Publications

Abstract not provided.

This SAND report is the final report on Sandia's Grand Challenge LDRD Project 27328, 'A Revolution in Lighting -- Building the Science and Technology Base for Ultra-Efficient Solid-state Lighting.' This project, which for brevity we refer to as the SSL GCLDRD, is considered one of Sandia's most successful GCLDRDs. As a result, this report reviews not only technical highlights, but also the genesis of the idea for Solid-state Lighting (SSL), the initiation of the SSL GCLDRD, and the goals, scope, success metrics, and evolution of the SSL GCLDRD over the course of its life. One way in which the SSL GCLDRD was different from other GCLDRDs was that it coincided with a larger effort by the SSL community - primarily industrial companies investing in SSL, but also universities, trade organizations, and other Department of Energy (DOE) national laboratories - to support a national initiative in SSL R&D. Sandia was a major player in publicizing the tremendous energy savings potential of SSL, and in helping to develop, unify and support community consensus for such an initiative. Hence, our activities in this area, discussed in Chapter 6, were substantial: white papers; SSL technology workshops and roadmaps; support for the Optoelectronics Industry Development Association (OIDA), DOE and Senator Bingaman's office; extensive public relations and media activities; and a worldwide SSL community website. Many science and technology advances and breakthroughs were also enabled under this GCLDRD, resulting in: 55 publications; 124 presentations; 10 book chapters and reports; 5 U.S. patent applications including 1 already issued; and 14 patent disclosures not yet applied for. Twenty-six invited talks were given, at prestigious venues such as the American Physical Society Meeting, the Materials Research Society Meeting, the AVS International Symposium, and the Electrochemical Society Meeting. This report contains a summary of these science and technology advances and breakthroughs, with Chapters 1-5 devoted to the five technical task areas: 1 Fundamental Materials Physics; 2 111-Nitride Growth Chemistry and Substrate Physics; 3 111-Nitride MOCVD Reactor Design and In-Situ Monitoring; 4 Advanced Light-Emitting Devices; and 5 Phosphors and Encapsulants. Chapter 7 (Appendix A) contains a listing of publications, presentations, and patents. Finally, the SSL GCLDRD resulted in numerous actual and pending follow-on programs for Sandia, including multiple grants from DOE and the Defense Advanced Research Projects Agency (DARPA), and Cooperative Research and Development Agreements (CRADAs) with SSL companies. Many of these follow-on programs arose out of contacts developed through our External Advisory Committee (EAC). In h s and other ways, the EAC played a very important role. Chapter 8 (Appendix B) contains the full (unedited) text of the EAC reviews that were held periodically during the course of the project.

Rare earth doped yttrium oxide (yttria) and silicate, Y{sub 2}O{sub 3}:Eu and Y{sub 2}SiO{sub 5}:Tb, are the most promising phosphors for advanced devices such as flat panel field-emission-displays. However, their light yield for electron excitation has proven to be lower than that predicted by early models. New experimental data are needed to improve the theoretical understanding of the cathodoluminescence (CL) that will, in turn, lead to materials that are significantly brighter. Beside the existing CL and photo luminescence (PL) measurements, one can provide new information by studying ion-induced luminescence (IL). Ions penetrate substantially deeper than electrons and their light yield should therefore not depend on surface effects. Moreover, the energy density released by ions can be much higher than that of electrons and photons, which results in possible saturation effects, further testing the adequacy of models. We exposed the above yttrium compounds to three ion beams, H (3 MeV), C (20 MeV), Cu (50 MeV), which have substantially different electronic stopping powers. H was selected to provide an excitation close to CL, but without surface effects. The C and Cu allowed an evaluation of saturation effects because of their higher stopping powers. The IL experiments involved measuring the transient light intensity signal radiating from thin phosphor layers following their exposure to {approx}200 ns ion beam pulses. We present the transient yield curves for the two materials and discuss a general model for this behavior.

Abstract not provided.

Mechanisms of H release from Mg-doped, p-type GaN were investigated in vacuum, in N{sub 2} and O{sub 2} gases, and in electron-cyclotron-resonance N{sub 2} plasmas. Replacing grown-in protium with deuterium (D) and employing sensitive nuclear-reaction analysis allowed the retained concentration to be followed quantitatively over two decades during isothermal heating, illuminating the kinetics of controlling processes. Oxidation attending the O{sub 2} exposures was monitored through nuclear-reaction analysis of {sup 18}O. N{sub 2} gas at atmospheric pressure increases the rate of D release appreciably relative to vacuum. The acceleration produced by O{sub 2} gas is much greater, but is diminished in later stages of the release by oxidation. The N{sub 2} plasma employed in these studies had no resolvable effect. We argue that surface desorption is rate controlling in the D release, and that it occurs by D-D recombination and the formation of N-D and O-D species. Our results are quantitatively consistent with a theoretical model wherein the bulk solution is in equilibrium with surface states from which desorption occurs by processes that are both first and second order in surface coverage.

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The design of field emission displays is severely constrained by the universally poor cathodoluminescence (CL) efficiency of most phosphors at low excitation energies. As part of the effort to understand this phenomenon, the authors have measured the time decay of spectrally-resolved, pulsed CL and photoluminescence (PL) in several phosphors activated by rare earth and transition metal impurities, including Y{sub 2}O{sub 3}:Eu, Y{sub 2}SiO{sub 5}:Tb, and Zn{sub 2}SiO{sub 4}:Mn. Activator concentrations ranged from {approximately}0.25 to 10%. The CL decay curves are always non-linear on a log(CL)-linear(time) plot--i.e. they deviate from first order decay kinetics. These deviations are always more pronounced at short times and larger activator concentrations and are largest at low beam energies where the decay rates are noticeably faster. PL decay is always slower than that seen for CL, but these differences disappear after most of the excited species have decayed. They have also measured the dependence of steady state CL efficiency on beam energy. They find that larger activator concentrations accelerate the drop in CL efficiency seen at low beam energies. These effects are largest for the activators which interact more strongly with the host lattice. While activator-activator interactions are known to limit PL and CL efficiency in most phosphors, the present data suggest that a more insidious version of this mechanism is partly responsible for poor CL efficiency at low beam energies. This enhanced concentration quenching is due to the interaction of nearby excited activators. These interactions can lead to non-radiative activator decay, hence lower steady state CL efficiency. Excited state clustering, which may be caused by the large energy loss rate of low energy primary electrons, appears to enhance these interactions. In support of this idea, they find that PL decays obtained at high laser pulse energies resemble the non-linear decays seen in the CL data.

The diffusion, uptake, and release of H in p-type GaN are modeled employing state energies from density-function theory and compared with measurements of deuterium uptake and release using nuclear-reaction analysis. Good semiquantitative agreement is found when account is taken of a surface permeation barrier.

The relatively poor efficiency of phosphor materials in cathodoluminescence with low accelerating voltages is a major concern in the design of field emission flat panel displays operated below 5 kV. The authors research on rare-earth-activated phosphors indicates that mechanisms involving interactions of excited activators have a significant impact on phosphor efficiency. Persistence measurements in photoluminescence (PL) and cathodoluminescence (CL) show significant deviations from the sequential relaxation model. This model assumes that higher excited manifolds in an activator de-excite primarily by phonon-mediated sequential relaxation to lower energy manifolds in the same activator ion. In addition to sequential relaxation, there appears to be strong coupling between activators, which results in energy transfer interactions. Some of these interactions negatively impact phosphor efficiency by nonradiatively de-exciting activators. Increasing activator concentration enhances these interactions. The net effect is a significant degradation in phosphor efficiency at useful activator concentrations, which is exaggerated when low-energy electron beams are used to excite the emission.

Electron and hole transport in compensated, InGaAsN ({approx} 2% N) are examined through Hall mobility, photoconductivity, and solar cell photoresponse measurements. Short minority carrier diffusion lengths, photoconductive-response spectra, and doping dependent, thermally activated Hall mobilities reveal a broad distribution of localized states. At this stage of development, lateral carrier transport appears to be limited by large scale (>> mean free path) material inhomogeneities, not a random alloy-induced mobility edge.

Formation energies and vibrational frequencies for H in wurtzite GaN were calculated from density functional theory and used to predict equilibrium state occupancies and solid solubilities for p-type, intrinsic, and n-type material. The solubility of deuterium (D) was measured at 600--800 C as a function of D{sub 2} pressure and doping and compared with theory. Agreement was obtained by reducing the H formation energies 0.2 eV from ab-initio theoretical values. The predicted stretch-mode frequency for H bound to the Mg acceptor lies 5% above an observed infrared absorption attributed to this complex. It is concluded that currently recognized H states and physical processes account for the equilibrium behavior of H examined in this work.

The LDRD entitled ``Role of Defects in III-Nitride Based Devices'' is aimed to place Sandia National Laboratory at the forefront of the field of GaN materials and devices by establishing a scientific foundation in areas such as material growth, defect characterization/modeling, and processing (metalization and etching) chemistry. In this SAND report the authors summarize their studies such as (1) the MOCVD growth and doping of GaN and AlGaN, (2) the characterization and modeling of hydrogen in GaN, including its bonding, diffusion, and activation behaviors, (3) the calculation of energetic of various defects including planar stacking faults, threading dislocations, and point defects in GaN, and (4) dry etching (plasma etching) of GaN (n- and p-types) and AlGaN. The result of the first AlGaN/GaN heterojunction bipolar transistor is also presented.

High resolution measurements of spectrally resolved cathodoluminescence (CL) decay have been made in several commercial and experimental phosphors doped with Eu and Tb at beam energies ranging from 0.8 to 4 keV. CL emission from the lowest two excited states of both rare earth activators was compared to the decay of photoluminescence (PL) after pulsed laser excitation. We find that, at long times after the cessation of electron excitation, the CL decay rates are comparable to those measured in PL, at short times, the decay process is considerably faster and has a noticeable dependence on the energy of the electron beam. These beam energy effects are largest for the higher excited states and for phosphors with larger activator concentrations. Measurements of the experimental phosphors over a range of activator fractions from 0.1 to 0.002 show that the beam energy dependence of the steady-state CL efficiency is larger for higher excited states and weakens as the activator concentration is reduced. The latter effect is strongest for Y{sub 2}SiO{sub 5}:Tb, but also quite evident in Y{sub 2}O{sub 3}:Eu. We suggest that the electron beam dependence of both the decay lifetimes and the steady state CL efficiency may be due to interaction of nearby excited states which occurs as a result of the large energy deposition rate for low energy electrons. This picture-for non-radiative quenching of rare earth emission is an excited state analog of the well-known (ground state-excited state) concentration quenching mechanism.

The behavior of H in p-GaN(Mg) at temperatures >400 C is modeled by using energies and vibrational frequencies from density-functional theory to parameterize transport and reaction equations. Predictions agree semiquantitatively with experiment for the solubility, uptake, and release of the H when account is taken of a surface barrier. Hydrogen is introduced into GaN during growth by metal-organic chemical vapor deposition (MOCVD) and subsequent device processing. This impurity affects electrical properties substantially, notably in p-type GaN doped with Mg where it reduces the effective acceptor concentration. Application of density-functional theory to the zincblende and wurtzite forms of GaN has indicated that dissociated H in interstitial solution assumes positive, neutral, and negative charge states. The neutral species is found to be less stable than one or the other of the charged states for all Fermi energies. Hydrogen is predicted to form a bound neutral complex with Mg, and a local vibrational mode ascribed to this complex has been observed. The authors are developing a unified mathematical description of the diffusion, reactions, uptake, and release of H in GaN at the elevated temperatures of growth and processing. Their treatment is based on zero-temperature energies from density functional theory. One objective is to assess the consistency of theory with experiment at a more quantitative level than previously. A further goal is prediction of H behavior pertinent to device processing. Herein is discussed aspects relating to p-type GaN(Mg).

The authors have used ion channeling to examine the lattice configuration of deuterium in Mg doped GaN grown by MOCVD. The deuterium is introduced both by exposure to deuterium gas and to ECR plasmas. A density functional approach including lattice relaxation, was used to calculate total energies for various locations and charge states of hydrogen in the wurtzite Mg doped GaN lattice. Computer simulations of channeling yields were used to compare results of channeling measurements with calculated yields for various predicted deuterium lattice configurations.

Along with the third-order nonlinear susceptibility, χ(3), the magnitude of the optical absorption in the transparent window below the principal absorption edge is an important parameter for conjugated polymers used in active integrated optical devices. Photothermal deflection spectroscopy (PDS) is an ideal technique for determining the absorption coefficients of thin films of 'transparent' materials. We have used PDS to measure the optical absorption spectra of the conjugated polymers, poly(1,4-phenylene-vinylene) (and derivatives) and polydiacetylene-4BCMU, in the spectral region from 0.55 to 3 eV. We find that the shape of the absorption edge varies considerably from polymer to polymer, with polydiacetylene-4BCMU having the steepest absorption edge. The minimum absorption coefficients measured varied somewhat with sample age and quality, but were typically in the range 1-10 cm-1. In the region below 1 eV, overtones of C-H stretching modes dominate the absorption behavior. We also observe that irradiation of all of these polymers with light above ∼ 2.5 eV produces enhanced absorption below the fundamental edge. In the absence of light, these excitations decay with characteristic times of 10-1000 s and in some cases they may determine the effective IR transparency in the energy range 1.0-1.8 eV. © 1992.

The debonding rates of H-passivated P and As in silicon have been observed to be very sensitive to the concentration of majority and minority charge carriers. A theoretical study of the stable and metastable configurations of the {l brace}P,H{r brace} and {l brace}As,H{r brace} pairs in the 0 and +1 charge states has been carried out at the near-ab-initio Hartree-Fock level. These calculations show that the lowest-energy configuration in the 0 charge state is the highest-energy configuration in the +1 charge state and vice-versa. This bistability of donor-hydrogen pairs implies that H cannot remain in place upon change of charge state, whether 0 {r arrow} +1 or +1 {r arrow} 0. Quantitative differences between the P and the As cases are qualitatively consistent with the observed differences in the temperature dependence of the debonding rates of {l brace}P,H{r brace} and {l brace}As,H{r brace}. 14 refs., 1 fig.

We have used the highly sensitive technique of Photothermal Deflection Spectroscopy (PDS) to measure changes in the infrared absorption spectra of MEHPPV, P3HT and Polydiacetylene-4BCMU induced by pumping these polymers with light above the {pi}--{pi}* transition energy. In contrast to previous chopped light transmission measurements of these effects, the PDS technique can directly measure the buildup or decay of the absorption coefficient, {alpha}, on the time scale of second to days. In the case of MEHPPV we observe that the time scale of seconds to days. In the case of MEHPPV we observe that above-gap light causes the appearance of a broad infrared peak in {alpha}, which continues to grow-in hours after the pump light is first applied. For this polymer the general shape of the absorption spectra in the unpumped state mimics the photo-induced changes, suggesting that remnant photo-induced states determine the maximum transparency observed under normal experimental conditions. For P3HT and to a lesser extent, MEHPPV, we also observe irreversible photo-induced absorption components which we tentatively identify with photo-induced oxidation of the polymer matrix. 10 refs., 8 figs.