Eric M. Gallo

Perovskite oxides for visible-light-absorbing ferroelectric and photovoltaic materials

Ferroelectrics have recently attracted attention as a candidate class of materials for use in photovoltaic devices, and for the coupling of light absorption with other functional properties. In these materials, the strong inversion symmetry breaking that is due to spontaneous electric polarization promotes the desirable separation of photo-excited carriers and allows voltages higher than the bandgap, which may enable efficiencies beyond the maximum possible in a conventional p–n junction solar cell. Ferroelectric oxides are also stable in a wide range of mechanical, chemical and thermal conditions and can be fabricated using low-cost methods such as sol–gel thin-film deposition and sputtering. Recent work has shown how a decrease in ferroelectric layer thickness and judicious engineering of domain structures and ferroelectric–electrode interfaces can greatly increase the current harvested from ferroelectric absorber materials, increasing the power conversion efficiency from about 10−4 to about 0.5 per cent. Further improvements in photovoltaic efficiency have been inhibited by the wide bandgaps (2.7–4 electronvolts) of ferroelectric oxides, which allow the use of only 8–20 per cent of the solar spectrum. Here we describe a family of single-phase solid oxide solutions made from low-cost and non-toxic elements using conventional solid-state methods: [KNbO3]1 − x[BaNi1/2Nb1/2O3 − δ]x (KBNNO). These oxides exhibit both ferroelectricity and a wide variation of direct bandgaps in the range 1.1–3.8 electronvolts. In particular, the x = 0.1 composition is polar at room temperature, has a direct bandgap of 1.39 electronvolts and has a photocurrent density approximately 50 times larger than that of the classic ferroelectric (Pb,La)(Zr,Ti)O3 material. The ability of KBNNO to absorb three to six times more solar energy than the current ferroelectric materials suggests a route to viable ferroelectric semiconductor-based cells for solar energy conversion and other applications.

Picosecond response times in GaAs/AlGaAs core/shell nanowire-based photodetectors

High-speed metal-semiconductor-metal (MSM) photodetectors based on Schottky-contacted core/shell GaAs/AlGaAs and bare GaAs nanowires were fabricated and characterized. The measured core/shell temporal response has a ∼10 ps full-width at half-maximum and an estimated corrected value less than 5 ps. The bare GaAs devices exhibit a slower response (∼35 ps) along with a slow decaying persistent photocurrent (∼80 s). The core/shell devices exhibit significantly improved dc and high-speed performance over bare nanowires and comparable performance to planar MSM photodetectors. The picosecond temporal response, coupled with picoampere dark current, demonstrate the potential for core/shell nanowires in high-speed imaging arrays and on-chip optical interconnects.

Finite curvature-mediated ferroelectricity.

We demonstrate that ferroelectric (FE) polarizations oriented along the finite thickness direction in ultrathin films are enhanced by the introduction of extreme curvature, thereby suppressing the finite-size-driven evolution of the FE phase transition temperature T(C). The measured responses within individual nanoshells possess magnitudes nearly three times that for their planar counterparts while exhibiting finite curvature-dependent offsets in FE switching hystereses. In stark contrast to the expected scaling of a depression of T(C) with inverse thickness, results based on modified Landau-Ginzburg model calculations indicate geometric curvature-driven polarization gradients in ultrathin films result in significant increases in T(C).

Excitation of Local Field Enhancement on Silicon Nanowires

The interaction between light and reduced-dimensionality silicon attracts significant interest due to the possibilities of designing nanoscaled optical devices, highly cost-efficient solar cells, and ultracompact optoelectronic systems that are integrated with standard microelectronic technology. We demonstrate that Si nanowires (SiNWs) possessing metal-nanocluster coatings support a multiplicatively enhanced near-field light-matter interaction. Raman scattering from chemisorbed probing molecules provides a quantitative measure of the strength of this enhanced coupling. An enhancement factor of 2 orders of magnitude larger than that for the surface plasmon resonance alone (without the SiNWs) along with the attractive properties of SiNWs, including synthetic controllability of shape, indicates that these nanostructures may be an attractive and versatile material platform for the design of nanoscaled optical and optoelectronic circuits.

On direct-writing methods for electrically contacting GaAs and Ge nanowire devices

The electronic transport and gating characteristics in GaAs and Ge nanowires (NWs) are altered significantly following either indirect or direct exposure to a focused Ga+ ion beam (FIB), such as that used to produce Pt electrical contacts to NWs. While these results challenge the assumptions made in some previously reported work relating to the electronic properties of semiconductor NWs using FIB-assisted production of contacts and/or their leads, local electron beam induced deposition is shown to be a reliable and facile route for producing robust electrical contacts to individual vapor phase-grown NWs in a manner that enables study of their actual carrier transport properties.

Redox-based resistive switching in ferroelectric perovskite nanotubes

Hysteresis in current and ferroelectric piezoelectric phase were collected across the walls of individual, electrically interfaced lead zirconate titanate (PZT) nanotubes. The nanotubes exhibit average on/off current ratios of ∼10 and ∼1000 in static local probe and top-electroded configurations, respectively. Reversibility in conduction state of an individual nanotube following different stages of an O2-rich/O2-deficient/O2-rich anneal cycle provide evidence of an oxygen vacancy concentration-based conduction mechanism.

Optically Modulated High-Sensitivity Heterostructure Varactor

A novel optically modulated high-sensitivity heterostructure varactor, demonstrated as a strong candidate for high-order frequency-multiplier applications, is reported. The device is a delta modulation-doped heterostructure of AlGaAs/GaAs with two Schottky contacts on the top. The capacitance-voltage (C-V) measurements show a C max/Cmin ratio up to 113 and an extremely high nonlinearity during the transition from high to low capacitance with sensitivity of up to 35. These results are one of the best obtained so far among similar structure devices. In addition, optoelectronic experimental results demonstrate that the slope of the C-V relationship can be modulated by the intensity of the incident optical power. A model describing the source of the reported C-V results is proposed along with the simulation results verifying the observed C-V behavior

Piezoresponse through a ferroelectric nanotube wall

We report on the controlled local switching and imaging of local ferroelectric polarizations oriented perpendicular to the long axis of a lead zirconate titanate (PZT) nanotube. Piezoresponse force microscopy and ferroelectric piezoelectric hysteresis data indicate stable polarizations oriented along the radial, finite-thickness direction can be formed in a nanoshell geometry. The results of infrared spectroscopy and of the character of as-found polarizations are consistent with recent findings linking surface chemical environment to ferroelectric stability and to orientation of ferroelectric polarizations.

A highly tunable heterostructure metal-semiconductor-metal capacitor utilizing embedded 2-dimensional charge

We report on a variable capacitor that is formed between Schottky contacts and the two dimensional electron gas (2DEG) in a planar metal-semiconductor-metal structure. Device capacitance at low bias is twice the series capacitance of anode and cathode, enhancing to a maximum value, Cmax, at a threshold voltage, before reaching a minimum, Cmin, lower than the geometric capacitance of the coplanar contacts, thus resulting in ultra high Cmax/Cmin tuning ratio. Sensitivity, the normalized change of capacitance with voltage, is also very large. The dense reservoir of the 2DEG charge maintained between contacts is shown to be responsible for this remarkable performance.

LaAlO 3 /SrTiO 3 Epitaxial Heterostructures by Atomic Layer Deposition

Thin films of LaAlO3 were deposited on TiO2-terminated (100) SrTiO3 crystals by atomic layer deposition (ALD), using tris(iso-propylcyclopentadienyl)lanthanum and trimethyl aluminum precursors. Water was used as the oxidizer. The film composition was shown to be controlled by the ratio of La/Al precursor pulses during ALD, with near-stoichiometric LaAlO3 resulting at precursor pulse ratios of 4/1 to 5/1. Films near the stoichiometric LaAlO3 composition were shown to crystallize on subsequent annealing to form epitaxial LaAlO3/SrTiO3 heterostructures. Electrical characterization of these structures was done by two-terminal direct-current (DC) current–voltage scans at room temperature and under high-vacuum conditions. The results show electrical conductivity for the ALD-deposited epitaxial LaAlO3/SrTiO3 heterostructures, which turns on for thickness above four unit cells for the LaAlO3 film.