S. P. Cooil

Spin-valley locking in the normal state of a transition-metal dichalcogenide superconductor

Metallic transition-metal dichalcogenides (TMDCs) are benchmark systems for studying and controlling intertwined electronic orders in solids, with superconductivity developing from a charge-density wave state. The interplay between such phases is thought to play a critical role in the unconventional superconductivity of cuprates, Fe-based and heavy-fermion systems, yet even for the more moderately-correlated TMDCs, their nature and origins have proved controversial. Here, we study a prototypical example, 2H-NbSe2, by spin- and angle-resolved photoemission and first-principles theory. We find that the normal state, from which its hallmark collective phases emerge, is characterized by quasiparticles whose spin is locked to their valley pseudospin. This results from a combination of strong spin–orbit interactions and local inversion symmetry breaking, while interlayer coupling further drives a rich three-dimensional momentum dependence of the underlying Fermi-surface spin texture. These findings necessitate a re-investigation of the nature of charge order and superconducting pairing in NbSe2 and related TMDCs.

One-dimensional spin texture of Bi(441): Quantum spin Hall properties without a topological insulator

The high index (441) surface of bismuth has been studied using scanning tunneling microscopy (STM), angle resolved photoemission spectroscopy (APRES), and spin-resolved ARPES. The surface is strongly corrugated, exposing a regular array of (110)-like terraces. Two surface localized states are observed, both of which are linearly dispersing in one in-plane direction (k(x)), and dispersionless in the orthogonal in-plane direction (k(y)), and both of which have a Dirac-like crossing at k(x) = 0. Spin ARPES reveals a strong in-plane polarization, consistent with Rashba-like spin-orbit coupling. One state has a strong out-of-plane spin component, which matches with the miscut angle, suggesting its possible origin as an edge state. The electronic structure of Bi(441) has significant similarities with topological insulator surface states and is expected to support one-dimensional quantum spin Hall-like coupled spin-charge transport properties with inhibited backscattering, without requiring a topological insulator bulk.

Graphene coatings for chemotherapy: avoiding silver-mediated degradation

Chemotherapy treatment usually involves the delivery of fluorouracil (5-Fu) together with other drugs through central venous catheters. Catheters and their connectors are increasingly treated with silver or argentic alloys/compounds. Complications arising from broken catheters are common, leading to additional suffering for patients and increased medical costs. Here, we uncover a likely cause of such failure through a study of the surface chemistry relevant to chemotherapy drug delivery, i.e. between 5-Fu and silver. We show that silver catalytically decomposes 5-Fu, compromising the efficacy of the chemotherapy treatment. Furthermore, HF is released as a product, which will be damaging to both patient and catheter. We demonstrate that graphene surfaces inhibit this undesirable reaction and would offer superior performance as nanoscale coatings in cancer treatment applications.

High temperature photoelectron emission and surface photovoltage in semiconducting diamond

A non-equilibrium photovoltage is generated in semiconducting diamond at above-ambient temperatures during x-ray and UV illumination that is sensitive to surface conductivity. The H-termination of a moderately doped p-type diamond (111) surface sustains a surface photovoltage up to 700 K, while the clean (2 × 1) reconstructed surface is not as severely affected. The flat-band C 1s binding energy is determined from 300 K measurement to be 283.87 eV. The true value for the H-terminated surface, determined from high temperature measurement, is (285.2 ± 0.1) eV, corresponding to a valence band maximum lying 1.6 eV below the Fermi level. This is similar to that of the reconstructed (2 × 1) surface, although this surface shows a wider spread of binding energy between 285.2 and 285.4 eV. Photovoltage quantification and correction are enabled by real-time photoelectron spectroscopy applied during annealing cycles between 300 K and 1200 K. A model is presented that accounts for the measured surface photovoltage in terms of a temperature-dependent resistance. A large, high-temperature photovoltage that is sensitive to surface conductivity and photon flux suggests a new way to use moderately B-doped diamond in voltage-based sensing devices.

Thermal migration of alloying agents in aluminium

The in situ thermal migration of alloying agents in an Al–Mg–Si–Li alloy is studied using surface sensitive photo-electron and electron diffraction/imaging techniques. Starting with the preparation of an almost oxide free surface (oxide thickness = 0.1 nm), the relative abundance of alloying agents (Mg, Li and Si) at the surface are recorded at various stages of thermal annealing, from room temperature to melting (which is observed at 550 ◦C). Prior to annealing, the surface abundances are below the detection limit 1%, in agreement with their bulk concentrations of 0.423% Si, 0.322% Mg and 0.101% Li (atomic %). At elevated temperatures, all three alloying agents appear at drastically increased concentrations (13.3% Si, 19.7% Mg and 45.3% Li), but decrease again with further elevation of the annealing temperature or after melting. The temperature at which the migration occurs is species dependent, with Li migration occurring at significantly higher temperatures than Si and Mg. The mechanism of migration also appears to be species dependent with Li migration occurring all over the surface but Mg migration being restricted to grain boundaries.

Transport and optical gaps and energy band alignment at organic-inorganic interfaces

The transport and optical band gaps for the organic semiconductor tin (II) phthalocyanine (SnPc) and the complete energy band profiles have been determined for organic-inorganic interfaces between SnPc and III-V semiconductors. High throughput measurement of interface energetics over timescales comparable to the growth rates was enabled using in situ and real-time photoelectron spectroscopy combined with Organic Molecular Beam Deposition. Energy band alignment at SnPc interfaces with GaAs, GaP, and InP yields interface dipoles varying from −0.08 (GaP) to −0.83 eV (GaAs). Optical and transport gaps for SnPc and CuPc were determined from photoelectron spectroscopy and from optical absorption using spectroscopic ellipsometry to complete the energy band profiles. For SnPc, the difference in energy between the optical and transport gaps indicates an exciton binding energy of (0.6 ± 0.3) eV.

Tautomerization of Thymine Using Ultraviolet Light

Ultraviolet-light-induced changes to the nucleobase thymine deposited onto a MoS2 surface were studied using photoelectron spectroscopy and first-principles calculations. These measurements suggest changes in the molecular structure indicated by changes in core electron binding energies. The experimental work has been interpreted by means of ab initio calculations using coupled cluster singles and doubles (CCSD) linear response theory. Contrary to the expected behavior, i.e., the dimerization of two thymine molecules into a pyrimidine dimer, a shift between two tautomeric forms was observed upon UV-exposure. Exposure to ionizing radiation is known to induce damage in many biological molecules, and the present work gives additional insight into its effects on thymine, the interactions of the molecules, and finally how certain UV photoproducts may be avoided.

Resonant photoemission spectroscopy for intermediate band materials

Resonant photoemission spectroscopy is used to study the intermediate-band material Cr doped ZnS. Using resonant photoemission, we show that the intermediate-band can be characterized, revealing the filling and specific orbital character of the states contributing to the resonant photoemission signal. We demonstrate that resonant photoemission spectroscopy is a powerful approach for understanding the origin of intermediate bands in doped ZnS. The methodology can be widely extended to a large variety of materials, providing useful information towards engineering of high efficiency intermediate band solar cells and of other optoelectronic devices.

Probing dimensionality using a simplified 4-probe method

4-probe electrical measurements have been in existence for many decades. One of the most useful aspects of the 4-probe method is that it is not only possible to find the resistivity of a sample (independently of the contact resistances), but that it is also possible to probe the dimensionality of the sample. In theory, this is straightforward to achieve by measuring the 4-probe resistance as a function of probe separation. In practice, it is challenging to move all four probes with sufficient precision over the necessary range. Here, we present an alternative approach. We demonstrate that the dimensionality of the conductive path within a sample can be directly probed using a modified 4-probe method in which an unconventional geometry is exploited; three of the probes are rigidly fixed, and the position of only one probe is changed. This allows 2D and 3D (and other) contributions the to resistivity to be readily disentangled. The required experimental instrumentation can be vastly simplified relative to traditional variable spacing 4-probe instruments.

In Situ Patterning of Ultrasharp Dopant Profiles in Silicon

We develop a method for patterning a buried two-dimensional electron gas (2DEG) in silicon using low kinetic energy electron stimulated desorption (LEESD) of a monohydride resist mask. A buried 2DEG forms as a result of placing a dense and narrow profile of phosphorus dopants beneath the silicon surface; a so-called δ-layer. Such 2D dopant profiles have previously been studied theoretically, and by angle-resolved photoemission spectroscopy, and have been shown to host a 2DEG with properties desirable for atomic-scale devices and quantum computation applications. Here we outline a patterning method based on low kinetic energy electron beam lithography, combined with in situ characterization, and demonstrate the formation of patterned features with dopant concentrations sufficient to create localized 2DEG states.