This PDF file contains the front matter associated with SPIE Proceedings Volume 10174, including the Title Page, Copyright information, Table of Contents, Introduction (if any), and Conference Committee listing.

Photoelectron spectroscopy in combination with computational chemistry has been used over the past decade to systematically elucidate the structures and chemical bonding of sizeselected boron clusters. Small boron clusters have been found to be planar or quasi-planar with both delocalized σ and π bonding. A particularly interesting cluster is B₃₆, which has been found to possess a planar structure with a central hexagonal vacancy. The hexagonal B₃₆ can be viewed as a repeating unit to assemble atom-thin boron monolayers (dubbed borophenes). This finding provides the first indirect experimental evidence that borophenes with hexagonal vacancies are potentially viable. Another exciting discovery has been the observation and characterization of the first all-boron fullerenes. Photoelectron spectroscopy revealed that the B₄₀ ⁻ cluster consisted of two isomers with very different electron binding energies. Global minimum searches led to two nearly degenerate isomers competing for the global minimum: a quasi-planar isomer and an unprecedented cage isomer. In the neutral, the B₄₀ cage is overwhelmingly the global minimum, which is the first all-boron fullerene to be observed and is named “borospherene”. There is evidence that there exists a family of borospherenes with B₂₈ being the smallest borospherene. It is expected that the pace of discovery will continue to accelerate in boron clusters, and more interesting structures and chemical bonds will be uncovered with heightened research interests and more sophisticated experimental and computational methods.

Inorganic nanoparticles, including metals, semiconductors and metal oxides, comprise a common set of structures exhibiting an inorganic core ‘passivated’ by an organic shell. Ligated inorganic nanoparticles currently provoke widespread fundamental interest in their structural, optical and magnetic properties, which differ fundamentally from bulk counterparts. These nanomaterials are already finding applications in biology, medicine, solar energy, and display panels. ^1-6 Conjugating inorganic nanoparticles with organic (biological) material for applications in nanobiology and nanomedicine creates significant challenges for controlling the effects on the environment, particularly regarding toxicity. Chemical reactions of almost identical substances can lead to drastically different outcomes in a biological environment. As a simplistic example one can consider the case of ethanol vs. methanol. Ethanol (CH₃CH₂OH) can be consumed by humans while even a small dose of methanol (CH₃OH) can be fatal, yet the difference between the molecular formulas of these substances is just the smallest meaningful hydrocarbon unit CH₂. This illuminates the fact that minute differences in the size and structure of molecular compounds can have drastically different end effects in a biological environment due to the way the compounds start to react with the environment. In recent years, gold nanoparticles covered by ligands that make them water-soluble have become a popular target for research in nanobiology and nanomedicine. ^1,2 In most cases up to now, colloidal nanoparticles (5 nm and larger) have been used for sensing and photothermal applications. However, this class of gold-based nanomaterials still has large uncertainties regarding the atomic composition of the nanoparticle surface and particularly the metal-ligand interface. A simple example illuminates the facts. The density of atoms in the fcc lattice of macrosocopic gold metal is about 59 atoms/nm³. This means that a spherical colloidal gold nanoparticle with radius of 5 nm has about 3850 atoms. Even in a sample of extremely narrow range of diameters ranging from 5.25 nm to 4.75 nm (+/- 5% of the mean) the particles will have anywhere between 3300 and 4750 atoms, and their surface area can differ up to 20%. It is clear that such particles are not suitable for applications that would need molecularly precise size, structure and shape of the metal nanoparticle and precise knowledge of the composition of its organic surface. In 1994, Brust, Schiffrin and coworkers published a landmark synthesis recipe on how to prepare thiol(ate)-stabilized small gold nanoparticles of about 2 nm in size. ⁷ This paper started a completely new field which has now matured to studies of several “atom-precise” or “molecularly precise” gold-thiolate compounds for which molecular formulas Aux(SR)y can be written and the substances in most cases have a good ambient stability allowing for storage and later use.⁸ Atomic structures of the gold core and the thiolate layer have been resolved for many of these compounds, opening doors for detailed density functional theory (DFT) simulations of their properties. This Perspective discusses developments in understanding the structure and properties of one of such compounds, which can be used for site-specific (or “molecularly precise”) targeting of capsid proteins on a viral surface.

We present density functional theory based results on the interaction of size-selected gold nanoclusters, Au₁₀ and Au₂₀, with dopamine molecule. The gold clusters interact strongly with the nitrogen site of dopamine, thereby forming stable gold-dopamine complexes. Our calculations further show that there is no site specificity on the planar Au₁₀ cluster with all the edge gold atoms equally preferred. On the other hand, in the pyramidal Au₂₀ cluster, the vertex metal atom is the most active site. As the size increased from Au₁₀ to Au₂₀, the interaction strength has shown a declining trend. The effect of aqueous environment on the interaction strengths were also studied by solvation model. It is found that the presence of solvent water stabilizes the interaction between the metal cluster and dopamine molecule, even though for Au₁₀ cluster the energy ordering of the isomers changed from that of the gas-phase.

Due to the special electronic configuration, small atomic size, light mass, and flexible bonding features, carbon exhibits many different structural configurations with very different physical and chemical properties. Here we focus our discussion on three recent forms of carbon, namely, metallic carbon, magnetic carbon, and all-pentagon-based carbon. The metallic carbon can be used for metallic interconnects in future electronic circuits, nano devices and microprocessors while the magnetic carbon can have applications in spintronics. All-pentagon-based carbon nano-structure, penta-graphene, not only expands the family of carbon materials with a number of new features, but also provides the materials basis for the 2D packing of pentagons pursued by mathematicians for almost a century.

We characterize the geometry and electronic structure of isomers of the five atom Manganese cluster for its highest spin state, multiplicity 26. DFT calculations with various functionals and basis sets. The lowest energy form is either a D_3h symmetric trigonal bipyramid or disphenoid C_2v structure which can be considered a distorted trigonal bipyramid. The regular pentagon (D_5h) is higher in energy but occupies a shallow relative minimum on the potential surface. The lowest energy square pyramid (C_4v) is a saddle point; it spontaneously rearranges to the bisphenoid structure or the trigonal bipyramid very similar in energy. Analysis of the wave functions shows that the clusters can be considered distinct and weakly bound atoms with stabilization derived from interatomic charge-transfer interactions. Dispersion attraction seem to play a lesser role. The clusters have moderate static polarizabilities α but large first hyperpolarizabilities β, comparable with the reference system para-nitro aniline. Dynamic polarizabilities for an exciting frequency of 0.1 atomic units (wavelength 450 nm) are higher still.

We describe the production of size selected manganese nanoclusters using a dc magnetron sputtering/aggregation source. Since nanoparticle production is sensitive to a range of overlapping operating parameters (in particular, the sputtering discharge power, the inert gas flow rates, and the aggregation length) we focus on a detailed map of the influence of each parameter on the average nanocluster size. In this way it is possible to identify the main contribution of each parameter to the physical processes taking place within the source. The discharge power and argon flow supply the atomic vapor, and argon also plays the crucial role in the formation of condensation nuclei via three-body collisions. However, neither the argon flow nor the discharge power have a strong effect on the average nanocluster size in the exiting beam. Here the defining role is played by the source residence time, which is governed by the helium supply and the aggregation path length. The size of mass selected nanoclusters was verified by atomic force microscopy of deposited particles.

We have been studying magnetic properties of magnetic ion clusters in ternary, quaternary, and quinary IV-VI and II-IV-V₂ diluted magnetic semiconductors with varying concentrations of different magnetic and non-magnetic cations. We observed clusters of different types, from non-random distribution of magnetic ions in the host lattice to precipitates with the crystalline structure different from that of the host. The size of such precipitates varied from 200 nm to 20 μm. Depending on the type and size of clusters we observed different magnetic properties of the compounds, such as paramagnetic, spin-glass, spin-glass-like, or ferromagnetic states. For example, Zn_1-xMn_xGeAs₂ compounds with x ≤ 0.053 were paramagnetic with evidence of small short-range magnetic interactions, while in the same material with x ≥ 0.078 we observed room-temperature ferromagnetism. In IV-VI DMS clusters usually created a spin-glass or spinglass- like state. However, in some Ge_1-x-yPb_xMn_yTe crystals we observed a co-existence of two very different spin-glasslike states with transition temperatures T₁ ≈ 5 K and T₂ ≈ 90 K.

In the present work, the effective field theory with correlations based on the probability distribution technique has been used to investigate the effect of the surface shell longitudinal cristal field on the magnetic properties of a diluted antiferromagnetic spin-1 Ising nanocube particle. This effect has also been studied on the hysteresis loops of the system. It is found that this parameter has a strong effect on the magnetization profiles, compensation temperature, coercive field and remanent magnetization.

Mg(BH₄)₂ contains 14.9 mass% of hydrogen and is considered as a promising hydrogen storage material. Reversible hydrogen sorption under moderate conditions represents a main challenge for Mg(BH₄)₂ being utilized for solid-state hydrogen storage. Here, we achieve the reversible storage of 4.0 mass% of hydrogen at 265°C in Mg(BH₄)₂. That is, desorption of 7.5 mass% H at 265°C under vacuum and absorption of 4.0 mass% at 265°C and 160 bar H₂. ¹¹B MAS NMR measurements indicate that the reversible hydrogen sorption involves the formation of a decisive intermediate which shows a major resonance with a chemical shift at -50.0 ppm. The phase evolution in the hydrogen cycles as well as the capacity loss in the hydrogen sorption cycles is discussed.

Thermoelectric materials are of great current interest for a number of energy-related applications such as waste heat recovery, terrestrial cooling, and thermoelectric power generation. There have been several significant recent advances in improving the thermoelectric figure of merit ZT; in some instances, ZT > 2 at high temperatures. Concepts like electron-crystal phonon-glass, dimensional confinement, nanostructuring, energy filtering, and intrinsic lattice anharmonicity have not only acted as guiding principles in synthesizing new materials but also for electronic structure engineering using theoretical calculations. In this review paper, we discuss these concepts and present a few examples of theoretical studies of electronic structure and transport properties illustrating how some of these ideas work. The four types of systems we discuss are quaternary chalcogenides LAST-m, nanoscale mixtures of half-Heusler and Heusler compounds, ternary chalcogenide compounds of type ABX₂ where the electronic structure near the band gap depends sensitively on the ordering of A and B atoms, and naturally occurring bulk superlattices formed out of alternating ionic and semiconducting bilayers as in SrFAgTe.

The waste heat generated by car engines, power plants, home furnaces and other fossil fuel-burning machinery play an adverse role in the climate. Development of efficient, light-weight, cost-effective, and environmentally-benign thermoelectric materials can help in converting wasted heat into useable energy, thus helping the environment. In this brief review we discuss theoretical methods that can complement experimental search for efficient thermoelectric materials. Using Boltzmann transport theory with a constant relaxation time approximation and non-equilibrium Green’s function approach we study thermoelectric parameters by focusing on two dimensional materials ranging from graphene and graphdiyne to phosphorene, transition metal dichalogenides and metal carbides. In some circumstances, the reduced dimension is found to increase the Seebeck coefficient and decrease the thermal conductivity, necessary for improving thermoelectric conversion performance. We also suggest some future studies in this topic.

Storage of renewable energy remains a significant challenge for the implementation of a future carbon neutral and sustainable society based on renewable energy. New technologies providing a paradigm shift for energy storage may likely be based on novel materials with new functionalities. This review provides new perspectives for rational design of functional materials for energy storage using dynamic, disorder or entropy effects as a design concept. These effects may be introduced into the solid state using complex anions such as BH₄^- or B₁₂H₁₂^2-. These dynamic effects may facilitate anion substitution and preparation of materials that may stabilize high temperature polymorphs at lower temperatures. This has provided new ion conductors for lithium batteries and perovskite type metal borohydrides, which can be modified to resemble the well-known useful metal halide photovoltaics. Completely new metal hydrides, which stores hydrogen and may also be ion conductors or have magnetic, optical or electronic properties may be designed and prepared. This review reveals extreme structural and compositional flexibility of metal hydrides and provides new inspiration for rational materials design towards multi-functionality.

Light propagation in two and three dimensional lattices for which the index of refraction exhibits spatial antisymmetry is investigated in the ray and photonic crystal regimes. In these regimes, all the two dimensional antisymmetry groups for which light fails to propagate are identified. In the ray-regime, it is observed that in tilings described by 7 of the 46 two dimensional antisymmetric groups, light is localized within a fundamental domain and does not propagate through the tiling, in contrast to the behavior in the other 39 groups. To understand the above phenomenon, a rule based on the number of anti-mirror planes passing through a single Bravais lattice point is derived. In the wave regime for photonic crystals, it is observed that there are no propagating eigensolutions for the same 7 tilings as above, whereas propagating solutions and energy pass band dispersion curves can be obtained for the other 39 groups. The reasons underlying this peculiar behavior are analyzed using the topological approach for modeling flow in dynamical billiards to shed light on the applicability of Bloch’s theorem for these periodic antisymmetric lattices.

Gallium phosphide bismide (GaP_1-xBi_x) epilayers with bismuth fractions from 0.9% to 3.2%, as calculated from lattice parameter measurements, were studied with Rutherford backscattering spectrometry (RBS) to directly measure bismuth incorporation. The total bismuth fractions found by RBS were higher than expected from the lattice parameter calculations. Furthermore, in one analyzed sample grown by molecular beam epitaxy at 300 °C, 55% of incorporated bismuth was found to occupy interstitial sites. We discuss implications of this high interstitial incorporation fraction and its possible relationship to x-ray diffraction and photoluminescence measurements of GaP_0.99Bi_0.01.

Stretchable and conformable optical devices open very exciting perspectives for the fabrication of systems incorporating diffracting and optical power in a single element and of tunable plasmonic filters and absorbers. The use of nanocomposites obtained by inserting metallic nanoparticles produced in the gas phase into polymeric matrices allows to effectively fabricate cheap and simple stretchable optical elements able to withstand thousands of deformations and stretching cycles without any degradation of their optical properties. The nanocomposite-based reflective optical devices show excellent performances and stability compared to similar devices fabricated with standard techniques. The nanocomposite-based devices can be therefore applied to arbitrary curved non-optical grade surfaces in order to achieve optical power and to minimize aberrations like astigmatism. Examples discussed here include stretchable reflecting gratings, plasmonic filters tunable by mechanical stretching and light absorbers.

As a geometric concept, “topology” is now used to describe the electronic properties of an insulator. Various topological materials have been predicted and observed, including topological insulators, Chern insulators, topological crystalline insulators, and Weyl semimetals. The first three of these materials can all be realized as two-dimensional nanomaterials. Due to their unique properties compared with normal insulators, these materials can exhibit quantum spin Hall effect and/or quantum anomalous Hall effect, protected by different symmetries. In this perspective, we review the current progress made in these topological nanomaterials, including their fundamental physical mechanisms and material realizations. We also discuss the possible material challenges and the issues that still need to be resolved in the future.

Platinum silicide thin films were prepared using DC magnetron sputtering at room temperature, 275°C and 350°C in order to study the phase transformation from amorphous to crystalline PtSi as well as the changes in film resistance in correlation to Pt composition and film structure. Platinum composition was controlled by placing Pt pellets on the Si sputtering target, film composition was determined via energy dispersive X-ray spectroscopy (EDAX), and structure was determined using powder X-ray diffraction (XRD). Crystalline platinum silicide (PtSi) films form when platinum accounts for more than 40% of the atomic composition in the films. There is a shift in the preferred orientation of the PtSi crystal structure in the plane of the film surface with increased Pt concentration and deposition temperature which corresponds to a sharp decrease in the resistance of the films.

One potential solution to the world’s expanding energy needs is the harnessing of solar energy—an inexhaustible energy source. In part because of the relatively low efficiency, high cost, and short durability of solar cells, only 2% of energy in the US presently comes from solar.[1] Thin film polymer solar cells offer the potential of making solar energy more affordable.[2- 5] However, one of the challenges of polymer solar cells is the limited absorption range. Certain conditions lead to a red shift in absorption offering the possibility of increased light absorption, but the effect is not fully understood. In order to understand what causes a red shift we must study morphology. The morphology of polymer chains refers to their form and structure. Two aspects of morphology are chain conformation and aggregation. Chain conformation refers to the structural arrangement of the chains and aggregation refers to direct mutual attraction of the molecules. The morphology of polymer chains in solution depends on the solvent used and the polymer concentration [6,7] and has a great influence on the conjugation lengths of the chains which in turn has a great influence on absorption. [6,8] Longer conjugation lengths cause the absorption spectrum to red shift. [6,7,9,10] Because of these effects, understanding solvent effects on absorption could make polymer solar cells more efficient. A popular polymer used in solar cells is MEH-PPV [Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4- phenylenevinylene and in particular, the morphology of MEH-PPV chains in solution has a great influence on absorption [6,7,11]. This study will investigate the absorption spectrum of MEH-PPV in solution both experimentally and theoretically.