Quantum cascade of correlated phases in trigonally warped bilayer graphene.

Divergent density of states offers an opportunity to explore a wide variety of correlated electron physics. In the thinnest limit, this has been predicted and verified in the ultraflat bands of magic-angle twisted bilayer graphene1-5, the band touching points of few-layer rhombohedral graphite6-8 and the lightly doped rhombohedral trilayer graphene9-11. The simpler and seemingly better understood Bernal bilayer graphene is also susceptible to orbital magnetism at charge neutrality7 leading to layer antiferromagnetic states12 or quantum anomalous Hall states13. Here we report the observation of a cascade of correlated phases in the vicinity of electric-field-controlled Lifshitz transitions14,15 and van Hove singularities16 in Bernal bilayer graphene. We provide evidence for the observation of Stoner ferromagnets in the form of half and quarter metals10,11. Furthermore, we identify signatures consistent with a topologically non-trivial Wigner-Hall crystal17 at zero magnetic field and its transition to a trivial Wigner crystal, as well as two correlated metals whose behaviour deviates from that of standard Fermi liquids. Our results in this reproducible, tunable, simple system open up new horizons for studying strongly correlated electrons.

Formation of moiré interlayer excitons in space and time.

Moiré superlattices in atomically thin van der Waals heterostructures hold great promise for extended control of electronic and valleytronic lifetimes1-7, the confinement of excitons in artificial moiré lattices8-13 and the formation of exotic quantum phases14-18. Such moiré-induced emergent phenomena are particularly strong for interlayer excitons, where the hole and the electron are localized in different layers of the heterostructure19,20. To exploit the full potential of correlated moiré and exciton physics, a thorough understanding of the ultrafast interlayer exciton formation process and the real-space wavefunction confinement is indispensable. Here we show that femtosecond photoemission momentum microscopy provides quantitative access to these key properties of the moiré interlayer excitons. First, we elucidate that interlayer excitons are dominantly formed through femtosecond exciton-phonon scattering and subsequent charge transfer at the interlayer-hybridized Σ valleys. Second, we show that interlayer excitons exhibit a momentum fingerprint that is a direct hallmark of the superlattice moiré modification. Third, we reconstruct the wavefunction distribution of the electronic part of the exciton and compare the size with the real-space moiré superlattice. Our work provides direct access to interlayer exciton formation dynamics in space and time and reveals opportunities to study correlated moiré and exciton physics for the future realization of exotic quantum phases of matter.

Quantum anomalous Hall octet driven by orbital magnetism in bilayer graphene.

The quantum anomalous Hall (QAH) effect-a macroscopic manifestation of chiral band topology at zero magnetic field-has been experimentally realized only by the magnetic doping of topological insulators1-3 and the delicate design of moiré heterostructures4-8. However, the seemingly simple bilayer graphene without magnetic doping or moiré engineering has long been predicted to host competing ordered states with QAH effects9-11. Here we explore states in bilayer graphene with a conductance of 2 e2 h-1 (where e is the electronic charge and h is Planck's constant) that not only survive down to anomalously small magnetic fields and up to temperatures of five kelvin but also exhibit magnetic hysteresis. Together, the experimental signatures provide compelling evidence for orbital-magnetism-driven QAH behaviour that is tunable via electric and magnetic fields as well as carrier sign. The observed octet of QAH phases is distinct from previous observations owing to its peculiar ferrimagnetic and ferrielectric order that is characterized by quantized anomalous charge, spin, valley and spin-valley Hall behaviour9.

Fast Twist Angle Mapping of Bilayer Graphene Using Spectroscopic Ellipsometric Contrast Microscopy.

Twisted bilayer graphene provides an ideal solid-state model to explore correlated material properties and opportunities for a variety of optoelectronic applications, but reliable, fast characterization of the twist angle remains a challenge. Here we introduce spectroscopic ellipsometric contrast microscopy (SECM) as a tool for mapping twist angle disorder in optically resonant twisted bilayer graphene. We optimize the ellipsometric angles to enhance the image contrast based on measured and calculated reflection coefficients of incident light. The optical resonances associated with van Hove singularities correlate well to Raman and angle-resolved photoelectron emission spectroscopy, confirming the accuracy of SECM. The results highlight the advantages of SECM, which proves to be a fast, nondestructive method for characterization of twisted bilayer graphene over large areas, unlocking process, material, and device screening and cross-correlative measurement potential for bilayer and multilayer materials.

Perspectives on weak interactions in complex materials at different length scales.

Nanocomposite materials consist of nanometer-sized quantum objects such as atoms, molecules, voids or nanoparticles embedded in a host material. These quantum objects can be exploited as a super-structure, which can be designed to create material properties targeted for specific applications. For electromagnetism, such targeted properties include field enhancements around the bandgap of a semiconductor used for solar cells, directional decay in topological insulators, high kinetic inductance in superconducting circuits, and many more. Despite very different application areas, all of these properties are united by the common aim of exploiting collective interaction effects between quantum objects. The literature on the topic spreads over very many different disciplines and scientific communities. In this review, we present a cross-disciplinary overview of different approaches for the creation, analysis and theoretical description of nanocomposites with applications related to electromagnetic properties.

Nanoscopic Electrolyte-Gated Vertical Organic Transistors with Low Operation Voltage and Five Orders of Magnitude Switching Range for Neuromorphic Systems.

Electrolyte-gated organic transistors (EGOTs) are promising candidates as a new class of neuromorphic devices in hardware-based artificial neural networks that can outperform their complementary metal oxide semiconductor (CMOS) counterparts regarding processing speed and energy consumption. Several ways in which to implement such networks exist, two prominent methods of which can be implemented by nanoscopic vertical EGOTs, as we show here. First, nanoscopic vertical electrolyte-gated transistors with a donor-acceptor diketopyrrolopyrrole-terthiophene polymer as an active material can be used to reversibly switch the channel conductivity over five orders of magnitude (3.8 nS to 392 µS) and perform switching at low operation voltages down to -1 mV. Second, nanoscopic EGOTs can also mimic fundamental synaptic functions, and we show an interconnection of up to three transistors, highlighting the possibility to emulate biological nerve cells.

Impact of Electric Field Disorder on Broken-Symmetry States in Ultraclean Bilayer Graphene.

Bilayer graphene (BLG) has multiple internal degrees of freedom and a constant density of states down to the charge neutrality point when trigonal warping is ignored. Consequently, it is susceptible to various competing ground states. However, a coherent experimental determination of the ground state has been challenging due to the interaction-disorder interplay. Here we present an extensive transport study in a series of dually gated freestanding BLG devices and identify the layer-antiferromagnet as the ground state with a continuous strength across all devices. This strength correlates with the width of the state in the electric field. We systematically identify electric-field disorder─spatial variations in the interlayer potential difference─as the main source responsible for the observations. Our results pinpoint for the first time the importance of electric-field disorder on spontaneous symmetry breaking in BLG and solve a long-standing debate on its ground state. The electric-field disorder should be universal to all 2D materials.

Spontaneous Gully-Polarized Quantum Hall States in ABA Trilayer Graphene.

Bernal-stacked multilayer graphene is a versatile platform to explore quantum transport phenomena and interaction physics due to its exceptional tunability via electrostatic gating. For instance, upon applying a perpendicular electric field, its band structure exhibits several off-center Dirac points (so-called Dirac gullies) in each valley. Here, the formation of Dirac gullies and the interaction-induced breakdown of gully coherence is explored via magnetotransport measurements in high-quality Bernal-stacked (ABA) trilayer graphene. At zero magnetic field, multiple Lifshitz transitions indicating the formation of Dirac gullies are identified. In the quantum Hall regime, the emergence of Dirac gullies is evident as an increase in Landau level degeneracy. When tuning both electric and magnetic fields, electron-electron interactions can be controllably enhanced until, beyond critical electric and magnetic fields, the gully degeneracy is eventually lifted. The arising correlated ground state is consistent with a previously predicted nematic phase that spontaneously breaks the rotational gully symmetry.

Annulated Azuleno[2,1,8-ija]azulenes: Synthesis and Properties.

Non-alternant non-benzenoid hydrocarbons exhibit very different optical and electronic properties than their well-studied benzenoid analogues. However, preparing such structures with extended conjugation length, remains challenging. Herein, we report the synthesis and properties of azuleno[2,1,8-ija]azulene derivatives using a two-step sequence involving a four-fold aldol condensation between aromatic dialdehydes and readily available tetrahydropentalene-2,5-(1H,3H)-dione. Molecules with band gap values ranging from 1.69 to 2.14 eV and molar extinction coefficients (ϵ) of nearly 3×105  M-1 cm-1 have been prepared. These annulene-like structures exhibit significant diatropic ring currents (aromatic), as supported by 1 H NMR spectroscopy and DFT calculations. Field-effect transistors (OFETs) using azuleno[2,1,8-ija]azulene derivatives as semiconductors exhibit charge mobility values of up to 0.05 cm2  V-1 s-1 .

Revealing and Controlling Energy Barriers and Valleys at Grain Boundaries in Ultrathin Organic Films.

In organic electronics, local crystalline order is of critical importance for the charge transport. Grain boundaries between molecularly ordered domains are generally known to hamper or completely suppress charge transfer and detailed knowledge of the local electronic nature is critical for future minimization of such malicious defects. However, grain boundaries are typically hidden within the bulk film and consequently escape observation or investigation. Here, a minimal model system in form of monolayer-thin films with sub-nm roughness of a prototypical n-type organic semiconductor is presented. Since these films consist of large crystalline areas, the detailed energy landscape at single grain boundaries can be studied using Kelvin probe force microscopy. By controlling the charge-carrier density in the films electrostatically, the impact of the grain boundaries on charge transport in organic devices is modeled. First, two distinct types of grain boundaries are identified, namely energetic barriers and valleys, which can coexist within the same thin film. Their absolute height is found to be especially pronounced at charge-carrier densities below 1012 cm- 2 -the regime at which organic solar cells and light emitting diodes typically operate. Finally, processing conditions by which the type or energetic height of grain boundaries can be controlled are identified.

High-Mobility, Ultrathin Organic Semiconducting Films Realized by Surface-Mediated Crystallization.

The functionality of common organic semiconductor materials is determined by their chemical structure and crystal modification. While the former can be fine-tuned via synthesis, a priori control over the crystal structure has remained elusive. We show that the surface tension is the main driver for the plate-like crystallization of a novel small organic molecule n-type semiconductor at the liquid-air interface. This interface provides an ideal environment for the growth of millimeter-sized semiconductor platelets that are only few nanometers thick and thus highly attractive for application in transistors. On the basis of the novel high-performance perylene diimide, we show in as-grown, only 3 nm thin crystals electron mobilities of above 4 cm2/(V s) and excellent bias stress stability. We suggest that the established systematics on solvent parameters can provide the basis of a general framework for a more deterministic crystallization of other small molecules.

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.

Aeshnid dragonfly larvae as bioindicators of methylmercury contamination in aquatic systems impacted by elevated sulfate loading.

Methylmercury (MeHg) levels in dragonfly larvae and water were measured over two years in aquatic systems impacted to varying degrees by sulfate releases related to iron mining activity. This study examined the impact of elevated sulfate loads on MeHg concentrations and tested the use of MeHg in dragonfly larvae as an indicator of MeHg levels in a range of aquatic systems including 16 river/stream sites and two lakes. MeHg concentrations in aeshnid dragonfly larvae were positively correlated (R(2) = 0.46, p < 0.01) to peak MeHg concentrations in the dissolved phase for the combined years of 2012 and 2013. This relation was strong in 2012 (R(2) = 0.85, p < 0.01), but showed no correlation in 2013 (R(2) = 0.02, p > 0.05). MeHg in dragonfly larvae were not elevated at the highest sulfate sites, but rather the reverse was generally observed. Record rainfall events in 2012 and above average rainfall in 2013 likely delivered the majority of Hg and MeHg to these systems via interflow and activated groundwater flow through reduced sediments. As a result, the impacts of elevated sulfate releases due to mining activities were not apparent in these systems where little of the sulfate is reduced. Lower bioaccumulation factors for MeHg in aeshnid dragonfly larvae were observed with increasing dissolved organic carbon (DOC) concentrations. This finding is consistent with previous studies showing that MeHg in high DOC systems is less bioavailable; an equilibrium model shows that more MeHg being associated with DOC rather than algae at the base of the food chain readily explains the lower bioaccumulation factors.

Diketopyrrolopyrrole (DPP)-Based Donor-Acceptor Polymers for Selective Dispersion of Large-Diameter Semiconducting Carbon Nanotubes.

Low-bandgap diketopyrrolopyrrole (DPP)-based polymers are used for the selective dispersion of semiconducting single-walled carbon nanotubes (s-SWCNTs). Through rational molecular design to tune the polymer-SWCNT interactions, highly selective dispersions of s-SWCNTs with diameters mainly around 1.5 nm are achieved. The influences of the polymer alkyl side-chain substitution (i.e., branched vs linear side chains) on the dispersing yield and selectivity of s-SWCNTs are investigated. Introducing linear alkyl side chains allows increased polymer-SWCNT interactions through close π-π stacking and improved C-H-π interactions. This work demonstrates that polymer side-chain engineering is an effective method to modulate the polymer-SWCNT interactions and thereby affecting both critical parameters in dispersing yield and selectivity. Using these sorted s-SWCNTs, high-performance SWCNT network thin-film transistors are fabricated. The solution-deposited s-SWCNT transistors yield simultaneously high mobilities of 41.2 cm(2) V(-1) s(-1) and high on/off ratios of greater than 10(4) . In summary, low-bandgap DPP donor-acceptor polymers are a promising class of polymers for selective dispersion of large-diameter s-SWCNTs.

Probing the tunable multi-cone band structure in Bernal bilayer graphene.

Bernal bilayer graphene (BLG) offers a highly flexible platform for tuning the band structure, featuring two distinct regimes. One is a tunable band gap induced by large displacement fields. Another is a gapless metallic band occurring at low fields, featuring rich fine structure consisting of four linearly dispersing Dirac cones and van Hove singularities. Even though BLG has been extensively studied experimentally, the evidence of this band structure is still elusive, likely due to insufficient energy resolution. Here, we use Landau levels as markers of the energy dispersion and analyze the Landau level spectrum in a regime where the cyclotron orbits of electrons or holes in momentum space are small enough to resolve the distinct mini Dirac cones. We identify the presence of four Dirac cones and map out topological transitions induced by displacement field. By clarifying the low-energy properties of BLG bands, these findings provide a valuable addition to the toolkit for graphene electronics.

Probing electron-hole Coulomb correlations in the exciton landscape of a twisted semiconductor heterostructure.

In two-dimensional semiconductors, cooperative and correlated interactions determine the material's excitonic properties and can even lead to the creation of correlated states of matter. Here, we study the fundamental two-particle correlated exciton state formed by the Coulomb interaction between single-particle holes and electrons. We find that the ultrafast transfer of an exciton's hole across a type II band-aligned semiconductor heterostructure leads to an unexpected sub-200-femtosecond upshift of the single-particle energy of the electron being photoemitted from the two-particle exciton state. While energy relaxation usually leads to an energetic downshift of the spectroscopic signature, we show that this upshift is a clear fingerprint of the correlated interaction of the electron and hole parts of the exciton. In this way, time-resolved photoelectron spectroscopy is straightforwardly established as a powerful method to access electron-hole correlations and cooperative behavior in quantum materials. Our work highlights this capability and motivates the future study of optically inaccessible correlated excitonic and electronic states of matter.

A Cu3BHT-Graphene van der Waals Heterostructure with Strong Interlayer Coupling for Highly Efficient Photoinduced Charge Separation.

Two-dimensional van der Waals heterostructures (2D vdWhs) are of significant interest due to their intriguing physical properties critically defined by the constituent monolayers and their interlayer coupling. Synthetic access to 2D vdWhs based on chemically tunable monolayer organic 2D materials remains challenging. Herein, the fabrication of a novel organic-inorganic bilayer vdWh by combining π-conjugated 2D coordination polymer (2DCP, i.e., Cu3BHT, BHT = benzenehexathiol) with graphene is reported. Monolayer Cu3BHT with detectable µm2-scale uniformity and atomic flatness is synthesized using on-water surface chemistry. A combination of diffraction and imaging techniques enables the determination of the crystal structure of monolayer Cu3BHT with atomic precision. Leveraging the strong interlayer coupling, Cu3BHT-graphene vdWh exhibits highly efficient photoinduced interlayer charge separation with a net electron transfer efficiency of up to 34% from Cu3BHT to graphene, superior to those of reported bilayer 2D vdWhs and molecular-graphene vdWhs. This study unveils the potential for developing novel 2DCP-based vdWhs with intriguing physical properties.

High-gain, low-voltage unipolar logic circuits based on nanoscale flexible organic thin-film transistors with small signal delays.

One of the circuit topologies for the implementation of unipolar integrated circuits (circuits that use either p-channel or n-channel transistors, but not both) is the zero-VGS architecture. Zero-VGS circuits often provide excellent static performance (large small-signal gain and large noise margins), but they suffer from the large signal delay imposed by the load transistor. To address this limitation, we have used electron-beam lithography to fabricate zero-VGS circuits based on organic transistors with channel lengths as small as 120 nm on flexible polymeric substrates. For a supply voltage of 3 V, these circuits have characteristic signal-delay time constants of 14 ns for the low-to-high transition and 560 ns for the high-to-low transition of the circuit's output voltage. These signal delays represent the best dynamic performance reported to date for organic transistor-based zero-VGS circuits. The signal-delay time constant of 14 ns is also the smallest signal delay reported to date for flexible organic transistors.

Dibenzannulated peri-acenoacenes from anthanthrene derivatives.

A series of dibenzannulated phenyl-annulated [4,2]peri-acenoacenes have been synthesized in three straightforward steps from 4,10-dibromoanthanthrone (vat orange 3). The phenyl bisannulation of [4,2]peri-acenoacene provides extra stability by increasing the overall aromatic character of the molecules, and allows for a 45-80% increase of the molar extinction coefficient (ε) compared to their [5,2]peri-acenoacene isomers. Depending on the substituents attached to the π-conjugated core, some derivatives exhibit strong aggregation in the solid state with association constant (Ka) up to 255 M-1, resulting in a significant broadening of the absorption spectrum and a substantial decrease of the bandgap value (more than 0.3 V) from solution to the solid state. One [4,2]peri-acenoacene derivative was doubly reduced using cesium and the crystal structure of the resulting salt has been obtained. Field-effect transistors showing a temperature-dependent hole mobility have been tested.