Clayton Cozzan

Stable, Heat-Conducting Phosphor Composites for High-Power Laser Lighting

Solid-state lighting using laser diodes is an exciting new development that requires new phosphor geometries to handle the greater light fluxes involved. The greater flux from the source results in more conversion and therefore more conversion loss in the phosphor, which generates self-heating, surpassing the stability of current encapsulation strategies used for light-emitting diodes, usually based on silicones. Here, we present a rapid method using spark plasma sintering (SPS) for preparing ceramic phosphor composites of the canonical yellow-emitting phosphor Ce-doped yttrium aluminum garnet (Ce:YAG) combined with a chemically compatible and thermally stable oxide, α-Al2O3. SPS allows for compositional modulation, and phase fraction, microstructure, and luminescent properties of ceramic composites with varying compositions are studied here in detail. The relationship between density, thermal conductivity, and temperature rise during laser-driven phosphor conversion is elucidated, showing that only modest densities are required to mitigate thermal quenching in phosphor composites. Additionally, the scattering nature of the ceramic composites makes them ideal candidates for laser-driven white lighting in reflection mode, where Lambertian scattering of blue light offers great color uniformity, and a luminous flux >1000 lm is generated using a single commercial laser diode coupled to a single phosphor element.

Monolithic translucent BaMgAl10O17:Eu2+ phosphors for laser-driven solid state lighting

With high power light emitting diodes and laser diodes being explored for white light generation and visible light communication, thermally robust encapsulation schemes for color-converting inorganic phosphors are essential. In the current work, the canonical blue-emitting phosphor, high purity Eu-doped BaMgAl10O17, has been prepared using microwave-assisted heating (25 min) and densified into translucent ceramic phosphor monoliths using spark plasma sintering (30 min). The resulting translucent ceramic monoliths convert UV laser light to blue light with the same efficiency as the starting powder and provide superior thermal management in comparison with silicone encapsulation.

Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si6−zAlzOzN8−z:Eu2+ phosphors

Inorganic phosphor materials play a crucial role in the creation of white light from blue and near-UV solid-state light-emitting diodes. Understanding the intricacies of the phosphor structure is key for setting the stage for improved, more efficient functionality. Average structure and coordination environment analysis of the robust and efficient green-emitting phosphor, β-SiAlON:Eu2+ (β-Si6−zAlzOzN8−zEu0.009), is combined here with a range of property measurements to elucidate the role of Al content (z) in luminescence properties, including the red shift of emission and the thermal quenching of luminescence as a function of increasing Al content z. Average structure techniques reveal changes in polyhedral distortion with increasing z for the 9-coordinate Eu site in β-SiAlON:Eu2+. X-ray absorption near edge structure (XANES) is used to confirm that the majority of the activator Eu is in the Eu2+ state, exhibiting the symmetry-allowed and efficient 4f75d0 → 4f65d1 transitions. Room temperature and temperature-dependent luminescence indicate a curious increase in thermal stability with increasing z over a small range due to an increasing barrier for thermal ionization, which is correlated to an increase in the quantum yield of the phosphor.

Structural Evolution and Atom Clustering in β-SiAlON: β-Si6–zAlzOzN8–z

SiAlON ceramics, solid solutions based on the Si3N4 structure, are important, lightweight structural materials with intrinsically high strength, high hardness, and high thermal and chemical stability. Described by the chemical formula β-Si6-zAlzOzN8-z, from a compositional viewpoint, these materials can be regarded as solid solutions between Si3N4 and Al3O3N. A key aspect of the structural evolution with increasing Al and O (z in the formula) is to understand how these elements are distributed on the β-Si3N4 framework. The average and local structural evolution of highly phase-pure samples of β-Si6-zAlzOzN8-z with z = 0.050, 0.075, and 0.125 are studied here, using a combination of X-ray diffraction, NMR studies, and density functional theory calculations. Synchrotron X-ray diffraction establishes sample purity and indicates subtle changes in the average structure with increasing Al content in these compounds. Solid-state magic-angle-spinning 27Al NMR experiments, coupled with detailed ab initio calculations of NMR spectra of Al in different AlOqN4-q tetrahedra (0 ≤ q ≤ 4), reveal a tendency of Al and O to cluster in these materials. Independently, the calculations suggest an energetic preference for Al-O bond formation, instead of a random distribution, in the β-SiAlON system.

Semipolar GaN-based laser diodes for Gbit/s white lighting communication: devices to systems

We report the high-speed performance of semipolar GaN ridge laser diodes at 410 nm and the dynamic characteristics including differential gain, damping, and the intrinsic maximum bandwidth. To the best of our knowledge, the achieved modulation bandwidth of 6.8 GHz is the highest reported value in the blue-violet spectrum. The calculated differential gain of ~3 x 10-16 cm2, which is a critical factor in high-speed modulation, proved theoretical predictions of higher gain in semipolar GaN laser diodes than the conventional c-plane counterparts. In addition, we demonstrate the first novel white lighting communication system by using our near-ultraviolet (NUV) LDs and pumping red-, green-, and blueemitting phosphors. This system satisfies both purposes of high-speed communication and high-quality white light illumination. A high data rate of 1.5 Gbit/s using on-off keying (OOK) modulation together with a high color rendering index (CRI) of 80 has been measured.

Structural Evolution and Atom Clustering in β-SiAlON: β-Si

C.C. thanks the National Science Foundation for a Graduate Research Fellowship under Grant DGE 1144085. K.J.G. thanks The Winston Churchill Foundation of the United States and the Herchel Smith Scholarship for funding. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE), Office of Science, by Argonne National Laboratory, was supported by the U.S. DOE under Contract DE-AC02-06CH11357. DFT calculations were performed on the Darwin Supercomputer of the University of Cambridge High Performance Computing Service (http://www.hpc.cam.ac.uk/), provided by Dell Inc. using Strategic Research Infrastructure Funding from the Higher Education Funding Council for England and funding from the Science and Technology Facilities Council (U.K.). This work made use of MRL-shared experimental facilities, supported by the MRSEC Program of the NSF under Award DMR 1121053. The MRL is a member of the NSF-funded Materials Research Facilities Network (www.mrfn.org).

_{6-z}

SiAlON ceramics, solid solutions based on the Si3N4 structure, are important, lightweight structural materials with intrinsically high strength, high hardness, and high thermal and chemical stability. Described by the chemical formula β-Si6-zAlzOzN8-z, from a compositional viewpoint, these materials can be regarded as solid solutions between Si3N4 and Al3O3N. A key aspect of the structural evolution with increasing Al and O (z in the formula) is to understand how these elements are distributed on the β-Si3N4 framework. The average and local structural evolution of highly phase-pure samples of β-Si6-zAlzOzN8-z with z = 0.050, 0.075, and 0.125 are studied here, using a combination of X-ray diffraction, NMR studies, and density functional theory calculations. Synchrotron X-ray diffraction establishes sample purity and indicates subtle changes in the average structure with increasing Al content in these compounds. Solid-state magic-angle-spinning 27Al NMR experiments, coupled with detailed ab initio calculations of NMR spectra of Al in different AlOqN4-q tetrahedra (0 ≤ q ≤ 4), reveal a tendency of Al and O to cluster in these materials. Independently, the calculations suggest an energetic preference for Al-O bond formation, instead of a random distribution, in the β-SiAlON system.

Al

SiAlON ceramics, solid solutions based on the Si3N4 structure, are important, lightweight structural materials with intrinsically high strength, high hardness, and high thermal and chemical stability. Described by the chemical formula β-Si6-zAlzOzN8-z, from a compositional viewpoint, these materials can be regarded as solid solutions between Si3N4 and Al3O3N. A key aspect of the structural evolution with increasing Al and O (z in the formula) is to understand how these elements are distributed on the β-Si3N4 framework. The average and local structural evolution of highly phase-pure samples of β-Si6-zAlzOzN8-z with z = 0.050, 0.075, and 0.125 are studied here, using a combination of X-ray diffraction, NMR studies, and density functional theory calculations. Synchrotron X-ray diffraction establishes sample purity and indicates subtle changes in the average structure with increasing Al content in these compounds. Solid-state magic-angle-spinning 27Al NMR experiments, coupled with detailed ab initio calculations of NMR spectra of Al in different AlOqN4-q tetrahedra (0 ≤ q ≤ 4), reveal a tendency of Al and O to cluster in these materials. Independently, the calculations suggest an energetic preference for Al-O bond formation, instead of a random distribution, in the β-SiAlON system.