Degradation mechanisms of 275-nm-band AlGaN quantum well deep-ultraviolet light-emitting diodes fabricated on a (0001) sapphire substrate were investigated under hard operation conditions. The optical output power (Po) initially decreased by about 20 % within the operating time less than 102 h and then gradually decreased to about 60 % by 484 h. Because the degradation of the wells was less significant than the Po reduction, the initial degradation is attributed essentially to the decrease in carrier injection efficiency, most likely due to de-passivation of initially H-passivated preexisting nonradiative recombination centers (NRCs) in a Mg-doped p-type Al0.85Ga0.15N electron blocking layer. According to our database on the species of vacancy-type defects acting as NRCs in GaN and AlN, vacancy clusters comprised of a cation vacancy and nitrogen vacancies are the most suspicious origins of the NRCs.
In this presentation, seeded growths of large diameter GaN crystals using the low-pressure acidic ammonothermal (LPAAT) method operated at around 100 MPa will be demonstrated. Nearly bowing- and mosaic-free GaN crystals exhibiting the full-width at half-maximum values for the 0002 X-ray rocking curves below 20 arcsec were achieved on high lattice coherency c-plane AAT seeds with gross dislocation densities in the order of 104 cm−2. The photoluminescence spectra of the grown crystals exhibited a predominant near-band-edge emission at 295 K, of which intensity was one order of magnitude higher than the characteristic deep-state emission called "yellow luminescence band". A nearly bowing-free large diameter c-plane GaN crystal was eventually obtained.
The results of complimentary time-resolved photoluminescence and positron annihilation measurements on Mg-implanted GaN on GaN fabricated using various I/I sequences will be shown to identify the species and quantify the concentrations and minority carrier capture coefficients of major midgap recombination centers (MGRCs) created by the I/I processes. Because vacancy clusters comprised of Ga vacancies (VGa) and N vacancies (VN) such as (VGaVN)3 were assigned as major vacancy-type defects and the room-temperature photoluminescence lifetime for the NBE emission increased with decreasing their concentration, (VGaVN)3 are assigned as major nonradiative recombination centers with electron capture coefficient of 5×10-6 cm3s-1, which is an order of magnitude larger than the hole capture coefficient of VGaVN in n-GaN (6×10-7 cm3s-1).
Financial supports: CSTI-SIP, MEXT (JPJ005357, JPJ009777, JP16H06427, JP21H01826), PNCRD TECHMATSTRATEG-III/0003/2019-00 and PNSC 2018/29/B/ST5/00338.
KEYWORDS: Deep ultraviolet, Light emitting diodes, Wireless communications, Signal to noise ratio, Sun, Signal attenuation, Lighting standards, Light sources and illumination, Interference (communication), Epitaxy
Since the intensity of deep ultraviolet (DUV) light with the wavelength below 300 nm is nearly zero in the sun spectrum, optical wireless communications (OWC) based on DUV light can have a unique “zero-background” characteristics. We recently demonstrated LED-based DUV OWC at 280-nm band over a 1.5-m direct line-of-site channel realizing the effective data rate of as fast as >2 Gbps under standard room lighting and >1 Gbps under direct sun with outdoor experiments. These experiments were performed off-the-shell DUV AlGaN light-emitting diodes, which was grown by metalorganic vapor-phase epitaxy using an AlN/sapphire template with dense macrosteps.
Behaviors of vacancy-type defects in ion-implanted GaN were studied by means of positron annihilation. Si or Mg ions were implanted into GaN to obtain 300-nm-deep box profiles of the impurities. The ion-implanted samples were annealed up to 1480°C under a N2 pressure of 1 GPa (ultra-high-pressure annealing: UHPA). For as-implanted GaN, the major defect species was identified as Ga-vacancy-type defects such as a divacancy (VGaVN). After annealing above 1000°C, vacancy clusters, such as (VGaVN)3, were introduced, and they were found to be remained even after 1480°C annealing. For Mg-implanted GaN with [Mg]=1018 cm-3, no large change in the depth distribution of Mg was observed before and after annealing at 1400°C. For the sample with [Mg]=1019 cm-3, however, Mg diffused into the bulk, which was attributed to the over-doping of Mg and their vacancy-assisted diffusion. The Mg diffusion was suppressed by sequential N-implantation, which was attributed to the reaction between Mg and vacancies under a N-rich condition. Interactions between vacancies, Mg, and H during UHPA were also discussed.
High-speed optical wireless communication (OWC) systems based on light-emitting diode (LED), such as Li-Fi, are promising solutions for the looming spectrum crisis in 6G wireless communications. OWCs typically extend the RF spectrum by harnessing the visible light and infrared spectra, but the recent advancements in deep-ultraviolet (DUV) LED device technology allow us to further extend the OWC spectrum down to the DUV range, namely the solar-blind band. This talk reviews the recent progress of the high-speed OWCs based on DUV-LEDs including Gbps-class transmission demonstrations in direct sunlight and analyses on the microscopic structural and optical characteristics of high-speed AlGaN-based LEDs.
Vacancies in Mg-implanted GaN were probed using positron annihilation technique. Mg was implanted into GaN with [Mg] = 1E19 /cm3. For an as-implanted sample, the major defect species was identified as Ga-vacancy related defects. The sample was annealed under a nitrogen pressure of 1 GPa in a temperature range of 1000–1480C without a protective capping layer. Comparing with the sample annealed with the capping layer, although no large difference in the defect spices was observed, their concentration was decreased by the cap-less annealing. The diffusion of Mg during annealing was influenced by the presence of residual vacancies. H was unintentionally incorporated into the sample during annealing, and its diffusion property were also affected by vacancies and Mg. A part of this work was supported by MEXT “Research and development of next-generation semiconductor to realize energy-saving society (JPJ005357)” and the Polish National Science Centre through project No 2018/29/B/ST5/00338.
Vacancy-type defects in Mg-implanted GaN were probed using monoenergetic positron beams. Mg+ ions were implanted to provide box profiles with Mg concentrations [Mg] of 1017-1019 cm-3. For as-implanted samples, the major defect species was determined to be Ga-vacancy (VGa) related defects such as divacancy (VGaVN) and/or their complexes with impurities. For Mg-implanted samples, an agglomeration of vacancies started at 800-1000°C annealing, leading to the formation of vacancy clusters such as (VGaVN)3. For the sample with [Mg]=1019 cm-3, the trapping rate of positrons to the vacancies decreased with increasing annealing temperature (≥1100°C), which was attributed to the change in the charge state of vacancy-type defects from neutral to positive (or negative to neutral) due to the activation of Mg. For Mg- and H-implanted samples, the hydrogenation of vacancy-type defects started after 800°C annealing. Comparing with the annealing behavior of defects for the samples without H-implantation, the clustering of vacancy-type defects was suppressed, which can be attributed to the interaction between Mg, H, and vacancies.
With respect to (Al,In,Ga)N epilayers and quantum wells, threading dislocations (TDs) have long been believed to as the principal limiting factor for the internal quantum efficiency of the near-band-edge emission. However, the realization of low TD density GaN and AlN substrates and (Al,In,Ga)N layers enabled investigating the roles of point defects and impurities without interferences by TDs, and vacancy-complexes have been revealed to act as origins of major Shockley- Read-Hall (SRH)-type nonradiative recombination centers (NRCs) in GaN. Accordingly, the concentration of NRCs (NNRC) must be decreased in both optical devices and power-switching electronic devices. Here we show the results of positron annihilation and time-resolved luminescence measurements on n- and p-type GaN, AlN, and Al0.6Ga0.4N alloys to reveal the origins of major intrinsic SRH-NRCs and to obtain their capture coefficients for minority carriers. For unintentionally doped and doped n-type GaN, divacancies comprising of a Ga-vacancy (VGa) and a N-vacancy (VN), namely VGaVN, are assigned as major SRH-NRCs with a hole capture-coefficient (Cp) of 6×10-7 cm3s-1. For Mg-doped ptype GaN epilayers grown by metalorganic vapor phase epitaxy (MOVPE), VGa(VN)2 are assigned as major NRCs with electron capture-coefficient (Cn) of 8×10-6 cm3s-1. For Mg-implanted GaN, VGaVN are the dominant NRCs right after implantation, and they agglomerate into (VGaVN)3 clusters with Cn of 5×10-6 cm3s-1 after high-temperature annealing. Since AlN films grown by MOVPE usually contain vacancy-clusters comprising of an Al-vacancy (VAl) such as VAl(VN)2-3, complexes of a cation-vacancy and a few VNs may be the major NRCs in AlN and Al0.6Ga0.4N alloys.
Recent progress of growth techniques of bulk GaN crystals is remarkable for realizing GaN-based power switching devices with a high breakdown voltage. Point defects play important role to characterize the high quality GaN, because structural defects like threading dislocations (TDs) and stacking faults are nearly disappeared. We have been investigating the relation between the near-band-edge (NBE) photoluminescence (PL) lifetime observed at room temperature and the concentration of intrinsic nonradiative recombination centers (NRCs) in n-GaN, of which origins are point defect complexes containing Ga vacancy, by combining positron annihilation spectroscopy (PAS) and time-resolved PL methods [S. F. Chichibu, et al., APL86, 021914 (2005)]. However, PAS becomes less sensitive below the concentration of Ga vacancy ([VGa]) of 10^16 cm^-3. Thus, the development of an alternative way to detect such dilute point defects (<10^16 cm^-3) in high quality GaN crystals is essential.
In this presentation, we will show the quantification of absolute quantum efficiency of radiation (AQE) by employing the omnidirectional PL (ODPL) technique to determine internal quantum efficiency (IQE) of the emission in GaN crystals with different excitation conditions. A high AQE of 8.22% corresponding to IQE of 70.9% was measured at room temperature for the NBE emission of a freestanding-GaN crystal grown by hydride vapor phase epitaxy on a GaN seed crystal manufactured with the acidic ammonothermal method, when cw photo pumping density was 66 W/cm^2.
Positron annihilation is a non-destructive technique for investigating vacancy-type defects in condensed matter. When a
positron is implanted into a sample, it annihilates with an electron and emits two 511-keV γ quanta. From measurements
of Doppler broadening spectra of the annihilation radiation and positron lifetimes, one can detect point defects such as
monovacancies, vacancy clusters, and vacancy-impurity complexes. The regions sampled can range from the surface to a
depth on the order of microns. In the present study, we have used the positron annihilation technique to study
relationship between the impurity doping and vacancies in GaN. Defects in ion-implanted GaN and their annealing
properties were studied. The defects introduced by the implantation were identified as divacancies, and the defect
reaction during isochronal annealing were found to depend on ion spices. A relationship between intra-4f transitions of
Er and vacancies was studied. A correlation between the defect concentration and the PL intensity was observed. We will
demonstrate that the positron annihilation technique is sensitive to vacancy-type defects in GaN, and it can contribute to
the development of optical and electronic devices based such materials.
Thin films of ZnO and MgxZn1-xO were epitaxially grown on Zn-polar ZnO substrates by plasma assisted
molecular beam epitaxy. The miscut of c-plane ZnO substrates toward the [1-100] axis direction leads to a flat substrate
surface with straight step edges. The growth mode of epitaxial ZnO films significantly depended on the growth
temperature, and a substrate temperature over 800°C was needed for flat film surfaces with monolayer-height steps.
Photoluminescence (PL) peak originating from the n = 2 state of A-free excitons was observed at 12 K for the ZnO films
grown under stoichiometric and O-rich growth conditions. MgxZn1-xO films were also fabricated under Zn-rich
conditions. The film surface exhibited a step-and-terrace structure. The effective PL lifetime of Mg0.08Zn0.92O film was as
long as 1.9 ns, which is the highest value ever reported, presumably due to a high purity level of the film.
We perform degenerate four-wave-mixing (FWM) studies of GaN excitons especially for an understanding of the strain-fields in the heteroepitaxial films. The shifts of exciton energies and their beating oscillation variations highlight the biaxial strain, allowing for a precise determination of the strain parameters.
The uniaxial strain field can be characterized by the polarization dependence of FWM, which shows distinct polarizations and energy variations depending on the sample and its position. The minimum changes of the polarized FWM intensity and exchange energy splittings correspond to a uniaxial strain of 5.0 × 10-5, which currently gives a lower resolution limit of this technique and is comparable with that of conventional X-ray diffraction.
In the time-evolutions, we investigate the strain effects on the phase of the quantum beats (QBs), giving insight into the excitons interactions. By using time-resolved FWM, difference between two-types of exciton transitions is identified. In addition, coherent manipulations of QBs are successfully realized in the FWM with a Michelson interferometer.
Time-integrated and spectrally-resolved four-wave mixing (FWM) has been used to study dephasing dynamics of excitons in a free-standing bulk ZnO. Clear FWM signals due to A〉Γ5- and BΓ5-excitions have been observed. We discuss the dephasing dynamics based on the polariton dispersion and four-particle Coulomb correlations.
Bound and unbound biexcitons in a free-standing bulk GaN are investigated by time-integrated and spectrally-resolved four-wave mixing measurements, where the formation of hetero-biexcitons that consist of A and B excitons (XXAB) as well as A-biexcitons (XXAA) and their unbound biexciton (XX*AA) are clearly observed. The FWM spectra and delay-time dependence are explained qualitatively and the interaction between A- and B-excitons gives rise to the phase shifts of the quantum beating and the energy shifts of the spectra, which is considered as the effect of the unbound state of XXAB (i.e. XX*AB). The unbound A-biexciton (XX*AA). Is also observed clearly in spectral and temporal domain and is found to play an important role in FWM signals for all polarizations.
Static, field-mounted and time-resolved spectroscopic measurements were carried out to compare the electronic structures between AlGaN/GaN binary and GaN/InGaN ternary single quantum wells (SQWs). The internal field exits across the quantum well (QW) naturally induces quantum-confined Stark effects, namely the redshift of the QW resonance energy and separation of electron-hole wavefunction overlap. Thus AlGaN/GaN SQWs exhibited a weak luminescence peak due to the presence of nonradiative channels. However, optical absorption and degenerate pump-probe measurements revealed that excitonic character still remains for the thin QWs having the well width nearly the same as the bulk free exciton Bohr radius even under high electric field as high as 0.73 MV/cm. A slightly In-alloyed InGaN SQW exhibited bright luminescence peak in spite of the pronounced effective bandgap inhomogeneity in the QW, which was confirmed by the point excitation and monochromatic cathodoluminescence mapping methods to have the lateral potential interval smaller than 40 nm. Therefore the light emitting area of the potential minima has the size defined as 'quantum-disk'. Carriers generated in the InGaN QWEs are effectively localized in these regions to form localized QW excitons exhibiting highly efficient spontaneous emissions.
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