In situ observations of the atomistic mechanisms of Ni catalyzed low temperature graphene growth.

The key atomistic mechanisms of graphene formation on Ni for technologically relevant hydrocarbon exposures below 600 °C are directly revealed via complementary in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. For clean Ni(111) below 500 °C, two different surface carbide (Ni2C) conversion mechanisms are dominant which both yield epitaxial graphene, whereas above 500 °C, graphene predominantly grows directly on Ni(111) via replacement mechanisms leading to embedded epitaxial and/or rotated graphene domains. Upon cooling, additional carbon structures form exclusively underneath rotated graphene domains. The dominant graphene growth mechanism also critically depends on the near-surface carbon concentration and hence is intimately linked to the full history of the catalyst and all possible sources of contamination. The detailed XPS fingerprinting of these processes allows a direct link to high pressure XPS measurements of a wide range of growth conditions, including polycrystalline Ni catalysts and recipes commonly used in industrial reactors for graphene and carbon nanotube CVD. This enables an unambiguous and consistent interpretation of prior literature and an assessment of how the quality/structure of as-grown carbon nanostructures relates to the growth modes.

Reversible nanoscale switching of polytwin orientation in a ferroelectric thin film induced by a local electric field

The response to a local, tip-induced electric field of ferroelastic domains in thin polycrystalline lead zirconate titanate films with predominantly (110) orientation has been studied using Enhanced Piezoresponse Force Microscopy. Two types of reversible polytwin switching between well-defined orientations have been observed. When a-c domains are switched to other forms of a-c domains, the ferroelastic domain walls rotate in-plane by 109.5°, and when a-c domains are switched to c-c domains (or vice-versa), the walls rotate by 54.75°. © 2013 AIP Publishing LLC.

Grain boundary interface mechanics in strain gradient crystal plasticity

Interactions between dislocations and grain boundaries play an important role in the plastic deformation of polycrystalline metals. Capturing accurately the behaviour of these internal interfaces is particularly important for applications where the relative grain boundary fraction is significant, such as ultra fine-grained metals, thin films and microdevices. Incorporating these micro-scale interactions (which are sensitive to a number of dislocation, interface and crystallographic parameters) within a macro-scale crystal plasticity model poses a challenge. The innovative features in the present paper include (i) the formulation of a thermodynamically consistent grain boundary interface model within a microstructurally motivated strain gradient crystal plasticity framework, (ii) the presence of intra-grain slip system coupling through a microstructurally derived internal stress, (iii) the incorporation of inter-grain slip system coupling via an interface energy accounting for both the magnitude and direction of contributions to the residual defect from all slip systems in the two neighbouring grains, and (iv) the numerical implementation of the grain boundary model to directly investigate the influence of the interface constitutive parameters on plastic deformation. The model problem of a bicrystal deforming in plane strain is analysed. The influence of dissipative and energetic interface hardening, grain misorientation, asymmetry in the grain orientations and the grain size are systematically investigated. In each case, the crystal response is compared with reference calculations with grain boundaries that are either 'microhard' (impenetrable to dislocations) or 'microfree' (an infinite dislocation sink). © 2013 Elsevier Ltd. All rights reserved.

Structural tunability and switchable exciton emission in inorganic-organic hybrids with mixed halides

Room-temperature tunable excitonic photoluminescence is demonstrated in alloy-tuned layered Inorganic-Organic (IO) hybrids, (C12H 25NH3)2PbI4(1-y)Br4y (y = 0 to 1). These perovskite IO hybrids adopt structures with alternating stacks of low-dimensional inorganic and organic layers, considered to be naturally self-assembled multiple quantum wells. These systems resemble stacked monolayer 2D semiconductors since no interlayer coupling exists. Thin films of IO hybrids exhibit sharp and strong photoluminescence (PL) at room-temperature due to stable excitons formed within the low-dimensional inorganic layers. Systematic variation in the observed exciton PL from 510 nm to 350 nm as the alloy composition is changed, is attributed to the structural readjustment of crystal packing upon increase of the Br content in the Pb-I inorganic network. The energy separation between exciton absorption and PL is attributed to the modified exciton density of states and diffusion of excitons from relatively higher energy states corresponding to bromine rich sites towards the lower energy iodine sites. Apart from compositional fluctuations, these excitons show remarkable reversible flips at temperature-induced phase transitions. All the results are successfully correlated with thermal and structural studies. Such structural engineering flexibility in these hybrids allows selective tuning of desirable exciton properties within suitable operating temperature ranges. Such wide-range PL tunability and reversible exciton switching in these novel IO hybrids paves the way to potential applications in new generation of optoelectronic devices. © 2013 AIP Publishing LLC.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

Oxide electronics for imaging and displays

Despite material weaknesses, considerable progress has been made in designing large area systems such as displays and imaging arrays. This talk will address the various large area technologies, and in particular, review amorphous oxide semiconductors and associated design approaches, along with driving schemes for displays, imaging and other applications. © 2013 IEEE.

Controllable nanodomain defects in ferroelectric/ferroelastic biferroic thin films

Ferroelectric thin films have been intensively studied at the nanometre scale due to the application in many fields, such as non-volatile memories. Enhanced piezo-response force microscopy (E-PFM) was used to investigate the evolution of ferroelectric and ferroelastic nanodomains in a polycrystalline thin film of the simple multi-ferroic PbZr0.3Ti0.7O 3 (PZT). By applying a d.c. voltage between the atomic force microscopy (AFM) tip and the bottom substrate of the sample, we created an electric field to switch the domain orientation. Reversible switching of both ferroelectric and ferroelastic domains towards particular directions with predominantly (111) domain orientations are observed. We also showed that along with the ferroelectric/ferroelastic domain switch, there are defects that also switch. Finally, we proposed the possible explanation of this controllable defect in terms of flexoelectricity and defect pinning. © 2013 IEEE.

Electrical properties of LiNbO3 (electrolyte)/Cu (anode) bi-layers

In this work specific film structures of Li-Nb-O/Li/Li-Nb-O are investigated by AC Impedance Spectroscopy measurements at different temperatures. This gives the opportunity to investigate properties of the material itself and, at the same time, to consider the influence of the grain boundaries on the ionic behavior of the polycrystalline Lithium Niobate. On the other hand, LiNbO3/Li/Cu multi-layers are studied as electrolyte/anode bi-layers and potential parts of "Li-free" microbatteries. The Li deficiency in the as deposited Li-Nb-O films is cured by forming a "sandwich" of Li-Nb-O/Li/Li-Nb-O, which after annealing becomes ionic conductor. The electrical behavior of an annealed film depends on two sources. The first is due to properties of the material itself and the second is based on the network of the grain boundaries. The average size of the grains is strongly influenced by the structure of the ohmic-contact/substrate. The electrical behavior of the electrolyte/anode interface of the "Li-free" structure LiNbO3/Li/Cu/Au is very similar to the impedance measurements of the single LiNbO3 single films. The whole multilayer structure, though, presents a third relaxation time which is consistent of a small resistance. This resistance is independent of temperature and it seems that is due to the metallic interface Li/Cu/Au. © 2010 Elsevier B.V. All rights reserved.

Superradiance: exploiting quantum phase transition in the real world

Superradiance (SR), or cooperative spontaneous emission, has been predicted by R. Dicke before the invention of the laser. During the last few years one can see a renaissance of both experimental and theoretical studies of the superradiant phase transition in a variety of media, ranging from quantum dots and Bose condensates through to black holes. Until recently, despite of many years of research, SR has been considered as a phenomenon of pure scientific interest without obvious potential applications. However, recent investigations of the femtosecond SR emission generation from semiconductors have opened up some practical opportunities for the exploitation of this quantum optics phenomenon. Here we present a brief review of some features, advantages and potential applications of the SR generation from semiconductor laser structures

Pt redistribution in N-MOS transistors during Ni salicide process

Atom probe tomography was used to study the redistribution of platinum during Ni(10 at.%Pt) silicidation of n-doped polycrystalline Si. These measurements were performed after the two annealing steps of standard salicide process both on a field-effect transistor and on unpatterned region submitted to the same process. Very similar results are obtained in unpatterned region and in transistor gate contact. The first phase to form is not the expected δ-Ni2Si but the non stoichiometric θ-Ni2Si. Pt redistribution is strongly influenced by this phase and the final distribution is different from what is reported in literature. © 2013 Elsevier B.V. All rights reserved.

Atom probe tomography for advanced metallization

In microelectronics, the increase in complexity and the reduction of devices dimensions make essential the development of new characterization tools and methodologies. Indeed advanced characterization methods with very high spatial resolution are needed to analyze the redistribution at the nanoscale in devices and interconnections. The atom probe tomography has become an essential analysis to study materials at the nanometer scale. This instrument is the only analytical microscope capable to produce 3D maps of the distribution of the chemical species with an atomic resolution inside a material. This technique has benefit from several instrumental improvements during last years. In particular, the use of laser for the analysis of semiconductors and insulating materials offers new perspectives for characterization. The capability of APT to map out elements at the atomic scale with high sensitivity in devices meets the characterization requirements of semiconductor devices such as the determination of elemental distributions for each device region. In this paper, several examples will show how APT can be used to characterize and understand materials and process for advanced metallization. The possibilities and performances of APT (chemical analysis of all the elements, atomic resolution, planes determination, crystallographic information...) will be described as well as some of its limitations (sample preparation, complex evaporation, detection limit, ...). The examples illustrate different aspect of metallization: dopant profiling and clustering, metallic impurities segregation on dislocation, silicide formation and alloying, high K/metal gate optimization, SiGe quantum dots, as well as analysis of transistors and nanowires. © 2013 Elsevier B.V. All rights reserved.

Dopant compensation in HfO2 and other high K oxides

The theory of doping limits in semiconductors and insulators is applied to the case of wide gap oxides, crystalline, or amorphous, and used to explain that impurities do not in general give rise to gap states or a doping response. Instead, the system tends to form defect complexes or undergo symmetry-lowering reconstructions to expel gap states out of the band gap. The model is applied to impurities, such as trivalent metals, carbon, N, P, and B, in HfO2, the main gate dielectric used in field effect transistors. © 2014 AIP Publishing LLC.

In situ intercalation dynamics in inorganic-organic layered perovskite thin films.

The properties of layered inorganic semiconductors can be manipulated by the insertion of foreign molecular species via a process known as intercalation. In the present study, we investigate the phenomenon of organic moiety (R-NH3I) intercalation in layered metal-halide (PbI2)-based inorganic semiconductors, leading to the formation of inorganic-organic (IO) perovskites [(R-NH3)2PbI4]. During this intercalation strong resonant exciton optical transitions are created, enabling study of the dynamics of this process. Simultaneous in situ photoluminescence (PL) and transmission measurements are used to track the structural and exciton evolution. On the basis of the experimental observations, a model is proposed which explains the process of IO perovskite formation during intercalation of the organic moiety through the inorganic semiconductor layers. The interplay between precursor film thickness and organic solution concentration/solvent highlights the role of van der Waals interactions between the layers, as well as the need for maintaining stoichiometry during intercalation. Nucleation and growth occurring during intercalation matches a Johnson-Mehl-Avrami-Kolmogorov model, with results fitting both ideal and nonideal cases.

First-principles prediction of the magnetism of 3d transition-metal-doped Rocksalt MgO

Using first-principles band structure methods, we have systematically studied the electronic structures, magnetic stabilities, and half-metal properties of 3d transition-metal (TM) doped Rocksalt MgO compounds TMMg3O4 (TM = V, Cr, Mn, Fe, Co, and Ni). The calculations reveal that only CrMg3O4 has a ferromagnetic stability among the six compounds, which is explained by double-exchange mechanism. The magnetic stability is affected by the doping concentration of TM if the top valance band is composed of partially occupied t(2g) states. In addition, CrMg3O4 is a half-metallic ferromagnet. The origins of half-metallic and ferromagnetic properties are explored. The Curie temperature (T-c) of CrMg3O4 is 182 K. And it is hard for CrMg3O4 to deform due to the large bulk modulus and shear modulus, so it is a promising spintronic material. Our calculations provide the first available information on the magnetic properties of 3d TM-doped MgO.

Theoretical gain of strained GeSn0.02/Ge1-x-y ' SixSny ' quantum well laser

Using effective-mass Hamiltonian model of semiconductors quantum well structures, we investigate the electronic structures of the Gamma-conduction and L-conduction subbands of GeSn/GeSiSn strained quantum well structure with an arbitrary composition. Our theoretical model suggests that the band structure could be widely modified to be type I, negative-gap or indirect-gap type II quantum well by changing the mole fraction of alpha-Sn and Si in the well and barrier layers, respectively. The optical gain spectrum in the type I quantum well system is calculated, taking into account the electrons leakage from the Gamma-valley to L-valley of the conduction band. We found that by increasing the mole fraction of alpha-Sn in the barrier layer and not in the well layer, an increase in the tensile strain effect can significantly enhance the transition probability, and a decrease in Si composition in the barrier layer, which lowers the band edge of Gamma-conduction subbands, also comes to a larger optical gain.