Alexander A. Puretzky

Perovskite Solar Cells with Near 100% Internal Quantum Efficiency Based on Large Single Crystalline Grains and Vertical Bulk Heterojunctions

Imperfections in organometal halide perovskite films such as grain boundaries (GBs), defects, and traps detrimentally cause significant nonradiative recombination energy loss and decreased power conversion efficiency (PCE) in solar cells. Here, a simple layer-by-layer fabrication process based on air exposure followed by thermal annealing is reported to grow perovskite films with large, single-crystal grains and vertically oriented GBs. The hole-transport medium Spiro-OMeTAD is then infiltrated into the GBs to form vertically aligned bulk heterojunctions. Due to the space-charge regions in the vicinity of GBs, the nonradiative recombination in GBs is significantly suppressed. The GBs become active carrier collection channels. Thus, the internal quantum efficiencies of the devices approach 100% in the visible spectrum range. The optimized cells yield an average PCE of 16.3 ± 0.9%, comparable to the best solution-processed perovskite devices, establishing them as important alternatives to growing ideal single crystal thin films in the pursuit toward theoretical maximum PCE with industrially realistic processing techniques.

Fast and highly anisotropic thermal transport through vertically aligned carbon nanotube arrays

This letter reports on fast and highly anisotropic thermal transport through millimeter-tall, vertically aligned carbon nanotube arrays (VANTAs) synthesized by chemical vapor deposition on Si substrates. Thermal diffusivity measurements were performed for both longitudinal and transverse to the nanotube alignment direction, with longitudinal values as large as 2.1±0.2cm2∕s and anisotropy ratios as large as 72. Longitudinal thermal conductivities of 15.3±1.8W∕(mK) for porous 8±1vol% VANTAs in air and 5.5±0.7W∕(mK) for epoxy-infiltrated VANTAs already exceed those of phase-changing thermal interface materials used in microelectronics. Data suggest that further improvements are possible through optimization of density and defects in the arrays.

Nonlinear Fano-Resonant Dielectric Metasurfaces

Strong nonlinear light-matter interaction is highly sought-after for a variety of applications including lasing and all-optical light modulation. Recently, resonant plasmonic structures have been considered promising candidates for enhancing nonlinear optical processes due to their ability to greatly enhance the optical near-field; however, their small mode volumes prevent the inherently large nonlinear susceptibility of the metal from being efficiently exploited. Here, we present an alternative approach that utilizes a Fano-resonant silicon metasurface. The metasurface results in strong near-field enhancement within the volume of the silicon resonator while minimizing two photon absorption. We measure a third harmonic generation enhancement factor of 1.5 × 10(5) with respect to an unpatterned silicon film and an absolute conversion efficiency of 1.2 × 10(-6) with a peak pump intensity of 3.2 GW cm(-2). The enhanced nonlinearity, combined with a sharp linear transmittance spectrum, results in transmission modulation with a modulation depth of 36%. The modulation mechanism is studied by pump-probe experiments.

Characterization of thin-film amorphous semiconductors using spectroscopic ellipsometry

Spectroscopic ellipsometry (SE) has been used to routinely characterize amorphous silicon nitride and diamond thin films. Since SE measurements do not yield quantities of interest directly, the SE data must first be fit to a model to obtain useful parameters such as film thickness and optical functions. Recently, we have developed the Tauc-Lorentz (TL) model for the optical functions of amorphous materials [Appl. Phys. Lett. 69, 371373, 2137 (1996).], which has been very useful in interpreting these SE results. A 4parameter model is usually sufficient to describe the optical functions of the thin film to the accuracy of the ellipsometer. One of these parameters, the band gap Eg, correlates with other mechanical and chemical properties of the film, such as the silicon-to-nitrogen ratio in silicon nitride films, and to the sp 3 -bonded carbon fraction and the hardness of

Controlled Vapor Phase Growth of Single Crystalline, Two-Dimensional GaSe Crystals with High Photoresponse

Compared with their bulk counterparts, atomically thin two-dimensional (2D) crystals exhibit new physical properties, and have the potential to enable next-generation electronic and optoelectronic devices. However, controlled synthesis of large uniform monolayer and multi-layer 2D crystals is still challenging. Here, we report the controlled synthesis of 2D GaSe crystals on SiO2/Si substrates using a vapor phase deposition method. For the first time, uniform, large (up to ~60 μm in lateral size), single-crystalline, triangular monolayer GaSe crystals were obtained and their structure and orientation were characterized from atomic scale to micrometer scale. The size, density, shape, thickness, and uniformity of the 2D GaSe crystals were shown to be controllable by growth duration, growth region, growth temperature, and argon carrier gas flow rate. The theoretical modeling of the electronic structure and Raman spectroscopy demonstrate a direct-to-indirect bandgap transition and progressive confinement-induced bandgap shifts for 2D GaSe crystals. The 2D GaSe crystals show p-type semiconductor characteristics and high photoresponsivity (~1.7 A/W under white light illumination) comparable to exfoliated GaSe nanosheets. These 2D GaSe crystals are potentially useful for next-generation electronic and optoelectronic devices such as photodetectors and field-effect transistors.

In situ control of the catalyst efficiency in chemical vapor deposition of vertically aligned carbon nanotubes on predeposited metal catalyst films

Premature termination of growth, presumably because of catalyst deactivation, is an undesirable side effect of chemical vapor deposition of vertically aligned carbon nanotubes on predeposited metal catalyst films. The addition of ferrocene, an effective precursor for in situ Fe formation, was found to enhance carbon nanotubegrowth rates and extend growth to 3.25 mm thick carbon nanotube films. Ferrocene was introduced into the gas stream by thermal evaporation concurrently with acetylene using a specially constructed source. The key factor facilitating the growth of thick carbon nanotube films was the independent and precise control of the ferrocene amount in the feedstock. The carbon nanotube films were characterized by scanning and transmission electron microscopy, and Raman spectroscopy. The temperature dependence of the carbon nanotubegrowth with ferrocene exhibits a steep drop at high substrate temperatures and a loss of vertical alignment at 900 ° C . The negative temperature coefficient of the growth rate suggests that the reaction mechanism of vertically aligned carbon nanotubegrowth is governed by a heterogeneous intermediate step.

Anisotropic Electron-Photon and Electron-Phonon Interactions in Black Phosphorus

Orthorhombic black phosphorus (BP) and other layered materials, such as gallium telluride (GaTe) and tin selenide (SnSe), stand out among two-dimensional (2D) materials owing to their anisotropic in-plane structure. This anisotropy adds a new dimension to the properties of 2D materials and stimulates the development of angle-resolved photonics and electronics. However, understanding the effect of anisotropy has remained unsatisfactory to date, as shown by a number of inconsistencies in the recent literature. We use angle-resolved absorption and Raman spectroscopies to investigate the role of anisotropy on the electron-photon and electron-phonon interactions in BP. We highlight, both experimentally and theoretically, a nontrivial dependence between anisotropy and flake thickness and photon and phonon energies. We show that once understood, the anisotropic optical absorption appears to be a reliable and simple way to identify the crystalline orientation of BP, which cannot be determined from Raman spectroscopy without the explicit consideration of excitation wavelength and flake thickness, as commonly used previously.

Low-Frequency Interlayer Breathing Modes in Few-Layer Black Phosphorus

As a new two-dimensional layered material, black phosphorus (BP) is a very promising material for nanoelectronics and optoelectronics. We use Raman spectroscopy and first-principles theory to characterize and understand the low-frequency (LF) interlayer breathing modes (<100 cm(-1)) in few-layer BP for the first time. Using a laser polarization dependence study and group theory analysis, the breathing modes are assigned to Ag symmetry. Compared to the high-frequency (HF) Raman modes, the LF breathing modes are considerably more sensitive to interlayer coupling and, thus, their frequencies show a stronger dependence on the number of layers. Hence, they constitute an effective means to probe both the crystalline orientation and thickness of few-layer BP. Furthermore, the temperature dependence shows that in the temperature range -150 to 30 °C, the breathing modes have a weak anharmonic behavior, in contrast to the HF Raman modes that exhibit strong anharmonicity.

In situ growth rate measurements and length control during chemical vapor deposition of vertically aligned multiwall carbon nanotubes

Time-resolved reflectivity is employed as an in situ diagnostic in thermal chemical vapor deposition of vertically aligned arrays of multiwall carbon nanotubes (VAA–MWNT). Fabry–Ṕerot interference fringes and attenuation of a reflected HeNe laser beam are used to measure the length of VAA–MWNT throughout the first 3–8 μm of growth yielding in situ measurements of growth rates and kinetics and the capability to observe the onset and termination of growth. VAA–MWNT growth is characterized between 565 and 750 °C on Si substrates with evaporated Al/Fe/Mo multilayer catalysts and acetylene feedstock. Nanotube lengths were controlled by rapid evacuation of the chamber at predetermined reflectivities, and it was demonstrated that growth can be restarted at later times. The extinction coefficients of the VAA–MWNT were studied and correlated with nanotube wall structure. Growth rates for VAA–MWNT are found to vary depending on the catalyst preparation, temperature, and time. Both the highest growth rates (0.3 μm/s...

In situ imaging and spectroscopy of single-wall carbon nanotube synthesis by laser vaporization

The synthesis of single-wall carbon nanotubes by Nd:YAG laser vaporization of a graphite/(Ni, Co) target is investigated by laser-induced luminescence imaging and spectroscopy of Co atoms, C2 and C3 molecules, and clusters at 1000 °C in flowing 500 Torr Ar. These laser-induced emission images under typical synthesis conditions show that the plume of vaporized material is segregated and confined within a vortex ring which maintains a ∼1 cm3 volume for several seconds. Using time-resolved spectroscopy and spectroscopic imaging, the time for conversion of atomic and molecular species to clusters was measured for both carbon (200 μs) and cobalt (2 ms). This rapid conversion of carbon to nanoparticles, combined with transmission electron microscopy analysis of the collected deposits, indicate that nanotube growth occurs over several seconds in a plume of mixed nanoparticles. By adjusting the time spent by the plume within the high-temperature zone using these in situ diagnostics, single-walled nanotubes of con...