Many materials systems are currently under consideration as potential replacements for SiO2 as the gate dielectric material for sub-0.1 μm complementary metal–oxide–semiconductor (CMOS) technology. A systematic consideration of the required properties of gate dielectrics indicates that the key guidelines for selecting an alternative gate dielectric are (a) permittivity, band gap, and band alignment to silicon, (b) thermodynamic stability, (c) film morphology, (d) interface quality, (e) compatibility with the current or expected materials to be used in processing for CMOS devices, (f) process compatibility, and (g) reliability. Many dielectrics appear favorable in some of these areas, but very few materials are promising with respect to all of these guidelines. A review of current work and literature in the area of alternate gate dielectrics is given. Based on reported results and fundamental considerations, the pseudobinary materials systems offer large flexibility and show the most promise toward success...

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High-κ gate dielectrics: Current status and materials properties considerations

Photoelectrochemical (PEC) cells offer the ability to convert electromagnetic energy from our largest renewable source, the Sun, to stored chemical energy through the splitting of water into molecular oxygen and hydrogen. Hematite (α-Fe(2)O(3)) has emerged as a promising photo-electrode material due to its significant light absorption, chemical stability in aqueous environments, and ample abundance. However, its performance as a water-oxidizing photoanode has been crucially limited by poor optoelectronic properties that lead to both low light harvesting efficiencies and a large requisite overpotential for photoassisted water oxidation. Recently, the application of nanostructuring techniques and advanced interfacial engineering has afforded landmark improvements in the performance of hematite photoanodes. In this review, new insights into the basic material properties, the attractive aspects, and the challenges in using hematite for photoelectrochemical (PEC) water splitting are first examined. Next, recent progress enhancing the photocurrent by precise morphology control and reducing the overpotential with surface treatments are critically detailed and compared. The latest efforts using advanced characterization techniques, particularly electrochemical impedance spectroscopy, are finally presented. These methods help to define the obstacles that remain to be surmounted in order to fully exploit the potential of this promising material for solar energy conversion.

Solar Water Splitting: Progress Using Hematite (α‐Fe2O3) Photoelectrodes

A new magneto-optical sum rule is derived for circular magnetic dichroism in the x-ray region (CMXD). The integral of the CMXD signal over a given edge allows one to determine the ground-state expectation value of the orbital angular momentum. Applications are discussed to transition-metal and rare-earth magnetic systems.

X-ray circular-dichroism as a probe of orbital magnetization

Sum rules are derived for the circular dichroic response of a core line (CMXD). They relate the intensity of the CMXD signal to the ground-state expectation value of the magnetic field operators (orbital, spin, and magnetic dipole) of the valence electrons. The results obtained are discussed and tested for transition metals and rare earths.

X-ray circular-dichroism and local magnetic-fields

Electronic structure calculations have become an indispensable tool in many areas of materials science and quantum chemistry. Even though the Kohn-Sham formulation of the density-functional theory (DFT) simplifies the many-body problem significantly, one is still confronted with several numerical challenges. In this article we present the projector augmented-wave (PAW) method as implemented in the GPAW program package (https://wiki.fysik.dtu.dk/gpaw) using a uniform real-space grid representation of the electronic wavefunctions. Compared to more traditional plane wave or localized basis set approaches, real-space grids offer several advantages, most notably good computational scalability and systematic convergence properties. However, as a unique feature GPAW also facilitates a localized atomic-orbital basis set in addition to the grid. The efficient atomic basis set is complementary to the more accurate grid, and the possibility to seamlessly switch between the two representations provides great flexibility. While DFT allows one to study ground state properties, time-dependent density-functional theory (TDDFT) provides access to the excited states. We have implemented the two common formulations of TDDFT, namely the linear-response and the time propagation schemes. Electron transport calculations under finite-bias conditions can be performed with GPAW using non-equilibrium Green functions and the localized basis set. In addition to the basic features of the real-space PAW method, we also describe the implementation of selected exchange-correlation functionals, parallelization schemes, Delta SCF-method, x-ray absorption spectra, and maximally localized Wannier orbitals.

https://iopscience.iop.org/article/10.1088/0953-8984/22/25/253202/pdf

Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method

Magnetic circular dichroism (MCD) has been observed at the ${\mathit{L}}_{2,3}$ absorption edges of ferromagnetic nickel by use of circularly-polarized soft-x-ray synchrotron radiation. The MCD intensity ratio between the ${\mathit{L}}_{2}$ and ${\mathit{L}}_{3}$ edges is found to differ appreciably from that predicted by a simple exchange-split-valence-band model. Fine MCD features, imperceptible in the absorption spectra, are also observed, and a tentative interpretation is given. This work, demonstrating the feasibility of MCD measurements in the soft-x-ray region, provides a new approach to study 3d and 4f ferromagnetic systems with their respective dipole-permitted 2p\ensuremath{\rightarrow}3d and 3d\ensuremath{\rightarrow}4f transitions.

Soft-x-ray magnetic circular dichroism at the l2,3 edges of nickel

Oxygen K-edge absorption spectra of carefully characterized ${\mathrm{La}}_{2\mathrm{\ensuremath{-}}\mathit{x}}$${\mathrm{Sr}}_{\mathit{x}}$${\mathrm{CuO}}_{4+\mathrm{\ensuremath{\delta}}}$ samples were measured using a bulk-sensitive fluoresence-yield-detection method. They reveal two distinct pre-edge peaks which evolve systematically as a function of Sr concentration. The measured spectra are quantitatively described by calculations based on the Hubbard model, including local Coulomb interactions and core-hole excitonic correlations. The absorption data are consistent with a description of electronic states based on a doped charge-transfer insulator.

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Electronic states in La2-xSrxCuO4+ delta probed by soft-x-ray absorption.

A multilayer dielectric stack is provided which has alternating layers of a high-k material and an interposing material. The presence of the interposing material and the thinness of the high-k material layers reduces or eliminate effects of crystallization within the high-k material, even at relatively high annealing temperatures. The high-k dielectric layers are a metal oxide of preferably zirconium or hafnium. The interposing layers are preferably amorphous aluminum oxide, aluminum nitride, or silicon nitride. Because the layers reduce the effects of crystalline structures within individual layers, the overall tunneling current is reduced. Also provided are atomic layer deposition, sputtering, and evaporation as methods of depositing desired materials for forming the above-mentioned multilayer dielectric stack.

Method of forming a multilayer dielectric stack

{ital K}-shell photoabsorption spectra of CO, {sup 13}C{sup 18}O, NO, O{sub 2}, CO{sub 2}, N{sub 2}O, C{sub 2}H{sub 2}, C{sub 2}D{sub 2}, C{sub 2}H{sub 4}, C{sub 2}D{sub 4}, C{sub 2}H{sub 6}, C{sub 2}D{sub 6} measured with unprecedented energy resolution and signal-to-noise ratio are presented. These spectra reveal many new features in core-excited valence and Rydberg states. Detailed vibrational structures are observed in these spectra, providing valuable information on the geometrical and vibrational properties of the core-excited molecules. In addition, C 1{ital s} and N 1{ital s} core-hole lifetimes are found to be {similar to}120 and {similar to}135 meV in these molecules with little dependence on their bonding environments. These results and the tentative peak assignments are discussed briefly in terms of the equivalent core model, multielectron excitations, exchange interactions, and the geometry of the excited molecules.

High-resolution K-shell photoabsorption measurements of simple molecules.

A high-k dielectric films is provided, which is doped with divalent or trivalent metals to vary the electron affinity, and consequently the electron and hole barrier height. The high-k dielectric film is a metal oxide of either zirconium (Zr) or hafnium (Hf), doped with a divalent metal, such as calcium (Ca) or strontium (Sr), or a trivalent metal, such as aluminum (Al), scandium (Sc), lanthanum (La), or yttrium (Y). By selecting either a divalent or trivalent doping metal, the electron affinity of the dielectric material can be controlled, while also providing a higher dielectric constant material then silicon dioxide. Preferably, the dielectric material will also be amorphous to reduce leakage caused by grain boundaries. Also provided are sputtering, CVD, Atomic Layer CVD, and evaporation deposition methods for the above-mentioned, doped high dielectric films.

Yanjun Ma

Papers

Soft-x-ray magnetic circular dichroism at the l2,3 edges of nickel

Electronic states in La2-xSrxCuO4+ delta probed by soft-x-ray absorption.

Method of forming a multilayer dielectric stack

High-resolution K-shell photoabsorption measurements of simple molecules.

Doped zirconia, or zirconia-like, dielectric film transistor structure and deposition method for same