AgScP2S6 van der Waals Layered Crystal: A Material with a Unique Combination of Extreme Nonlinear Optical Properties.

Research in two-dimensional layered materials (2DLMs) has exploded over the past several years for a variety of applications in photonics and optoelectronics. The 2D nature of these materials allows for a very local electronic probe of material as well as flexible integration with other functional components. Herein, using the femtosecond Z-scan technique, we report a giant two photon absorption (TPA) process and its saturation in the van der Waals gapped silver scandium thiophosphate (AgScP2S6) crystal. We have found a TPA coefficient of the order of 104 cm/GW which is orders of magnitude larger compared to many existing semiconductors and nonlinear crystals. Furthermore, we found a TPA cross-section of 103 GM and characterized the optical limiting (OL) response (0.2 mJ/cm2) and the multipulse laser damage threshold (1.09 ± 0.19 J/cm2). The combination of giant TPA, extremely low OL, and very high damage threshold suggests that this material could be extremely useful in applications like optical limiters or switches.

Ultrafast Nonlinear Absorption and Second Harmonic Generation in Cu0.33In1.30P2S6 van der Waals Layered Crystals.

The advancement of ultrafast photonics and optoelectronic devices necessitates the exploration of new materials with optical and chemical stability to implement practical applications. Layered quaternary metal-thio/selenophosphate has attracted much interest over the past few years. Ferroelectric CuInP2S6 (CIPS) is an emerging material that belongs to this family. When synthesized with Cu deficiencies, CIPS forms self-assembled in-plane heterostructures, which in turn exhibit properties that are both compositionally and thermally dependent. These characteristics can be explored for applications in nonlinear optoelectronic and photonic devices. Herein, we study the second and third order nonlinear optical behavior of Cu0.33In1.30P2S6 bulk heterostructure. We observed large two photon induced nonlinear absorptions and self-defocusing at 1032 nm pulsed laser excitation using the Z-scan technique. Furthermore, we identified a polarization-dependent second harmonic signal and determined the laser-induced optical damage threshold. Our observations allow for the designing of optoelectronic and ultrafast photonic devices based on these materials.

Excimer-Mediated Intermolecular Charge Transfer in Self-Assembled Donor-Acceptor Dyes on Metal Oxides.

When conjugate molecules are self-assembled on the surface of semiconductors, emergent properties resulting from the electronic coupling between the conjugate moieties are of importance in the interfacial electron-transfer dynamics for photoelectrochemical and optoelectronics devices. In this work, we investigate the self-assembly of triphenylamine-oligothiophene-perylenemonoimide (PMI) molecules, denoted as BH4, on metal oxide surfaces via UV-vis absorption, photoluminescence, and transient near-infrared absorption spectroscopies and molecular dynamics simulations, and we report the excimer formation due to the π-π interaction of the PMI units between the neighboring dye molecules. To our best knowledge, this is the first experimental observation of intermolecular excimer formation when conjugate donor-acceptor molecules form a self-assembled monolayer. In addition, a long-lived (4.3 µs) intermolecular charge separation is observed, and a new excimer-mediated intermolecular charger-transfer mechanism is proposed. This work demonstrates that, through the design of dye molecules, the excited complexes or aggregates can provide a pathway to slow down the recombination rate in photoelectrodes that utilize donor-acceptor dyad molecules.

Nano-Cathodoluminescence Measurement of Asymmetric Carrier Trapping and Radiative Recombination in GaN and InGaN Quantum Disks.

The ability to characterize recombination and carrier trapping processes in group-III nitride-based nanowires is vital to further improvements in their overall efficiencies. While advances in scanning transmission electron microscope (STEM)-based cathodoluminescence (CL) have offered some insight into nanowire behavior, inconsistencies in nanowire emission along with CL detector limitations have resulted in the incomplete understanding in nanowire emission processes. Here, two nanowire heterostructures were explored with STEM-CL: a polarization-graded AlGaN nanowire light-emitting diode (LED) with a GaN quantum disk and a polarization-graded AlGaN nanowire with three different InGaN quantum disks. Most nanowires explored in this study did not emit. For the wires that did emit in both structures, they exhibited asymmetrical emission consistent with the polarization-induced electric fields in the barrier regions of the nano-LEDs. In the AlGaN/InGaN sample, two of the quantum disks exhibited no emission potentially due to the three-dimensional landscape of the sample or due to limitations in the CL detection.

Nanoscale Electronic Conditioning for Improvement of Nanowire Light-Emitting-Diode Efficiency.

Commercial III-Nitride LEDs and lasers spanning visible and ultraviolet wavelengths are based on epitaxial films. Alternatively, nanowire-based III-Nitride optoelectronics offer the advantage of strain compliance and high crystalline quality growth on a variety of inexpensive substrates. However, nanowire LEDs exhibit an inherent property distribution, resulting in uneven current spreading through macroscopic devices that consist of millions of individual nanowire diodes connected in parallel. Despite being electrically connected, only a small fraction of nanowires, sometimes <1%, contribute to the electroluminescence (EL). Here, we show that a population of electrical shorts exists in the devices, consisting of a subset of low-resistance nanowires that pass a large portion of the total current in the ensemble devices. Burn-in electronic conditioning is performed by applying a short-term overload voltage; the nanoshorts experience very high current density, sufficient to render them open circuits, thereby forcing a new current path through more nanowire LEDs in an ensemble device. Current-voltage measurements of individual nanowires are acquired using conductive atomic force microscopy to observe the removal of nanoshorts using burn-in. In macroscopic devices, this results in a 33× increase in peak EL and reduced leakage current. Burn-in conditioning of nanowire ensembles therefore provides a straightforward method to mitigate nonuniformities inherent to nanowire devices.

Ultrathin GaN quantum disk nanowire LEDs with sub-250 nm electroluminescence.

By quantum confining GaN at monolayer thickness with AlN barriers inside of a nanowire, deep ultraviolet LEDs are demonstrated. Full three-dimensional strain dependent energy band simulations are carried out within multiple quantum disk (MQD) GaN/AlN nanowire superlattice heterostructures. It is found that, even within the same nanowire MQD, the emission energy of the ultrathin GaN QDs varies from disk to disk due to the changing strain distribution and polarization charge induced energy band bending along the axial nanowire direction. MQD heterostructures are grown by plasma-assisted molecular beam epitaxy to form self-assembled catalyst-free nanowires with 1 to 2 monolayer thick GaN insertions within an AlN matrix. Photoluminescence peaks are observed at 295 nm and 283 nm from the 2 ML and 1 ML thick MQD samples, respectively. Polarization-doped nanowire LEDs are grown incorporating 1 ML thick GaN MQD active regions from which we observe deep ultraviolet electroluminescence. The shortest LED wavelength peak observed is 240 nm and attributed to electron hole recombination within 1 ML thick GaN QDs.

Semiconductor Nanowire Light-Emitting Diodes Grown on Metal: A Direction Toward Large-Scale Fabrication of Nanowire Devices.

Bottom-up nanowires are attractive for realizing semiconductor devices with extreme heterostructures because strain relaxation through the nanowire sidewalls allows the combination of highly lattice mismatched materials without creating dislocations. The resulting nanowires are used to fabricate light-emitting diodes (LEDs), lasers, solar cells, and sensors. However, expensive single crystalline substrates are commonly used as substrates for nanowire heterostructures as well as for epitaxial devices, which limits the manufacturability of nanowire devices. Here, nanowire LEDs directly grown and electrically integrated on metal are demonstrated. Optical and structural measurements reveal high-quality, vertically aligned GaN nanowires on molybdenum and titanium films. Transmission electron microscopy confirms the composition variation in the polarization-graded AlGaN nanowire LEDs. Blue to green electroluminescence is observed from InGaN quantum well active regions, while GaN active regions exhibit ultraviolet emission. These results demonstrate a pathway for large-scale fabrication of solid state lighting and optoelectronics on metal foils or sheets.

Phonon-induced diamagnetic force and its effect on the lattice thermal conductivity.

Phonons are displacements of atoms around their rest positions in a crystalline solid. They carry sound and heat, but are not classically associated with magnetism. Here, we show that phonons are, in fact, sensitive to magnetic fields, even in diamagnetic materials. We do so by demonstrating experimentally that acoustic phonons in a diamagnetic semiconductor (InSb) scatter more strongly from one another when a magnetic field is applied. We attribute this observation to the magnetic-field sensitivity of the anharmonicity of the interatomic bonds that govern the probability of phonon-phonon interactions. The displacements of atoms locally affect the orbital motion of valence band electrons, which, in the presence of an external magnetic field, spatially modulates the orbital diamagnetism around the displaced atoms. The spatial gradient in magnetic moment results in an anharmonic magnetic force exerted on the displaced atom. The process is modelled by ab initio calculations that, without the use of a single adjustable parameter, reproduce the observed 12% decrease in the lattice thermal conductivity under a 7 T magnetic field at a temperature of 5.2 K.

Deep ultraviolet emitting polarization induced nanowire light emitting diodes with AlxGa1-xN active regions.

In this report, we demonstrate band gap tuning of the active region emission wavelength from 365 nm to 250 nm in light emitting diodes fashioned from catalyst-free III-nitride nanowires. Optical characteristics of the nanowire heterostructures and fabricated devices are studied via electroluminescence (EL) and photoluminescence spectroscopy over a wide range of active region compositions. It is observed that for typical nanowire plasma assisted molecular beam epitaxy growth conditions, tuning of emission to wavelengths shorter than 300 nm is hampered by the presence of an optically active defect level. We show that by increasing the AlGaN nanowire growth temperatures this defect emission can be suppressed. These findings are applied to growth of the active region of a nanowire light emitting diode, resulting in a polarization-induced nanowire light emitting diode with peak EL at 250 nm.

Mixed polarity in polarization-induced p-n junction nanowire light-emitting diodes.

Polarization-induced nanowire light emitting diodes (PINLEDs) are fabricated by grading the Al composition along the c-direction of AlGaN nanowires grown on Si substrates by plasma-assisted molecular beam epitaxy (PAMBE). Polarization-induced charge develops with a sign that depends on the direction of the Al composition gradient with respect to the [0001] direction. By grading from GaN to AlN then back to GaN, a polarization-induced p-n junction is formed. The orientation of the p-type and n-type sections depends on the material polarity of the nanowire (i.e., Ga-face or N-face). Ga-face material results in an n-type base and a p-type top, while N-face results in the opposite. The present work examines the polarity of catalyst-free nanowires using multiple methods: scanning transmission electron microscopy (STEM), selective etching, conductive atomic force microscopy (C-AFM), and electroluminescence (EL) spectroscopy. Selective etching and STEM measurements taken in annular bright field (ABF) mode demonstrate that the preferred orientation for catalyst-free nanowires grown by PAMBE is N-face, with roughly 10% showing Ga-face orientation. C-AFM and EL spectroscopy allow electrical and optical differentiation of the material polarity in PINLEDs since the forward bias direction depends on the p-n junction orientation and therefore on nanowire polarity. Specifically, C-AFM reveals that the direction of forward bias for individual nanowire LEDs changes with the polarity, as expected, due to reversal of the sign of the polarization-induced charge. Electroluminescence measurements of mixed polarity PINLEDs wired in parallel show ambipolar emission due to the mixture of p-n and n-p oriented PINLEDs. These results show that, if catalyst-free III-nitride nanowires are to be used to form polarization-doped heterostructures, then it is imperative to understand their mixed polarity and to design devices using these nanowires accordingly.

GdN nanoisland-based GaN tunnel junctions.

Tunnel junctions could have a great impact on gallium nitride and aluminum nitride-based devices such as light-emitting diodes and lasers by overcoming critical challenges related to hole injection and p-contacts. This paper demonstrates the use of GdN nanoislands to enhance interband tunneling and hole injection into GaN p-n junctions by several orders of magnitude, resulting in low tunnel junction specific resistivity (1.3 × 10(-3) Ω-cm(2)) compared to the previous results in wide band gap semiconductors. Tunnel injection of holes was confirmed by low-temperature operation of GaN p-n junction with a tunneling contact layer, and strong electroluminescence down to 20 K. The low tunnel junction resistance combined with low optical absorption loss in GdN is very promising for incorporation in GaN-based light emitters.

Full-scale characterization of UVLED Al(x)Ga(1-x)N nanowires via advanced electron microscopy.

III-Nitride semiconductor heterostructures continue to attract a great deal of attention due to the wide range of wavelengths at which they can emit light, and the subsequent desire to employ them in optoelectronic applications. Recently, a new type of pn-junction which relies on polarization-induced doping has shown promise for use as an ultraviolet light emitting diode (UVLED); nanowire growth of this device has been successfully demonstrated. However, as these devices are still in their infancy, in order to more fully understand their physical and electronic properties, they require a multitude of characterization techniques. Specifically, the present contribution will discuss the application of advanced scanning transmission electron microscopy (STEM) to AlxGa1-xN UVLED nanowires. In addition to structural data, chemical and electronic properties will also be probed through various spectroscopy techniques, with the focus remaining on practically applying the knowledge gained via STEM to the growth procedures in order to optimize device peformance.

Polarization-induced pn diodes in wide-band-gap nanowires with ultraviolet electroluminescence.

Almost all electronic devices utilize a pn junction formed by random doping of donor and acceptor impurity atoms. We developed a fundamentally new type of pn junction not formed by impurity-doping, but rather by grading the composition of a semiconductor nanowire resulting in alternating p and n conducting regions due to polarization charge. By linearly grading AlGaN nanowires from 0% to 100% and back to 0% Al, we show the formation of a polarization-induced pn junction even in the absence of any impurity doping. Since electrons and holes are injected from AlN barriers into quantum disk active regions, graded nanowires allow deep ultraviolet LEDs across the AlGaN band-gap range with electroluminescence observed from 3.4 to 5 eV. Polarization-induced p-type conductivity in nanowires is shown to be possible even without supplemental acceptor doping, demonstrating the advantage of polarization engineering in nanowires compared with planar films and providing a strategy for improving conductivity in wide-band-gap semiconductors. As polarization charge is uniform within each unit cell, polarization-induced conductivity without impurity doping provides a solution to the problem of conductivity uniformity in nanowires and nanoelectronics and opens a new field of polarization engineering in nanostructures that may be applied to other polar semiconductors.

Three-dimensional GaN/AlN nanowire heterostructures by separating nucleation and growth processes.

Bottom-up nanostructure assembly has been a central theme of materials synthesis over the past few decades. Semiconductor quantum dots and nanowires provide additional degrees of freedom for charge confinement, strain engineering, and surface sensitivity-properties that are useful to a wide range of solid state optical and electronic technologies. A central challenge is to understand and manipulate nanostructure assembly to reproducibly generate emergent structures with the desired properties. However, progress is hampered due to the interdependence of nucleation and growth phenomena. Here we show that by dynamically adjusting the growth kinetics, it is possible to separate the nucleation and growth processes in spontaneously formed GaN nanowires using a two-step molecular beam epitaxy technique. First, a growth phase diagram for these nanowires is systematically developed, which allows for control of nanowire density over three orders of magnitude. Next, we show that by first nucleating nanowires at a low temperature and then growing them at a higher temperature, height and density can be independently selected while maintaining the target density over long growth times. GaN nanowires prepared using this two-step procedure are overgrown with three-dimensionally layered and topologically complex heterostructures of (GaN/AlN). By adjusting the growth temperature in the second growth step either vertical or coaxial nanowire superlattices can be formed. These results indicate that a two-step method allows access to a variety of kinetics at which nanowire nucleation and adatom mobility are adjustable.