On the Origin of the 4.7 eV Absorption and 2.8 eV Emission Bands in Bulk AlN Substrates
Authors: Alden Dorian , Bryan Zachary , Gaddy Benjamin , Bryan Isaac , Callsen Gordon , Koukitu Akinori , Kumagai Yoshinao , Hoffmann Axel , Irving Doug , Sitar Zlatko , Collazo Ramon 
Published: February 2020

AlGaN alloys are the building blocks for deep UV optoelectronics and high-power devices. It has been demonstrated that the highest crystalline quality AlGaN films with high Al content are obtained on AlN single crystal substrates. The resulting mismatch between AlGaN and AlN causes a compressive strain within the AlGaN layers, which varies with composition. Nevertheless, pseudomorphic AlGaN films with Al content higher than 50%, and dislocation densities lower than 104 cm-2 have been achieved, sustaining compressive stresses with thicknesses exceeding 3 µm. Such results demonstrate the advantages of using AlN substrates for this technology, and at such some have been realized on several deep-UV optoelectronics applications. Kinoshita et al. have demonstrated UV LEDs emitting at 265 nm with output powers exceeding 80 mW. UV LEDs grown on these native substrates have higher reliabilities and higher output powers. In addition, optically pumped lasers emitting at wavelengths between 230 nm and 280 nm that display cavity modes and single polarized-state emission with low lasing thresholds have been developed. Nevertheless, there are several limitations related to the performance and further improvement of the active regions as related to their quantum efficiencies and the polarization of their emission is desired. These limitations will be classified in two main categories: (1) identification and control of point defects, and (2) efficient doping.
One of the main limitations based on point defects is the one related to the UV absorption band present at 265 nm in AlN. This relatively broad absorption band limits the use of the substrate within the deep UV range and several complicated fabrication procedures were devised to overcome this limitation. In this work, the origin of this absorption band will be discussed, along with other related optical features and the use of co-doping as a way of removing this undesired absorption. Experimental and theoretical results that explore the optical properties of native and impurity point defects as well as point-defect complexes in AlN with respect to the 265 nm absorption band will be presented. Theoretical results, based on DFT, are compared to photoluminescence and absorption measurements of AlN samples grown by physical vapor transport, metal-organic chemical vapor deposition, and hydride vapor-phase epitaxy . Our results demonstrate that there are multiple sources of a deep-UV absorption between 4.5 and 5.0 eV. The presence of the isolated carbon substitutional CN
- produces an absorption band centered at 4.7 eV and emission at 3.9 eV, thus its reduction leads to the reduction of the absorption band. In addition, one mechanism that contributes to the apparent UV transparency when the material is co-doped with Si is discussed. These schemes produced transparent AlN wafers suitable for deep UV LED production.
The other limitation relates to obtaining technologically useful n-type conductivities in high Al-content AlGaN within the low and high doping regimes. Besides dislocation density reduction, identification and elimination of compensating defects are necessary to achieve this goal. AlGaN films with high Al mole fractions (0.65<x<1) were grown by MOCVD on single crystalline AlN and sapphire. It is found that with an increase in Al content, there was both a decrease in the free carrier concentration and mobility. The reduction in free carrier concentration for x>0.8 was primarily caused by an increase in activation energy. This is due to the formation of a Si DX-center, thus inspiring the search for alternative dopants. Preliminary data on Ge doping of AlGaN will be presented to assess its effectiveness as a donor throughout the whole composition regime.
In addition, for samples grown with different Si doping levels it is observed that up to a critical Si concentration, the carrier concentration was always proportional to the Si source flow. Any further increase led to a free carrier concentration reduction. PL spectra exhibited deep defect-related peaks corresponding to transitions between Si and deep acceptor states. For Si concentrations less than an Al-content dependent critical concentration, a higher energy peak dominates the spectra. This peak was related to a (VAl-complex)2- based on DFT calculations. For Si concentrations greater than the critical concentration, a (VAl)3- related lower energy peak dominates the spectra. The energy levels associated with these defects increased with Al composition where the energy increase was the same as the increase in band gap.

Acknowledgement: Partial financial support from NSF (DMR-1312582 and ECCS-1508854), DARPA (W911QX-10-C-0027), ARPA-E (DE-AR0000299), ARO (W911NF14C0008) is greatly appreciated. All PVT AlN wafers used for homoepitaxial growth were supplied by HexaTech, Inc., Morrisville, NC.