Polar Polymorphism: A New Intermediate Structure toward the Thin-Film Phase in Asymmetric Benzothieno[3,2-b][1]-benzothiophene Derivatives.

Understanding structure and polymorphism is relevant for any organic device optimization, and it is of particular relevance in 7-decyl-2-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) since high carrier mobility in Ph-BTBT-10 thin films has been linked to the structural transformation from the metastable thin-film phase to the thermodynamically stable bilayer structure via thermal annealing. We combine here a systematic nanoscale morphological analysis with local Kelvin probe force microcopy (KPFM) that demonstrates the formation of a polar polymorph in thin films as an intermediate structure for thicknesses lower than 20 nm. The polar structure develops with thickness a variable amount of structural defects in the form of individual flipped molecules (point defects) or sizable polar domains, and evolves toward the reported nonpolar thin-film phase. The direct experimental evidence is supported by electronic structure density functional theory calculations. The structure of the film has dramatic effects on the electronic properties, leading to a decrease in the film work function (by up to 1 eV) and a considerable broadening of the occupied molecular orbitals, attributed to electrostatic disorder. From an advanced characterization point of view, KPFM stands out as a valuable tool for evaluating electrostatic disorder and the conceivable emergence of polar polymorphs in organic thin films. The emergence of polar assemblies introduces a critical consideration for other asymmetric BTBT derivatives, which may be pivotal to understanding the structure-property relationships in organic field-effect transistors (OFETs). A precise determination of any polar assemblies close to the dielectric interface is critical for the judicious design and upgrading of high-performance OFETs.

Synergistic Effect of Solvent Vapor Annealing and Chemical Doping for Achieving High-Performance Organic Field-Effect Transistors with Ideal Electrical Characteristics.

Contact resistance and charge trapping are two key obstacles, often intertwined, that negatively impact on the performance of organic field-effect transistors (OFETs) by reducing the overall device mobility and provoking a nonideal behavior. Here, we expose organic semiconductor (OSC) thin films based on blends of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8) with polystyrene (PS) to (i) a CH3CN vapor annealing process, (ii) a doping I2/water procedure, and (iii) vapors of I2/CH3CN to simultaneously dope and anneal the films. After careful analysis of the OFET electrical characteristics and by performing local Kelvin probe force microscopy studies, we found that the vapor annealing process predominantly reduces interfacial shallow traps, while the chemical doping of the OSC film is responsible for the diminishment of deeper traps and promoting a significant reduction of the contact resistance. Remarkably, the devices treated with I2/CH3CN reveal ideal electrical characteristics with a low level of shallow/deep traps and a very high and almost gate-independent mobility. Hence, this work demonstrates the promising synergistic effects of performing simultaneously a solvent vapor annealing and doping procedure, which can lead to trap-free OSC films with negligible contact resistance problems.

Temperature-induced polymorphism of a benzothiophene derivative: reversibility and impact on the thin film morphology.

The identification of polymorphs in organic semiconductors allows for establishing structure-property relationships and gaining understanding of microscopic charge transport physics. Thin films of 2,7-bis(octyloxy)[1]benzothieno[3,2-b]-benzothiophene (C8O-BTBT-OC8) exhibit a substrate-induced phase (SIP) that differs from the bulk structure, with important implications for the electrical performance in organic field effect transistors (OFETs). Here we combine grazing incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) to study how temperature affects the morphology and structure of C8O-BTBT-OC8 films grown by physical vapor deposition on SiO2. We report a structural transition for C8O-BTBT-OC8 films, from the SIP encountered at room temperature (RT) to a high temperature phase (HTP) when the films are annealed at a temperature T ≥ 90 °C. In this HTP structure, the molecules are packed with a tilt angle (≈39° respect to the surface normal) and an enlarged in-plane unit cell. Although the structural transition is reversible on cooling at RT, AFM reveals that molecular layers at the SiO2 interface can remain with the HTP structure, buried under the film ordered in the SIP. For annealing temperatures close to 150 °C, dewetting occurs leading to a more complex morphological and structural scenario upon cooling, with coexistence of different molecular tilts. Because the molecular packing at the interface has direct impact in the charge carrier mobility of OFETs, identifying the different polymorphs of a material in the thin film form and determining their stability at the interfaces are key factors for device optimization.

Charge-Transfer Complexes in Organic Field-Effect Transistors: Superior Suitability for Surface Doping.

We demonstrate the key role of charge-transfer complexes in surface doping as a successful methodology for improving channel field-effect mobility and reducing the threshold voltage in organic field-effect transistors (OFETs), as well as raising the film conductivity. Demonstrated here for 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile (F6TCNNQ), channel doping by sequential deposition is consistently rationalized by the development of a cocrystalline structure that forms and evolves from the surface of the organic semiconductor film without trading the thin-film structure integrity. This scenario brings higher benefits for the device operation than doping by codeposition, where a decrease in the field-effect mobility of the device, even for a dopant content of only 1 mol %, makes codeposition less suitable. Insight into the structural and electronic properties of the interface satisfactorily explains the improved performance of OFETs upon the incorporation of the dopant and provides an understanding of the mechanism of doping in this system.

Real-Space Image of Charged Patches in Tunable-Size Nanocrystals.

The remarkable dual nature of faceted-charge patchy metal fluoride nanocrystals arises from the spontaneous selective coordination of anionic and cationic ligands on the different facets of the nanocrystals. In previous studies, the identification and origin of the charge at the patches were obtained by combining computer simulations with indirect experimental evidence. Taking a step further, we report herein the first direct real-space identification by Kelvin probe force microscopy of the predicted faceted-charge patchy behavior, allowing the image of the dual faceted-charge surfaces. High-resolution transmission electron microscopy reveals the detailed nanocrystal faceting and allows unambiguously inferring the hydrophilic or hydrophobic role of each facet from the identification of the surface atoms exposed at the respective crystallographic planes. The success of the study lies in a foresighted synthesis methodology designed to tune the nanocrystal size to be suitable for microscopy studies and demanding applications.

From high quality packing to disordered nucleation or phase separation in donor/acceptor interfaces: ClAlPc-C60 on Au(111).

The dramatic consequences that the orientation adopted by the molecular dipoles, in diverse arrays of chloroaluminum phthalocyanine (ClAlPc) on Au(111), have on the ulterior adsorption and growth of C60 are explored by means of an all scanning probe microscopy approach. The unidirectional downwards organization of the molecular dipoles at the first layer reduces charge transfer from the metal to C60. Imbalance between attractive and repulsive interactions of the fullerenes are crucial for their ordered supramolecular aggregation. The effect at the basis of such self-assembling seems to be released by the all upwards dipole orientation adopted on the ClAlPc second layer. The low electronic corrugation of the bilayer results in a higher mobility of the fullerenes which for similar coverages diffuse large distances to reach uncovered first layer regions. Density functional theory calculations corroborate the experimental observations indicating the relevance of charge transfer, potential energy surface corrugation, C60 on-surface diffusion barriers and screening. The structure of the co-adsorbed C60 and ClAlPc layers strongly depends on the deposition sequence. Phase-separation, where each molecule adopts the single-component assembly, occurs if C60 is deposited first. The present results contribute to understanding the influence of the dipolar nature of molecular layers on the electronic and structure of donor/acceptor heterojunctions, which is crucial for device design via engineering the energy level alignment at organic-organic and organic-metal interfaces.

Effect of the Organic Semiconductor Side Groups on the Structural and Electronic Properties of Their Interface with Dopants.

Two derivatives of [1]benzothieno[3,2-b][1]benzothiophene (BTBT), namely, 2,7-dioctyl-BTBT (C8-BTBT) and 2,7-diphenyl-BTBT (DPh-BTBT), belonging to one of the best performing organic semiconductor (OSC) families, have been employed to investigate the influence of the substitutional side groups on the properties of the interface created when they are in contact with dopant molecules. As a molecular p-dopant, the fluorinated fullerene C60F48 is used because of its adequate electronic levels and its bulky molecular structure. Despite the dissimilarity introduced by the OSC film termination, dopant thin films grown on top adopt the same (111)-oriented FCC crystalline structure in the two cases. However, the early stage distribution of the dopant on each OSC film surface is dramatically influenced by the group side, leading to distinct host-dopant interfacial morphologies that strongly affect the nanoscale local work function. In this context, Kelvin probe force microscopy and photoelectron emission spectroscopy provide a comprehensive picture of the interfacial electronic properties. The extent of charge transfer and energy level alignment between OSCs and dopant are debated in light of the differences in the ionization potential of the OSC in the films, the interface nanomorphology, and the electronic coupling with the substrate.

Impact of Nanomorphology on Surface Doping of Organic Semiconductors: The Pentacene-C60F48 Interface.

Establishing the rather complex correlation between the structure and the charge transfer in organic-organic heterostructures is of utmost importance for organic electronics and requires spatially resolved structural, chemical, and electronic details. Insight into this issue is provided here by combining atomic force microscopy, Kelvin probe force microscopy, photoemission electron microscopy, and low-energy electron microscopy for investigating a case study. We select the interface formed by pentacene (PEN), benchmark among the donor organic semiconductors, and a p-type dopant from the family of fluorinated fullerenes. As for Buckminsterfullerene (C60), the growth of its fluorinated derivative C60F48 is influenced by the thickness and crystallinity of the PEN buffer layer, but the behavior is markedly different. We provide a microscopic description of the C60F48/PEN interface formation and analyze the consequences in the electronic properties of the final heterostructure. For just one single layer of PEN, a laterally complete but noncompact C60F48/PEN interface is created, importantly affecting the surface work function. Nonetheless, from the very beginning of the second layer formation, the presence of epitaxial and nonepitaxial PEN domains dramatically influences the growth dynamics and extremely well packed two-dimensional C60F48 islands develop. Insightful elemental maps of the C60F48/PEN surface spatially resolve the nonuniform distribution of the dopant molecules, which leads to a heterogeneous work function landscape.

Double Beneficial Role of Fluorinated Fullerene Dopants on Organic Thin-Film Transistors: Structural Stability and Improved Performance.

The present work assesses improved carrier injection in organic field-effect transistors by contact doping and provides fundamental insight into the multiple impacts that the dopant/semiconductor interface details have on the long-term and thermal stability of devices. We investigate donor [1]benzothieno[3,2-b]-[1]benzothiophene (BTBT) derivatives with one and two octyl side chains attached to the core, therefore constituting asymmetric (BTBT-C8) and symmetric (C8-BTBT-C8) molecules, respectively. Our results reveal that films formed out of the asymmetric BTBT-C8 expose the same alkyl-terminated surface as the C8-BTBT-C8 films do. In both cases, the consequence of depositing fluorinated fullerene (C60F48) as a molecular p-dopant is the formation of C60F48 crystalline islands decorating the step edges of the underlying semiconductor film surface. We demonstrate that local work function changes along with a peculiar nanomorphology lead to the double beneficial effect of lowering the contact resistance and providing long-term and enhanced thermal stability of the devices.

Surface specificity and mechanistic pathway of de-fluorination of C60F48 on coinage metals.

We provide experimental and theoretical understanding on fundamental processes taking place at room temperature when a fluorinated fullerene dopant gets close to a metal surface. By employing scanning tunneling microscopy and photoelectron spectroscopies, we demonstrate that the on-surface integrity of C60F48 depends on the interaction with the particular metal it approaches. Whereas on Au(111) the molecule preserves its chemical structure, on more reactive surfaces such as Cu(111) and Ni(111), molecules interacting with the bare metal surface lose the halogen atoms and transform to C60. Though fluorine-metal bonding can be detected depending on the molecular surface density, no ordered fluorine structures are observed. We show the implications of the metal-dependent de-fluorination in the electronic structure of the molecules and the energy alignment at the molecule-metal interface. Molecular dynamics simulations with ReaxFF reactive force field corroborate the experimental facts and provide a detailed mechanistic picture of the surface-induced de-fluorination, which involves the rotation of the molecule on the surface. Outstandingly, a thermodynamic analysis indicates that the effect of the metal surface is lowering and diminishing the energy barrier for C-F cleave, demonstrating the catalytic role of the surface. The present study contributes to in-depth knowledge of the mechanisms that affect the degree of stability of chemical species on surfaces, which is essential to advance our understanding of the chemical reactivity of metals and their role in on-surface chemical reactions.

Boosting Self-Assembly Diversity in the Solid-State by Chiral/Non-Chiral ZnII -Porphyrin Crystallization.

A chiral ZnII porphyrin derivative 1 and its achiral analogue 2 were studied in the solid state. Considering the rich molecular recognition of designed metalloporphyrins 1 and 2 and their tendency to crystallize, they were recrystallized from two solvent mixtures (CH2 Cl2 /CH3 OH and CH2 Cl2 /hexane). As a result, four different crystalline arrangements (1 a,b and 2 a,b, from 0D to 2D) were obtained. Solid-state studies were performed on all the species to analyze the role played by chirality, solvent mixtures, and surfaces (mica and HOPG) in the supramolecular arrangements. By means of combinations of solvents and substrates a variety of microsized species was obtained, from vesicles to flower-shaped arrays, including geometrical microcrystals. Overall, the results emphasize the environmental susceptibility of metalloporphyrins and how this feature must be taken into account in their design.

Decoding the Vertical Phase Separation and Its Impact on C8-BTBT/PS Transistor Properties.

Disentangling the details of the vertical distribution of small semiconductor molecules blended with polystyrene (PS) and the contact properties are issues of fundamental value for designing strategies to optimize small-molecule:polymer blend organic transistors. These questions are addressed here for ultrathin blends of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) and PS processed by a solution-shearing technique using three different blend composition ratios. We show that friction force microscopy (FFM) allows the determination of the lateral and vertical distribution of the two materials at the nanoscale. Our results demonstrate a three-layer stratification of the blend: a film of C8-BTBT of few molecular layers with crystalline order sandwiched between a PS-rich layer at the bottom (a few nm thick) acting as a passivating dielectric layer and a PS-rich skin layer on the top (∼1 nm) conferring stability to the devices. Kelvin probe force microscopy (KPFM) measurements performed in operating organic field-effect transistors (OFETs) reveal that the devices are strongly contact-limited and suggest contact doping as a route for device optimization. By excluding the effect of the contacts, field-effect mobility values in the channel as high as 10 cm2 V-1 s-1 are obtained. Our findings, obtained via a combination of FFM and KPFM, provide a satisfactory explanation of the different electrical performances of the OFETs as a function of the blend composition ratio and by doping the contacts.

Electron Accumulative Molecules.

With the goal to produce molecules with high electron accepting capacity and low reorganization energy upon gaining one or more electrons, a synthesis procedure leading to the formation of a B-N(aromatic) bond in a cluster has been developed. The research was focused on the development of a molecular structure able to accept and release a specific number of electrons without decomposing or change in its structural arrangement. The synthetic procedure consists of a parallel decomposition reaction to generate a reactive electrophile and a synthesis reaction to generate the B-N(aromatic) bond. This procedure has paved the way to produce the metallacarboranylviologen [M(C2B9H11)(C2B9H10)-NC5H4-C5H4N-M'(C2B9H11)(C2B9H10)] (M = M' = Co, Fe and M = Co and M' = Fe) and semi(metallacarboranyl)viologen [3,3'-M(8-(NC5H4-C5H4N-1,2-C2B9H10)(1',2'-C2B9H11)] (M = Co, Fe) electron cumulative molecules. These molecules are able to accept up to five electrons and to donate one in single electron steps at accessible potentials and in a reversible way. By targeted synthesis and corresponding electrochemical tests each electron transfer (ET) step has been assigned to specific fragments of the molecules. The molecules have been carefully characterized, and the electronic communication between both metal centers (when this situation applies) has been definitely observed through the coplanarity of both pyridine fragments. The structural characteristics of these molecules imply a low reorganization energy that is a necessary requirement for low energy ET processes. This makes them electronically comparable to fullerenes, but on their side, they have a wide range of possible solvents. The ET from one molecule to another has been clearly demonstrated as well as their self-organizing capacity. We consider that these molecules, thanks to their easy synthesis, ET, self-organizing capacity, wide range of solubility, and easy processability, can find important application in any area where ET is paramount.

In-Situ Scrutiny of the Relationship between Polymorphic Phases and Properties of Self-Assembled Monolayers of a Biphenyl Based Thiol.

Two polymorphic phases of ω-(4'-methylbiphenyl-4-yl) butane-1-thiol (BP4) molecules formed on Au(111) were investigated by multidimensional atomic force microscopy, combining conductivity measurements, electrostatic characterization, friction force mapping, and normal force spectroscopy. Based on the same molecular structure but differing in molecular order, packing density, and molecular tilt, the two phases serve as a test bench to establish the structure-property relationships in self-assembled monolayers (SAMs). From a detailed analysis of the charge transport and electrostatics, the contributions of geometrical and electronic effects to the tunneling are discussed.

Real Space Demonstration of Induced Crystalline 3D Nanostructuration of Organic Layers.

The controlled 3D nanostructuration of molecular layers of the semiconducting molecules C22H14 (pentacene) and N,N'-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C8) is addressed. A tip-assisted method using atomic force microscopy (AFM) is developed for removing part of the organic material and relocating it in up to six layer thick nanostructures. Moreover, unconventional molecular scale imaging combining diverse friction force microscopy modes reveals the stacking sequence of the piled layers. In particular, we unambiguously achieve epitaxial growth, an issue of fundamental importance in thin film strategies for the nanostructuration of more efficient organic nanodevices.

A molecular-scale portrait of domain imaging in organic surfaces.

Progress in the general understanding of structure-property relationships in organic devices requires experimental tools capable of imaging structural details, such as molecular packing or domain attributes, on ultra-thin films. An operation mode of scanning force microscopy, related to friction force microscopy (FFM) and known as transverse shear microscopy (TSM), has demonstrated the ability to reveal the orientation of crystalline domains in organic surfaces with nanometer resolution. In spite of these promising results, numerous questions remain about the physical origin of the TSM domain imaging mechanism. Taking as a benchmark a PTCDI-C8 sub-monolayer, we demonstrate experimentally and theoretically that such a mechanism is the same atomic scale stick-slip ruling FFM leading to the angular dependence of both signals. Lattice-resolved images acquired on top of differently oriented PTCDI-C8 molecular domains are crucial to permit azimuthal sampling, without the need for sample rotation. The simulations reveal that, though the surface crystallography is the direct cause of the FFM and TSM signals, the manifestation of anisotropy will largely depend on the amplitude of the surface potential corrugation as well as on the temperature. This work provides a novel nanoscale strategy for the quantitative analysis of organic thin films based on their nanotribological response.

Coming across a novel copper oxide 2D framework during the oxidation of Cu(111).

Two dimensional copper oxides obtained on Cu(111) by air-enriched argon sputtering plus annealing have been measured at room temperature by means of scanning tunneling microscopy (STM) and atomic force microscopy (AFM) under ultra-high vacuum (UHV) conditions. Depending on the oxygen content different oxide frameworks and diverse stoichiometric metal/oxide interfaces exist. In particular, we report on a novel open honeycomb structure with a large unit cell which is modeled as a two dimensional network made out of Cu3O units. This lattice coexists with other oxide structures richer in oxygen and is suggested to develop towards these denser phases by oxygen incorporation.

Microfluidic Pneumatic Cages: A Novel Approach for In-chip Crystal Trapping, Manipulation and Controlled Chemical Treatment.

The precise localization and controlled chemical treatment of structures on a surface are significant challenges for common laboratory technologies. Herein, we introduce a microfluidic-based technology, employing a double-layer microfluidic device, which can trap and localize in situ and ex situ synthesized structures on microfluidic channel surfaces. Crucially, we show how such a device can be used to conduct controlled chemical reactions onto on-chip trapped structures and we demonstrate how the synthetic pathway of a crystalline molecular material and its positioning inside a microfluidic channel can be precisely modified with this technology. This approach provides new opportunities for the controlled assembly of structures on surface and for their subsequent treatment.

Threshold-Voltage Shifts in Organic Transistors Due to Self-Assembled Monolayers at the Dielectric: Evidence for Electronic Coupling and Dipolar Effects.

The mechanisms behind the threshold-voltage shift in organic transistors due to functionalizing of the gate dielectric with self-assembled monolayers (SAMs) are still under debate. We address the mechanisms by which SAMs determine the threshold voltage, by analyzing whether the threshold voltage depends on the gate-dielectric capacitance. We have investigated transistors based on five oxide thicknesses and two SAMs with rather diverse chemical properties, using the benchmark organic semiconductor dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene. Unlike several previous studies, we have found that the dependence of the threshold voltage on the gate-dielectric capacitance is completely different for the two SAMs. In transistors with an alkyl SAM, the threshold voltage does not depend on the gate-dielectric capacitance and is determined mainly by the dipolar character of the SAM, whereas in transistors with a fluoroalkyl SAM the threshold voltages exhibit a linear dependence on the inverse of the gate-dielectric capacitance. Kelvin probe force microscopy measurements indicate this behavior is attributed to an electronic coupling between the fluoroalkyl SAM and the organic semiconductor.

Giant reversible nanoscale piezoresistance at room temperature in Sr2IrO4 thin films.

Layered iridates have been the subject of intense scrutiny on account of their unusually strong spin-orbit coupling, which opens up a narrow bandgap in a material that would otherwise be a metal. This insulating state is very sensitive to external perturbations. Here, we show that vertical compression at the nanoscale, delivered using the tip of a standard scanning probe microscope, is capable of inducing a five orders of magnitude change in the room temperature resistivity of Sr2IrO4. The extreme sensitivity of the electronic structure to anisotropic deformations opens up a new angle of interest on this material, with the giant and fully reversible perpendicular piezoresistance rendering iridates as promising materials for room temperature piezotronic devices.