Superlattice-Induced Variations in Morphological and Emission Properties of GaInN/GaN Multiquantum Nanowire-Based Micro-LEDs.

Core-shell GaInN/GaN multiquantum shell (MQS) nanowires (NWs) are gaining great attention for high-efficiency micro-light-emitting diodes (micro-LEDs) owing to the minimized etching region on their sidewall, nonpolar or semipolar emission planes, and ultralow density of dislocations. In this study, we evaluated the changes in NW morphologies and the corresponding device properties induced by GaInN/GaN superlattice (SL) structures. The cathodoluminescence intensities of the samples with 20 and 40 pairs of SLs were about 2.2 and 3.4 times higher, respectively, than that of the sample without SLs. The high-resolution scanning transmission electron microscopy (STEM) inspection confirmed that the high growth temperature of SLs prevented growth in the semipolar plane region close to the n-GaN core. A similar phenomenon was also observed for the GaN quantum barriers of the semipolar MQS region under a high growth temperature of 810 °C. This phenomenon was ascribed to the passivation of the semipolar plane surface by hydrogen atoms and the high probability of decomposition through NH3 or N-H-related bonds. Although no clear SL grew on the semipolar plane near the n-core region, the top area of the nonpolar plane SL was expected to adequately suppress the point defects propagating from the n-GaN core to the semipolar plane MQS. The electroluminescence (EL) spectra and light output curves demonstrated a clear enhancement of more than 3-folds compared to the fabricated micro-LEDs without SL structures, which was associated with the improved crystalline quality of the MQS and enlarged area of the semipolar planes. Moreover, by increasing the growth time of GaN quantum barriers, the EL emission intensity of the micro-LED devices exhibited a 4-fold improvement owing to the reduced carrier overflow in the thickened GaN barriers on the semipolar (11̅01) planes. Thus, the results verified the possibility of realizing highly efficient NW-based micro-LEDs by optimizing the NW morphology using SL structures.

Morphology Control and Crystalline Quality of p-Type GaN Shells Grown on Coaxial GaInN/GaN Multiple Quantum Shell Nanowires.

The morphology and crystalline quality of p-GaN shells on coaxial GaInN/GaN multiple quantum shell (MQS) nanowires (NWs) were investigated using metal-organic chemical vapor deposition. By varying the trimethylgallium (TMG) flow rate, Mg doping, and growth temperature, it was verified that the TMG supply and growth temperature were the dominant parameters in the control of the p-GaN shape on NWs. Specifically, a sufficiently high TMG supply enabled the formation of a pyramid-shaped NW structure with a uniform p-GaN shell. The ratio of the growth rate between the c- and m-planes on the NWs was calculated to be approximately 0.4545. High-angle annular dark-field scanning transmission electron microscopy characterization confirmed that no clear extended defects were present in the n-GaN core and MQS/p-GaN shells on the sidewall. Regarding the p-GaN shell above the c-plane MQS region, only a few screw dislocations and Frank-type partial dislocations appeared at the interface between the serpentine c-plane MQS and the p-GaN shell near the tips. This suggested that the crystalline quality of the MQS structure can trigger the formation of screw dislocations and Frank-type partial dislocations during the p-GaN growth. The growth mechanism of the p-GaN shell on NWs was also discussed. To inspect the electronic properties, a prototype of a micro light-emitting diode (LED) with a chip size of 50 × 50 µm2 was demonstrated in the NWs with optimal growth. By correlating the light output curve with the electroluminescence spectra, three different emission peaks (450, 470, and 510 nm) were assignable to the emission from the m-, r-, and c-planes, respectively.

Crystal Growth and Characterization of n-GaN in a Multiple Quantum Shell Nanowire-Based Light Emitter with a Tunnel Junction.

Here, we systematically investigated the growth conditions of an n-GaN cap layer for nanowire-based light emitters with a tunnel junction. Selective-area growth of multiple quantum shell (MQS)/nanowire core-shell structures on a patterned n-GaN/sapphire substrate was performed by metal-organic vapor phase epitaxy, followed by the growth of a p-GaN, an n++/ p++-GaN tunnel junction, and an n-GaN cap layer. Specifically, two-step growth of the n-GaN cap layer was carried out under various growth conditions to determine the optimal conditions for a flat n-GaN cap layer. Scanning transmission electron microscopy characterization revealed that n++-GaN can be uniformly grown on the m-plane sidewall of MQS nanowires. A clear tunnel junction, involving 10-nm-thick p++-GaN and 3-nm-thick n++-GaN, was confirmed on the nonpolar m-planes of the nanowires. The Mg doping concentration and distribution profile of the p++-GaN shell were inspected using three-dimensional atom probe tomography. Afterward, the reconstructed isoconcentration mapping was applied to identify Mg-rich clusters. The density and average size of the Mg clusters were estimated to be approximately 4.3 × 1017 cm-3 and 5 nm, respectively. Excluding the Mg atoms contained in the clusters, the remaining Mg doping concentration in the p++-GaN region was calculated to be 1.1 × 1020 cm-3. Despite the lack of effective activation, a reasonably low operating voltage and distinct light emissions were preliminarily observed in MQS nanowire-based LEDs under the optimal n-GaN cap growth conditions. In the fabricated MQS-nanowire devices, carriers were injected into both the r-plane and m-plane of the nanowires without a clear quantum confinement Stark effect.

Identification of multi-color emission from coaxial GaInN/GaN multiple-quantum-shell nanowire LEDs.

Multi-color emission from coaxial GaInN/GaN multiple-quantum-shell (MQS) nanowire-based light-emitting diodes (LEDs) was identified. In this study, MQS nanowire samples for LED processes were selectively grown on patterned commercial GaN/sapphire substrates using metal-organic chemical vapor deposition. Three electroluminescence (EL) emission peaks (440, 540, and 630 nm) were observed, which were primarily attributed to the nonpolar m-planes, semipolar r-planes, and the polar c-plane tips of nanowire arrays. A modified epitaxial growth sequence with improved crystalline quality for MQSs was used to effectively narrow the EL emission peaks. Specifically, nanowire-based LEDs manifested a clear redshift from 430 nm to 520 nm upon insertion of AlGaN spacers after the growth of each GaInN quantum well. This demonstrates the feasibility of lengthening the EL emission wavelength since an AlGaN spacer can suppress In decomposition of the GaInN quantum wells during ramping up the growth temperature for GaN barriers. EL spectra showed stable emission peaks as a function of the injection current, verifying the critical feature of the non-polarization of GaN/GaInN MQSs on nanowires. In addition, by comparing EL and photoluminescence spectra, the yellow-red emission linked to the In-fluctuation and point defects in the c-plane MQS was verified by varying the activation annealing time and lowering the growth temperature of the GaInN quantum wells. Therefore, optimization of MQS nanowire growth with a high quality of c-planes is considered critical for improving the luminous efficiency of nanowire-based micro-LEDs/white LEDs.

Correlation between Optical and Structural Characteristics in Coaxial GaInN/GaN Multiple Quantum Shell Nanowires with AlGaN Spacers.

High crystalline quality coaxial GaInN/GaN multiple quantum shells (MQSs) grown on dislocation-free nanowires are highly in demand for efficient white-/micro-light-emitting diodes (LEDs). Here, we propose an effective approach to improve the MQS quality during the selective growth by metal-organic chemical vapor deposition. By increasing the growth temperature of GaN barriers, the cathodoluminescent intensity yielded enhancements of 0.7 and 3.9 times in the samples with GaN and AlGaN spacers, respectively. Using an AlGaN spacer before increasing the barrier temperature, the decomposition of GaInN quantum wells was suppressed on all planes, resulting in a high internal quantum efficiency up to 69%. As revealed by scanning transmission electron microscopy (STEM) characterization, the high barrier growth temperature allowed to achieve a clear interface between GaInN quantum wells and GaN quantum barriers on the c-, r-, and m-planes of the nanowires. Moreover, the correlation between the In incorporation and structure features in MQS was quantitatively assessed based on the STEM energy-dispersive X-ray spectroscopy mapping and line-scan profiles of In and Al fractions. Ultimately, it was demonstrated that the unintentional In incorporation in GaN barriers was induced by the evaporation of predeposited In-rich particles during low-temperature growth of GaInN wells. Such residual In contamination was sufficiently inhibited by inserting low Al fraction (∼6%) AlGaN spacers after each GaInN well. During the growth of AlGaN spacers, AlN polycrystalline particles were deposited on the surrounding dummy substrate, which suppressed the evaporation of the predeposited In-rich particles. Thus, the presence of AlGaN spacers certainly improved the uniformity of In fraction through five GaInN quantum wells and reduced the diffusion of point defects from n-core to MQS active structures. The superior coaxial GaInN/GaN MQS structures with the AlGaN spacer are supposed to improve the emission efficiency in white-/micro-LEDs.

Development of Monolithically Grown Coaxial GaInN/GaN Multiple Quantum Shell Nanowires by MOCVD.

Broadened emission was demonstrated in coaxial GaInN/GaN multiple quantum shell (MQS) nanowires that were monolithically grown by metalorganic chemical vapor deposition. The non-polar GaInN/GaN structures were coaxially grown on n-core nanowires with combinations of three different diameters and pitches. To broaden the emission band in these three nanowire patterns, we varied the triethylgallium (TEG) flow rate and the growth temperature of the quantum barriers and wells, and investigated their effects on the In incorporation rate during MQS growth. At higher TEG flow rates, the growth rate of MQS and the In incorporation rate were promoted, resulting in slightly higher cathodoluminescence (CL) intensity. An enhancement up to 2-3 times of CL intensity was observed by escalating the growth temperature of the quantum barriers to 800 °C. Furthermore, decreasing the growth temperature of the quantum wells redshifted the peak wavelength without reducing the MQS quality. Under the modified growth sequence, monolithically grown nanowires with a broaden emission was achieved. Moreover, it verified that reducing the filling factor (pitch) can further promote the In incorporation probability on the nanowires. Compared with the conventional film-based quantum well LEDs, the demonstrated monolithic coaxial GaInN/GaN nanowires are promising candidates for phosphor-free white and micro light-emitting diodes (LEDs).

Effect of AlGaN undershell on the cathodoluminescence properties of coaxial GaInN/GaN multiple-quantum-shells nanowires.

Coaxial GaInN/GaN multiple-quantum-shells (MQSs) nanowires (NWs) were grown on an n-type GaN/sapphire template employing selective growth by metal-organic chemical vapour deposition (MOCVD). To improve the cathodoluminescence (CL) emission intensity, an AlGaN shell was grown underneath the MQS active structures. By controlling the growth temperature and duration, an impressive and up to 11-fold enhancement of CL intensity is achieved at the top area of the GaInN/GaN MQS NWs. The spatial distribution of Al composition in the AlGaN undershell was assessed as a function of position along the NW and analysed by energy-dispersive X-ray measurement and CL characterisation. By introducing an AlGaN shell underneath GaInN/GaN MQS, the diffusion of point defects from the n-core to MQS is effectively suppressed because of the lower formation energy of vacancies-complexes in AlGaN in comparison to GaN. Moreover, the spatial distribution of Al and In was attributed to the insufficient delivery of gas precursors to the bottom of the NWs and the anisotropy diffusion on the nonpolar m-planes. This investigation can shed light on the effect of the AlGaN undershell on improving the emission efficiency of NW-based white and micro-light-emitting diodes (LEDs).