arXiv subjects

Graziâni Candiotto

Publications and source records attributed to Graziâni Candiotto.

14 recordsLinked to original sources

arXiv2024

TMM$-$Sim: A Versatile Tool for Optical Simulation of Thin$-$Film Solar Cells

The Transfer Matrix Method (TMM) has become a prominent tool for the optical simulation of thin$-$film solar cells, particularly among researchers specializing in organic semiconductors and perovskite materials. As the commercial viability of these solar cells continues to advance, driven by rapid developments in materials and production processes, the importance of optical simulation has grown significantly. By leveraging optical simulation, researchers can gain profound insights into photovoltaic phenomena, empowering the implementation of device optimization strategies to achieve enhanced performance. However, existing TMM$-$based packages exhibit limitations, such as requiring programming expertise, licensing fees, or lack of support for bilayer device simulation. In response to these gaps and challenges, we present the TMM Simulator (TMM$-$Sim), an intuitive and user$-$friendly tool to calculate essential photovoltaic parameters, including the optical electric field profile, exciton generation profile, fraction of light absorbed per layer, photocurrent, external quantum efficiency, internal quantum efficiency, and parasitic losses. An additional advantage of TMM$-$Sim lies in its capacity to generate outcomes suitable as input parameters for electro$-$optical device simulations. In this work, we offer a comprehensive guide, outlining a step$-$by$-$step process to use TMM$-$Sim, and provide a thorough analysis of the results. TMM$-$Sim is freely available, accessible through our web server (nanocalc.org), or downloadable from the TMM$-$Sim repository (for \textit{Unix}, \textit{Windows}, and \textit{macOS}) on \textit{GitHub}. With its user$-$friendly interface and powerful capabilities, TMM$-$Sim aims to facilitate and accelerate research in thin$-$film solar cells, fostering advancements in renewable energy technologies.

cond-mat.mtrl-sci↗

arXiv2024

RI$-$Calc: A User Friendly Software and Web Server for Refractive Index Calculation

The refractive index of an optical medium is essential for studying a variety of physical phenomena. One useful method for determining the refractive index of scalar materials (i.e, materials which are characterized by a scalar dielectric function) is to employ the Kramers-Kronig (K-K) relations. The K-K method is particularly useful in cases where ellipsometric measurements are unavailable, a situation that frequently occurs in many laboratories. Although some packages can perform this calculation, they usually lack a graphical interface and are complex to implement and use. Those deficiencies inhibits their utilization by a plethora of researchers unfamiliar with programming languages. To address the aforementioned gap, we have developed the Refractive Index Calculator (RI-Calc) program that provides an intuitive and user-friendly interface. The RI-Calc program allows users to input the absorption coefficient spectrum and then easily calculate the complex refractive index and the complex relative permittivity of a broad range of thin films, including of molecules, polymers, blends, and perovskites. The program has been thoroughly tested, taking into account the Lorentz oscillator model and experimental data from a materials' refractive index database, demonstrating consistent outcomes. It is compatible with Windows, Unix, and macOS operating systems. You can download the RI-Calc binaries from our GitHub repository or conveniently access the program through our dedicated web server at nanocalc.org.

cond-mat.mtrl-sci↗

arXiv2024

Synthesis of Polyglobalide by Enzymatic Ring Opening Polymerization Using Pressurized Fluids

Here, the synthesis of polyglobalide (PGl) by enzymatic ring-opening polymerization (e-ROP) is investigated, using pressurized carbon dioxide (CO2), pressurized CO2 + dichloromethane (DCM), and pressurized propane as solvents. Particularly, the effects of phase equilibrium on the course of e-ROP and PGl final properties are discussed. The partition coefficients of CO2, DCM, propane, globalide and PGl were calculated with help of thermodynamic models, providing proper understanding of monomer partitioning in the reaction system. Reactions performed in pure CO2 resulted in monomer conversions of 100%. Besides, when only one liquid phase was present inside the reactor, PGl samples presented low polydispersities and high average molecular weights. When carried out in CO2 + DCM, e-ROP resulted in lower monomer conversions and PGl samples with higher polydispersities and lower average molecular weights. Finally, reactions carried out in pressurized propane (200 bar) produced PGl samples with the highest average molecular weights among the analyzed products.

physics.chem-ph↗

arXiv2024

In vitro degradation and cytotoxicity response of biobased nanoparticle prepared by thiol-ene polymerization in miniemulsion

Biodegradability is a key feature for the application of polymeric devices in medicine. This study reports an experimental and theoretical study of the degradation of poly(thioether-ester) (PTEe) nanoparticles in aqueous media. The $α$,$ω$-diene diester derived from vegetable oil, 1,3-propylene diundeca-10-polenoate (Pd10e) was used as monomer in the solvent-free synthesis of Pd10e-based nanoparticles (A-PTEe nanoparticles) via thiol-ene miniemulsion polymerization. The theoretical partition coefficients of A-PTEe and a PTEe based on dianhydro-D-glucityl diundec-10-enoate (DGU) (B-PTEe nanoparticles) were calculated using density functional theory (DFT), in order to compare their degradation behavior. The results showed that A-PTEe is more hydrophilic than B-PTEe, thus indicating the possible faster degradation of the former. The experimental degradation studies showed that, in fact, A-PTEe nanoparticles are faster degraded than B-PTEe, presenting substantial molecular weight decrease, which confirms the theoretical results. The effects of degradation could be observed in the chemical composition and thermal properties of the polymer. Considering its applicability potential as a biomaterial due to its fast degradation behavior, the cytotoxicity of A-PTEe nanoparticles and its degradation products were evaluated. In vitro assays confirmed the biocompatibility of A-PTEe nanoparticles and its degradation products when exposed on fibroblasts and red blood cells. These results suggest A-PTEe nanoparticles can be promising candidates as biobased nanocarriers for biomedical applications.

physics.chem-ph↗

arXiv2024

Controlling the biodegradation rates of poly(globalide-co-ε-caprolactone) copolymers by post polymerization modification

Controlling the degradation rates of polymers is crucial for their application in tissue engineering or to achieve degradation of the polymers in the wastewater purification. As hydrophobic polyesters often exhibit very slow degradation rates, we report here increased biodegradation rates of poly(globalide-co-ε-caprolactone) copolymers (PGlCL) produced by enzymatic ring-opening copolymerization and post-functionalized with N-acetylcysteine by thiol-ene reaction. The degradation rates of the PGlCL and post-modified PGlCL-NAC films were determined by weight-loss experiments. The polymer films were immersed in phosphate-buffered saline (PBS) solution, and PBS containing lipase from Pseudomonas cepacia. The degree of functionalization affected the degradation behavior, and samples with a higher degree of functionalization presented higher weight loss. Finally, a degradation assay was performed in activated sludge, and PGlCL-NAC presented high degradability, having a degradation behavior similar to starch. Density Functional Theory (DFT) calculations were used to assess the changes in chemical properties and electronic charge distribution of PGlCL after its functionalization with NAC, helping to understand its influence in their degradability. The results obtained confirm the possibility to increase the degradation rates of copolyesters based on caprolactone and globalide by thiol-ene post-functionalization, being a promising alternative for applications in biomedicine or the packaging sector.

physics.chem-ph↗

arXiv2024

Exploring the Electronic Potential of Effective Tight$-$Binding Hamiltonians

The linear combination of atomic orbitals (LCAO) is a standard method for studying solids and molecules, it is also known as the tight$-$binding (TB) method. In most of the implementations only the basis set and the coupling constants are provided, without the explicit definition of kinetic and potential energy operators. The tight$-$binding scheme is, nonetheless, capable of providing an accurate description of properties such as the electronic bands and elastic constants for many materials. However, for some applications, the knowledge of the underlying electronic potential associated with the tight$-$binding hamiltonian might be important to guarantee that the actual physics is preserved by the semiempirical scheme. In this work the electronic potentials that arise from the use of tight$-$binding effective hamiltonians it is explored. The formalism is applied to the extended Hückel tight$-$binding (EHTB) hamiltonian, which is a two$-$center Slater$-$Koster approach that makes explicit use of the overlap matrix.

cond-mat.mtrl-sci↗

arXiv2023

Strain, Anharmonicity and Finite-Size Effects on the Vibrational Properties of Linear Carbon Chains

Linear carbon chains (LCCs) are the ultimate 1D molecular system and they show unique mechanical, optical and electronic properties that can be tuned by altering the number of carbon atoms, strain, encapsulation, and other external parameters. In this work, we probe the effects of quantum anharmonicity, strain and finite size on the structural and vibrational properties of these chains, using high$-$level density functional theory (DFT) calculations. We find strong anharmonicity effects for infinite chains, leading to ground$-$state nuclear wavefunctions that are barely localized at each of the dimerized geometries, i.e. strong tunneling occurs between the two minima of the potential energy surface. This effect is enhanced for compressive strains. In addition, vibrational C$-$band frequencies deviate substantially from experimental measurements in long chains encapsulated in carbon nanotubes. On the other hand, calculations for finite chains suggest that quantum anharmonicity effects are strongly suppressed in finite system, even in the extrapolation to the infinite case. For finite systems, vibrational C$-$band frequencies agree well with experimental values at zero pressure. However, these frequencies increase under compressive strain, in contradiction with recent results. This contradiction is not resolved by adding explicitly the encapsulating carbon nanotubes to our calculations. Our results indicate that LCCs embody an intriguing 1D system in which the behavior of very large finite systems do not reproduce or converge to the behavior of truly infinite ones.

cond-mat.mtrl-sci↗

arXiv2023

Reorganization energy from charge transport measurements in a monolithically$-$integrated molecular device

Intermolecular charge transfer reactions are key processes in physical chemistry. The electron-transfer rates depend on a few system's parameters, such as temperature, electromagnetic field, distance between adsorbates and, especially, the molecular reorganization energy. This microscopic greatness is the energetic cost to rearrange each single$-$molecule and its surrounding environment when a charge is transferred. Reorganization energies are measured by electrochemistry and spectroscopy techniques as well as at the single-molecule limit using atomic force microscopy approaches, but not from temperature$-$dependent charge transport measurements nor in a monolithically$-$integrated molecular device. Nowadays self$-$rolling nanomembrane (rNM) devices, with strain$-$engineered mechanical properties, on$-$a$-$chip monolithic integration, and operable in distinct environments, overcome those challenges. Here, we investigate the charge transfer reactions occurring within a ca. 6 nm thick copper$-$phthalocyanine (CuPc) film employed as electrode-spacer in a monolithically integrated nanocapacitor. Employing the rNM technology allows us to measure the molecules' charge$-$transport dependence on temperature for different electric fields. Thereby, the CuPc reorganization energy is determined as (930 $\pm$ 40) meV, whereas density functional theory (DFT) calculations support our findings with the atomistic picture of the CuPc charge transfer reaction. Our approach presents a consistent route towards electron transfer reaction characterization using current$-$voltage spectroscopy and provides insight into the role of the molecular reorganization energy when it comes to electrochemical nanodevices.

cond-mat.mtrl-sci↗

arXiv2023

Improved Performance of Organic Light-Emitting Transistors Enabled by Polyurethane Gate Dielectric

Organic light-emitting transistors (OLETs) are multifunctional optoelectronic devices that combine in a single structure the advantages of organic light emitting diodes (OLEDs) and organic field-effect transistors (OFETs). However, low charge mobility and high threshold voltage are critical hurdles to practical OLETs implementation. This work reports on the improvements obtained by using polyurethane films as dielectric layer material in place of the standard poly(methylmethacrylate) (PMMA) in OLET devices. It was found that polyurethane drastically reduces the number of traps in the device thereby improving electrical and optoelectronic device parameters. In addition, a model was developed to rationalize an anomalous behavior at the pinch-off voltage. Our findings represent a step forward to overcome the limiting factors of OLETs that prevent their use in commercial electronics by providing a simple route for low-bias device operation.

cond-mat.mtrl-sci↗

arXiv2023

FRET$-$Calc: A Free Software and Web Server for Förster Resonance Energy Transfer Calculation

Förster Resonance Energy Transfer Calculator (FRET$-$Calc) is a program and web server that analyzes molar extinction coefficient of the acceptor, emission spectrum of the donor, and the refractive index spectrum of the donor/acceptor blend. Its main function is to obtain important parameters of the FRET process from experimental data, such as: (i) effective refractive index, (ii) overlap integral, (iii) Förster radius, (iii) FRET efficiency and (iv) FRET rate. FRET$-$Calc is license free software that can be run via dedicated web server (nanocalc.org) or downloading the program executables (for Unix, Windows, and macOS) from the FRET$-$Calc repository on GitHub. The program features a user$-$friendly interface, making it suitable for materials research and teaching purposes. In addition, the program is optimized to run on normal computers and is lightweight. An example will be given with the step by step of its use and results obtained.

cond-mat.mtrl-sci↗

arXiv2023

PLQ-Sim: A Computational Tool for Simulating Photoluminescence Quenching Dynamics in Organic Donor/Acceptor Blends

Photoluminescence Quenching Simulator (PLQ-Sim) is a user-friendly software to study the photoexcited state dynamics at the interface between two organic semiconductors forming a blend: an electron donor (D), and an electron acceptor (A). Its main function is to provide substantial information on the photophysical processes relevant to organic photovoltaic and photothermal devices, such as charge transfer state formation and subsequent free charge generation or exciton recombination. From input parameters provided by the user, the program calculates the transfer rates of the D/A blend and employs a kinetic model that provides the photoluminescence quenching efficiency for initial excitation in the donor or acceptor. When calculating the rates, the user can choose to use disorder parameters to better describe the system. In addition, the program was developed to address energy transfer phenomena that are commonly present in organic blends. The time evolution of state populations is also calculated providing relevant information for the user. In this article, we present the theory behind the kinetic model, along with suggestions for methods to obtain the input parameters. A detailed demonstration of the program, its applicability, and an analysis of the outputs are also presented. PLQ-Sim is license free software that can be run via dedicated webserver nanocalc.org or downloading the program executables (for Unix, Windows, and macOS) from the PLQ-Sim repository on GitHub.

cond-mat.mtrl-sci↗

arXiv2023

Emission Redshift in DCM2-Doped Alq$_{3}$ Caused by Non-Linear Stark Shifts and Förster-Mediated Exciton Diffusion

Organic light-emitting diodes (OLEDs) devices in the archetype small molecule fluorescent guest-host system tris(8-hydroxyquinolinato) aluminum (Alq$_{3}$) doped with 4-(dicyanomethylene)-2-methyl-6-julolidyl-9-enyl-4H-pyran (DCM2) displays a redshift in light-emission frequency which is extremely sensitive to the dopant concentration. This effect can be used to tune the emission frequency in this particular class of OLEDs. In this work, a model is proposed to describe this effect using a combination of density functional theory (DFT) quantum-chemical calculations and stochastic simulations of exciton diffusion via a Förster mechanism. The results show that the permanent dipole moments of the Alq$_{3}$ molecules generate random electric fields that are large enough to cause a non-linear Stark shift in the band gap of neighboring DCM2 molecules. As a consequence of these non-linear shifts, a non-Gaussian probability distribution of highest-occupied molecular orbital to lowest-unoccupied molecular orbital (HOMO-LUMO) gaps for the DCM2 molecules in the Alq$_{3}$ matrix is observed, with long exponential tails to the low-energy side. Surprisingly, this probability distribution of DCM2 HOMO-LUMO gaps is virtually independent of DCM2 concentration into Alq$_{3}$ matrix, at least up to a fraction of 10%. This study shows that this distribution of gaps, combined with out-of-equilibrium exciton diffusion among DCM2 molecules, are sufficient to explain the experimentally observed emission redshift.

cond-mat.mtrl-sci↗

arXiv2023

Patterning edge-like defects and tuning defective areas on the basal plane of ultra-large MoS$_{2}$ monolayers toward hydrogen evolution reaction

The catalytic sites of MoS$_{2}$ monolayers towards hydrogen evolution are well known to be vacancies and edge-like defects. However, it is still very challenging to control the position, size, and defective areas on the basal plane of Mo$S_{2}$ monolayers by most of defect-engineering routes. In this work, the fabrication of etched arrays on ultra-large supported and free-standing MoS$_{2}$ monolayers using focused ion beam (FIB) is reported for the first time. By tuning the Ga+ ion dose, it is possible to confine defects near the etched edges or spread them over ultra-large areas on the basal plane. The electrocatalytic activity of the arrays toward hydrogen evolution reaction (HER) was measured by fabricating microelectrodes using a new method that preserves the catalytic sites. We demonstrate that the overpotential can be decreased up to 290 mV by assessing electrochemical activity only at the basal plane. High-resolution transmission electron microscopy images obtained on FIB patterned freestanding MoS$_{2}$ monolayers reveal the presence of amorphous regions and X-ray photoelectron spectroscopy indicates sulfur excess in these regions. Density-functional theory calculations provide identification of catalytic defect sites. Our results demonstrate a new rational control of amorphous-crystalline surface boundaries and future insight for defect optimization in MoS$_{2}$ monolayers.

cond-mat.mtrl-sci↗

arXiv2023

Enhancing Chemical Stability and Photovoltaic Properties of Highly Efficient Nonfullerene Acceptors by Chalcogen Substitution: Insights from Quantum Chemical Calculations

The chemical stability of nonfullerene acceptor (NFA) is the Achilles' heel of the research on state-of-the-art organic solar cells (OSC). The fragility of the NFA is essentially due to the weak bond that links the central donor core of the molecules with their acceptor moieties at the edges. Here we proposed the replacement of thiophene at the outer-core position of traditional NFAs for tellurophene, a hitherto unexplored modification. Since tellurium is a distinctive element among chalcogens, the basic features of Te compounds cannot be deduced straightforwardly from the properties of their lighter analogues, S and Se. The modeled Te-based NFAs presented interesting features like stronger intra- and intermolecular interactions induced by a distinctive secondary bond effect between the end acceptor moiety and the outer chalcogen atom. This design strategy resulted in stiffer molecules with red-shifted absorption spectra and less susceptible to degradation verified through stress tests and vibrational spectra analysis. Besides that, a weakened exciton binding energy has been found, opening the possibility of blends with a lower driving force. Our results shed light on several aspects of selenation and telluration of traditional NFAs, providing valuable insights into the possible consequences for OSCs applications.

cond-mat.mtrl-sci↗