Anthony Fu

Atomically thin two-dimensional organic-inorganic hybrid perovskites

Flat perovskite crystals Bulk crystals and thick films of inorganic-organic perovskite materials such as CH3NH3PbI3 have shown promise as active material for solar cells. Dou et al. show that thin films—a single unit cell or a few unit cells thick—of a related composition, (C4H9NH3)2PbBr4, form squares with edges several micrometers long. These materials exhibit strong and tunable blue photoluminescence. Science, this issue p. 1518 Several inorganic-organic perovskite materials grown as atomically thin crystals exhibit strong photoluminescence. Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials.

Growth and Anion Exchange Conversion of CH3NH3PbX3 Nanorod Arrays for Light-Emitting Diodes

The nanowire and nanorod morphology offers great advantages for application in a range of optoelectronic devices, but these high-quality nanorod arrays are typically based on high temperature growth techniques. Here, we demonstrate the successful room temperature growth of a hybrid perovskite (CH3NH3PbBr3) nanorod array, and we also introduce a new low temperature anion exchange technique to convert the CH3NH3PbBr3 nanorod array into a CH3NH3PbI3 nanorod array while preserving morphology. We demonstrate the application of both these hybrid perovskite nanorod arrays for LEDs. This work highlights the potential utility of postsynthetic interconversion of hybrid perovskites for nanostructured optoelectronic devices such as LEDs, which enables new strategies for the application of hybrid perovskites.

Epitaxial Growth of InGaN Nanowire Arrays for Light Emitting Diodes

Significant synthetic challenges remain for the epitaxial growth of high-quality InGaN across the entire compositional range. One strategy to address these challenges has been to use the nanowire geometry because of its strain relieving properties. Here, we demonstrate the heteroepitaxial growth of In(x)Ga(1-x)N nanowire arrays (0.06 ≤ x ≤ 0.43) on c-plane sapphire (Al(2)O(3)(001)) using a halide chemical vapor deposition (HCVD) technique. Scanning electron microscopy and X-ray diffraction characterization confirmed the long-range order and epitaxy of vertically oriented nanowires. Structural characterization by transmission electron microscopy showed that single crystalline nanowires were grown in the ⟨002⟩ direction. Optical properties of InGaN nanowire arrays were investigated by absorption and photoluminescence measurements. These measurements show the tunable direct band gap properties of InGaN nanowires into the yellow-orange region of the visible spectrum. To demonstrate the utility of our HCVD method for implementation into devices, LEDs were fabricated from In(x)Ga(1-x)N nanowires epitaxially grown on p-GaN(001). Devices showed blue (x = 0.06), green (x = 0.28), and orange (x = 0.43) electroluminescence, demonstrating electrically driven color tunable emission from this p-n junction.

Cleaved-coupled nanowire lasers

The miniaturization of optoelectronic devices is essential for the continued success of photonic technologies. Nanowires have been identified as potential building blocks that mimic conventional photonic components such as interconnects, waveguides, and optical cavities at the nanoscale. Semiconductor nanowires with high optical gain offer promising solutions for lasers with small footprints and low power consumption. Although much effort has been directed toward controlling their size, shape, and composition, most nanowire lasers currently suffer from emitting at multiple frequencies simultaneously, arising from the longitudinal modes native to simple Fabry–Pérot cavities. Cleaved-coupled cavities, two Fabry–Pérot cavities that are axially coupled through an air gap, are a promising architecture to produce single-frequency emission. The miniaturization of this concept, however, imposes a restriction on the dimensions of the intercavity gaps because severe optical losses are incurred when the cross-sectional dimensions of cavities become comparable to the lasing wavelength. Here we theoretically investigate and experimentally demonstrate spectral manipulation of lasing modes by creating cleaved-coupled cavities in gallium nitride (GaN) nanowires. Lasing operation at a single UV wavelength at room temperature was achieved using nanoscale gaps to create the smallest cleaved-coupled cavities to date. Besides the reduced number of lasing modes, the cleaved-coupled nanowires also operate with a lower threshold gain than that of the individual component nanowires. Good agreement was found between the measured lasing spectra and the predicted spectral modes obtained by simulating optical coupling properties. This agreement between theory and experiment presents design principles to rationally control the lasing modes in cleaved-coupled nanowire lasers.

Single-nanowire photoelectrochemistry

Photoelectrochemistry is one of several promising approaches for the realization of efficient solar-to-fuel conversion. Recent work has shown that photoelectrodes made of semiconductor nano-/microwire arrays can have better photoelectrochemical performance than their planar counterparts because of their unique properties, such as high surface area. Although considerable research effort has focused on studying wire arrays, the inhomogeneity in the geometry, doping, defects and catalyst loading present in such arrays can obscure the link between these properties and the photoelectrochemical performance of the wires, and correlating performance with the specific properties of individual wires is difficult because of ensemble averaging. Here, we show that a single-nanowire-based photoelectrode platform can be used to reliably probe the current-voltage (I-V) characteristics of individual nanowires. We find that the photovoltage output of ensemble array samples can be limited by poorly performing individual wires, which highlights the importance of improving nanowire homogeneity within an array. Furthermore, the platform allows the flux of photogenerated electrons to be quantified as a function of the lengths and diameters of individual nanowires, and we find that the flux over the entire nanowire surface (7-30 electrons nm(-2) s(-1)) is significantly reduced as compared with that of a planar analogue (∼1,200 electrons nm(-2) s(-1)). Such characterization of the photogenerated carrier flux at the semiconductor/electrolyte interface is essential for designing nanowire photoelectrodes that match the activity of their loaded electrocatalysts.

Widely Tunable Distributed Bragg Reflectors Integrated into Nanowire Waveguides

Periodic structures with dimensions on the order of the wavelength of light can tailor and improve the performance of optical components, and they can enable the creation of devices with new functionalities. For example, distributed Bragg reflectors (DBRs), which are created by periodic modulations in a structures dielectric medium, are essential in dielectric mirrors, vertical cavity surface emitting lasers, fiber Bragg gratings, and single-frequency laser diodes. This work introduces nanoscale DBRs integrated directly into gallium nitride (GaN) nanowire waveguides. Photonic band gaps that are tunable across the visible spectrum are demonstrated by precisely controlling the gratings parameters. Numerical simulations indicate that in-wire DBRs have significantly larger reflection coefficients in comparison with the nanowires end facet. By comparing the measured spectra with the simulated spectra, the index of refraction of the GaN nanowire waveguides was extracted to facilitate the design of photonic coupling structures that are sensitive to phase-matching conditions. This work indicates the potential to design nanowire-based devices with improved performance for optical resonators and optical routing.