Cristiano F. Woellner

The theoretical current-voltage dependence of a non-degenerate disordered organic material obtained with conductive atomic force microscopy

We develop a simple continuum model for the current voltage characteristics of a material as measured by the conducting atomic force microscopy, including space charge effects. We address the effect of the point contact on the magnitude of the current and on the transition voltages between the different current regimes by comparing these with the corresponding expressions obtained with planar electrodes.

Understanding molecular structure dependence of exciton diffusion in conjugated small molecules

First-principles simulations are carried out to understand molecular structure dependence of exciton diffusion in a series of small conjugated molecules arranged in a disordered, crystalline, and blend structure. Exciton diffusion length (LD), lifetime, and diffusivity in four diketopyrrolopyrrole derivatives are calculated and the results compare very well with experimental values. The correlation between exciton diffusion and molecular structure is examined in detail. In the disordered molecule structure, a longer backbone length leads to a shorter exciton lifetime and a higher exciton diffusivity, but it does not change LD substantially. Removal of the end alkyl chains or the extra branch on the side alkyl chains reduces LD. In the crystalline structure, exciton diffusion exhibits a strong anisotropy whose origin can be elucidated from the intermolecular transition density interaction point of view. In the blend structure, LD increases with the crystalline ratios, which are estimated and consistent wit...

Reformulated space-charge-limited current model and its application to disordered organic systems.

We have reformulated a traditional model used to describe the current-voltage dependence of low mobility materials sandwiched between planar electrodes by using the quasi-electrochemical potential as the fundamental variable instead of the local electric field or the local charge carrier density. This allows the material density-of-states to enter explicitly in the equations and dispenses with the need to assume a particular type of contact. The diffusion current is included and as a consequence the current-voltage dependence obtained covers, with increasing bias, the diffusion limited current, the space-charge limited current, and the injection limited current regimes. The generalized Einstein relation and the field and density dependent mobility are naturally incorporated into the formalism; these two points being of particular relevance for disordered organic semiconductors. The reformulated model can be applied to any material where the carrier density and the mobility may be written as a function of the quasi-electrochemical potential. We applied it to the textbook example of a nondegenerate, constant mobility material and showed how a single dimensionless parameter determines the form of the I(V) curve. We obtained integral expressions for the carrier density and for the mobility as a function of the quasi-electrochemical potential for a Gaussianly disordered organic material and found the general form of the I(V) curve for such materials over the full range of bias, showing how the energetic disorder alone can give rise, in the space-charge limited current regime, to an I∝V(n) dependence with an exponent n larger than 2.

Hybrid MoS2/h-BN Nanofillers As Synergic Heat Dissipation and Reinforcement Additives in Epoxy Nanocomposites

Two-dimensional (2D) nanomaterials as molybdenum disulfide (MoS2), hexagonal boron nitride (h-BN), and their hybrid (MoS2/h-BN) were employed as fillers to improve the physical properties of epoxy composites. Nanocomposites were produced in different concentrations and studied in their microstructure, mechanical and thermal properties. The hybrid 2D mixture imparted efficient reinforcement to the epoxy leading to increases of up to 95% in tensile strength, 60% in ultimate strain, and 58% in Youngs modulus. Moreover, an enhancement of 203% in thermal conductivity was achieved for the hybrid composite as compared to the pure polymer. The incorporation of MoS2/h-BN mixture nanofillers in epoxy resulted in nanocomposites with multifunctional characteristics for applications that require high mechanical and thermal performance.

Multiscale Geometric Design Principles Applied to 3D Printed Schwarzites

Schwartzites are 3D porous solids with periodic minimal surfaces having negative Gaussian curvatures and can possess unusual mechanical and electronic properties. The mechanical behavior of primitive and gyroid schwartzite structures across different length scales is investigated after these geometries are 3D printed at centimeter length scales based on molecular models. Molecular dynamics and finite elements simulations are used to gain further understanding on responses of these complex solids under compressive loads and kinetic impact experiments. The results show that these structures hold great promise as high load bearing and impact-resistant materials due to a unique layered deformation mechanism that emerges in these architectures during loading. Easily scalable techniques such as 3D printing can be used for exploring mechanical behavior of various predicted complex geometrical shapes to build innovative engineered materials with tunable properties.

Lightweight Hexagonal Boron Nitride Foam for CO2 Absorption

Weak van der Waals forces between inert hexagonal boron nitride (h-BN) nanosheets make it easy for them to slide over each other, resulting in an unstable structure in macroscopic dimensions. Creating interconnections between these inert nanosheets can remarkably enhance their mechanical properties. However, controlled design of such interconnections remains a fundamental problem for many applications of h-BN foams. In this work, a scalable in situ freeze-drying synthesis of low-density, lightweight 3D macroscopic structures made of h-BN nanosheets chemically connected by poly(vinyl alcohol) (PVA) molecules via chemical cross-link is demonstrated. Unlike pristine h-BN foam which disintegrates upon handling after freeze-drying, h-BN/PVA foams exhibit stable mechanical integrity in addition to high porosity and large surface area. Fully atomistic simulations are used to understand the interactions between h-BN nanosheets and PVA molecules. In addition, the h-BN/PVA foam is investigated as a possible CO2 absorption and as laser irradiation protection material.

Experimental and computational investigation of reduced graphene oxide nanoplatelets stabilized in poly(styrene sulfonate) sodium salt

The production of large-area interfaces and the use of scalable methods to build up designed nanostructures generating advanced functional properties are of high interest for many materials science applications. Nevertheless, large-area coverage remains a major problem even for pristine graphene, and here we present a hybrid, composite graphene-like material soluble in water that can be exploited in many areas such as energy storage, electrodes fabrication, selective membranes and biosensing. Graphene oxide (GO) was produced by the traditional Hummers’ method being further reduced in the presence of poly(styrene sulfonate) sodium salt (PSS), thus creating stable reduced graphene oxide (rGO) nanoplatelets wrapped by PSS (GPSS). Molecular dynamics simulations were carried out to further clarify the interactions between PSS molecules and rGO nanoplatelets, with calculations supported by Fourier transform infrared spectroscopy analysis. The intermolecular forces between rGO nanoplatelets and PSS lead to the formation of a hybrid material (GPSS) stabilized by van der Waals forces, allowing the fabrication of high-quality layer-by-layer (LbL) films with poly(allylamine hydrochloride) (PAH). Raman and electrical characterizations corroborated the successful modifications in the electronic structures from GO to GPSS after the chemical treatment, resulting in (PAH/GPSS) LbL films four orders of magnitude more conductive than (PAH/GO).

Mechanical and Thermal Stability of Graphyne and Graphdiyne Nanoscrolls

Graphynes and graphdiynes are carbon 2D allotrope structures presenting both sp 2 and sp hybridized atoms. These materials have been theoretically predicted but due to intrinsic difficulties in their synthesis, only recently some of these structures have been experimentally realized. Graphyne nanoscrolls are structures obtained by rolling up graphyne sheets into papyrus-like structures. In this work, we have investigated, through fully atomistic reactive molecular dynamics simulations, the dynamics of nanoscroll formation for a series of graphyne (α, β, and δ types) structures. We have also investigated their thermal stability for a temperature range of 200-1000K. Our results show that stable nanoscrolls can be formed for all structures considered here. Their stability depends on a critical value of the ratio between length and height of the graphyne sheets. Our findings also show that these structures are structurally less stable then graphene-based nanoscrolls. This can be explained by the graphyne higher structural porosity which results in a decreased pi-pi stacking interactions.

Structural transformations of carbon and boron nitride nanoscrolls at high impact collisions

The behavior of nanostructures under high strain-rate conditions has been the object of theoretical and experimental investigations in recent years. For instance, it has been shown that carbon and boron nitride nanotubes can be unzipped into nanoribbons at high-velocity impacts. However, the response of many nanostructures to high strain-rate conditions is still unknown. In this work, we have investigated the mechanical behavior of carbon (CNS) and boron nitride nanoscrolls (BNS) colliding against solid targets at high velocities, using fully atomistic reactive (ReaxFF) molecular dynamics (MD) simulations. CNS (BNS) are graphene (boron nitride) membranes rolled up into papyrus-like structures. Their open-ended topology leads to unique properties not found in their close-ended analogs, such as nanotubes. Our results show that collision products are mainly determined by impact velocities and by two orientation angles, which define the position of the scroll (i) axis and (ii) open edge relative to the target. Our MD results showed that for appropriate velocities and orientations, large-scale deformations and nanoscroll fractures could occur. We also observed unscrolling (scrolls going back to quasi-planar membranes), scroll unzipping into nanoribbons, and significant reconstruction due to breaking and/or formation of new chemical bonds. For particular edge orientations and velocities, conversion from open to close-ended topology is also possible, due to the fusion of nanoscroll walls.

Exfoliation of a non-van der Waals material from iron ore hematite

ABSTRACTWith the advent of graphene, the most studied of all two-dimensional materials, many inorganic analogues have been synthesized and are being exploited for novel applications. Several approaches have been used to obtain large-grain, high-quality materials. Naturally occurring ores, for example, are the best precursors for obtaining highly ordered and large-grain atomic layers by exfoliation. Here, we demonstrate a new two-dimensional material ‘hematene’ obtained from natural iron ore hematite (α-Fe2O3), which is isolated by means of liquid exfoliation. The two-dimensional morphology of hematene is confirmed by transmission electron microscopy. Magnetic measurements together with density functional theory calculations confirm the ferromagnetic order in hematene while its parent form exhibits antiferromagnetic order. When loaded on titania nanotube arrays, hematene exhibits enhanced visible light photocatalytic activity. Our study indicates that photogenerated electrons can be transferred from hematene to titania despite a band alignment unfavourable for charge transfer.A new non-van der Waals 2D material hematene, exfoliated from natural iron ore hematite, shows ferromagnetic ordering and enhanced photocatalytic activity.