Christian Kloc

A soluble and air-stable organic semiconductor with high electron mobility

Electronic devices based on organic semiconductors offer an attractive alternative to conventional inorganic devices due to potentially lower costs, simpler packaging and compatibility with flexible substrates. As is the case for silicon-based microelectronics, the use of complementary logic elements—requiring n- and p-type semiconductors whose majority charge carriers are electrons and holes, respectively—is expected to be crucial to achieving low-power, high-speed performance. Similarly, the electron-segregating domains of photovoltaic assemblies require both n- and p-type semiconductors. Stable organic p-type semiconductors are known, but practically useful n-type semiconductor materials have proved difficult to develop, reflecting the unfavourable electrochemical properties of known, electron-demanding polymers. Although high electron mobilities have been obtained for organic materials, these values are usually obtained for single crystals at low temperatures, whereas practically useful field-effect transistors (FETs) will have to be made of polycrystalline films that remain functional at room temperature. A few organic n-type semiconductors that can be used in FETs are known, but these suffer from low electron mobility, poor stability in air and/or demanding processing conditions. Here we report a crystallographically engineered naphthalenetetracarboxylic diimide derivative that allows us to fabricate solution-cast n-channel FETs with promising performance at ambient conditions. By integrating our n-channel FETs with solution-deposited p-channel FETs, we are able to produce a complementary inverter circuit whose active layers are deposited entirely from the liquid phase. We expect that other complementary circuit designs can be realized by this approach as well.

Evolution of Electronic Structure in Atomically Thin Sheets of WS2 and WSe2

Geometrical confinement effect in exfoliated sheets of layered materials leads to significant evolution of energy dispersion in mono- to few-layer thickness regime. Molybdenum disulfide (MoS(2)) was recently found to exhibit indirect-to-direct gap transition when the thickness is reduced to a single monolayer. Emerging photoluminescence (PL) from monolayer MoS(2) opens up opportunities for a range of novel optoelectronic applications of the material. Here we report differential reflectance and PL spectra of mono- to few-layer WS(2) and WSe(2) that indicate that the band structure of these materials undergoes similar indirect-to-direct gap transition when thinned to a single monolayer. The transition is evidenced by distinctly enhanced PL peak centered at 630 and 750 nm in monolayer WS(2) and WSe(2), respectively. Few-layer flakes are found to exhibit comparatively strong indirect gap emission along with direct gap hot electron emission, suggesting high quality of synthetic crystals prepared by a chemical vapor transport method. Fine absorption and emission features and their thickness dependence suggest a strong effect of Se p-orbitals on the d electron band structure as well as interlayer coupling in WSe(2).

Photoluminescence emission and Raman response of monolayer MoS 2 , MoSe 2 , and WSe 2

We mechanically exfoliate mono- and few-layers of the transition metal dichalcogenides molybdenum disulfide, molybdenum diselenide, and tungsten diselenide. The exact number of layers is unambiguously determined by atomic force microscopy and high-resolution Raman spectroscopy. Strong photoluminescence emission is caused by the transition from an indirect band gap semiconductor of bulk material to a direct band gap semiconductor in atomically thin form.

Origin of indirect optical transitions in few-layer MoS2, WS2, and WSe2.

It has been well-established that single layer MX2 (M = Mo, W and X = S, Se) are direct gap semiconductors with band edges coinciding at the K point in contrast to their indirect gap multilayer counterparts. In few-layer MX2, there are two valleys along the Γ-K line with similar energy. There is little understanding on which of the two valleys forms the conduction band minimum (CBM) in this thickness regime. We investigate the conduction band valley structure in few-layer MX2 by examining the temperature-dependent shift of indirect exciton photoluminescence peak. Highly anisotropic thermal expansion of the lattice and the corresponding evolution of the band structure result in a distinct peak shift for indirect transitions involving the K and Λ (midpoint along Γ-K) valleys. We identify the origin of the indirect emission and concurrently determine the relative energy of these valleys.

Single-crystal field-effect transistors based on copper phthalocyanine

Copper phthalocyanine (Cu–Pc) single crystals were grown by physical vapor transport and field-effect transistors (FETs) on the surface of these crystals were prepared. These FETs function as p-channel accumulation-mode devices. Charge carrier mobilities of up to 1cm2∕Vs combined with a low field-effect threshold were obtained. These remarkable FET characteristics, along with the highly stable chemical nature of Cu–Pc, make it an attractive candidate for device applications.

Charge-transfer complexes: new perspectives on an old class of compounds

The discovery of the organic metal TTF–TCNQ in 1973 led to an explosion of research conducted on organic charge-transfer complexes. While these materials have been studied intensely for several decades, the research was mostly aimed at the discovery of materials with high room-temperature conductivity or high-temperature superconductivity. Recently, attention has turned to technologically-relevant properties of charge-transfer complexes, such as ambipolar transport, metallicity, photoconductivity, ferroelectricity or magnetoresistance. This manuscript reviews the growth, structure and properties of charge-transfer complexes and underlines recent progress in their application in organic devices. Their prospects in future applications are discussed, as well as the challenges yet to be overcome to understand the fundamental parameters governing their operation.

Synthesis, characterization, self-assembly, and physical properties of 11-methylbenzo[d]pyreno[4,5-b]furan.

Synthesis, structure, and physical properties of a novel 11-methylbenzo[d]pyreno[4,5-b]furan (BPF) and its self-assembly in water have been reported. The performance of nanowire-based films in organic light-emitting diodes is much better than that of the thin film deposited by directly drop-coating BPF molecules in THF solution. SEM study indicates that the well-organized structure (nanowires) is an important factor in enhancing the performance of OLED devices.

Crystal structure and phototransistor behavior of N-substituted heptacence.

6,8,15,17-Tetraaza-1.18,4.5,9.10,13.14-tetrabenzoheptacene (TTH, 1) has been prepared and characterized by single-crystal X-ray structure analysis. A phototransistor device based on TTH single crystal demonstrated that TTH showed a good performance in signal amplification under the photoconductive effect as well as photocontrolled switches.

Evolution of the low-frequency spin dynamics in ferromagnetic manganites

Neutron scattering was used to study the ferromagnetic manganites Nd0.7Sr0.3MnO3 (T-C = 197.9 K) and PT0.63Sr0.37MnO3 (T-C = 300.9 K). The spin dynamical behavior of these two systems is similar at low temperatures but drastically different at temperatures around T-C. While the formation of spin clusters of size (similar to 20 Angstrom) dominates the spin dynamics of the 197.9 K sample close to T-C, the paramagnetic to ferromagnetic transition for the 300.9 K sample is mon conventional. These results, combined with seemingly inconsistent earlier reports, reveal clear systematics in the spin dynamics of the manganites.

Weak Van der Waals Stacking, Wide-Range Band Gap, and Raman Study on Ultrathin Layers of Metal Phosphorus Trichalcogenides

2D semiconducting metal phosphorus trichalcogenides, particularly the bulk crystals of MPS3 (M = Fe, Mn, Ni, Cd and Zn) sulfides and MPSe3 (M = Fe and Mn) selenides, have been synthesized, crystallized and exfoliated into monolayers. The Raman spectra of monolayer FePS3 and 3-layer FePSe3 show the strong intralayer vibrations and structural stability of the atomically thin layers under ambient condition. The band gaps can be adjusted by element choices in the range of 1.3-3.5 eV. The wide-range band gaps suggest their optoelectronic applications in a broad wavelength range. The calculated cleavage energies of MPS3 are smaller than that of graphite. Therefore, the monolayers used for building of heterostructures by van der Waals stacking could be considered as the candidates for artificial 2D materials with unusual ferroelectric and magnetic properties.