XUV Absorption Spectroscopy and Photoconversion of a Tin-Oxo Cage Photoresist.

Extreme ultraviolet lithography has recently been introduced in high-volume production of integrated circuits for manufacturing the smallest features in high-end computer chips. Hybrid organic/inorganic materials are considered as the next generation of photoresists for this technology, but detailed knowledge about the response of such materials to the ionizing radiation used (13.5 nm, 92 eV) is still scarce. In the present work, we use broadband high-harmonic radiation in the energy range 22-70 eV for absorption spectroscopy and photobleaching (that is, the decrease of absorbance) of thin films of an n-butyltin oxo-cage, a representative of the class of metal-based EUV photoresist. The shape of the absorption spectrum in the range 22-92 eV matches well with the spectrum predicted using tabulated atomic cross sections. The photobleaching results are consistent with loss of the butyl side groups due to the breaking of Sn-C bonds following photoionization. Bleaching is strongest in the low-energy range (<40 eV), where the absorption is largely due to the carbon atoms in the organic groups. At higher energies (42-70 eV), absorption is dominated by the tin atoms, and since these remain in the film after photoconversion, the absorption change in this region is smaller. It is estimated that after prolonged irradiation (up to ∼3 J cm-2 in the range 22-40 eV) about 70% of the hydrocarbon groups are removed from the film. The rate of bleaching is high at the beginning of exposure, but it rapidly decreases with increasing conversion. We rationalize this using density functional theory calculations: the first Sn-C bonds are efficiently cleaved (quantum yield Φ ≈ 0.9), because the highest occupied molecular orbitals (HOMOs) (from which an electron is removed after photoionization) are located on Sn-C sigma bonds. In the photoproducts, the HOMO is localized on tin atoms that have lost their hydrocarbon group (formally reduced to the Sn(II) oxidation state), and holes formed on those tin atoms lead to less efficient cleavage reactions. Our results reveal the primary reaction steps following excitation with ionizing radiation of tin-oxo cages. Our methodology represents a systematic approach of studying and quantitatively assessing the performance of new photoresists and as such enables the development of future EUV photoresists.

Incorporation of Photo- and Thermoresponsive N-Salicylidene Aniline Derivatives into Cobalt and Zinc Layered Hydroxides.

In search of new multifunctional hybrid materials and in order to investigate the influence of chemical modification on the possible synergy between properties, the carboxylate and sulfonate derivatives of photo- and thermochromic N-salicylidene aniline were successfully inserted into Co(II)- and Zn(II)-based layered simple hydroxides, resulting in four novel hybrids: Co-N-Sali-COO, Co-N-Sali-SO3, Zn-N-Sali-COO, and Zn-N-Sali-SO3. All synthesized hybrids adopt a double organic layered configuration, which prevents the cis-trans photoisomerization ability of N-Sali-R molecules in the hybrids. However, the Zn hybrids exhibit fluorescence upon exposure to UV light due to the excited-state intramolecular proton transfer (ESIPT) mechanism. The thermally stimulated keto-enol tautomerization of N-salicylidene aniline in the hybrids was related with the changes in interlamellar spacings observed by temperature-dependent PXRD. This tautomerization process was prominently evident in the Co-N-Sali-SO3 hybrid (about 11% increase in d-spacing upon decreasing the temperature to -180 °C). Finally, the Co-N-Sali-R hybrids exhibit the typical magnetic behavior associated with Co(II)-based LSHs (ferrimagnetic ordering at TN = 6.8 and 7.7 K for Co-N-Sali-COO and Co-N-Sali-SO3, respectively). This work offers insights into isomerization in LSHs and the ESIPT mechanism's potential in new luminescent materials and prospects for designing new multifunctional materials.

Daily Activity Patterns and Co-Occurrence of Duikers Revealed by an Intensive Camera Trap Survey across Central African Rainforests.

The duiker community in Central African rainforests includes a diversity of species that can coexist in the same area. The study of their activity patterns is needed to better understand habitat use or association between the species. Using camera traps, we studied the temporal activity patterns, and quantified for the first time the temporal overlap and spatial co-occurrence between species. Our results show that: (i) Two species are strongly diurnal: Cephalophus leucogaster, and Philantomba congica, (ii) two species are mostly diurnal: C.callipygus and C. nigrifrons, (iii) one species is strongly nocturnal: C.castaneus, (iv) and one species is mostly nocturnal: C.silvicultor. Analyses of temporal activities (for five species) identified four species pairs that highly overlapped (Δ^≥ 0.80), and six pairs that weakly overlapped (Δ^ between 0.06 and 0.35). Finally, co-occurrence tests reveal a truly random co-occurrence (plt > 0.05 and pgt > 0.05) for six species pairs, and a positive co-occurrence (pgt < 0.05) for four pairs. Positive co-occurrences are particularly noted for pairs formed by C.callipygus with the other species (except C. nigrifrons). These results are essential for a better understanding of the coexistence of duikers and the ecology of poorly known species (C. leucogaster and C. nigrifrons), and provide clarification on the activity patterns of C. silvicultor which was subject to controversy. Camera traps proved then to be a powerful tool for studying the activity patterns of free-ranging duiker populations.

Sonocrystallization as an Efficient Way to Control the Size, Morphology, and Purity of Coordination Compound Microcrystallites: Application to a Single-Chain Magnet.

The size, morphology, and purity control of coordination compound powders is a key stage for their conversion into materials and devices. In particular, surface science techniques require highly pure bulk materials with a narrow crystallite-size distribution together with straightforward, scalable, and reproducible crystallization procedures. In this work we demonstrate how sonocrystallization, i.e. the application of ultrasound during the crystallization process, can afford very quickly powders made of crystallites with controlled size, morphology, and purity. We show that this process drastically diminishes the crystallite-size distribution (low polydispersity indexes, PDI) and crystallite aspect ratio. By comparing sonicated samples with samples obtained by various silent crystallization conditions, we unambiguously show that the improvement in the crystallite morphology and size distribution is not due to any thermal effect but to the sonication of the crystallizing media. The application of sonocrystallization on crystallization batches of single-chain magnets (SCMs) maintains the chemical integrity of the SCMs together with their original magnetic behavior. Moreover, luminescent measurements show that sonocrystallization induces an efficient micromixing that drastically enhances the purity of the SCM powders. We thus propose that sonocrystallization, which is already used on organic or MOF compounds, can be applied to (magnetic) coordination compounds to readily afford bulk powders for characterization or shaping techniques that require pure, morphology- and crystallite-size-controlled powder samples.

Chiral Supramolecular Nanotubes of Single-Chain Magnets.

We report a single-chain magnet (SCM) made of a terbium(III) building block and a nitronyl-nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long-range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self-organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each TbIII ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite-size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (Hc =2400 Oe MR =2.09 µB at 0.5 K) for this class of compounds.

Self-assembly of a terbium(III) 1D coordination polymer on mica.

The terbium(III) ion is a particularly suitable candidate for the creation of surface-based magnetic and luminescent devices. In the present work, we report the epitaxial growth of needle-like objects composed of [Tb(hfac)3·2H2O] n (where hfac = hexafluoroacetylacetonate) polymeric units on muscovite mica, which is observed by atomic force microscopy. The needle-like shape mimics the structure observed in the crystalline bulk material. The growth of this molecular organization is assisted by water adsorption on the freshly air-cleaved muscovite mica. This deposition technique allows for the observation of a significant amount of nanochains grown along three preferential directions 60° apart from another. The magnetic properties and the luminescence of the nanochains can be detected without the need of surface-dedicated instrumentation. The intermediate value of the observed luminescence lifetime of the deposits (132 µs) compared to that of the bulk (375 µs) and the CHCl3 solution (13 µs) further reinforces the idea of water-induced growth.