Presence of Short Intermolecular Contacts Screens for Kinetic Stability in Packing Polymorphs.

Polymorphism is pervasive in molecular solids. While computational predictions of the molecular polymorphic landscape have improved significantly, identifying which polymorphs are preferentially accessed and experimentally stable remains a challenge. We report a framework that correlates short intermolecular contacts with polymorphic stability. The presence of short contacts between neighboring molecules prevents structural rearrangement and stabilizes the packing arrangement, even when the stabilized polymorph is not enthalpically favored. In the absence of such intermolecular short contacts, the molecules have added degrees of freedom for structural rearrangement, and solid-solid polymorphic transformations occur readily. Starting with a series of core-halogenated naphthalene tetracarboxylic diimides, we establish this framework with the packing polymorphs of more than 20 compounds, ranging from molecular semiconductors to pharmaceutics and biological building blocks. This framework, widely applicable across molecular solids, can help refine computational predictions by identifying the polymorphs that are kinetically stable.

Length separation of single-walled carbon nanotubes and its impact on structural and electrical properties of wafer-level fabricated carbon nanotube-field-effect transistors.

For an industrial realization of devices based on single-walled carbon nanotube (SWCNTs) such as field-effect transistors (FETs) it becomes increasingly important to consider technological aspects such as intrinsic device structure, integration process controllability as well as yield. From the perspective of a wafer-level integration technology, the influence of SWCNT length on the performance of short-channel CNT-FETs is demonstrated by means of a statistical and comparative study. Therefore, a methodological development of a length separation process based on size-exclusion chromatography was conducted in order to extract well-separated SWCNT dispersions with narrowed length distribution. It could be shown that short SWCNTs adversely affect integrability and reproducibility, underlined by a 25% decline of the integration yield with respect to long SWCNTs. Furthermore, it turns out that the significant changes in electrical performance are directly linked to a SWCNT chain formation in the transistor channel. In particular, CNT-FETs with long SWCNTs outperform reference and short SWCNTs with respect to hole mobility and subthreshold controllability by up to 300% and up to 140%, respectively. As a whole, this study provides a statistical and comparative analysis towards chain-less CNT-FETs fabricated with a wafer-level technology.

Core-Fluorinated Naphthalene Diimides: Synthesis, Characterization, and Application in n-Type Organic Field-Effect Transistors.

A series of difluoro- and tetrafluoro-substituted naphthalene diimides (NDIs) were synthesized by halogen exchange reactions of corresponding bromo-NDIs with CsF in dioxane. Two strong electron acceptor molecules 6 and 8 with low-lying LUMO energy levels of -4.27 and -4.54 eV were obtained, starting from tetrafluoro-NDI. Organic field-effect transistors (OFETs) based on these fluorinated NDIs were fabricated by vapor deposition, exhibiting n-channel field-effect character under ambient conditions with the highest mobility of 0.1 cm(2) V(-1) s(-1).

Integration of an Optical Ring Resonator Biosensor into a Self-Contained Microfluidic Cartridge with Active, Single-Shot Micropumps.

While there have been huge advances in the field of biosensors during the last decade, their integration into a microfluidic environment avoiding external tubing and pumping is still neglected. Herein, we show a new microfluidic design that integrates multiple reservoirs for reagent storage and single-use electrochemical pumps for time-controlled delivery of the liquids. The cartridge has been tested and validated with a silicon nitride-based photonic biosensor incorporating multiple optical ring resonators as sensing elements and an immunoassay as a potential target application. Based on experimental results obtained with a demonstration model, subcomponents were designed and existing protocols were adapted. The newly-designed microfluidic cartridges and photonic sensors were separately characterized on a technical basis and performed well. Afterwards, the sensor was functionalized for a protein detection. The microfluidic cartridge was loaded with the necessary assay reagents. The integrated pumps were programmed to drive the single process steps of an immunoassay. The prototype worked selectively, but only with a low sensitivity. Further work must be carried out to optimize biofunctionalization of the optical ring resonators and to have a more suitable flow velocity progression to enhance the system's reproducibility.

Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(ii) acetylacetonate: a combined first-principles and reactive molecular dynamics study.

Atomistic mechanisms for the atomic layer deposition using the Cu(acac)2 (acac = acetylacetonate) precursor are studied using first-principles calculations and reactive molecular dynamics simulations. The results show that Cu(acac)2 chemisorbs on the hollow site of the Cu(110) surface and decomposes easily into a Cu atom and the acac-ligands. A sequential dissociation and reduction of the Cu precursor [Cu(acac)2 → Cu(acac) → Cu] are observed. Further decomposition of the acac-ligand is unfavorable on the Cu surface. Thus additional adsorption of the precursors may be blocked by adsorbed ligands. Molecular hydrogen is found to be nonreactive towards Cu(acac)2 on Cu(110), whereas individual H atoms easily lead to bond breaking in the Cu precursor upon impact, and thus release the surface ligands into the gas-phase. On the other hand, water reacts with Cu(acac)2 on a Cu2O substrate through a ligand-exchange reaction, which produces gaseous H(acac) and surface OH species. Combustion reactions with the main by-products CO2 and H2O are observed during the reaction between Cu(acac)2 and ozone on the CuO surface. The reactivity of different co-reactants toward Cu(acac)2 follows the order H > O3 > H2O.

On-Chip Micro-Pseudocapacitors for Ultrahigh Energy and Power Delivery.

Microscale supercapapcitors based on hierarchical nanoporous hybrid electrodes consisting of 3D bicontinuous nanoporous gold and pseudocapacitive manganese oxide deliver an excellent stack capacitance of 99.1 F cm-3 and a high energy density of 12.7 mW h cm-3 with a retained high power density of 46.6 W cm-3.

Toward perylene dyes by the Hundsdiecker reaction.

An efficient method to synthesize 3,4,9,10-tetrabromoperylenes is reported under optimized Hunsdiecker conditions. Various octasubstituted perylenes were obtained by reaction of 1,6,7,12-tetrachloro-3,4,9,10-tetrabromoperylene with phenol, trimethylsilyl chloride, cooper cyanide, or sulfur via metal-catalyzed couplings or nucleophilic substitutions. These new perylenes show completely different optical and redox properties, thus opening a facile way to develop new chromophophore structures.

Extended Hückel theory for carbon nanotubes: band structure and transport properties.

Extended Hückel theory (EHT) is a well established method for the description of the electronic structure of molecules and solids. In this article, we present a set of extended Hückel parameters for carbon nanotubes (CNTs), obtained by fitting the ab initio band structure of the (6,0) CNT. The new parameters are highly transferable to different types of CNTs. To demonstrate the versatility of the approach, we perform self-consistent EHT-based electron transport calculations for finite length CNTs with metal electrodes.

Conductive AFM for CNT characterization.

We report on and emphasize the versatility of conductive atomic force microscopy in characterizing vertically aligned carbon nanotubes (CNTs) aimed to be used in via interconnect technology. The study is conducted on multi-walled CNT arrays vertically grown on a copper-based metal line. Voltage-dependent current mapping and current-voltage characteristics recorded down to single CNT allow for a comprehensive insight into the electric behaviour of the hybrid structure.

Micromirror with large-tilting angle using Fe-based metallic glass.

For enhancing the micromirror properties like tilting angle and stability during actuation, Fe-based metallic glass (MG) was applied for torsion bar material. A micromirror with mirror-plate diameter of 900 µm and torsion bar dimensions length 250 µm, width 30 µm and thickness 2.5 µm was chosen for the tilting angle tests, which were performed by permanent magnets and electromagnet setup. An extremely large tilting angle of over -270° was obtained from an activation test by permanent magnet that has approximately 0.2 T of magnetic strength. A large mechanical tilting angle of over -70° was obtained by applying approximately 1.1 mT to the mirror when 93 mAwas applied to solenoid setup. The large-tilting angle of the micromirror is due to the torsion bar, which was fabricated with Fe-based MG thin film that has large elastic strain limit, fracture toughness, and excellent magnetic property.

Phosphite copper(I) trifluoroacetates [((RO)3P)mCuO2CCF3] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors.

Metal-organics [((RO)(3)P)(m)CuO(2)CCF(3)] (R = CH(3): 11a, m = 1; 11b, m = 2; 11c, m = 3. R = CH(2)CH(3): 12a, m = 1; 12b, m = 2; 12c, m = 3. R = CH(2)CF(3): 13a, m = 1; 13b, m = 2; 13c, m = 3) are either accessible by the reaction of [((RO)(3)P)(m)CuCl] (R = CH(3): 5a, m = 1; 5b, m = 2; 5c, m = 3. R = CH(2)CH(3): 6a, m = 1; 6b, m = 2; 6c, m = 3) with [KO(2)CCF(3)] (7), or treatment of [Cu(2)O] (8) with HO(2)CCF(3) (9) and P(OR)(3) (2, R = CH(3); 3, R = CH(2)CH(3); 4, R = CH(2)CF(3)). (31)P{(1)H} NMR spectra [((CH(3)O)(3)P)(m)CuO(2)CCF(3)] (m = 1, 1.5, 2, 2.5, 3, 3.5, and 4) have been studied at 25 and -80 °C showing phosphite ligand exchange in solution. The molecular structures of 11a and 13a-13c in the solid state are reported. Complexes 11a and 13a are tetramers featuring µ-η(2)(1κO:2κO')- and µ(3)-η(2)(1κO:2κO':3κO')-(11a) or µ(3)-η(2)(1κO:2κO':3κO')-bonded O(2)CCF(3) ligands (13a) with the Cu(I) ions being part of CuPO(2) and CuPO(3) units (11a), while in 13a solely a CuPO(3) moiety is present. Skeletal isomerism of 11a vs. 13a is discussed. Compound 13b is dimeric ({CuP(2)O(2)}(2)) with pseudo-tetrahedral Cu environments and µ-η(2)(1κO:2κO')O(2)CCF(3) functionalities. In monomeric 13c the O(2)CCF(3) ligand is η(1)(κO)-bonded to a tetra-coordinated Cu(i) ion. The thermal solid state properties of 11, 12 and 13 were studied by Thermo Gravimetry (TG). These complexes decompose by phosphite elimination, decarboxylation and dealkylation. Hot-wall Chemical Vapour Deposition (CVD) experiments were carried out at 380 °C using 11c as precursor for the deposition of copper onto pieces of TiN-coated oxidized silicon substrates. Copper layers of high purity were obtained with grain sizes between 200-1200 nm.

Synthesis, photophysics, and photoresponse of fullerene-based azoaromatic dyads.

The synthesis and photophysical characterization of a series of fullerene-based, donor-acceptor dyads is presented, along with a description of their behavior as single molecular components in photovoltaic cells. The spectroscopic and photophysical properties of the dyads, investigated by steady-state fluorescence spectroscopy, pico- and nanosecond transient optical spectroscopy and time-resolved electron paramagnetic resonance (EPR) spectroscopy, revealed that the dyads undergo multiple-step energy transfer from the donor singlet excited state to the fullerene triplet excited state, which in turn decays to the donor triplet state. The inefficient formation of a charge-separated state, both in solution and in the solid state, translates into a poor photovoltaic performance of dyads 2 b-4 b if compared to that of dyad 1 b, in which photoinduced electron transfer is operative in the solid state. In addition, the results of the photophysical investigation suggested that the performance of the solar cells was also limited by the low-lying donor triplet excited state that acts as a photoexcitation energy sink.