Rafael Dalmau

The growth and optical properties of large, high-quality AlN single crystals

The effect of impurities and defects on the optical properties of AlN was investigated. High-quality AlN single crystals of more than 20mm2 size were examined. Different crucible materials and growth procedures were applied to the growth of bulk AlN by physical vapor transport method to vary the defect and the impurity concentrations. The crystalline orientation was investigated by Raman spectroscopy. Glow discharge mass spectrometry was used to determine the trace concentration of the incorporated impurities such as oxygen and carbon. The photoluminescence emission and absorption properties of the crystals revealed bands around 3.5 and 4.3eV at room temperature. Absorption edges ranging between 4.1 and 5.95eV were observed. Since no straight correlation of the oxygen concentration was obtained, a major contribution of oxygen or oxygen-related impurities was ruled out to generate the observed emission and absorption bands in the Ultraviolet spectral range. The carbon-related impurities and intrinsic defec...

Surface preparation and homoepitaxial deposition of AlN on (0001)-oriented AlN substrates by metalorganic chemical vapor deposition

Chemical surface treatments were conducted on mechanically polished (MP) and chemomechanically polished (CMP) (0001)-oriented single crystalline aluminum nitride (AlN) substrates to determine a surface preparation procedure for the homoepitaxial deposition of AlN epitaxial layers by metalorganic chemical vapor deposition. MP AlN substrates characterized by atomic force microscopy exhibited 0.5 nm rms roughness and polishing scratches, while CMP AlN substrates exhibited 0.1 nm rms roughness and were scratch-free. X-ray photoelectron spectroscopy analysis of MP and CMP AlN substrates indicated the presence of a surface hydroxide layer composed of mixed aluminum oxide hydroxide and aluminum trihydroxide. Wet etching with sulfuric and phosphoric acid mixtures reduced the amount of surface hydroxide. Ammonia annealing at 1250 °C converted the substrate hydroxide layer to AlN and increased the rms roughness of MP and CMP AlN substrates to 2.2 nm and 0.2 nm, respectively. AlN epitaxial layers were deposited at 1...

Influence of gallium supersaturation on the properties of GaN grown by metalorganic chemical vapor deposition

A thermodynamic supersaturation model for gallium (Ga) was developed to describe GaN growth characteristics in low-pressure metalorganic chemical vapor deposition. The model takes into account the simplified GaN chemical reaction that occurs at the growth interface, Ga+NH3=GaN+3/2H2. The supersaturation was varied in two ways: (1) by the V/III ratio and (2) by the choice of the diluent gas. Two diluent gases were considered: H2, a commonly used diluent gas, and N2, a reaction inert gas. The choice of the diluent played a role in the degree of Ga supersaturation; since H2 is the product in the GaN formation, the addition of hydrogen significantly lowered the supersaturation. Atomic force microscopy revealed that surface morphology was associated with the different Ga supersaturation and the Burton–Cabrera–Frank model was used to relate it to the observed spiral size and terrace width. In addition to growth morphology, the degree of Ga supersaturation also influenced the carrier compensation level in n-type...

Deep-Ultraviolet Light-Emitting Diodes Fabricated on AlN Substrates Prepared by Hydride Vapor Phase Epitaxy

AlGaN-based deep-ultraviolet light-emitting diodes (DUV-LEDs) were fabricated on AlN substrates. The AlN substrates were prepared by growing thick hydride vapor phase epitaxy (HVPE)-AlN layers on bulk AlN substrates prepared by physical vapor transport (PVT). After growing an LED structure, the PVT-AlN substrates were removed by mechanical polishing. This process allowed the fabrication of DUV-LEDs on HVPE-AlN substrates with high crystalline quality and DUV optical transparency. The DUV-LEDs exhibited a single emission peaking at 268 nm through the HVPE-AlN substrates. The output power as high as 28 mW was obtained at an injection current of 250 mA.

Growth and Characterization of AlN and AlGaN Epitaxial Films on AlN Single Crystal Substrates

AlN and AlGaN epitaxial films were deposited by metal organic chemical vapor deposition on single crystal AlN substrates processed from AlN boules grown by physical vapor transport. Structural, chemical, and optical characterization demonstrated the high crystalline quality of the films and interfaces.

On the origin of the 265 nm absorption band in AlN bulk crystals

Single crystal AlN provides a native substrate for Al-rich AlGaN that is needed for the development of efficient deep ultraviolet light emitting and laser diodes. An absorption band centered around 4.7 eV (∼265 nm) with an absorption coefficient above 1000 cm−1 is observed in these substrates. Based on density functional theory calculations, substitutional carbon on the nitrogen site introduces absorption at this energy. A series of single crystalline wafers were used to demonstrate that this absorption band linearly increased with carbon, strongly supporting the model that CN- is the predominant state for carbon in AlN.

Preparation of a Freestanding AlN Substrate from a Thick AlN Layer Grown by Hydride Vapor Phase Epitaxy on a Bulk AlN Substrate Prepared by Physical Vapor Transport

The structural and optical quality of a freestanding AlN substrate prepared from a thick AlN layer grown by hydride vapor phase epitaxy (HVPE) on a bulk (0001)AlN substrate prepared by physical vapor transport (PVT) were investigated. The prepared HVPE-AlN substrate was crack- and stress-free. High-resolution X-ray diffraction ω-rocking curves of symmetric (0002) and skew-symmetric (1011) reflections had small full widths at half maximum (FWHMs) of 31 and 32 arcsec, respectively. Deep-ultraviolet optical transparency of the HVPE-AlN substrate was higher than that of the PVT-AlN substrate, which was related to lower concentrations of C, O impurities, and Al vacancy.

Band-edge exciton states in AlN single crystals and epitaxial layers

The band-edge excitonic properties of AlN are investigated using low-temperature (1.7K) optical reflectance and transmission measurements of samples with various crystal orientations. The A, B, and C excitons are found to have energies of 6.025, 6.243, and 6.257eV in unstrained material, which shift with strain. The results are compared to a calculation of exciton energies and oscillator strengths to yield a crystal-field splitting of −230meV in unstrained AlN, in good agreement with previous ab initio calculations.

Synchrotron white beam topography characterization of physical vapor transport grown AlN and ammonothermal GaN

Structural defects in AlN single crystals grown by the sublimation method and GaN single crystals grown by the ammonothermal method are characterized by synchrotron white-beam X-ray topography in conjunction with optical microscopy. AlN platelets are either of (1120) or (0001) type depending on the growth conditions. Dislocation densities of the order of 10 3 cm -2 or lower are observed in some crystals. X-ray topographs reveal the presence of growth sector boundaries, inclusions, and growth dislocations that indicate slight impurity contamination. The 2H crystal structure of GaN single crystals obtained by the ammonothermal method was verified by Laue X-ray pattern analysis. GaN crystals grown are of the order of 1 mm in size and are either (0001) platelets or [0001] prismatic needles. Generally, prismatic needles are characterized by lower degree of mosaicity than (0001) platelets.

Vacancy compensation and related donor-acceptor pair recombination in bulk AlN

A prominent 2.8 eV emission peak is identified in bulk AlN substrates grown by physical vapor transport. This peak is shown to be related to the carbon concentration in the samples. Density functional theory calculations predict that this emission is caused by a donor-acceptor pair (DAP) recombination between substitutional carbon on the nitrogen site and a nitrogen vacancy. Photoluminescence and photoluminescence-excitation spectroscopy are used to confirm the model and indicate the DAP character of the emission. The interaction between defects provides a pathway to creating ultraviolet-transparent AlN substrates for optoelectronics applications.