC is correlated with sulfur deficiency. We use this understanding to vary the photoconductivity of CdS films over nine orders of magnitude, and vary the LPPC characteristic decay time from seconds to 10^4 seconds, by controlling the activities of Cd^{2+} and S^{2-} ions during chemical bath deposition. We suggest a screening method to identify other materials with long-lived, non-equilibrium, photo-excited states based on the results of ground-state calculations of atomic rearrangements following defect redox reactions, with a conceptual connection to polaron formation.

Transient terahertz photoconductivity measurements of minority-carrier lifetime in tin sulfide thin films: Advanced metrology for an early-stage photovoltaic material

Materials research with a focus on enhancing the minority-carrier lifetime of the light-absorbing semiconductor is key to advancing solar energy technology for both early-stage and mature material platforms alike. Tin sulfide (SnS) is an absorber material with several clear advantages for manufacturing and deployment, but the record power conversion efficiency remains below 5%. We report measurements of bulk and interface minority-carrier recombination rates in SnS thin films using optical-pump, terahertz (THz)-probe transient photoconductivity (TPC) measurements. Post-growth thermal annealing in H_2S gas increases the minority-carrier lifetime, and oxidation of the surface reduces the surface recombination velocity. However, the minority-carrier lifetime remains below 100 ps for all tested combinations of growth technique and post-growth processing. Significant improvement in SnS solar cell performance will hinge on finding and mitigating as-yet-unknown recombination-active defects. We describe in detail our methodology for TPC experiments, and we share our data analysis routines as freely-available software.

Using atom probe tomography to understand Schottky barrier height pinning at the ZnO:Al / SiO2 / Si interface

We use electronic transport and atom probe tomography to study ZnO:Al / SiO2 / Si Schottky junctions on lightly-doped n- and p-type Si. We vary the carrier concentration in the the ZnO:Al films by two orders of magnitude but the Schottky barrier height remains constant, consistent with Fermi level pinning seen in metal / Si junctions. Atom probe tomography shows that Al segregates to the interface, so that the ZnO:Al at the junction is likely to be metallic even when the bulk of the ZnO:Al film is semiconducting. We hypothesize that Fermi level pinning is connected to the insulator-metal transition in doped ZnO, and that controlling this transition may be key to un-pinning the Fermi level in oxide / Si Schottky junctions.

Origins of bad metal conductivity and the insulator-metal transition in the rare-earth nickelates

For most metals, increasing temperature (T) or disorder will quicken electron scattering. This hypothesis informs the Drude model of electronic conductivity. However, for so-called bad metals this predicts scattering times so short as to conflict with Heisenbergs uncertainty principle. Here we introduce the rare-earth nickelates (RNiO_3, R = rare earth) as a class of bad metals. We study SmNiO_3 thin films using infrared spectroscopy while varying T and disorder. We show that the interaction between lattice distortions and Ni-O bond covalence explains both the bad metal conduction and the insulator-metal transition in the nickelates by shifting spectral weight over the large energy scale established by the Ni-O orbital interaction, thus enabling very low sigma while preserving the Drude model and without violating the uncertainty principle.

Hall effect measurements on epitaxial SmNiO3 thin films and implications for antiferromagnetism

The rare-earth nickelates (RNiO3) exhibit interesting phenomena such as unusual antiferromagnetic order at wavevector q = (1/2, 0, 1/2) and a tunable insulator-metal transition that are subjects of active research. Here we present temperature-dependent transport measurements of the resistivity, magnetoresistance, Seebeck coefficient, and Hall coefficient (RH) of epitaxial SmNiO3 thin films with varying oxygen stoichiometry. We find that from room temperature through the high temperature insulator-metal transition, the Hall coefficient is hole-like and the Seebeck coefficient is electron-like. At low temperature the Neel transition induces a crossover in the sign of RH to electron-like, similar to the effects of spin density wave formation in metallic systems but here arising in an insulating phase ~200 K below the insulator-metal transition. We propose that antiferromagnetism can be stabilized by bandstructure even in insulating phases of correlated oxides, such as RNiO3, that fall between the limits of strong and weak electron correlation.

Order parameter fluctuations at a buried quantum critical point

Quantum criticality is a central concept in condensed matter physics, but the direct observation of quantum critical fluctuations has remained elusive. Here we present an x-ray diffraction study of the charge density wave (CDW) in 2H-NbSe2 at high pressure and low temperature, where we observe a broad regime of order parameter fluctuations that are controlled by proximity to a quantum critical point. X-rays can track the CDW despite the fact that the quantum critical regime is shrouded inside a superconducting phase, and, in contrast to transport probes, allow direct measurement of the critical fluctuations of the charge order. Concurrent measurements of the crystal lattice point to a critical transition that is continuous in nature. Our results confirm the longstanding expectations of enhanced quantum fluctuations in low dimensional systems, and may help to constrain theories of the quantum critical Fermi surface.

Chromium at High Pressures: Weak Coupling and Strong Fluctuations in an Itinerant Antiferromagnet

The spin- and charge-density-wave order parameters of the itinerant antiferromagnet chromium are measured directly with non-resonant x-ray diffraction as the system is driven towards its quantum critical point with high pressure using a diamond anvil cell. The exponential decrease of the spin and charge diffraction intensities with pressure confirms the harmonic scaling of spin and charge, while the evolution of the incommensurate ordering vector provides important insight into the difference between pressure and chemical doping as means of driving quantum phase transitions. Measurement of the charge density wave over more than two orders of magnitude of diffraction intensity provides the clearest demonstration to date of a weakly-coupled, BCS-like ground state. Evidence for the coexistence of this weakly-coupled ground state with high-energy excitations and pseudogap formation above the ordering temperature in chromium, the charge-ordered perovskite manganites, and the blue bronzes, among other such systems, raises fundamental questions about the distinctions between weak and strong coupling.

Pressure-Tuned Spin and Charge Ordering in an Itinerant Antiferromagnet

Elemental chromium orders antiferromagnetically near room temperature, but the ordering temperature can be driven to zero by applying large pressures. We combine diamond anvil cell and synchrotron x-ray diffraction techniques to measure directly the spin and charge order in the pure metal at the approach to its quantum critical point. Both spin and charge order are suppressed exponentially with pressure, well beyond the region where disorder cuts off such a simple evolution, and they maintain a harmonic scaling relationship over decades in scattering intensity. By comparing the development of the order parameter with that of the magnetic wavevector, it is possible to ascribe the destruction of antiferromagnetism to the growth in electron kinetic energy relative to the underlying magnetic exchange interaction.

Microscopic and Macroscopic Signatures of Antiferromagnetic Domain Walls

Magnetotransport measurements on small single crystals of Cr, the elemental antiferromagnet, reveal the hysteretic thermodynamics of the domain structure. The temperature dependence of the transport coefficients is directly correlated with the real-space evolution of the domain configuration as recorded by x-ray microprobe imaging, revealing the effect of antiferromagnetic domain walls on electron transport. A single antiferromagnetic domain wall interface resistance is deduced to be of order $5times10^{-5}mathrm{muOmegacdot cm^{2}}$ at a temperature of 100 K.