3D Strain in 2D Materials: To What Extent is Monolayer Graphene Graphite?

This work addresses a fundamental question: To what extent is graphene graphite? In particular does 2D graphene have many of the same 3D mechanical properties as graphite, such as the bulk modulus and elastic constant c_{33}? We have obtained, for the first time, unambiguous Raman spectra from unsupported monolayer graphene under pressure. We have used these data to quantify the out-of-plane stiffness of monolayer graphene, which is hard to define due to its 2D nature. Our data indicate a first physically meaningful out-of-plane stiffness of monolayer graphene, and find it to be consistent with that of graphite. We also report a shift rate of the in-plane phonon frequency of unsupported monolayer graphene to be 5.4 cm^{-1} GPa^{-1}, very close to that of graphite (4.7 cm^{-1} GPa^{-1}), contrary to the previous value for supported graphene. Our results imply that monolayer graphene has similar in-plane and out-of-plane stiffnesses, and anharmonicities to graphite.

Resonant photoluminescence studies of carrier localisation in c-plane InGaN/GaN quantum well structures.

In this paper we report on changes in the form of the low temperature (12 K) photoluminescence spectra of an InGaN/GaN quantum well structure as a function of excitation photon energy. As the photon energy is progressively reduced we observe at a critical energy a change in the form of the spectra from one which is determined by the occupation of the complete distribution of hole localisation centres to one which is determined by the resonant excitation of specific localisation sites. This change is governed by an effective mobility edge whereby the photo-excited holes remain localised at their initial energy and are prevented from scattering to other localisation sites. This assignment is confirmed by the results of atomistic tight binding calculations which show that the wave function overlap of the lowest lying localised holes with other hole states is low compared with the overlap of higher lying hole states with other higher lying hole states.

The atomic structure of polar and non-polar InGaN quantum wells and the green gap problem.

We have used high resolution transmission electron microscopy (HRTEM), aberration-corrected quantitative scanning transmission electron microscopy (Q-STEM), atom probe tomography (APT) and X-ray diffraction (XRD) to study the atomic structure of (0001) polar and (11-20) non-polar InGaN quantum wells (QWs). This paper provides an overview of the results. Polar (0001) InGaN in QWs is a random alloy, with In replacing Ga randomly. The InGaN QWs have atomic height interface steps, resulting in QW width fluctuations. The electrons are localised at the top QW interface by the built-in electric field and the well-width fluctuations, with a localisation energy of typically 20meV. The holes are localised near the bottom QW interface, by indium fluctuations in the random alloy, with a localisation energy of typically 60meV. On the other hand, the non-polar (11-20) InGaN QWs contain nanometre-scale indium-rich clusters which we suggest localise the carriers and produce longer wavelength (lower energy) emission than from random alloy non-polar InGaN QWs of the same average composition. The reason for the indium-rich clusters in non-polar (11-20) InGaN QWs is not yet clear, but may be connected to the lower QW growth temperature for the (11-20) InGaN QWs compared to the (0001) polar InGaN QWs.

High-quality III-nitride films on conductive, transparent (2Ì 01)-oriented ß-Ga2O3 using a GaN buffer layer.

We demonstrate the high structural and optical properties of InxGa1-xN epilayers (0 ≤ x ≤ 23) grown on conductive and transparent (01)-oriented ß-Ga2O3 substrates using a low-temperature GaN buffer layer rather than AlN buffer layer, which enhances the quality and stability of the crystals compared to those grown on (100)-oriented ß-Ga2O3. Raman maps show that the 2″ wafer is relaxed and uniform. Transmission electron microscopy (TEM) reveals that the dislocation density reduces considerably (~4.8 × 10(7) cm(-2)) at the grain centers. High-resolution TEM analysis demonstrates that most dislocations emerge at an angle with respect to the c-axis, whereas dislocations of the opposite phase form a loop and annihilate each other. The dislocation behavior is due to irregular (01) ß-Ga2O3 surface at the interface and distorted buffer layer, followed by relaxed GaN epilayer. Photoluminescence results confirm high optical quality and time-resolved spectroscopy shows that the recombination is governed by bound excitons. We find that a low root-mean-square average (≤1.5 nm) of InxGa1-xN epilayers can be achieved with high optical quality of InxGa1-xN epilayers. We reveal that (01)-oriented ß-Ga2O3 substrate has a strong potential for use in large-scale high-quality vertical light emitting device design.

Heterogeneous integration of gallium nitride light-emitting diodes on diamond and silica by transfer printing.

We report the transfer printing of blue-emitting micron-scale light-emitting diodes (micro-LEDs) onto fused silica and diamond substrates without the use of intermediary adhesion layers. A consistent Van der Waals bond was achieved via liquid capillary action, despite curvature of the LED membranes following release from their native silicon growth substrates. The excellence of diamond as a heat-spreader allowed the printed membrane LEDs to achieve optical power output density of 10 W/cm(2) when operated at a current density of 254 A/cm(2). This high-current-density operation enabled optical data transmission from the LEDs at 400 Mbit/s.

Direct observation of depth-dependent atomic displacements associated with dislocations in gallium nitride.

We demonstrate that the aberration-corrected scanning transmission electron microscope has a sufficiently small depth of field to observe depth-dependent atomic displacements in a crystal. The depth-dependent displacements associated with the Eshelby twist of dislocations in GaN normal to the foil with a screw component of the Burgers vector are directly imaged. We show that these displacements are observed as a rotation of the lattice between images taken in a focal series. From the sense of the rotation, the sign of the screw component can be determined.

Prospects of III-nitride optoelectronics grown on Si.

The use of III-nitride-based light-emitting diodes (LEDs) is now widespread in applications such as indicator lamps, display panels, backlighting for liquid-crystal display TVs and computer screens, traffic lights, etc. To meet the huge market demand and lower the manufacturing cost, the LED industry is moving fast from 2 inch to 4 inch and recently to 6 inch wafer sizes. Although Al2O3 (sapphire) and SiC remain the dominant substrate materials for the epitaxy of nitride LEDs, the use of large Si substrates attracts great interest because Si wafers are readily available in large diameters at low cost. In addition, such wafers are compatible with existing processing lines for 6 inch and larger wafers commonly used in the electronics industry. During the last decade, much exciting progress has been achieved in improving the performance of GaN-on-Si devices. In this contribution, the status and prospects of III-nitride optoelectronics grown on Si substrates are reviewed. The issues involved in the growth of GaN-based LED structures on Si and possible solutions are outlined, together with a brief introduction to some novel in situ and ex situ monitoring/characterization tools, which are especially useful for the growth of GaN-on-Si structures.

Mg doping affects dislocation core structures in GaN.

Aberration-corrected scanning transmission electron microscopy was used to investigate the core structures of threading dislocations in undoped GaN films with both high and low dislocation densities, and in a comparable high dislocation density Mg-doped GaN film. All a-type dislocations in all samples have a 5/7-atom core structure. In contrast, most (a+c)-type dislocations in undoped GaN dissociate due to local strain variations from nearby dislocations. In contrast, Mg doping prevents (a+c)-type dislocation dissociation. Our data indicate that Mg affects dislocation cores in GaN significantly.

The significance of Bragg's law in electron diffraction and microscopy, and Bragg's second law.

Bragg's second law, which deserves to be more widely known, is recounted. The significance of Bragg's law in electron diffraction and microscopy is then discussed, with particular emphasis on differences between X-ray and electron diffraction. As an example of such differences, the critical voltage effect in electron diffraction is described. It is then shown that the lattice imaging of crystals in high-resolution electron microscopy directly reveals the Bragg planes used for the imaging process, exactly as visualized by Bragg in his real-space law. Finally, it is shown how in 2012, for the first time, on the centennial anniversary of Bragg's law, single atoms have been identified in an electron microscope using X-rays emitted from the specimen. Hence atomic resolution X-ray maps of a crystal in real space can be formed which give the positions and identities of the different atoms in the crystal, or of a single impurity atom in the crystal.

Atom probe tomography and transmission electron microscopy of a Mg-doped AlGaN/GaN superlattice.

The electronic characteristics of semiconductor-based devices are greatly affected by the local dopant atom distribution. In Mg-doped GaN, the clustering of dopants at structural defects has been widely reported, and can significantly affect p-type conductivity. We have studied a Mg-doped AlGaN/GaN superlattice using transmission electron microscopy (TEM) and atom probe tomography (APT). Pyramidal inversion domains were observed in the TEM and the compositional variations of the dopant atoms associated with those defects have been studied using APT. Rarely has APT been used to assess the compositional variations present due to structural defects in semiconductors. Here, TEM and APT are used in a complementary fashion, and the strengths and weaknesses of the two techniques are compared.

Imaging dislocations in gallium nitride across broad areas using atomic force microscopy.

We have employed an atomic force microscope with a high sampling rate to image GaN samples grown using an epitaxial layer overgrowth technique and treated with silane and ammonia to enlarge the surface pits associated with threading dislocations (TDs). This allows TDs to be identified in high pixel density images tens of microns in size providing detailed information about the spatial distribution of the TDs. An automated software tool has been developed, which identifies the coordinates of the TDs in the image. Additionally, we have imaged the same sample using Kelvin probe force microscopy, again at high pixel density, providing data about the local changes in surface potential associated with hundreds of dislocations.

Combined structure-factor phase measurement and theoretical calculations for mapping of chemical bonds in GaN.

For non-centrosymmetric crystals, the refinement of charge-density maps requires highly accurate measurements of structure-factor phase, which can now be obtained using the extinction-free convergent-beam electron microdiffraction method. We report here accurate low-order structure-factor phases and amplitudes for gallium nitride (GaN) in the wurtzite structure. The measurement accuracy is up to 0.1% for amplitude and 0.2 degrees for phases. By combining these with high-order structure factors from electronic structure calculation, charge-density maps were obtained. Fine bonding features suggest that the Ga-N bonds are polar and covalent, with charge transfer from Ga to N; however, the polarity effect is extremely small.

Lattice distortions in GaN on sapphire using the CBED-HOLZ technique.

The convergent beam electron diffraction (CBED) methodology was developed to investigate the lattice distortions in wurtzite gallium nitride (GaN) from a single zone-axis pattern. The methodology enabled quantitative measurements of lattice distortions (alpha, beta, gamma and c) in transmission electron microscope (TEM) specimens of a GaN film grown on (0,0,0,1) sapphire by metal-organic vapour-phase epitaxy. The CBED patterns were obtained at different distances from the GaN/sapphire interface. The results show that GaN is triclinic above the interface with an increased lattice parameter c. At 0.85 microm from the interface, alpha=90 degrees , beta=8905 degrees and gamma=11966 degrees . The GaN lattice relaxes steadily back to hexagonal further away from the sapphire substrate. The GaN distortions are mainly confined to the initial stages of growth involving the growth and the coalescence of 3D GaN islands.

HANSIS software tool for the automated analysis of HOLZ lines.

A software tool, named as HANSIS (HOLZ analysis), has been developed for the automated analysis of higher-order Laue zone (HOLZ) lines in convergent beam electron diffraction (CBED) patterns. With this tool, the angles and distances between the HOLZ intersections can be measured and the data can be presented graphically with a user-friendly interface. It is capable of simultaneous analysis of several HOLZ patterns and thus provides a tool for systematic studies of CBED patterns.

Observation of long-range compositional fluctuations in glasses: implications for atomic and electronic structure.

Experimental evidence for long-range compositional fluctuations in glasses is given. The implications for electronic structure and stoichiometry-induced structural variations are analyzed. These fluctuations were discovered by examining the spatial dependence of inner shell near-edge absorption spectra obtained using a 50nm diameter probe. This spectroscopy is sensitive to both angular and distance correlations in bonding. Comparisons with spectra from compositionally equivalent crystals, and multiple-scattering calculations which include core-hole effects are used to analyze the data.

Electron energy loss near edge structure (ELNES) spectra of AlN and AlGaN: a theoretical study using the Wien2k and Telnes programs.

Several aspects of the modelling of the energy loss near edge structure (ELNES) using the Wien2k code and the Telnes program are discussed in this paper. A case study with ground state, partial and full core-hole calculations of wurtzite AlN was performed and the results were compared with experimental transmission electron microscopy data. The best agreement with the experimental observations was obtained for the full core-hole case. Changes in the ELNES spectra for various core-hole charges are explained by investigating the site and symmetry projected density of states. Directionally resolved N K-edge ELNES of AlN are discussed and the magic angle beta approximately 2.5mrad is identified which is in a good agreement with other theoretical predictions. Finally, preliminary results on a compositional study of Al(x)Ga(1-x)N are explored.

Quantitative secondary electron energy filtering in a scanning electron microscope and its applications.

Two-dimensional dopant mapping in the scanning electron microscope (SEM) has recently attracted attention due to its ability to measure dopant levels rapidly with high spatial resolution while requiring little or no sample preparation. The dopant concentration could be derived from the energy distribution of secondary electrons emitted per doped region. However, the lack of reliable quantification, when standard SEM imaging is used, has so far hindered a wide application of the technique. This paper aims to resolve this problem with quantitative energy-filtering using a through-the-lens (TTL) detector in a field emission gun SEM (FEG-SEM). We have used the linear shift obtained in the SE energy distribution with variable specimen bias using sample containing copper wires, defined as the experimental detector response R(exp), to quantify the energy filtering. Using different experimental conditions, values of (2.42+/-0.04)

Electrophoretic manipulation of single DNA molecules in nanofabricated capillaries.

We demonstrate the use of nanofabricated capillaries, integrated as part of a microfluidic structure, to study the electrophoretic behaviour of single, fluorescently-labelled, molecules of DNA as a function of capillary size. The nanocapillaries, fabricated using a focused ion beam, have cross-sections down to 150 x 180 nm. Control of single-molecule direction and velocity was achieved using voltage manipulation. DNA mobility was found to increase with decreasing cross-section, which we interpret in terms of reduced electro-osmotic counter-flow. Such nanofabricated capillaries as part of larger fluidic structures have great potential for biotechnology, particularly single molecule manipulation and analysis.

Electron energy-loss near edge structure (ELNES) of InGaN quantum wells.

Lasers and light-emitting diodes (LEDs) that emit in the blue to green region are often based on InxGa1-xN quantum well structures. Ionization edges in the electron energy-loss spectrum contain fine structures (called the energy-loss near edge structure (ELNES)) and provide information about the electronic structure. In this paper we compare the experimental and calculated ELNES for the N-K ionization edge of InxGa1-xN quantum wells. When the effects of the core-hole are included in the calculations, agreement between experimental and calculated spectra is very good. Strain has been shown to accentuate the effects of In on the ELNES and moves the ionization edge onset down in energy, relative to the other features. These results suggest that ELNES may provide an alternative method to lattice imaging to determine the presence of strain in this system.

Analysis of contacts and V-defects in GaN device structures by transmission electron microscopy.

This paper describes the microstructure of ohmic contacts to an AlGaN/GaN heterostructure, of interest for high power transistors, and an analysis of V-defects in an InGaN/GaN multi-quantum well (MQW) light-emitting structure. A combination of different transmission electron microscopy (TEM) techniques has been employed, as they provide complementary information. These include bright field and dark field TEM, high-resolution electron microscopy, X-ray mapping, energy filtered TEM and high angle annular dark field. A full determination of the phase distribution in the ohmic contacts was achieved. The onset of low contact resistance was found to correspond with the formation of an interfacial layer containing both TiN and AlN, and of an intermetallic layer containing Al, Ti and Au in contact with it. The MQW structures were capped with a p-type GaN layer, and TEM and ADF studies of the samples show a number of V-defects 100-200 nm apart along the MQW. Each V-defect incorporates a pure edge (b = 1/3 <11-20>) dislocation, which runs through its apex up to the free surface. The defects contain GaN with no InGaN layers, suggesting the V-pits have been filled in by the capping layer.