Controllable quantum systems are under active investigation for quantum computing, secure information processing, and nonvolatile memory. The optical manipulation of spin quantum states provides an important strategy for quantum control with both temporal and spatial resolution. Challenges in increasing the lifetime of photoinduced magnetic states at T > 200 K have hindered progress toward utilizing photomagnetic materials in quantum device architectures. Here we demonstrate reversible light-induced magnetization switching in an organic thin film at device operating temperatures of 300−330 K. By utilizing photochromic ligands that undergo structural changes in the solid state, the changes in ligand field associated with photoisomerization modulate the ligand field and in turn the oxidation and spin state of a bound metal center. Green light irradiation (λ exc = 550 nm) of a spirooxazine cobalt−dioxolene complex induces photoisomerization of the ligand that in turn triggers a reversible intramolecular charge-transfer coupled spin-transition process at the cobalt center. The generation of photomagnetic states through conversion between a low-spin Co(III)−semiquinone doublet and a high-spin Co(II)−bis-semiquinone sextet state has been demonstrated in both solution and the solid state and is described as a photoisomerization-induced spin−charge excited state (PISCES) process. The high transition temperature (325 K) and long-lived photoinduced state (τ = 10 s at 300 K) are dictated by the photochromic ligand. Theory provides effective modeling of the phenomenon and long-term strategies to further modulate the lifetimes of photomagnetic states for quantum information technologies at the single molecule level.

The effects of solution-state dielectric and intermolecular interactions on the degree of charge separation in metastable spirooxazine photomerocyanines (PMCs) is investigated. We report the first X-ray diffraction (XRD) analyses of an open form, a metastable photomerocyanine, of the spirooxazine class of photochromic molecules in two derivatives: spiro[azahomoadamantane-isoquinolinoxazine] (1) and spiro[azahomoadamantane-phenanthrolinoxazine] (2). Using the results of XRD analysis of the open photomerocyanine forms, in conjunction with computation, solvatochromism, and solution NMR studies, we have investigated the effect of the medium on the ground-state structure of these photomerocyanines. Solvatochromism and NMR chemical shift studies of 1 and 2 support the assignment of a quinoidal structure in nonpolar solvents and a zwitterionic structure in high-polarity solvents. The effect of azahomoadamantyl substitution is explored by comparing 1 and 2 with the analogous indolyl derivatives, spiro[indoline-isoquinolinoxazine] (3) and spiro[indoline-phenanthrolinoxazine] (4) through XRD analysis of the closed spirooxazine (SO) forms, solution-state kinetic experiments, solvatochromism, and NMR studies. Longer C(spiro)-O bond lengths in the SO form and slower rates of thermal PMC --> SO isomerization for the azahomoadamantyl derivatives are associated with greater zwitterionic character in the PMC form, as found in the solvatochromism studies. XRD analysis of photomerocyanines 1 and 2 indicate a greater contribution from the canonical zwitterionic resonance form relative to the quinoidal form in the solid state. Structural differences observed in two pseudopolymorphs of 2-PMC suggest that the degree of charge-separated character is influenced by the crystal packing environment. These results provide direct structural evidence for the effects of the medium polarity on charge-separated states of photomerocyanines.

Atomic layer deposited (ALD) high-dielectric-constant (high-k) materials have found extensive applications in a variety of electronic, optical, optoelectronic, and photovoltaic devices. While electrical, optical, and interfacial properties have been the primary consideration for such devices, thermal and mechanical properties are becoming an additional key consideration for many new and emerging applications of ALD high-k materials in electromechanical, energy storage, and organic light emitting diode devices. Unfortunately, a clear correspondence between thermal/mechanical and electrical/optical properties in ALD high-k materials has yet to be established, and a detailed comparison to conventional silicon-based dielectrics to facilitate optimal material selection is also lacking. In this regard, we have conducted a comprehensive investigation and review of the thermal, mechanical, electrical, optical, and structural properties for a series of prevalent and emerging ALD high-k materials including aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), hafnium oxide (HfO 2 ), and beryllium oxide (BeO). For comparison, more established silicon-based dielectrics were also examined, including thermally grown silicon dioxide (SiO 2 ) and plasma-enhanced chemically vapor deposited hydrogenated silicon nitride (SiN:H). We find that in addition to exhibiting high values of dielectric permittivity and electrical resistance that exceed those of SiO 2 and SiN:H, the ALD high-k materials exhibit equally exceptional thermal and mechanical properties with coefficients of thermal expansion ≤ 6 × 10 -6 / • C, thermal conductivites (κ) of 3-15 W/m K, and Young's modulus and hardness values exceeding 200 and 25 GPa, respectively. In many cases, the observed extreme thermal/mechanical properties correlate with the presence of crystallinity in the ALD high-k films. In contrast, some of the electrical and optical properties correlate more strongly with the percentage of ionic vs. covalent bonds present in the high-k film. Overall, the ALD high-k dielectrics investigated concurrently exhibit compelling thermal/mechanical and electrical/optical properties. The drive to reduce gate leakage currents in highly scaled complementary metal-oxide-semiconductor (CMOS) transistors has led to the exploration and development of a wide variety of high-dielectricconstant (high-k) materials to replace silicon dioxide (SiO 2 ) as the insulating gate dielectric material.1-8 Many of these same high-k materials have found additional applications in future non-CMOS logic and memory storage products such as solid-state electrolytes in resistive switching devices, 9,10 tunnel barriers in spin-transport devices, 11 and as a ferroelectric in magnetoelectric devices. While electrical, physical, and thermodynamic properties have clearly been a key consideration in all of the above applications, thermal properties have become an additional important consideration for higk-k dielectrics as aggressive dimensional scaling of devices has created the need to dissipate ...

Because of its high electrical resistivity, low dielectric constant (j), high thermal neutron capture cross section, and robust chemical, thermal, and mechanical properties, amorphous hydrogenated boron carbide (a-B x C:H y) has garnered interest as a material for low-j dielectric and solid-state neutron detection applications. Herein, we investigate the relationships between chemical structure (atomic concentration B, C, H, and O), physical/mechanical properties (density, porosity, hardness, and Young's modulus), electronic structure [band gap, Urbach energy (E U), and Tauc parameter (B 1/2)], optical/dielectric properties (frequency-dependent dielectric constant), and electrical transport properties (resistivity and leakage current) through the analysis of a large series of a-B x C:H y thin films grown by plasma-enhanced chemical vapor deposition from ortho-carborane. The resulting films exhibit a wide range of properties including H concentration from 10% to 45%, density from 0.9 to 2.3 g/cm 3 , Young's modulus from 10 to 340 GPa, band gap from 1.7 to 3.8 eV, Urbach energy from 0.1 to 0.7 eV, dielectric constant from 3.1 to 7.6, and electrical resistivity from 10 10 to 10 15 X cm. Hydrogen concentration is found to correlate directly with thin-film density, and both are used to map and explain the other material properties. Hardness and Young's modulus exhibit a direct power law relationship with density above $1.3 g/cm 3 (or below $35% H), below which they plateau, providing evidence for a rigidity percolation threshold. An increase in band gap and decrease in dielectric constant with increasing H concentration are explained by a decrease in network connectivity as well as mass/electron density. An increase in disorder, as measured by the parameters E U and B 1/2 , with increasing H concentration is explained by the release of strain in the network and associated decrease in structural disorder. All of these correlations in a-B x C:H y are found to be very similar to those observed in amorphous hydrogenated silicon (a-Si:H), which suggests parallels between the influence of hydrogenation on their material properties and possible avenues for optimization. Finally, an increase in electrical resistivity with increasing H at <35 at. % H concentration is explained, not by disorder as in a-Si:H, but rather by a lower rate of hopping associated with a lower density of sites, assuming a variable range hopping mechanism interpreted in the framework of percolation theory. V

The ability to optically switch or tune the intrinsic properties of transition metals (e.g., redox potentials, emission/absorption energies, and spin states) with photochromic metal-ligand complexes is an important strategy for developing "smart" materials. We have described a methodology for using metal-carbonyl complexes as spectroscopic probes of ligand field changes associated with light-induced isomerization of photochromic ligands. Changes in ligand field between the ring-closed spirooxazine (SO) and ring-opened photomerocyanine (PMC) forms of photochromic azahomoadamantyl and indolyl phenanthroline-spirooxazine ligands are demonstrated through FT-IR, (13)C NMR, and computational studies of their molybdenum-tetracarbonyl complexes. The frontier molecular orbitals (MOs) of the SO and PMC forms differ considerably in both electron density distributions and energies. Of the multiple π* MOs in the SO and PMC forms of the ligands, the LUMO+1, a pseudo-b(1)-symmetry phenanthroline-based MO, mixes primarily with the Mo(CO)(4) fragment and provides the major pathway for Mo(d)→phen(π*) backbonding. The LUMO+1 is found to be 0.2-0.3 eV lower in energy in the SO form relative to the PMC form, suggesting that the SO form is a better π-acceptor. Light-induced isomerization of the photochromic ligands was therefore found to lead to changes in the energies of their frontier MOs, which in turn leads to changes in π-acceptor ability and ligand field strength. Ligand field changes associated with photoisomerizable ligands allow tuning of excited-state and ground-state energies that dictate energy/electron transfer, optical/electrical properties, and spin states of a metal center upon photoisomerization, positioning photochromic ligand-metal complexes as promising targets for smart materials.