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Empetroxepins A and B, which are 10,11-dihydrodibenz[b,f]oxepins produced by the Black Crowberry (Empetrum nigrum), displayed weak anti-tubercular activity upon isolation, but have not been explored for antibiotic activity despite their molecular similarity to other phenolic antibacterial natural products. Herein we detail the first total synthesis of Empetroxepins A and B via a selective demethylation strategy and antibacterial structure activity relationship (SAR) study of the natural products and related analogs. Empetroxepin A was found to be weakly active against susceptible strains of Staphylococcus aureus (SA) and Bacillus subtilis (BS) with a minimum inhibitory concentration (MIC) of 256 μg/mL against both bacteria, whereas Empetroxepin B was found to be weakly active against only BS (MIC = 256 μg/mL). Neither natural product was active against Escherichia coli (EC). Antibiotic activity was improved through derivatization of the 10,11-dihydrodibenz[b,f]oxepin core with the best compound of the SAR series, 9-chloro-10,11-dihydrodibenzo[b,f]oxepine-2,3,4-triol, having MICs of 8 μg/mL, 16 μg/mL, and 256 μg/mL against SA, BS, and EC respectively.

Biofilm formation in the human intestinal pathogen Vibrio cholerae is in part regulated by norspermidine, spermidine and spermine. V. cholerae senses these polyamines through a signalling pathway consisting of the periplasmic protein, NspS, and the integral membrane c-di-GMP phosphodiesterase MbaA. NspS and MbaA belong to a proposed class of novel signalling systems composed of periplasmic ligand-binding proteins and membrane-bound c-di-GMP phosphodiesterases containing both GGDEF and EAL domains. In this signal transduction pathway, NspS is hypothesized to interact with MbaA in the periplasm to regulate its phosphodiesterase activity. Polyamine binding to NspS likely alters this interaction, leading to the activation or inhibition of biofilm formation depending on the polyamine. The purpose of this study was to determine the amino acids important for NspS function. We performed random mutagenesis of the nspS gene, identified mutant clones deficient in biofilm formation, determined their responsiveness to norspermidine and mapped the location of these residues onto NspS homology models. Single mutants clustered on two lobes of the NspS model, but the majority were found on a single lobe that appeared to be more mobile upon norspermidine binding. We also identified residues in the putative ligand-binding site that may be important for norspermidine binding and interactions with MbaA. Ultimately, our results provide new insights into this novel signalling pathway in V. cholerae and highlight differences between periplasmic binding proteins involved in transport versus signal transduction.

Biofilm formation in the human intestinal pathogen Vibrio cholerae is in part regulated by norspermidine, spermidine and spermine. V. cholerae senses these polyamines through a signalling pathway consisting of the periplasmic protein, NspS, and the integral membrane c-di-GMP phosphodiesterase MbaA. NspS and MbaA belong to a proposed class of novel signalling systems composed of periplasmic ligand-binding proteins and membrane-bound c-di-GMP phosphodiesterases containing both GGDEF and EAL domains. In this signal transduction pathway, NspS is hypothesized to interact with MbaA in the periplasm to regulate its phosphodiesterase activity. Polyamine binding to NspS likely alters this interaction, leading to the activation or inhibition of biofilm formation depending on the polyamine. The purpose of this study was to determine the amino acids important for NspS function. We performed random mutagenesis of the nspS gene, identified mutant clones deficient in biofilm formation, determined their responsiveness to norspermidine and mapped the location of these residues onto NspS homology models. Single mutants clustered on two lobes of the NspS model, but the majority were found on a single lobe that appeared to be more mobile upon norspermidine binding. We also identified residues in the putative ligand-binding site that may be important for norspermidine binding and interactions with MbaA. Ultimately, our results provide new insights into this novel signalling pathway in V. cholerae and highlight differences between periplasmic binding proteins involved in transport versus signal transduction.

Gallium Nitride (GaN) grown by ammonia molecular beam epitaxy and doped with elemental Germanium (Ge) is presented. Growth studies varying the GaN growth rate, substrate growth temperature and the elemental Ge flux reveal several incorporation dependencies. Ge incorporation increases with flux, as expected, and a doping range from ∼1017 cm−3 to 1020 cm−3 was readily achieved. A strong substrate temperature dependence on the electrical properties of films grown is observed, with an optimal growth temperature of 740 °C, lower than standard GaN growth conditions for ammonia molecular beam epitaxy. Compensation effects at higher growth temperatures are suspected, as observed with other techniques. Crystallographic defects are apparent at the highest doping concentrations from electrical and optical measurements, however thin layers of such highly doped films are of great interest for contact layers and tunnel junctions in devices.

International audience; We report on the direct measurement of hot electrons generated in the active region of blue light-emitting diodes grown by ammonia molecular beam epitaxy by electron emission spectroscopy. The external quantum efficiency of these devices is

Highly doped n-Al0.6Ga0.4N can be used to form tunnel junctions (TJs) on deep ultraviolet (UVC) LEDs and markedly increase the light extraction efficiency (LEE) compared to the use of p-GaN/p-AlGaN. High quality Al0.6Ga0.4N was grown by NH3-assisted molecular beam epitaxy (NH3 MBE) on top of AlN on SiC substrate. The films were crack free under scanning electron microscope (SEM) for the thickness investigated (up to 1 µm). X-ray diffraction reciprocal space map scan was used to determine the Al composition and the result is in close agreement with atom probe tomography (APT) measurements. By varying the growth parameters including growth rate, and Si cell temperature, n-Al0.6Ga0.4N with an electron density of 4×1019 /cm3 and a resistivity of 3 mΩ·cm was achieved. SIMS measurement shows that a high Si doping level up to 2×1020 /cm3 can be realized using a Si cell temperature of 1450 °C and a growth rate of 210 nm/hr. Using a vanadium-based annealed contact, ohmic contact with a specific resistance of 10−6 Ω·cm2 was achieved as determined by circular transmission line measurement (CTLM). Finally, the n-type AlGaN regrowth was done on MOCVD grown UVC LEDs to form UVC TJ LED. The sample was processed into thin film flip chip (TFFC) configuration. The emission wavelength is around 278 nm and the excess voltage of processed UV LED is around 4.1 V.

Coherent In x Al 1−x N (x = 0.15 to x = 0.28) films were grown by metalorganic chemical vapor deposition on GaN templates to investigate if the films obey Vegard’s Law by comparing the film stress-thickness product from wafer curvature before and after In x Al 1−x N deposition. The In composition and film thickness were verified using atom probe tomography and high resolution X-ray diffraction, respectively. Ex-situ curvature measurements were performed to analyze the curvature before and after the In x Al 1−x N deposition. At ∼In 0.18 Al 0.82 N, no change in curvature was observed following InAlN deposition; confirming that films of this composition are latticed matched to GaN, obeying Vegard’s law. The relaxed a 0 - and c 0 - lattice parameters of In x Al 1−x N were experimentally determined and in agreement with lattice parameters predicted by Vegard’s law.

Vibrio cholerae is an aquatic bacterium that is also the causative agent of the diarrheal disease cholera. In this bacterium, the secondary messenger, cyclic di-GMP, regulates the lifestyle transition between a motile state and a sessile biofilm state as well as other key processes such as virulence factor production. The V. cholerae genome encodes 62 proteins that contain GGDEF, EAL, or HD-GYP domains that are predicted to be involved in the synthesis or degradation of cyclic di-GMP. Presumably, one or more signals modulate the activity of each of these proteins to regulate cyclic di-GMP levels in the cell; however, to date, only a few of these signals have been elucidated. In this chapter, we present our current knowledge about the signals that have an effect on cyclic di-GMP signaling in V. cholerae and the signaling networks that play direct or indirect roles in processing these signals. These signals include polyamines, bile acids, temperature, and molecular oxygen. We also discuss how cyclic di-GMP signaling networks interact with other signal transduction pathways, such as quorum sensing, to regulate behavior. In addition to the many unidentified signals, there are other gaps in our knowledge including how signal specificity and processing is achieved and what is the nature and the extent of crosstalk among cyclic di-GMP and other signal transduction networks. Future research addressing these questions will help us better understand how V. cholerae assimilates cues in both aquatic habitats and host organisms to optimize its response to specific environments through cyclic di-GMP signaling.

We demonstrate high-power edge-emitting laser diodes (LDs) with tunnel junction contacts grown by molecular beam epitaxy (MBE). Under pulsed conditions, lower threshold current densities were observed from LDs with MBE-grown tunnel junctions than from similarly fabricated control LDs with ITO contacts. LDs with tunnel junction contacts grown by metal-organic chemical vapor deposition (MOCVD) were additionally demonstrated. These LDs were fabricated using a p-GaN activation scheme utilizing lateral diffusion of hydrogen through the LD ridge sidewalls. Secondary ion mass spectroscopy measurements of the [Si] and [Mg] profiles in the MBE-grown and MOCVD-grown tunnel junctions were conducted to further investigate the results.

The use of III-nitride tunnel junction (TJ) diodes in light-emitting diodes (LEDs) and laser diodes (LDs) has attracted much attention. However, there are concerns about using III-nitride tunnel junctions, especially in commercial devices, primarily due to the excess voltage needed to allow for tunneling. On the other hand, ultra-violet (UV) LEDs suffer from low light extraction efficiency (LEE). The use of tunnel junctions in UV LEDs can potentially double the LEE by allowing the use of highly reflective mirrors and eliminating the need for absorption p-GaN.

Tunnel junctions (TJs) offer alternative designs and promise in some cases improved performances for nitride-based light-emitting diode (LEDs) and laser diodes (LDs) and are widely used in academic studies. However, the voltage penalty of the LEDs and LDs, in comparison with standard contact technologies, has been a major concern especially for commercial applications. In this study, we investigated methods to achieve low excess voltage. Using ammonia molecular beam epitaxy (NH3 MBE), GaN TJs were grown on commercial metalorganic chemical vapor deposition (MOCVD) grown blue LED wafers. Atom probe tomography (APT) and secondary ion mass spectrometry (SIMS) indicate 1 min buffered HF (BHF) clean of the regrowth interface reduced Mg and impurity incorporation into the n++ regrown TJ layers. The wafers were processed and measured in parallel to reference wafers using both university processes and industry processes. At 20 A cm−2, TJ LEDs grown with Si δ-doping at the junction interface processed in the university cleanroom had a forward voltage of 3.17 V in comparison to 2.86 V for LEDs processed with a standard indium tin oxide (ITO) contact. Unencapsulated TJ LEDs processed by industrial process without ITO or current blocking layer had about 0.3 V excess voltage compared to reference LEDs. The TJ LEDs also had more uniform light emission profile. The low excess voltage and consistent results acquired in both settings suggest that TJ can be scaled for industrial processes.

Mid-infrared intersubband transitions are investigated in nonpolar m-plane and a-plane GaN/AlGaN multi-quantum well heterostructures. Nominally identical heterostructures were grown by ammonia molecular-beam epitaxy on free-standing m-plane and a-plane GaN substrates. A total of 12 well- and barrier-doped samples with intersubband transition energies in the range of 220–320 meV (wavelength range 3.8–5.6 μm) were grown. The intersubband absorption lines of the m-plane samples were 10–40% narrower than those of the a-plane samples, and a very narrow intersubband absorption linewidth of 38 meV (full width at half maximum) at a transition energy of approximately 250 meV (5 μm wavelength) was observed in an m-plane sample. Narrower intersubband absorption linewidths of m-plane samples can be explained by more abrupt heterostructure interfaces revealed by structural characterization, which is attributed to a higher stability of the m-plane compared to the a-plane. No significant difference in the intersubband absorption linewidth was observed between the barrier- and well-doped samples.

In this paper we demonstrate ultraviolet (UV) light emitting diodes (LEDs) grown on metamorphic AlGaN buffers on freestanding GaN ( 20 2 ¯ 1 ) substrates by ammonia assisted molecular beam epitaxy (MBE). Misfit and related threading dislocations were confined to the stress relaxed, compositionally graded buffer layers, and single quantum well devices emitting at 355, 310 and 274 nm were grown on top of the graded buffers. The devices showed excellent structural and electrical (I–V) characteristics.

This is the first demonstration of continuous-wave (CW) operation of nonpolar GaN-based VCSELs. These devices had a dual-dielectric distributed Bragg reflector (DBR) design with ion implanted apertures and III-nitride tunnel junction (TJ) intracavity contacts. Unlike c-plane devices, nonpolar GaN-based VCSELs have anisotropic gain that leads to a 100% polarization ratio and polarization-locked VCSEL arrays. Previous nonpolar devices were unable to lase under CW operation, notably due to the thermally-insulating bottom dielectric DBR. Based on thermal modeling using COMSOL, the main thermal pathway was restricted to a thin p-side metal contact that goes around the bottom DBR to the submount. Heat flow was further impaired as the Au-Au thermocompression flip-chip bond created cracks and voids in the p-side metal. The thermal performance was improved in our latest VCSELs by increasing the cavity length to 23λ and utilizing Au-In solid liquid interdiffusion bonding to create a more robust pathway for heat transport. This led to stable CW VCSEL operation for over 20 minutes. The peak output powers for a 6 μm aperture VCSEL under CW and pulsed operation were 150 μW and 700 μW, respectively. Lasing wavelengths were observed at 406 nm, 412 nm, and 419 nm. The fundamental transverse mode was observed without the presence of filamentary lasing.

We demonstrate electrically injected III-nitride VCSELs with ion implanted apertures, tunnel junction intracavity contacts, and a dual dielectric DBR flip-chip design. Precise cavity length control has been achieved using photoelectrochemical band gap selective etching of InGaN/GaN multiple quantum wells.

We present an analytical model describing misfit stresses relaxation in semipolar III-nitride heterostructures caused by misfit dislocations (MDs) originating from basal or prismatic slip and by sessile MDs. We analyze the critical thickness hc for the formation of MDs depending on crystal lattice mismatch and orientation of the semipolar growth plane. We explore transversely isotropic elasticity solutions to describe the relaxation processes in III-nitride semipolar heterostructures and compare the results for hc with those calculated within the isotropic elasticity approach. We find that the value of angle ϑ between the polar с-axis, and the direction of heterostructure growth has an impact on the realization of the stress relaxation mechanism by the generation of MDs originating either from basal or prismatic slip. A comparison of theoretical calculations with experimental data on the observation of MDs in the III-nitride heterostructures is provided.

By studying low radiative efficiency blue III-nitride light emitting diodes (LEDs), we find that the ABC model of recombination commonly used for understanding efficiency behavior in LEDs is insufficient and that additional effects should be taken into account. We propose a modification to the standard recombination model by incorporating a bimolecular nonradiative term. The modified model is shown to be in much better agreement with the radiative efficiency data and to be more consistent than the conventional model with very short carrier lifetimes measured by time-resolved photoluminescence in similar, low radiative efficiency material. We present experimental evidence that a hot carrier-generating process is occurring within these devices, in the form of measurements of forward photocurrent under forward bias. The forward photocurrent, due to hot carrier generation in the active region, is present despite the lack of any “efficiency droop”—the usual signature of band-to-band Auger recombination in high-quality III-nitride LEDs. Hot carrier generation in the absence of band-to-band Auger recombination implies that some other source of hot carriers exists within these low radiative efficiency devices, such as trap-assisted Auger recombination.By studying low radiative efficiency blue III-nitride light emitting diodes (LEDs), we find that the ABC model of recombination commonly used for understanding efficiency behavior in LEDs is insufficient and that additional effects should be taken into account. We propose a modification to the standard recombination model by incorporating a bimolecular nonradiative term. The modified model is shown to be in much better agreement with the radiative efficiency data and to be more consistent than the conventional model with very short carrier lifetimes measured by time-resolved photoluminescence in similar, low radiative efficiency material. We present experimental evidence that a hot carrier-generating process is occurring within these devices, in the form of measurements of forward photocurrent under forward bias. The forward photocurrent, due to hot carrier generation in the active region, is present despite the lack of any “efficiency droop”—the usual signature of band-to-band Auger recombination in high...

The onset of plastic relaxation via misfit dislocation (MD) formation in In x Ga 1− x N layers grown by metal-organic chemical vapor deposition on the ( 11 2 ¯ 2 ) semipolar plane of GaN substrates is investigated using high-resolution X-ray diffraction, transmission electron microscopy and cathodoluminescence. The results of critical thickness calculations for MD formation as a function of In x Ga 1− x N alloy composition x are compared with experimental observations. MD generation is observed initially as a result of slip on the (0001) slip plane, and subsequently as a result of additional slip on inclined { 1 1 ¯ 00 } - type m -planes, which eventually leads to an increase in threading dislocation density.

We employ near-bandgap terahertz emission spectroscopy to study lateral heterostructures resulting from basal plane stacking faults in m -plane GaN. The predominant stacking faults have I1 character and behave as an array of spontaneously forming layers comprised of a single cubic stacking sequence within the wurtzite matrix that terminate the spontaneous polarization along the in-plane c-axis, leading to strong lateral electric fields. Spectral tuning of femtosecond excitation pulses enables observation of the transition from carrier transport in the continuum to formation of instantaneous dipoles and nonlinear susceptibility associated with both the quantum-well-like regions of the cubic layers and polarization-induced triangular-like potentials. (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

In this paper we demonstrate work on developing the kinetic Wulff plots and quasi-equilibrium crystal shapes of GaN by hydride vapor phase epitaxy to understand the stable polar, semipolar, and nonpolar planes that emerge naturally from the GaN crystal. High quality bulk m -plane GaN substrates were masked with circular openings to perform selective area growth studies. Growths were performed by hydride vapor phase epitaxy over a range of temperatures, pressures and carrier gases. The quasi-equilibrium crystal shapes were shown to have clear m -plane { 1 1 ¯ 00 } facets and a sharp and flat ( 000 1 ¯ ) N-face or c− face. The (0001) Ga-face or c+ face became faceted with { 10 1 ¯ 1 } planes emerging with reduced pressures and temperatures. Based on the stable facets, kinetic Wulff plots were constructed.

Lattice mismatch stresses in heteroepitaxial (In,Al,Ga)N structures based on nonpolar and semipolar orientations of GaN can result in relaxation via dislocation glide as a result of shear stresses on inclined slip planes, with important consequences for optoelectronic device design.

Calcium can be unintentionally incorporated during the growth of semiconductor devices. Using hybrid functional first-principles calculations, we assess the role of Ca impurities in GaN. Ca substituted on the cation site acts as a deep acceptor with a level ~1 eV above the GaN valence-band maximum. We find that for Ca concentrations of 1017 cm−3, the Shockley–Read–Hall recombination coefficient, A, of InGaN exceeds 106 s−1 for band gaps less than 2.5 eV. A values of this magnitude can lead to significant reductions in the efficiency of light-emitting diodes.

Tunnel junctions in the III-Nitride system have the potential to revolutionize GaN device design and capabilities. However, the high doping densities required and difficulty in activating buried p-GaN prevent widespread use. We combine MOCVD and MBE growth techniques to produce GaN tunnel junction devices with a total device series resistance as low as 1.5 × 10−4 Ω cm2. III-Nitride edge emitting lasers and VCSELs were fabricated and will be discussed. In addition, a regrowth technique for growing tunnel junctions on commercial c-plane wafers has been developed and LEDs with an EQE of 78% and wall plug efficiency (WPE) of 72% have been fabricated using this technique.

We investigate the bow of free standing (0001) oriented HVPE grown GaN wafers and demonstrate that their curvature is consistent with a compressive to tensile stress gradient (bottom to top) present in the wafers. The origin of the stress gradient and the curvature is attributed to the inclination of edge threading dislocations (TDs) with respect to original [0001] GaN wafer or boule growth direction. A model is proposed and a relation is derived for bulk GaN wafer curvature dependence on the inclination angle and the density of TDs. The model is used to analyze the curvature for commercially available GaN substrates, and is supported by X-ray diffraction and cathodoluminescence measurements. The results show a close correlation between the experimentally determined wafer curvature and TD density and those predicted from the theoretical model for varying inclination angles.

We demonstrate a III-nitride edge emitting laser diode (EELD) grown on a (2021) bulk GaN substrate with a GaN tunnel junction contact for hole injection. The tunnel junction was grown using a combination of metal-organic chemical-vapor deposition (MOCVD) and ammonia-based molecular-beam epitaxy (MBE) which allowed to be regrown over activated p-GaN. For a laser bar with dimensions of 1800 µm x 2.5 µm, without facet coatings, the threshold current was 284 mA (6.3 kA/cmsup2/sup) and the single facet slope efficiency was 0.33 W/A (12% differential efficiency). A differential resistivity at high current density of 2.3 × 10sup-4/supΩ cmsup2/supwas measured.

Active regions for mid-ultraviolet laser diodes grown on bulk AlGaN templates are investigated by time-resolved photoluminescence. The active regions were grown pseudomorphically on thick, relaxed AlGaN on bulk GaN in the semi-polar () orientation where it has been shown that the glide of dislocations create strain relieving defects confined to the AlGaN/GaN interface, away from the active region. The photoluminescence lifetimes were found to have mono-exponential decays of around 500 ps and calculated radiative and non-radiative lifetimes are compared to previously reported results for active regions on bulk m-plane GaN.

We report the first demonstration of III–nitride vertical-cavity surface-emitting lasers (VCSELs) with tunnel junction (TJ) intracavity contacts grown completely by metal–organic chemical vapor deposition (MOCVD). For the TJs, n++-GaN was grown on in-situ activated p++-GaN after buffered HF surface treatment. The electrical properties and epitaxial morphologies of the TJs were first investigated on TJ LED test samples. A VCSEL with a TJ intracavity contact showed a lasing wavelength of 408 nm, a threshold current of ~15 mA (10 kA/cm2), a threshold voltage of 7.8 V, a maximum output power of 319 µW, and a differential efficiency of 0.28%.

We have achieved continuous-wave (CW) operation of an optically polarized m-plane GaN-based vertical-cavity surface-emitting laser (VCSEL) with an ion implanted current aperture, a tunnel junction intracavity contact, and a dual dielectric distributed Bragg reflector design. The reported VCSEL has 2 quantum wells, with a 14 nm quantum well width, 1 nm barriers, a 5 nm electron-blocking layer, and a 23 λ total cavity thickness. The thermal performance was improved by increasing the cavity length and using Au-In solid-liquid interdiffusion bonding, which led to lasing under CW operation for over 20 min. Lasing wavelengths under pulsed operation were observed at 406 nm, 412 nm, and 419 nm. Only the latter two modes appeared under CW operation due to the redshifted gain at higher temperatures. The peak output powers for a 6 μm aperture VCSEL under CW and pulsed operation were 140 μW and 700 μW, respectively. The fundamental transverse mode was observed without the presence of filamentary lasing. The therma...

We report the fabrication of low-droop high-efficiency green c-plane light-emitting diodes (LEDs) utilizing GaN tunnel junction (TJ) contacts. The LED epitaxial layers with a top p-GaN layer were grown by metal organic chemical vapor deposition and an n++-GaN layer was deposited by molecular beam epitaxy to form a TJ. The TJ LEDs were then compared with equivalent LEDs having a tin-doped indium oxide (ITO) contact. The TJ LEDs exhibited a higher performance and a lower efficiency droop than did the ITO LEDs. At 35 A/cm2, the external quantum efficiencies for the TJ and ITO LEDs were 31.2 and 27%, respectively.

The optical absorption of GaAsN films grown by molecular beam epitaxy on GaAs substrates is measured using the mirage effect photothermal deflection spectroscopy (PDS). The PDS spectra were fitted with a modified Fernelius model, which takes into account multiple reflections within the GaAsN layer and GaAs substrate. This allowed the extraction of bandedge parameters for a series of GaAsN films with N content varying from 0.24% to 1.4% N. All films show a clear Urbach absorption edge with a composition-dependent bandgap consistent with literature and Urbach slope parameters roughly 3 times larger than GaAs values.

We report on the lasing of III-nitride nonpolar, violet, vertical-cavity surface-emitting lasers (VCSELs) with IIInitride tunnel-junction (TJ) intracavity contacts and ion implanted apertures (IIAs). The TJ VCSELs are compared to similar VCSELs with tin-doped indium oxide (ITO) intracavity contacts. Prior to analyzing device results, we consider the relative advantages of III-nitride TJs for blue and green emitting VCSELs. The TJs are shown to be most advantageous for violet and UV VCSELs, operating near or above the absorption edge for ITO, as they significantly reduce the total internal loss in the cavity. However, for longer wavelength III-nitride VCSELs, TJs primarily offer the advantage of improved cavity design flexibility, allowing one to make the p-side thicker using a thick n-type III-nitride TJ intracavity contact. This offers improved lateral current spreading and lower loss, compare to using ITO and p-GaN, respectively. These aspects are particularly important for achieving high-power CW VCSELs, making TJs the ideal intracavity contact for any III-nitride VCSEL. A brief overview of III-nitride TJ growth methods is also given, highlighting the molecular-beam epitaxy (MBE) technique used here. Following this overview, we compare 12 μm aperture diameter, violet emitting, TJ and ITO VCSEL experimental results, which demonstrate the significant improvement in differential efficiency and peak power resulting from the reduced loss in the TJ design. Specifically, the TJ VCSEL shows a peak power of ~550 μW with a threshold current density of ~3.5 kA/cm2, while the ITO VCSELs show peak powers of ~80 μW and threshold current densities of ~7 kA/cm2.

We achieved a −3dB modulation bandwidth of 1GHz with an ultra-low capacitance of < 1pF in a 419nm vertical-cavity surface-emitting lasers (VCSEL). The VCSEL is based on nonpolar InGaN/GaN quantum-wells and a tunnel-junction intracavity contact.

Dilute nitride semiconductors of composition GaAs1−xNx (0.0017

The dilute bismide semiconductor GaAs1–xBix is an interesting new semiconductor alloy with novel properties and potential device applications. Like the dilute nitride alloy GaAs1–xNx, the dilute bismide shows a giant bandgap bowing effect. Bi alloying primarily affects the states in the vicinity of the top of the valence band rather than the bottom of the conduction band as in the case of N alloying. MBE growth of dilute bismides requires low growth temperatures (320-390 °C) and near stochiometric group III/V ratios, due to the strong tendency of Bi to surface segregate under usual GaAs growth conditions. Optimal growth conditions are close to conditions that produce Bi and/or Ga droplets. In-situ light scattering is found to be a useful tool for defining growth conditions that do not produce droplets on the surface. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Ill-Nitride molecular beam epitaxy (MBE] is a flexible and fast research tool for development and demonstration of new alloys and device structures. While MBE is typically not used as a production technique for optoelectronic devices, excellent material quality can be achieved, as evidenced by extremely high IQE deep UV active regions [1], as well as laser quality active regions with emission wavelengths from the near UV to visible [2]. Ammonia MBE in particular also offers the ability to achieve highly doped layers with world record mobility [3]. In this paper, we will present recent research results using ammonia-assisted MBE that are relevant to developing high efficiency UV emitters.

The effect of dilute N alloying and Bi surfactant growth on strain relaxation in highly strained InGaAs single quantum well (QWs) was investigated by using high resolution X-ray diffraction (HRXRD) and transmission electron microscopy (TEM). Dilute nitride InxGa1–xAs0.99N0.01 QWs of varying thickness, constant lattice mismatch 1.7%, were grown by molecular beam epitaxy on oriented GaAs (001) substrates. Some samples were exposed to a flux of Bi surfactant during the growth procedure, which acts to enhance the N incorporation, increase the optical emission, and create smoother interfaces. The QWs were observed to relax through the formation of pure edge-type, misfit dislocations aligned with in-plane 〈100〉 directions. These were found to be directly associated with degradation in the optical emission, however, 1% N addition, with or without Bi surfactant, did not have a detectable effect on the critical thickness nor the rate of this relaxation mechanism. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

The presence of a bismuth surfactant is found to increase the nitrogen incorporation in the dilute nitride GaN x As 1− x by as much as 60% during growth by molecular beam epitaxy. Films with nitrogen concentrations in the 0.4–0.95% range were grown using an RF plasma source for nitrogen. The Bi surface coverage is inferred from reflection high-energy electron diffraction as a function of Bi flux and substrate temperature, and the nitrogen content is obtained by high-resolution X-ray diffraction. At constant substrate temperature the nitrogen content is found to increase with Bi coverage, which has the form of a Langmuir isotherm when plotted as a function of Bi flux.

Dilute nitride GaNAs thin films and InGaNAs single quantum wells (QWs) have been grown by molecular beam epitaxy with a concurrent bismuth flux. Bi does not incorporate into the films and acts as a surfactant. Atomic force microscopy images reveal that, at sufficiently high bismuth flux, step flow growth occurs in GaN0.004As0.996 even at substrate temperatures as low as 4601C. This results in an order of magnitude decrease in the surface roughness. A similar smoothing effect is obtained when growing GaAs and AlGaAs thin films with bismuth. Furthermore, Bi is found to enhance the incorporation of nitrogen into GaNAs. The peak photoluminescence intensity from an In0.26Ga0.74N0.011As0.989 QW is increased by more than a factor of two with the surfactant. We conclude that Bi reduces the incorporation of defects and/or impurities in the dilute GaNAs based alloys. r 2002 Elsevier Science B.V. All rights reserved. PACS: 81.15.Hi; 68.35.Ct

Ohmic contacts to both c-plane and n-GaN are demonstrated using a pure aluminum layer which was vacuum annealed to prevent oxidation. Specific contact resistivities of 4.4 × 10−7 and 2.3 × 10−5 Ωcm2 were obtained without annealing for c-plane and samples respectively. A reflectivity of over 85% at 450 nm was measured for both samples. After a 300 °C anneal specific contact resistivities of 1.5 × 10−7 and 1.8 × 10−7 Ωcm2 were obtained for c-plane and samples respectively and the reflectivities remained higher than 80%.

Improved turn-on voltages and reduced series resistances were realized by depositing highly Si-doped n-type GaN using molecular beam epitaxy on polarization-enhanced p-type InGaN contact layers grown using metal–organic chemical vapor deposition. We compared the effects of different Si doping concentrations and the addition of p-type InGaN on the forward voltages of p–n diodes and light-emitting diodes, and found that increasing the Si concentrations from 1.9 × 1020 to 4.6 × 1020 cm−3 and including a highly doped p-type InGaN at the junction both contributed to reductions in the depletion width, the series resistance of 4.2 × 10−3–3.4 × 10−3 Ωcm2, and the turn-on voltages of the diodes.

The results of tensile strained AlN/GaN, AlGaN/GaN, and compressive strained InGaN/GaN superlattices (SLs) grown by Ammonia MBE (NH3-MBE) are presented. A combination of atom probe tomography and high-resolution X-ray diffraction confirms that periodic heterostructures of high crystallographic quality are achieved. Strain induced misfit dislocations (MDs), however, are revealed by cathodoluminescence (CL) of the strained AlN/GaN, AlGaN/GaN, and InGaN/GaN structures. MDs in the active region of a device are a severe problem as they act as non-radiative charge recombination centers, affecting the reliability and efficiency of the device. Strain compensated SL structures are subsequently developed, composed of alternating layers of tensile strained AlGaN and compressively strained InGaN. CL reveals the absence of MDs in such structures, demonstrating that strain compensation offers a viable route towards MD free active regions in III-Nitride SL based devices.

A model of basal plane stacking faults as boundaries between incoherently scattering domains in m-plane GaN films is reviewed. m-Plane GaN films are analyzed with a modified version of the Williamson–Hall analysis in order to determine the length-scale of coherent scattering and tilt-mosaic contribution to X-ray rocking curve widths for the primary in-plane directions. This analysis shows that basal plane stacking faults are the predominant source of rocking-curve width anisotropy in the m-plane films, and indicate that the modified Williamson–Hall analysis can be used as a non-destructive technique for measuring basal plane stacking fault densities in m-GaN films.

Growth of InGaN/GaN light-emitting devices on nonpolar planes offers a viable approach to eliminating the issues associated with polarization-related electric fields present in c-plane III-nitride heterostructures. Although progress in device performance has been rapid since the introduction of high-quality free-standing nonpolar substrates, a full appreciation of the materials challenges unique to nonpolar III-nitride semiconductors has been slower to emerge. Only recently have researchers begun to understand issues such as the origins of the pyramidal hillocks typically observed on nominally on-axis m-plane GaN films, the effects of m-plane substrate misorientation on surface morphology, and the effects of m-plane substrate misorientation on device performance. In this article, we review the materials and growth issues unique to high-performance nonpolar light-emitting devices grown on high-quality free-standing substrates and provide an outlook for the opportunities and challenges that lie ahead.

We report a device that monolithically integrates optically pumped (20-21) III-nitride quantum wells (QWs) with 560 nm emission on top of electrically injected QWs with 450 nm emission. The higher temperature growth of the blue light-emitting diode (LED) was performed first, which prevented thermal damage to the higher indium content InGaN of the optically pumped QWs. A tunnel junction (TJ) was incorporated between the optically pumped and electrically injected QWs; this TJ enabled current spreading in the buried LED. Metalorganic chemical vapor deposition enabled the growth of InGaN QWs with high radiative efficiency, while molecular beam epitaxy was leveraged to achieve activated buried p-type GaN and the TJ. This initial device exhibited dichromatic optically polarized emission with a polarization ratio of 0.28. Future improvements in spectral distribution should enable phosphor-free polarized white light emission.

Ca as an unintentional impurity has been investigated in III-nitride layers grown by molecular beam epitaxy (MBE). It is found that Ca originates from the substrate surface, even if careful cleaning and rinsing procedures are applied. The initial Ca surface coverage is ∼1012 cm−2, which is consistent with previous reports on GaAs and silicon wafers. At the onset of growth, the Ca species segregates at the growth front while incorporating at low levels. The incorporation rate is strongly temperature dependent. It is about 0.03% at 820 °C and increases by two orders of magnitude when the temperature is reduced to 600 °C, which is the typical growth temperature for InGaN alloy. Consequently, [Ca] is as high as 1018 cm−3 in InGaN/GaN quantum well structures. Such a huge concentration might be detrimental for the efficiency of light emitting diodes (LEDs) if one considers that Ca is potentially a source of Shockley-Read-Hall (SRH) defects. We thus developed a specific growth strategy to reduce [Ca] in the MBE ...

A molecular beam epitaxy regrowth technique was demonstrated on standard industrial patterned sapphire substrate light-emitting diode (LED) epitaxial wafers emitting at 455 nm to form a GaN tunnel junction. By using an HF pretreatment on the wafers before regrowth, a voltage of 3.08 V at 20 A/cm2 was achieved on small area devices. A high extraction package was developed for comparison with flip chip devices which utilize an LED floating in silicone over a BaSO4 coated header and produced a peak external quantum efficiency (EQE) of 78%. A high reflectivity mirror was designed using a seven-layer dielectric coating backed by aluminum which has a calculated angular averaged reflectivity over 98% between 400 and 500 nm. This was utilized to fabricate a flip chip LED which had a peak EQE and wall plug efficiency of 76% and 73%, respectively. This flip chip could increase light extraction over a traditional flip chip LED due to the increased reflectivity of the dielectric based mirror.

We investigate the bow of free standing (0001) oriented hydride vapor phase epitaxy grown GaN substrates and demonstrate that their curvature is consistent with a compressive to tensile stress gradient (bottom to top) present in the substrates. The origin of the stress gradient and the curvature is attributed to the correlated inclination of edge threading dislocation (TD) lines away from the [0001] direction. A model is proposed and a relation is derived for bulk GaN substrate curvature dependence on the inclination angle and the density of TDs. The model is used to analyze the curvature for commercially available GaN substrates as determined by high resolution x-ray diffraction. The results show a close correlation between the experimentally determined parameters and those predicted from theoretical model.

We present the effects of partial strain relaxation on the optical properties in lattice mismatched semipolar (1122) InGaN using polarization-dependent photoluminescence measurements to probe the strain dependent band mixing of the valence bands.

We report operation of AlGaN laser diodes grown on semipolar buffer layers partially relaxed by misfit dislocation formation at heterointerfaces remote from the active region. This approach offers a pathway to mid-UV AlGaN based lasers.