Efficiency Improvement of Nitride-Based Solid State Light Emitting Materials -- CRADA Final Report

The development of In{sub x}Ga{sub 1-x} N/GaN thin film growth by Molecular Beam Epitaxy has opened a new route towards energy efficient solid-state lighting. Blue and green LED's became available that can be used to match the whole color spectrum of visible light with the potential to match the eye response curve. Moreover, the efficiency of such devices largely exceeds that of incandescent light sources (tungsten filaments) and even competes favorably with lighting by fluorescent lamps. It is, however, also seen in Figure 1 that it is essential to improve on the luminous performance of green LED's in order to mimic the eye response curve. This lack of sufficiently efficient green LED's relates to particularities of the In{sub x}Ga{sub 1-x}N materials system. This ternary alloy system is polar and large strain is generated during a lattice mismatched thin film growth because of the significantly different lattice parameters between GaN and InN and common substrates such as sapphire. Moreover, it is challenging to incorporate indium into GaN at typical growth temperatures because a miscibility gap exists that can be modified by strain effects. As a result a large parameter space needs exploration to optimize the growth of In{sub x}Ga{sub 1-x}N and to date it is unclear what the detailed physical processes are that affect device efficiencies. In particular, an inhomogeneous distribution indium in GaN modifies the device performance in an unpredictable manner. As a result technology is pushed forward on a trial and error basis in particular in Asian countries such as Japan and Korea, which dominate the market and it is desirable to strengthen the competitiveness of the US industry. This CRADA was initiated to help Lumileds Lighting/USA boosting the performance of their green LED's. The tasks address the distribution of the indium atoms in the active area of their blue and green LED's and its relation to internal and external quantum efficiencies. Procedures to measure the indium distribution with near atomic resolution were developed and applied to test samples and devices that were provided by Lumilids. Further, the optical performance of the device materials was probed by photoluminescence, electroluminescence and time resolved optical measurements. Overall, the programs objective is to provide a physical basis for the development of a simulation program that helps making predictions to improve the growth processes such that the device efficiency can be increased to about 20%. Our study addresses all proposed aspects successfully. Carrier localization, lifetime and recombination as well as the strain-induced generation of electric fields were characterized and modeled. Band gap parameters and their relation to the indium distribution were characterized and modeled. Electron microscopy was developed as a unique tool to measure the formation of indium clusters on a nanometer length scale and it was demonstrated that strain induced atom column displacements can reliably be determined in any materials system with a precision that approaches 2 pm. The relation between the local indium composition x and the strain induced lattice constant c(x) in fully strained In{sub x}Ga{sub 1-x}N quantum wells was found to be: c(x) = 0.5185 + {alpha}x with {alpha} = 0.111 nm. It was concluded that the local indium concentration in the final product can be modulated by growth procedures in a predictable manner to favorably affect external quantum efficiencies that approached target values and that internal quantum efficiencies exceeded them

Torsional instability in the single-chain limit of a transition metal trichalcogenide

We report the synthesis of the quasi-one-dimensional transition metal trichalcogenide NbSe3 in the few chain limit, including the realization of isolated single chains. The chains are encapsulated in protective boron nitride or carbon nanotube sheaths to prevent oxidation and to facilitate characterization. Transmission electron microscopy reveals static and dynamic structural torsional waves not found in bulk NbSe3 crystals. Electronic structure calculations indicate that charge transfer drives the torsional wave instability. Very little covalent bonding is found between the chains and the nanotube sheath, leading to relatively unhindered longitudinal and torsional dynamics for the encapsulated chains.Comment: 27 pages, 12 figure

Atomic Resolution Imaging with a sub-50 pm Electron Probe

Using a highly coherent focused electron probe in a 5th order aberration-corrected transmission electron microscope, we report on resolving a crystal spacing less than 50 pm. Based on the geometrical source size and residual coherent and incoherent axial lens aberrations, an electron probe is calculated, which is theoretically capable of resolving an ideal 47 pm spacing with 29percent contrast. Our experimental data show the 47 pm spacing of a Ge 114 crystal imaged with 11-18percent contrast at a 60-95percent confidence level, providing the first direct evidence for sub 50-pm resolution in ADF STEM imaging

FePt icosahedra with magnetic cores and catalytic shells

Surprisingly oxidation resistant icosahedral FePt nanoparticles showing hard-magnetic properties have been fabricated by an inert-gas condensation method with in-flight annealing. High-resolution transmission electron microscopy (HRTEM) images with sub-Angstrom resolution of the nanoparticle have been obtained with focal series reconstruction, revealing noncrystalline nature of the nanoparticle. Digital dark-field method combined with structure reconstruction as well as HRTEM simulations reveal that these nanoparticles have icosahedral structure with shell periodicity. Localized lattice relaxations have been studied by extracting the position of individual atomic columns with a precision of about (0.002 nm. The lattice spacings of (111) planes from the surface region to the center of the icosahedra are found to decrease exponentially with shell numbers. Computational studies and energy-filtered transmission electron microscopy analyses suggest that a Pt-enriched surface layer is energetically favored and that site-specific vacancies are formed at the edges of facettes, which was experimentally observed. The presence of the Pt-enriched shell around an Fe/Pt core explains the environmental stability of the magnetic icosahedra and strongly reduces the exchange coupling between neighboring particles, thereby possibly providing the highest packing density for future magnetic storage media based on FePt nanoparticles

Direct imaging and chemical analysis of unstained DNA origami performed with a transmission electron microscope

Here, we report a simple and rapid characterisation technique combining physical and chemical analysis for DNA origami with conventional TEM.close4

Uniqueness in Discrete Tomography of Delone Sets with Long-Range Order

We address the problem of determining finite subsets of Delone sets $\varLambda\subset\R^d$ with long-range order by $X$-rays in prescribed $\varLambda$-directions, i.e., directions parallel to non-zero interpoint vectors of $\varLambda$. Here, an $X$-ray in direction $u$ of a finite set gives the number of points in the set on each line parallel to $u$. For our main result, we introduce the notion of algebraic Delone sets $\varLambda\subset\R^2$ and derive a sufficient condition for the determination of the convex subsets of these sets by $X$-rays in four prescribed $\varLambda$-directions.Comment: 15 pages, 2 figures; condensed and revised versio

Conversion of self-assembled monolayers into nanocrystalline graphene: Structure and electric transport

Graphene-based materials have been suggested for applications ranging from nanoelectronics to nanobiotechnology. However, the realization of graphene-based technologies will require large quantities of free-standing two-dimensional (2D) carbon materials with tuneable physical and chemical properties. Bottom-up approaches via molecular self-assembly have great potential to fulfil this demand. Here, we report on the fabrication and characterization of graphene made by electron-radiation induced cross-linking of aromatic self-assembled monolayers (SAMs) and their subsequent annealing. In this process, the SAM is converted into a nanocrystalline graphene sheet with well defined thickness and arbitrary dimensions. Electric transport data demonstrate that this transformation is accompanied by an insulator to metal transition that can be utilized to control electrical properties such as conductivity, electron mobility and ambipolar electric field effect of the fabricated graphene sheets. The suggested route opens broad prospects towards the engineering of free-standing 2D carbon materials with tuneable properties on various solid substrates and on holey substrates as suspended membranes.Comment: 30 pages, 5 figure

Tautomerism unveils a self-inhibition mechanism of crystallization

Modifiers are commonly used in natural, biological, and synthetic crystallization to tailor the growth of diverse materials. Here, we identify tautomers as a new class of modifiers where the dynamic interconversion between solute and its corresponding tautomer(s) produces native crystal growth inhibitors. The macroscopic and microscopic effects imposed by inhibitor-crystal interactions reveal dual mechanisms of inhibition where tautomer occlusion within crystals that leads to natural bending, tunes elastic modulus, and selectively alters the rate of crystal dissolution. Our study focuses on ammonium urate crystallization and shows that the keto-enol form of urate, which exists as a minor tautomer, is a potent inhibitor that nearly suppresses crystal growth at select solution alkalinity and supersaturation. The generalizability of this phenomenon is demonstrated for two additional tautomers with relevance to biological systems and pharmaceuticals. These findings offer potential routes in crystal engineering to strategically control the mechanical or physicochemical properties of tautomeric materials