The irradiation of thin insulating films by high-energy ions (374 MeV Au{sup +25} or 241 MeV I{sup +19}) was used to attempt to form nanometer-size pores through the films spontaneously. Such ions deposit a large amount of energy into the target materials ({approx}20 keV/nm), which significantly disrupts their atomic lattice and sputters material from the surfaces, and might produce nanopores for appropriate ion-material combinations. Transmission electron microscopy was used to examine the resulting ion tracks. Tracks were found in the crystalline oxides quartz, sapphire, and mica. Sapphire and mica showed ion tracks that are likely amorphous and exhibit pits 5 nm in diameter on the surface at the ion entrance and exit points. This suggests that nanopores might form in mica if the film thickness is less than {approx}10 nm. Tracks in quartz showed strain in the matrix around them. Tracks were not found in the amorphous thin films examined: 20 nm-SiN{sub x}, deposited SiOx, fused quartz (amorphous SiO{sub 2}), formvar and 3 nm-C. Other promising materials for nanopore formation were identified, including thin Au and SnO{sub 2} layers.
High-energy ion tracks (374 MeV Au{sup 26+}) in thin films were examined with transmission electron microscopy to investigate nanopore formation. Tracks in quartz and mica showed diffraction contrast. Tracks in sapphire and mica showed craters formed at the positions of ion incidence and exit, with a lower-density track connecting them. Direct nanopore formation by ions (without chemical etching) would appear to require film thicknesses less than 10 nm.
Solid-state light sources emitting at wavelengths less than 300 nm would enable technological advances in many areas such as fluorescence-based biological agent detection, non-line-of-sight communications, water purification, and industrial processing including ink drying and epoxy curing. In this paper, we present our recent progress in the development of LEDs with emission between 237 and 297 nm. We will discuss growth and design issues of deep-UV LEDs, including transport in Si-doped AlGaN layers. The LEDs are designed for bottom emission so that improved heat sinking and light extraction can be achieved by flip chipping. To date, we have demonstrated 2.25 mW of output power at 295 nm from 1 mm x 1 mm LEDs operated at 500 mA. Shorter wavelength LEDs emitting at 276 nm have achieved an output power of 1.3 mW at 400 mA. The heterostructure designs that we have employed have suppressed deep level emission to intensities that are up to 330 x lower than the primary quantum well emission.
The plastic behavior of crystalline materials is mainly controlled by the nucleation and motion of lattice dislocations. We report in situ dynamic transmission electron microscope observations of nanocrystalline nickel films with an average grain size of about 10 nanometers, which show that grain boundary-mediated processes have become a prominent deformation mode. Additionally, trapped lattice dislocations are observed in individual grains following deformation. This change in the deformation mode arises from the grain size-dependent competition between the deformation controlled by nucleation and motion of dislocations and the deformation controlled by diffusion-assisted grain boundary processes.
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.
We demonstrate that when vertical threading dislocations in (0001) GaN are imaged in plan-view by transmission electron microscopy, a surface-relaxation contrast operates in addition to that due to the strain fields of dislocations passing through the specimen. We show that all three dislocation types (edge, screw, and mixed) can be detected in the same image using g = (11{bar 2}0) and 18{sup o} specimen tilt from [0001], allowing total densities to be assessed properly. The type of an individual dislocation can also be readily identified.
Thin-film mechanical properties can be measured using nanoindentation combined with detailed finite element modeling. This technique was used for a study of very fine grained Ni films, formed using pulsed-laser deposition on fused silica, sapphire, and Ni substrates. The grain sizes in the films were characterized by electron microscopy, and the mechanical properties were determined by ultra-low load indentation, analyzed using finite element modeling to separate the mechanical properties of the thin layers from those of the substrates. Some Ni films were deposited at high temperature or annealed after deposition to enlarge the grain sizes. The observed hardnesses and grain sizes in these thin Ni films are consistent with the empirical Hall-Petch relationship for grain sizes ranging from a few micrometers to as small as 10 nm, suggesting that deformation occurs preferentially by dislocation movement even in such nanometer-size grains.
Ion implantation of O and Al were used to form nanometer-size precipitates of NiO or Al{sub 2}O{sub 3} in the near-surface of Ni. The yield strengths of the treated layers were determined by nanoindentation testing in conjunction with finite-element modeling. The strengths range up to {approximately}5 GPa, substantially above values for hard bearing steels. These results agree quantitatively with predictions of dispersion-hardening theory based on the precipitate microstructures observed by transmission electron microscopy. Such surface hardening by ion implantation may be beneficial for Ni components in micro-electromechanical systems.
This LDRD is aimed to place Sandia at the forefront of GaN-based technologies. Two important themes of this LDRD are: (1) The demonstration of novel GaN-based devices which have not yet been much explored and yet are coherent with Sandia's and DOE's mission objectives. UV optoelectronic and piezoelectric devices are just two examples. (2) To demonstrate front-end monolithic integration of GaN with Si-based microelectronics. Key issues pertinent to the successful completion of this LDRD have been identified to be (1) The growth and defect control of AlGaN and GaN, and (2) strain relief during/after the heteroepitaxy of GaN on Si and the separation/transfer of GaN layers to different wafer templates.
Very fine-grained Ni and Cu films were formed using pulsed laser deposition onto fused silica substrates. The grain sizes in the films were characterized by electron microscopy, and the mechanical properties were determined by ultra-low load indentation, with finite-element modeling used to evaluate the properties of the layers separately from those of the substrate. Some Ni films were also examined after annealing to 350 and 450 °C to enlarge the grain sizes. These preliminary results show that the observed hardnesses are consistent with a simple extension of the Hall-Petch relationship to grain sizes as small as 11 nm for Ni and 32 nm for Cu.
The density of threading dislocations (TD) in GaN grown directly on flat sapphire substrates is typically greater than 10{sup 9}/cm{sup 2}. Such high dislocation densities degrade both the electronic and photonic properties of the material. The density of dislocations can be decreased by orders of magnitude using cantilever epitaxy (CE), which employs prepatterned sapphire substrates to provide reduced-dimension mesa regions for nucleation and etched trenches between them for suspended lateral growth of GaN or AlGaN. The substrate is prepatterned with narrow lines and etched to a depth that permits coalescence of laterally growing III-N nucleated on the mesa surfaces before vertical growth fills the etched trench. Low dislocation densities typical of epitaxial lateral overgrowth (ELO) are obtained in the cantilever regions and the TD density is also reduced up to 1 micrometer from the edge of the support regions.
The effect of lateral composition modulation, spontaneously generated during the epitaxial growth of a AlAs/InAs short-period superlattice, on the electronic band structure is investigated using photo-transmission and photoluminescence spectroscopy. Compared with uniform layers of similar average composition, the presence of the composition modulation considerably reduces the band gap energy and produces strongly polarized emission and absorption spectra. The authors demonstrate that the dominant polarization can selectively be aligned along the [{bar 1}10] or [010] crystallographic directions. In compressively strained samples, the use of (001) InP substrates slightly miscut toward [111]A or [101] resulted in modulation directions along [110] or [100], respectively, and dominant polarizations along a direction orthogonal to the respective composition modulation. Band gap reduction as high as 350 meV and 310 meV are obtained for samples with composition modulation along [110] and [100], respectively. Polarization ratios up to 26 are observed in transmission spectra.
Growth of InAs/AlAs short-period superlattices on appropriately miscut (001) InP substrates is shown to alter the microstructure of composition modulation from a 2D organization of short compositionally enriched wires to a single dominant modulation direction and wire lengths up to {approximately}1 {micro}m. The effects of miscut are interpreted in terms of surface step orientation and character. The material is strongly modulated and exhibits intense optical emission. The 1D modulations appear potentially useful for new devices that take advantage of the preferred direction formed in the growth plane.
Strained-layer semiconductor films offer tremendous potential with regards to optoelectronic applications for high speed communications, mobile communications, sensing, and novel logic devices. It is an unfortunate reality that many of the possible film/substrate combinations that could be exploited technologically are off limits because of large differences in lattice parameters, chemical compatibilities, or thermal expansion rates. These mechanical, chemical, and thermal incompatibilities manifest themselves primarily in terms of lattice defects such as dislocations and antiphase boundaries, and in some cases through enhanced surface roughness. An additional limitation, from a production point of view, is money. Device manufacturers as a rule want the cheapest substrate possible. Freeing the heteroepitaxial world of the bonds of (near) lattice matching would vastly expand the types of working devices that could be grown. As a result, a great deal of effort has been expended finding schemes to integrate dissimilar film/substrate materials while preserving the perfection of the film layer. One such scheme receiving significant attention lately is the so-called compliant substrate approach.
The nature and origin of lateral composition modulations in (AlAs){sub m}(InAs){sub n} SPSs grown by MBE on InP substrates have been investigated by XRD, AFM, and TEM. Strong modulations were observed for growth temperatures between {approx} 540 and 560 C. The maximum strength of modulations was found for SPS samples with InAs mole fraction x (=n/(n+m)) close to {approx} 0.50 and when n {approx} m {approx} 2. The modulations were suppressed at both high and low values of x. For x >0.52 (global compression) the modulations were along the <100> directions in the (001) growth plane. For x < 0.52 (global tension) the modulations were along the two <310> directions rotated {approx} {+-} 27{degree} from [110] in the growth plane. The remarkably constant wavelength of the modulations, between {approx} 20--30 nm, and the different modulation directions observed, suggest that the origin of the modulations is due to surface roughening associated with the high misfit between the individual SPS layers and the InP substrate. Highly uniform unidirectional modulations have been grown, by control of the InAs mole fraction and growth on suitably offcut substrates, which show great promise for application in device structures.
The microstructure of lateral composition modulation in InAs/AlAs superlattices grown by MBE on InP is examined. The use of x-ray diffraction, TEM, AFM, and STEM to characterize the modulations is discussed. Combining the information from these techniques gives increased insight into the phenomenon and how to manipulate it. Diffraction measures the intensity of modulation and its wavelength, and is used to identify growth conditions giving strong modulation. The TEM and STEM analyses indicate that local compositions are modulated by as much as 0.38 InAs mole fraction. Plan-view images show that modulated structures consists of short ({approx_lt}0.2 {micro}m) In-rich wires with a 2D organization in a (001) growth plane. However, growth on miscut substrates can produce a single modulation along the miscut direction with much longer wires ({approx_gt}0.4 {micro}m), as desired for potential applications. Photoluminescence studies demonstrate that the modulation has large effects on the bandgap energy of the superlattice.
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.
The authors have directly measured the stress evolution during metal organic chemical vapor deposition of AlGaN/GaN heterostructures on sapphire. In situ stress measurements were correlated with ex situ microstructural analysis to directly determine a critical thickness for cracking and the subsequent relaxation kinetics of tensile-strained Al{sub x}Ga{sub 1{minus}x}N on GaN. Cracks appear to initiate the formation of misfit dislocations at the AlGaN/GaN interface, which account for the majority of the strain relaxation.
The formation of quantum wires has much interest due to their novel electronic properties which may lead to enhanced optoelectronic device performance and greater photovoltaic efficiencies. One method of forming these structures is through spontaneous lateral modulation found during the epitaxial growth of III/V alloys. In this paper, we report and summarize our investigations on the formation of lateral moduation in the MBE grown InAlAs/InP(001) system. This system was grown as a short-period superlattice where n-monolayers of InAs are deposited followed by m-Monolayers of AlAs (with n and m~2) and this sequence is repeated to grown a low strain InAlAs ternary alloy on InP(001) that exhibits lateral modulation. Films were grown under a variety of condition (growth temperature, effective alloy composition, superlattice period, and growth rate). These films have been extensively analyzed using X-ray diffraction, atomic force microscopy, and transmission electron microscopy (TEM) and microcharacterization, in addition to photon-based spectroscopes. Here we present results of several microstructural characterizations using a wide range of TEM-based techniques, and compare them to results from the other methods to obtain a unified understanding of composition modulation. Two strong points consistently emerge: 1) The lateral modulation wavelength is insensitive to growth temperature and effective alloy composition, but the strength of the lateral modulation is greatest near an effective alloy composition of In(0.46)Al(0.54)As, which corresponds to a slightly tensile global strain with respect to InP. 2) The composition variation for the strongly modulated films is as much as 0.38 InAs mole fraction. In addition, for these strongly modulated films, the modulation wave is asymmetric showing strongly peaked, narrower InAs-rich regions separated by flat AlAs-rich regions. We discuss these results and their possible implications in addition to detailing the techniques used to obtain them.