Dynamic self-stabilization in the electronic and nanomechanical properties of an organic polymer semiconductor.

The field of organic electronics has profited from the discovery of new conjugated semiconducting polymers that have molecular backbones which exhibit resilience to conformational fluctuations, accompanied by charge carrier mobilities that routinely cross the 1 cm2/Vs benchmark. One such polymer is indacenodithiophene-co-benzothiadiazole. Previously understood to be lacking in microstructural order, we show here direct evidence of nanosized domains of high order in its thin films. We also demonstrate that its device-based high-performance electrical and thermoelectric properties are not intrinsic but undergo rapid stabilization following a burst of ambient air exposure. The polymer's nanomechanical properties equilibrate on longer timescales owing to an orthogonal mechanism; the gradual sweating-out of residual low molecular weight solvent molecules from its surface. We snapshot the quasistatic temporal evolution of the electrical, thermoelectric and nanomechanical properties of this prototypical organic semiconductor and investigate the subtleties which play on competing timescales. Our study documents the untold and often overlooked story of a polymer device's dynamic evolution toward stability.

Fluorescence and Electroluminescence of J-Aggregated Polythiophene Monolayers on Hexagonal Boron Nitride.

The photophysics of a semiconducting polymer is manipulated through molecular self-assembly on an insulating surface. Adsorption of polythiophene (PT) monolayers on hexagonal boron nitride (hBN) leads to a structurally induced planarization and a rebalancing of inter- and intrachain excitonic coupling. This conformational control results in a dominant 0-0 photoluminescence peak and a reduced Huang-Rhys factor, characteristic of J-type aggregates, and optical properties which are significantly different to both PT thin films and single polymer strands. Adsorption on hBN also provides a route to explore electroluminescence from PT monolayers though incorporation into hybrid van der Waals heterostructures whereby the polymer monolayer is embedded within a hBN tunnel diode. In these structures we observe up-converted singlet electroluminescence from the PT monolayer, with an excitation mechanism based upon inelastic electron scattering. We argue that surface adsorption provides a methodology for the study of fundamental optoelectronic properties of technologically relevant polymers.

Triplet Excitation and Electroluminescence from a Supramolecular Monolayer Embedded in a Boron Nitride Tunnel Barrier.

We show that ordered monolayers of organic molecules stabilized by hydrogen bonding on the surface of exfoliated few-layer hexagonal boron nitride (hBN) flakes may be incorporated into van der Waals heterostructures with integral few-layer graphene contacts forming a molecular/two-dimensional hybrid tunneling diode. Electrons can tunnel through the hBN/molecular barrier under an applied voltage VSD, and we observe molecular electroluminescence from an excited singlet state with an emitted photon energy hν > eVSD, indicating upconversion by energies up to ∼1 eV. We show that tunneling electrons excite embedded molecules into singlet states in a two-step process via an intermediate triplet state through inelastic scattering and also observe direct emission from the triplet state. These heterostructures provide a solid-state device in which spin-triplet states, which cannot be generated by optical transitions, can be controllably excited and provide a new route to investigate the physics, chemistry, and quantum spin-based applications of triplet generation, emission, and molecular photon upconversion.

Epitaxial multilayers of alkanes on two-dimensional black phosphorus as passivating and electrically insulating nanostructures.

Mechanically exfoliated two-dimensional (2D) black phosphorus (bP) is epitaxially terminated by monolayers and multilayers of tetracosane, a linear alkane, to form a weakly interacting van der Waals heterostructure. Atomic force microscopy (AFM) and computational modelling show that epitaxial domains of alkane chains are ordered in parallel lamellae along the principal crystalline axis of bP, and this order is extended over a few layers above the interface. Epitaxial alkane multilayers delay the oxidation of 2D bP in air by 18 hours, in comparison to 1 hour for bare 2D bP, and act as an electrical insulator, as demonstrated using electrostatic force microscopy. The presented heterostructure is a technologically relevant insulator-semiconductor model system that can open the way to the use of 2D bP in micro- and nanoelectronic, optoelectronic and photonic applications.

Ultra-high resolution imaging of thin films and single strands of polythiophene using atomic force microscopy.

Real-space images of polymers with sub-molecular resolution could provide valuable insights into the relationship between morphology and functionality of polymer optoelectronic devices, but their acquisition is problematic due to perceived limitations in atomic force microscopy (AFM). We show that individual thiophene units and the lattice of semicrystalline spin-coated films of polythiophenes (PTs) may be resolved using AFM under ambient conditions through the low-amplitude (≤ 1 nm) excitation of higher eigenmodes of a cantilever. PT strands are adsorbed on hexagonal boron nitride near-parallel to the surface in islands with lateral dimensions ~10 nm. On the surface of a spin-coated PT thin film, in which the thiophene groups are perpendicular to the interface, we resolve terminal CH3-groups in a square arrangement with a lattice constant 0.55 nm from which we can identify abrupt boundaries and also regions with more slowly varying disorder, which allow comparison with proposed models of PT domains.

The growth and fluorescence of phthalocyanine monolayers, thin films and multilayers on hexagonal boron nitride.

Free-base phthalocyanine forms distinct interfacial phases and thin films on hexagonal boron nitride including a monolayer arrangement as determined using high resolution atomic force microscopy. The phases reveal significant differences in photoluminescence with an intense peak for monolayer coverages of flat-lying molecules which is red-shifted in agreement with theoretical models.

Substrate-induced shifts and screening in the fluorescence spectra of supramolecular adsorbed organic monolayers.

We have investigated the influence of the substrate on the fluorescence of adsorbed organic molecules. Monolayer films of perylene-3,4,9,10-tetracarboxylic-3,4,9,10-diimide (PTCDI), a supramolecular network formed from PTCDI and melamine, and perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride have been deposited on hexagonal boron nitride (hBN). The principal peaks in the fluorescence spectra of these films were red-shifted by up to 0.37 eV relative to published measurements for molecules in helium droplets. Smaller shifts (∼0.03 eV) arising from interactions between neighbouring molecules are investigated by comparing the fluorescence of distinct arrangements of PTCDI, which are templated by supramolecular self-assembly and determined with molecular resolution using atomic force microscopy under ambient conditions. We compare our experimental results with red-shifts calculated using a combination of a perturbative model and density functional theory which account for, respectively, resonant and non-resonant effects of a dielectric hBN substrate. We show that the substrate gives rise to a red-shift in the fluorescence of an adsorbed molecule and also screens the interactions between neighbouring transition dipole moments; both these effects depend on the refractive index of the substrate.

Lattice-Matched Epitaxial Graphene Grown on Boron Nitride.

Lattice-matched graphene on hexagonal boron nitride is expected to lead to the formation of a band gap but requires the formation of highly strained material and has not hitherto been realized. We demonstrate that aligned, lattice-matched graphene can be grown by molecular beam epitaxy using substrate temperatures in the range 1600-1710 °C and coexists with a topologically modified moiré pattern with regions of strained graphene which have giant moiré periods up to ∼80 nm. Raman spectra reveal narrow red-shifted peaks due to isotropic strain, while the giant moiré patterns result in complex splitting of Raman peaks due to strain variations across the moiré unit cell. The lattice-matched graphene has a lower conductance than both the Frenkel-Kontorova-type domain walls and also the topological defects where they terminate. We relate these results to theoretical models of band gap formation in graphene/boron nitride heterostructures.

Supramolecular heterostructures formed by sequential epitaxial deposition of two-dimensional hydrogen-bonded arrays.

Two-dimensional (2D) supramolecular arrays provide a route to the spatial control of the chemical functionality of a surface, but their deposition is in almost all cases limited to a monolayer termination. Here we investigated the sequential deposition of one 2D array on another to form a supramolecular heterostructure and realize the growth-normal to the underlying substrate-of distinct ordered layers, each of which is stabilized by in-plane hydrogen bonding. For heterostructures formed by depositing terephthalic acid or trimesic acid on cyanuric acid/melamine, we have determined, using atomic force microscopy under ambient conditions, a clear epitaxial arrangement despite the intrinsically distinct symmetries and/or lattice constants of each layer. Structures calculated using classical molecular dynamics are in excellent agreement with the orientation, registry and dimensions of the epitaxial layers. Calculations confirm that van der Waals interactions provide the dominant contribution to the adsorption energy and registry of the layers.

Supramolecular networks stabilise and functionalise black phosphorus.

The limited stability of the surface of black phosphorus (BP) under atmospheric conditions is a significant constraint on the exploitation of this layered material and its few layer analogue, phosphorene, as an optoelectronic material. Here we show that supramolecular networks stabilised by hydrogen bonding can be formed on BP, and that these monolayer-thick films can passivate the BP surface and inhibit oxidation under ambient conditions. The supramolecular layers are formed by solution deposition and we use atomic force microscopy to obtain images of the BP surface and hexagonal supramolecular networks of trimesic acid and melamine cyanurate (CA.M) under ambient conditions. The CA.M network is aligned with rows of phosphorus atoms and forms large domains which passivate the BP surface for more than a month, and also provides a stable supramolecular platform for the sequential deposition of 1,2,4,5-tetrakis(4-carboxyphenyl)benzene to form supramolecular heterostructures.

Strain-Engineered Graphene Grown on Hexagonal Boron Nitride by Molecular Beam Epitaxy.

Graphene grown by high temperature molecular beam epitaxy on hexagonal boron nitride (hBN) forms continuous domains with dimensions of order 20 µm, and exhibits moiré patterns with large periodicities, up to ~30 nm, indicating that the layers are highly strained. Topological defects in the moiré patterns are observed and attributed to the relaxation of graphene islands which nucleate at different sites and subsequently coalesce. In addition, cracks are formed leading to strain relaxation, highly anisotropic strain fields, and abrupt boundaries between regions with different moiré periods. These cracks can also be formed by modification of the layers with a local probe resulting in the contraction and physical displacement of graphene layers. The Raman spectra of regions with a large moiré period reveal split and shifted G and 2D peaks confirming the presence of strain. Our work demonstrates a new approach to the growth of epitaxial graphene and a means of generating and modifying strain in graphene.

van der Waals-Induced Chromatic Shifts in Hydrogen-Bonded Two-Dimensional Porphyrin Arrays on Boron Nitride.

The fluorescence of a two-dimensional supramolecular network of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) adsorbed on hexagonal boron nitride (hBN) is red-shifted due to, primarily, adsorbate-substrate van der Waals interactions. TCPP is deposited from solution on hBN and forms faceted islands with typical dimensions of 100 nm and either square or hexagonal symmetry. The molecular arrangement is stabilized by in-plane hydrogen bonding as determined by a combination of molecular-resolution atomic force microscopy performed under ambient conditions and density functional theory; a similar structure is observed on MoS2 and graphite. The fluorescence spectra of submonolayers of TCPP on hBN are red-shifted by ∼30 nm due to the distortion of the molecule arising from van der Waals interactions, in agreement with time-dependent density functional theory calculations. Fluorescence intensity variations are observed due to coherent partial reflections at the hBN interface, implying that such hybrid structures have potential in photonic applications.

Study of NAP adsorption and assembly on the surface of HOPG.

NAP is an octapeptide that has demonstrated a neuroprotective/therapeutic efficacy at very low concentrations in preclinical studies and in a number of clinical trials. Yet little is known about its structural organization at low concentrations. Here, we have employed atomic force microscopy to investigate NAP peptide assembly on graphite in aqueous media at nanomolar concentration. High spatial resolution scans of NAP assemblies reveal their fine structure with clearly resolved single NAP units. This observation leads us to conclude that NAP molecules do not form complex self-assembled structures at nanomolar concentration when adsorbed on graphite surface.

Bimolecular porous supramolecular networks deposited from solution on layered materials: graphite, boron nitride and molybdenum disulphide.

A two-dimensional porous network formed from perylene tetracarboxylic diimide (PTCDI) and melamine may be deposited from solution on the surfaces of highly oriented pyrolytic graphite (HOPG), hexagonal boron nitride (hBN) and molybdenum disulphide (MoS2). Images acquired using high resolution atomic force microscopy (AFM) operating under ambient conditions have revealed that the network forms extended ordered monolayers (>1 µm(2)) on HOPG and hBN whereas on MoS2 much smaller islands are observed.

Surface mediated L-phenylalanyl-L-phenylalanine assembly into large dendritic structures.

We report a new class of dipeptide dendritic structures fabricated on the surface of mica via spin casting and the conditions required to achieve them. Both their structure and formation mechanism have been investigated in detail using Atomic Force Microscopy (AFM) at the nanometre scale. Formation of nanotubular structures and their further interaction is shown to be a key step in dendritic structure growth. A possible candidate for the primary building block in the nanotubular structure has been identified. The dendritic structures were found to be stable in ambient conditions for several months, however, they transform into needle-like crystals upon exposure to 100% (relative humidity) humid air.

The structure and formation of hydrogen-bonded molecular networks on Au(111) surfaces revealed by scanning tunnelling and torsional-tapping atomic force microscopy.

A comprehensive scanning probe microscopy study has been carried out to characterise 3,4,9,10-Perylenetetracarboxylic diimide (PTCDI)-melamine hydrogen-bonded networks deposited on Au(111)-surfaces. Both scanning tunnelling and atomic force microscopy were utilized. Such complementary analysis revealed a multilayered structure of the networks on the Au(111)-surface as opposed to a widely reported monolayer structure. Details of the network formation mechanism are presented. We have also demonstrated that despite the apparent network stability in ambient conditions it is unstable in aqueous solutions of pH 4.5 and 7.1.