Analysis of functional materials by X-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy (XPS) can play an important role in guiding the design of new materials, tailored to meet increasingly stringent constraints on performance devices, by providing insight into their surface compositions and the fundamental interactions between the surfaces and the environment. This chapter outlines the principles and application of XPS as a versatile, chemically specific analytical tool in determining the electronic structures and (usually surface) compositions of constituent elements within diverse functional materials. Advances in detector electronics have opened the way for development of photoelectron microscopes and instruments with XPS imaging capabilities. Advances in surface science instrumentation to enable time-resolved spectroscopic measurements offer exciting opportunities to quantitatively investigate the composition, structure and dynamics of working catalyst surfaces. Attempts to study the effects of material processing in realistic environments currently involves the use of high- or ambient-pressure XPS in which samples can be exposed to reactive environments.

Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

Electronic properties of homoepitaxial (111) highly boron-doped diamond films

The use of diamond as a semiconductor for the realization of transistor structures, which can operate at high temperatures (>700 K), is of increasing interest. In terms of bipolar devices, the growth of n-type phosphorus doped diamond is more efficient on the (111) growth plane; p-type boron-doped diamond growth has been most usually grown in the (100) direction and, hence, this study into the electronic properties, at high temperatures, of boron-doped diamond (111) homoepitaxial layers. It is shown that highly doped layers (hole carrier concentrations as high as 2×1020 cm-3) can be produced without promoting the onset of (unwanted) hopping conduction. The persistence of valance-band conduction in these films enables relatively high mobility values to be measured ( ~ 20 cm2/V?s) and, intriguingly, these values are not significantly reduced at high temperatures. The layers also display very low compensation levels, a fact that may explain the high mobility values since compensation is required for hopping conduction. The results are discussed in terms of the potential of these types of layers for use with high temperature compatible diamond transistors.

Copper(II) complexes with unsymmetrical pentadentate ed3a-type diamino-tricarboxylate ligands. Crystal structures, configurational analysis and DFT study of complexes

The O–O–N–N–O-type pentadentate ligands H3ed3a, H3pd3a and H3pd3p (H3ed3a stands ethylenediamine-N,N,N′-triacetic acid; H3pd3a stands 1,3-propanediamine-N,N,N′-triacetic acid and H3pd3p stands 1,3-propanediamine-N,N,N′-tri-3-propionic acid) and the corresponding novel octahedral or square-planar/trigonal-bipyramidal copper(II) complexes have been prepared and characterized. H3ed3a, H3pd3a and H3pd3p ligands coordinate to copper(II) ion via five donor atoms (three deprotonated carboxylate atoms and two amine nitrogens) affording octahedral in case of ed3a3− and intermediate square-pyramidal/trigonal-bipyramidal structure in case of pd3a3− and pd3p3−. A six coordinate, octahedral geometry has been established crystallographically for the [Mg(H2O)6][Cu(ed3a)(H2O)]2 · 2H2O complex and five coordinate square-pyramidal for the [Mg(H2O)5Cu(pd3a)][Cu(pd3a)] · 2H2O. Structural data correlating similar chelate Cu(II) complexes have been used for the better understanding the pathway: octahedral → square-pyramidal ↔ trigonal- bipyramid geometry. An extensive configuration analysis is discussed in relation to information obtained for similar complexes. The infra-red and electronic absorption spectra of the complexes are discussed in comparison with related complexes of known geometries. Molecular mechanics and density functional theory (DFT) programs have been used to model the most stable geometric isomer yielding, at the same time, significant structural data. The results from density functional studies have been compared with X-ray data.

Purchasing consortia and electronic markets:a procurement direction in integrated supply chain management

In supply chain management literature, there has been little empirical research investigation on purchasing consortium issues focusing on a detailed analysis of information and communication (ICT) based procurement strategies. Based on the exploration of academic literature and two surveys among purchasing organisations as well as e-Marketplaces / procurement service providers (PSPs) in the automotive and electronics industry sectors, the research methodology follows a positivistic approach in order to assess the overall statement: ‘Effective participation in electronic purchasing consortia (EPC) can have the potential to enhance competitive advantage. Implementation therefore requires a clear and detailed understanding of the major process structures and drivers, based upon thetechnology-organisation-environment framework.’ Key factors and structures that affect the adoption and diffusion of EPC and the performance impact of adoption are investigated. The empirically derived model for EPC can be a valuable starting point to EPC research.

Electronic purchasing consortia:a procurement direction for the future?

In literature, there has been little empirical research investigation on purchasing consortium issues focusing on a detailed analysis of ICT-based procurement strategies. Based on the exploration of academic literature and a survey on e-Marketplaces / procurement service providers (PSPs) in the automotive and electronics industry sectors, an overall statement is proposed: Effective participation in electronic purchasing consortia can have the potential to enhance competitive advantage. Implementation therefore requires a clear and detailed understanding of the major process structures and drivers at the e-Marketplace / PSP level of analysis.

Laboratory focussed learning of core electronic engineering concepts in the first year of an honours degree programme

In common with most universities teaching electronic engineering in the UK, Aston University has seen a shift in the profile of its incoming students in recent years. The educational background of students has moved away from traditional Alevel maths and science and if anything this variation is set to increase with the introduction of engineering diplomas. Another major change to the circumstances of undergraduate students relates to the introduction of tuition fees in 1998 which has resulted in an increased likelihood of them working during term time. This may have resulted in students tending to concentrate on elements of the course that directly provide marks contributing to the degree classification. In the light of these factors a root and branch rethink of the electronic engineering degree programme structures at Aston was required. The factors taken into account during the course revision were:. Changes to the qualifications of incoming students. Changes to the background and experience of incoming students. Increase in overseas students, some with very limited practical experience. Student focus on work directly leading to marks. Modular compartmentalisation of knowledge. The need for provision of continuous feedback on performance We discuss these issues with specific reference to a 40 credit first year electronic engineering course and detail the new course structure and evaluate the effectiveness of the changes. The new approach appears to have been successful both educationally and with regards to student satisfaction. The first cohort of students from the new course will graduate in 2010 and results from student surveys relating particularly to project and design work will be presented at the conference. © 2009 K Sugden, D J Webb and R P Reeves.