Blue Luminescence Band Research Articles

Research on Evolution of Relevant Defects in Heavily Mg-Doped GaN by H Ion Implantation Followed by Thermal Annealing.

This study focuses on the heavily Mg-doped GaN in which the passivation effect of hydrogen and the compensation effect of nitrogen vacancies (VN) impede its further development. To investigate those two factors, H ion implantation followed by thermal annealing was performed on the material. The evolution of relevant defects (H and VN) was revealed, and their distinct behaviors during thermal annealing were compared between different atmospheres (N2/NH3). The concentration of H and its associated yellow luminescence (YL) band intensity decrease as the thermal annealing temperature rises, regardless of the atmosphere being N2 or NH3. However, during thermal annealing in NH3, the decrease in H concentration is notably faster compared to N2. Furthermore, a distinct trend is observed in the behavior of the blue luminescence (BL) band under N2 and NH3. Through a comprehensive analysis of surface properties, we deduce that the decomposition of NH3 during thermal annealing not only promotes the out-diffusion of H ions from the material, but also facilitates the repair of VN on the surface of heavily Mg-doped GaN. This research could provide crucial insights into the post-growth process of heavily Mg-doped GaN.

Improved midgap recombination lifetimes in GaN crystals grown by the low-pressure acidic ammonothermal method

To investigate the carrier recombination processes in GaN crystals grown by the low-pressure acidic ammonothermal (LPAAT) method, the photoluminescence (PL) spectra and PL lifetimes of LPAAT GaN crystals grown on acidic ammonothermal (AAT) GaN seed crystals were correlated with the growth polarity and species/concentration of point defects. The PL spectra of LPAAT GaN grown toward the (0001¯) direction (−c region), which provided the highest growth rate, exhibited a predominant near-band edge (NBE) emission. Neither bandgap narrowing nor Burstein–Moss shifts due to high concentration residual impurities were observed in the NBE emissions, indicating higher purity than the previously reported AAT GaN crystals. In addition, strain-induced energy shift or energy broadening of excitonic emission peaks was not observed, indicating excellent crystal coherency. Because of the reduced concentration of midgap recombination centers, a record-long room-temperature PL lifetime for the NBE emission of ammonothermal GaN (40 ps) was obtained from the −c region. Meanwhile, the PL spectra also exhibited the yellow and blue luminescence bands originating from particular deep-state radiative recombination centers. The major vacancy-type defects acting as midgap recombination centers are identified as vacancy complexes comprising a Ga vacancy (VGa) and a few N vacancies (VN), namely, VGa(VN)n buried by H and/or O, where n is an integer. Further reduction of such defect complexes will allow less compensated stable carrier concentration in the LPAAT GaN crystals.

Role of defects in tailoring optical, electronic, and luminescent properties of Cu-doped ZnO films

We present a detailed characterization study on copper-doped ZnO films to correlate the films' electronic and optical properties with the existing native defects in the lattice. In addition, we describe the variation in the concentration of these defects with Cu dopant and temperature. The results of XRD confirmed the single-phase würtzite-structure of the synthesized films. The SEM images showed a homogeneous and dense grain morphology with a granular form and a signature for a hexagonal-like shape. The EDX, XPS, and UV–Vis spectra showed the proper doping of Cu ions into the lattice. The XPS analysis indicated mixed electronic states of both Cu2+ and Cu1+ and showed a clear increase in the Cu2+ intensity relative to Cu1+, with Cu dopant. The transmittance spectra exhibited an average value above 80% in all doped films in the visible and infrared regions. The overall results indicated a clear link between the films’ optical and electronic responses and the level of the intrinsic defects in the lattice. By increasing the Cu dopant, we find a slight reduction in the energy bandgap (Eg). This is correlated with a clear reduction in the blue emission luminescence band associated with the VZn and in the yellow emission band associated with the Oi. On the other hand, we observed a clear enhancement in the green emission band originating from the VO, and in the emission band related to possible transitions from Zni levels to Oi levels. The slight reduction in the Eg signals a weak sp-d hybridization between the ZnO conduction band electrons and the Cu2+ ions, which is mediated by the intrinsic defects. With reducing the temperature, the photoluminescence temperature profiles indicated a slight increase in the Eg values and a negligible effect on the distribution of the native defects.

Luminescence Characteristics of the MOCVD GaN Structures with Chemically Etched Surfaces.

Gallium nitride is a wide-direct-bandgap semiconductor suitable for the creation of modern optoelectronic devices and radiation tolerant detectors. However, formation of dislocations is inevitable in MOCVD GaN materials. Dislocations serve as accumulators of point defects within space charge regions covering cores of dislocations. Space charge regions also may act as local volumes of enhanced non-radiative recombination, deteriorating the photoluminescence efficiency. Surface etching has appeared to be an efficient means to increase the photoluminescence yield from MOCVD GaN materials. This work aimed to improve the scintillation characteristics of MOCVD GaN by a wet etching method. An additional blue photo-luminescence (B-PL) band peaking at 2.7-2.9 eV and related to dislocations was discovered. This B-PL band intensity appeared to be dependent on wet etching exposure. The intensity of the B-PL was considerably enhanced when recorded at rather low temperatures. This finding resembles PL thermal quenching of B-PL centers. The mechanisms of scintillation intensity and spectrum variations were examined by coordinating the complementary photo-ionization and PL spectroscopy techniques. Analysis of dislocation etch pits was additionally performed by scanning techniques, such as confocal and atomic force microscopy. It was proved that this blue luminescence band, which peaked at 2.7-2.9 eV, is related to point defects those decorate dislocation cores. It was shown that the intensity of this blue PL band was increased due to enhancement of light extraction efficiency, dependent on the surface area of either single etch-pit or total etched crystal surface.

Dislocations as natural quantum wires in diamond

We study the electronic properties of the glide set of dislocations in diamond from first principles using hybrid exchange correlation functionals and find that the atomic-scale dislocation core states give rise to a prototypical one-dimensional (1D) band structure, i.e., natural quantum wires. The position and character of the core states varies strongly with local structure, where mixed dislocations with dangling bonds exhibit a 1D metallic band with a characteristic 1D density of states ($1/\sqrt{E}$). This 1D Fermi gas is spatially localized to a single atomic diameter orbital chain along the dislocation core. When the dangling bonds within the core are reconstructed, the 1D metallic band disappears. In contrast, pure edge dislocations in diamond reveal a 1D semiconductor with a direct band gap of 3.21 eV. These calculations provide a possible explanation to the long-standing observation of a blue luminescence band correlated with dislocations in diamond. This opens the door to using dislocations as 1D quantum phases with functional (electronic and optical) properties arising from the atomic-scale core states.

Lead-Free MDABCO-NH4I3 Perovskite Crystals Embedded in Electrospun Nanofibers.

In this work, we introduce lead-free organic ferroelectric perovskite N-methyl-N'-diazabicyclo[2.2.2]octonium)-ammonium triiodide (MDABCO-NH4I3) nanocrystals embedded in three different polymer fibers fabricated by the electrospinning technique, as mechanical energy harvesters. Molecular ferroelectrics offer the advantage of structural diversity and tunability, easy fabrication, and mechanical flexibility. Organic-inorganic hybrid materials are new low-symmetry emerging materials that may be used as energy harvesters because of their piezoelectric or ferroelectric properties. Among these, ferroelectric metal-free perovskites are a class of recently discovered multifunctional materials. The doped nanofibers, which are very flexible and have a high Young modulus, behave as active piezoelectric energy harvesting sources that produce a piezoelectric voltage coefficient up to geff = 3.6 VmN-1 and show a blue intense luminescence band at 325 nm. In this work, the pyroelectric coefficient is reported for the MDABCO-NH4I3 perovskite inserted in electrospun fibers. At the ferroelectric-paraelectric phase transition, the embedded nanocrystals display a pyroelectric coefficient as high as 194 × 10-6 Cm-2k-1, within the same order of magnitude as that reported for the state-of-the-art bulk ferroelectric triglycine sulfate (TGS). The perovskite nanocrystals embedded into the polymer fibers remain stable in their piezoelectric output response, and no degradation is caused by oxidation, making the piezoelectric perovskite nanofibers suitable to be used as flexible energy harvesters.

Transient behavior of AlGaN photoluminescence induced by carbon-related defect reactions.

We have observed the transient behavior in the AlGaN photoluminescence. Under an excitation of 325 nm He-Cd laser beam, the blue luminescence (BL) bands and yellow luminescence (YL) bands of AlGaN vary with increasing illumination time. We propose that the chemical reactions between BL-related CNON-Hi (CN-Hi) and YL-related CN-Hi (CN) defect states are the cause of such a phenomenon. The BL transition temperature (Tt) is defined as the temperature at which the intensity of BL bands induced by CNON-Hi is equal to that originated from CN-Hi. Only at Tt, BL shows a peak energy variation due to the exposure. The Tt of AlGaN is higher than what is similarly detected in GaN because of the high reactivity of Al to O.

Role of low temperature Al(Ga)N interlayers on the polarity and quality control of GaN epitaxy

Polarity control is essential for lateral polarity heterostructures. N-polar GaN films were directly grown on high temperature AlN buffer layer. A thin low temperature AlN interlayer could invert the polarity of subsequent GaN layer to Ga-polarity but a low temperature GaN interlayer with the same condition could not do it rather deteriorate the quality of GaN film. In addition, a relationship between the yellow luminescence band and the surface roughness was discovered. The blue luminescence band was found only on the inverted Ga-polar GaN film and was connected to screw dislocation density.

Europium (II)-Doped CaF2 Nanocrystals in Sol-Gel Derived Glass-Ceramic: Luminescence and EPR Spectroscopy Investigations.

The remarkable properties of Eu2+-activated phosphors, related to the broad and intense luminescence of Eu2+ ions, showed a high potential for a wide range of optical-related applications. Oxy-fluoride glass-ceramic containing Europium (II)-doped CaF2 nanocrystals embedded in silica matrix were produced in two steps: glass-ceramization in air at 800° with Eu3+-doped CaF2 nanocrystals embedded followed by Eu3+ to Eu2+ reduction during annealing in reducing atmosphere. The broad, blue luminescence band at 425 nm and with the long, weak tail in the visible range is assigned to the d → f type transition of the Eu2+ located inside the CaF2 nanocrystals in substitutional and perturbed sites, respectively; the photoluminescence quantum yield was about 0.76. The X-ray photoelectron spectroscopy and Electron paramagnetic spectroscopy confirmed the presence of Eu2+ inside the CaF2 nanocrystals. Thermoluminescence curves recorded after X-ray irradiation of un-doped and Eu2+-doped glass-ceramics showed a single dominant glow peak at 85 °C related to the recombination between F centers and Eu2+ related hole within the CaF2 nanocrystals. The applicability of the procedure can be tested to obtain an oxy-fluoride glass-ceramic doped with other divalent ions such as Sm2+, Yb2+, as nanophosphors for radiation detector or photonics-related applications.

Fine Structure of the Carbon-Related Blue Luminescence Band in GaN

Photoluminescence studies reveal three CN-related luminescence bands in GaN doped with carbon: the YL1 band at 2.17 eV caused by electron transitions via the −/0 level of the CN, the BLC band at 2.85 eV due to transitions via the 0/+ level of the CN and the BL2 band at 3.0 eV attributed to the CNHi complex. The BLC band studied here has the zero-phonon line at 3.17 eV and a phonon-related fine structure at low temperatures. The 0/+ level of the CN is found at 0.33 ± 0.01 eV above the valence band, in agreement with recent theoretical predictions. These results will help to choose an optimal correction scheme in hybrid functional calculations.

Gamma radiation-induced photoluminescence in calcium phosphate glass and inhibiting effect from copper

The influence of gamma-ray irradiation on the optical properties of 50P2O5–30CaO–20Na2O glass and quaternary ones prepared with [CuO]/[Na2O] molar ratios of 0.1, 0.7 and 1.5 at fixed [P2O5]/[CaO] is reported. The glasses prepared by melting were subjected to 100 kGy Co-60 gamma ray irradiation and studied by optical transmission and photoluminescence (PL) spectroscopy. The gamma-irradiated 50P2O5–30CaO–20Na2O ternary developed a ruby-red color and showed absorption features around 425 and 500 nm attributed to oxygen hole centers. The quaternary with [CuO]/[Na2O] molar ratio of 0.1 merely showed a weak absorption feature around 425 nm, whereas the highest molar ratios did not show significant differences relative to the pristine. Analyses of band gap and Urbach energies were made to aid in evaluating radiation-induced changes. Further, the irradiated copper-free glass exhibited a distinct blue luminescence band around 415 nm (not observed prior). It was most favorably excited in the UV at 265 nm, suggesting a phosphorus electron center at its origin. Its decay kinetics appeared relatively slow with a first-order exponential decay with lifetime of 4412 (±4) μs. Conversely, such emission was not detected for the copper-containing glasses, which instead exhibited PL properties comparable to the unirradiated counterparts. Finally, the effect of heat treatment after the gamma ray exposure was evaluated. The radiation-induced color centers showed a bleaching effect whereas the new PL vanished thus supporting the defects-related origin.

Cathodoluminescence Study of m‐Plane α‐Ga2O3 Grown by Mist Chemical Vapor Deposition

The cathodoluminescence (CL) properties of m‐plane α‐Ga2O3 grown by mist chemical vapor deposition are investigated. The m‐plane α‐Ga2O3 is found to have two types of characteristic luminescence bands: blue luminescence (BL) band (centered at 2.8 eV) and UV luminescence (UVL) band (centered at 3.7 eV). To characterize these bands, the Sn concentration and temperature dependences of the CL spectra are investigated using samples with varying Sn concentrations from 1 × 1017 to 1 × 1019 cm−3. The Sn concentration‐dependent CL spectra show that the luminescence from the UVL band is dominant in the low Sn concentration region, while that from the BL band is dominant in the high Sn concentration region. The temperature‐dependent CL spectra indicate that the peak intensity of the UVL band depending on temperature is larger than that of the BL band. The activation energies in the UVL band of the undoped and lightly Sn‐doped samples are determined as 110 meV. In addition, the parameters of the Huang–Rhys factor in the UVL band are obtained as 28.6 and 18.8, respectively. These results strongly suggest that the UVL band is derived from self‐trapped excitons, which is the recombination of free electrons and self‐trapped holes.

Heteroepitaxial ZnGeN2on AlN: Growth, Structure, and Optical Properties

ZnGeN2 is a potential green-to-amber emitter which can be integrated into existing GaN LED heterostructures due to structural similarity. However, for accurate material characterization, ZnGeN2 must be grown without GaN due to their similar optical and structural properties. This is exemplified by ZnGeN2/GaN heterostructures with luminescence signatures that overlap a well-known Zn-doped GaN blue luminescence band. In this work we present the molecular beam epitaxy growth of ZnGeN2 on lattice mismatched AlN templates with regrown AlN buffer layers enabling GaN-free structural and optical characterization. Fully relaxed ZnGeN2 on AlN shows cation-disordered lattice parameters a = 3.1962 Å ± 0.0032 Å and c = 5.2162 Å ± 0.0015 Å (c/a ratio = 1.632) determined from multiple reflections and a least-squares regression. Reflection high-energy electron diffraction, X-ray diffraction, and atomic force microscopy characterization reveal an optimal growth temperature for ZnGeN2 on AlN of 450 °C. Photoluminescence shows broad recombination centered around 2.96 eV, clearly attributed to ZnGeN2, which is distinct from the 2.88 eV Zn-doped GaN blue luminescence band. This work offers insight into the properties of ZnGeN2, enabling new characterization and new heteroepitaxial devices based on AlN.

Plasma assisted molecular beam epitaxial growth of GaN with low growth rates and their properties

A systematic investigation on PA-MBE grown GaN with low growth rates (less than 0.2 µm/h) has been conducted in a wide growth temperature range, in order to guide future growth of sophisticated fine structures for quantum device applications. Similar to usual growths with higher growth rates, three growth regions have been revealed, namely, Ga droplets, slightly Ga-rich and N-rich 3D growth regions. The slightly Ga-rich region is preferred, in which GaN epilayers demonstrate optimal crystalline quality, which has been demonstrated by streaky RHEED patterns, atomic smooth surface morphology, and very low defect related yellow and blue luminescence bands. The growth temperature is a critical parameter to obtain high quality materials and the optimal growth temperature window (~ 700–760 °C) has been identified. The growth rate shows a strong dependence on growth temperatures in the optimal temperature window, and attention must be paid when growing fine structures at a low growth rate. Mg and Si doped GaN were also studied, and both p- and n-type materials were obtained.

Stability of the CNHi Complex and the Blue Luminescence Band in GaN

The dissociation of the CNHi complex in GaN is studied in detail using photoluminescence measurements and first‐principles calculations. The blue luminescence (BL2) band with a maximum at 3.0 eV is caused by electron transitions from an excited state located at 0.02 eV below the conduction band to the ground state of the CNHi donor with the 0/+ level 0.15 eV above the valence band. The dissociation releases hydrogen atom, and the remaining CN defect with the −/0 state at 0.92 eV above the valence band is responsible for the yellow band (YL1) with a maximum at about 2.2 eV. The dissociation of the CNHi complex can be caused by the photoinduced defect reaction mechanism under UV illumination at low temperature (≈20 K), leading to the bleaching of the BL2 band and simultaneous rise in the YL1 band. The bleaching is reversible. Alternatively, the complex dissociates after annealing at temperatures above 600 °C. The activation energy of this process (3–4 eV, depending on the annealing geometry) corresponds to the removal of hydrogen from the sample and not to the dissociation of the complex itself.

The effect of thermal annealing on the optical properties of Mg-doped zincblende GaN epilayers

The effects of thermal annealing on the optical properties of Mg-doped cubic zincblende GaN epilayers grown by metalorganic chemical vapor deposition on 3C-SiC/Si (001) substrates are investigated. The photoluminescence spectra show near band edge features and a blue luminescence band that depend on Mg concentration, temperature, and excitation power density. Annealing the sample in a N2 atmosphere causes the intensity of the blue band to increase by a factor of 5. Power dependent photoluminescence measurements show a reduction in the laser excitation density required for saturation of the blue band after annealing, indicating an increase in the recombination lifetime. Time decay measurements confirm this increase, which is attributed to a reduction in the concentration of non-radiative defects after annealing. The results presented here are compared to those reported previously for Mg-doped hexagonal wurtzite GaN.

Carbon complexes in highly C-doped GaN

We investigate the properties of heavily C-doped GaN grown by hydride vapor phase epitaxy using both optical experiments and hybrid density functional theory calculations. Previous work has established that carbon acceptors $({\mathrm{C}}_{\mathrm{N}})$ give rise to a yellow luminescence band near 2.2 eV along with a blue luminescence band near 2.9 eV. Photoluminescence measurements show the yellow band shifting as a function of carbon concentration, suggesting a change in the behavior of carbon species as carbon content increases. With hybrid density functional theory we calculate the electrical and optical behavior of carbon centers containing multiple carbon impurities, which may arise in heavily doped material. We compare the behavior of these complexes to the isolated centers, and find that the dicarbon donor-acceptor $({\mathrm{C}}_{\mathrm{Ga}}\text{\ensuremath{-}}{\mathrm{C}}_{\mathrm{N}})$ complex is a candidate to explain the shift in the yellow luminescence peak. Tricarbon complexes have high formation energies and modest binding energies, and also give rise to optical transitions that are inconsistent with the observed spectra. We also identify the split dicarbon interstitial on the gallium site as a low-energy species with a large binding energy that may act to compensate carbon acceptors. Local vibrational modes are calculated for carbon impurity centers, and we compare these results to recent experiments. Dicarbon and tricarbon complexes involving ${\mathrm{C}}_{\mathrm{Ga}}$ and ${\mathrm{C}}_{\mathrm{N}}$ exhibit modes that are only slightly higher than the isolated species, while carbon interstitials and related complexes give rise to vibrational modes much higher than ${\mathrm{C}}_{\mathrm{Ga}}$ and ${\mathrm{C}}_{\mathrm{N}}$.

Impact of sandwiched strain periodic multilayer AlN/GaN on strain and crystalline quality of a-plane GaN

We demonstrated high-quality single crystalline a-plane undoped-gallium nitride grown on a nonpatterned r-plane sapphire substrate via metal–organic chemical vapor deposition. The effect of four different numbers of sandwiched strain-periodic AlN/GaN multilayers on the strain state, crystal quality, optical and electrical properties was investigated. Field emission scanning electron microscopy and atomic force microscopy showed that the surface morphology was improved upon insertion of 120 pairs of AlN/GaN thin layers with a root-mean-square roughness of 2.15 nm. On-axis X-ray ω-scan rocking curves showed enhanced crystalline quality: the full width at half maximum decreased from 1224 to 756 arcsec along the [0001] direction and from 2628 to 1360 arcsec along the [1–100] direction for a-GaN grown with 120 pairs of AlN/GaN compared to a-GaN without AlN/GaN pairs. Reciprocal space mapping showed that a-plane GaN with a high number of AlN/GaN pairs exhibits near-relaxation strain states. Room-temperature photoluminescence spectra showed that the sample with the highest number of AlN/GaN pairs exhibited the lowest-intensity yellow and blue luminescence bands, indicating a reduction in defects and dislocations. The a-plane InGaN/GaN LEDs with 120 pairs of SSPM-L AlN/GaN exhibited a significant increase (~ 250%) in light output power compared to that of LEDs without SSPM-L AlN/GaN pairs.

Is blue luminescence a fingerprint for good p-type conductivity in Mg-doped GaN?

Researchers uncover the mechanism and origin of a mysterious blue luminescence band in an important semiconductor material.

Origin of blue luminescence in Mg-doped GaN

In this work, dual acceptor-bound exciton peaks are observed by low-temperature photoluminescence. The peaks correspond to the dual Mg-related acceptor levels in GaN based on the Haynes rule. By calibrating the energy-level structure, a mechanism for the origin of blue luminescence (BL) in Mg-doped GaN is proposed. The BL band is separated by thermal treatment at different temperatures, confirming the rationality of the dual-factor origin of the BL band. As the annealing temperature increases, the PL spectrum and the p-type conductivity of Mg-doped GaN also change. The experimental results indicate that there is not necessarily a relationship between the BL band and p-type conductivity in GaN grown by metalorganic chemical vapor deposition.