Santino D. Carnevale

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.

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.

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.

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.

Coaxial nanowire resonant tunneling diodes from non-polar AlN/GaN on silicon

Resonant tunneling diodes are formed using AlN/GaN core-shell nanowire heterostructures grown by plasma assisted molecular beam epitaxy on n-Si(111) substrates. By using a coaxial geometry, these devices take advantage of non-polar (m-plane) nanowire sidewalls. Device modeling predicts non-polar orientation should enhance resonant tunneling compared to a polar structure, and that AlN double barriers will lead to higher peak-to-valley current ratios compared to AlGaN barriers. Electrical measurements of ensembles of nanowires show negative differential resistance appearing only at cryogenic temperature. Individual nanowire measurements show negative differential resistance at room temperature with peak current density of 5 × 105 A/cm2.

GaAs

Monolithic, epitaxial, series-connected GaAs0.75P0.25/Si dual-junction solar cells, grown via both molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition (MOCVD), are reported for the first time. Fabricated test devices for both cases show working tandem behavior, with clear voltage addition and spectral partitioning. However, due to thermal budget limitations in the MBE growth needed to prevent tunnel junction failure, the MBE-grown GaAs0.75P0.25 top cell was found to be lower quality than the equivalent MOCVD-grown device. Additionally, despite the reduced thermal budget, the MBE-grown tunnel junction exhibited degraded behavior, further reducing the overall performance of the MBE/MOCVD combination cell. The all-MOCVD-grown structure displayed no such issues and yielded significantly higher overall performance. These initial prototype cells show promising performance and indicate several important pathways for further device refinement.

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Electron channeling contrast imaging (ECCI) is used to characterize misfit dislocations in heteroepitaxial layers of GaP grown on Si(100) substrates. Electron channeling patterns serve as a guide to tilt and rotate sample orientation so that imaging can occur under specific diffraction conditions. This leads to the selective contrast of misfit dislocations depending on imaging conditions, confirmed by dynamical simulations, similar to using standard invisibility criteria in transmission electron microscopy (TEM). The onset and evolution of misfit dislocations in GaP films with varying thicknesses (30 to 250 nm) are studied. This application simultaneously reveals interesting information about misfit dislocations in GaP/Si layers and demonstrates a specific measurement for which ECCI is preferable versus traditional plan-view TEM.

P

We report a systematic study of p-type polarization-induced doping in graded AlGaN nanowire light emitting diodes grown on silicon wafers by plasma-assisted molecular beam epitaxy. The composition gradient in the p-type base is varied in a set of samples from 0.7%Al/nm to 4.95%Al/nm corresponding to negative bound polarization charge densities of 2.2 × 1018 cm−3 to 1.6 × 1019 cm−3. Capacitance measurements and energy band modeling reveal that for gradients greater than or equal to 1.30%Al/nm, the deep donor concentration is negligible and free hole concentrations roughly equal to the bound polarization charge density are achieved up to 1.6 × 1019 cm−3 at a gradient of 4.95%Al/nm. Accurate grading lengths in the p- and n-side of the pn-junction are extracted from scanning transmission electron microscopy images and are used to support energy band calculation and capacitance modeling. These results demonstrate the robust nature of p-type polarization doping in nanowires and put an upper bound on the magnitu...

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Electron channeling contrast imaging (ECCI) is a nondestructive diffraction-based scanning electron microscopy (SEM) technique that can provide microstructural analysis similar to transmission electron microscopy (TEM). However, because ECCI is performed within an SEM and requires little to no sample preparation, such analysis can be accomplished in a fraction of the time. Like TEM, ECCI can be used to image a variety of extended defects and enables the use of standard invisibility criteria to provide further defect characterization (e.g., Burgers vector determination). Here, we use ECCI to characterize various extended defects, including threading dislocations, misfit dislocations, and stacking faults, in heteroepitaxial GaP/Si(1 0 0) samples. We also present applications for which ECCI is particularly well suited compared with conventional methods. First, misfit dislocations are surveyed via ECCI across the radius of a 4-in GaP/Si wafer, yielding a proof-of-concept rapid (~3 h) approach to large-area defect characterization. Second, by simply wet etching away a portion of a thick epitaxial GaP-on-Si layer, we use ECCI to image specific targeted interfaces within a heterostructure. Both of these applications are prime examples of how ECCI is a compelling alternative to TEM in circumstances where the required sample preparation would be prohibitively time-consuming or difficult.