Search Results (50)

A large number of the thin-film organic structures (polyimides, 2-cyclooctylarnino-5-nitropyridine, N-(4-nitrophenyl)-(L)-prolinol, 2-(n-Prolinol)-5-nitropyridine) sensitized with the different types of the nano-objects (fullerenes, carbon nanotubes, quantum dots, shungites, reduced graphene oxides) are presented, which are studied using the holographic technique under the Raman–Nath diffraction conditions. Pulsed laser irradiation testing of these materials predicts a dramatic increase of the laser-induced refractive index, which is in several orders of the magnitude greater compared to pure materials. The estimated nonlinear refraction coefficients and the cubic nonlinearities for the materials studied are close to or larger than those known for volumetric inorganic crystals. The role of the intermolecular charge transfer complex formation is considered as the essential in the refractivity increase in nano-objects-doped organics. As a new idea, the shift of charge from the intramolecular donor fragment to the intermolecular acceptors can be proposed as the development of Janus particles. The energy losses via diffraction are considered as an additional mechanism to explain the nonlinear attenuation of the laser beam. Full article

Due to the continuous miniaturization and high current-carrying demands in the field of integrated circuits, as well as the desire to save space and improve computational capabilities, there is a constant drive to reduce the size of integrated circuits. However, highly integrated circuits also bring about challenges such as high current density and excessive Joule heating, leading to a series of reliability issues caused by electromigration. Therefore, the service reliability of integrated circuits has always been a concern. Sn-based solders are widely recognized in the industry due to their availability, minimal technical issues during operation, and good compatibility with traditional solders. However, solders that are mostly Sn-based, such as SAC305 and SnZn, have a high melting point for sophisticated electronic circuits. When Bi is added, the melting point of the solder decreases but may also lead to problems related to electromigration reliability. This article reviews the general principles of electromigration in SnBi solder joints on Cu substrates with current flow, as well as the phenomena of whisker formation, voids/cracks, phase separation, and resistance increase caused by atomic migration due to electromigration. Furthermore, it explores methods to enhance the reliability of solder joint by additives including Fe, Ni, Ag, Zn, Co, RA (rare earth element), GNSs (graphene nanosheets), FNS (Fullerene) and Al₂O₃. Additionally, modifying the crystal orientation within the solder joint or introducing stress to the joint can also improve its reliability to some extent without changing the composition conditions. The corresponding mechanisms of reliability enhancement are also compared and discussed among the literature. Full article

Organic photovoltaics (OPVs) have attracted widespread attention and became an important member of clean energy. Recently, their power conversion efficiency (PCE) has surpassed 19%. As is well known, the morphology of the active layer in OPVs crucially influences the PCE. In consideration of the intricate interactions between the donor molecules and acceptor molecules, the precise control of the morphology of the active layer is extremely challenging. Hence, it is urgent to develop effective methods to fabricate the hierarchical structure of the active layer. One significant driving force for the morphological evolution of the active layer is crystallization. Therefore, regulating the crystallization kinetics is an effective strategy for morphology control. In this review, we present the kinetic strategies recently developed to highlight their significance and effectiveness in morphology control. By applying these kinetic strategies, the hierarchical structure, including phase separation, domain size, crystallinity, and molecular orientation of the active layer can be optimized in different blend systems, leading to an improved PCE of OPVs. The outcomes set the stage for future advancements in device performance. Full article

Diamond-like phases are materials with crystal lattices very similar to diamond. Recent results suggest that diamond-like phases are superhard and superstrong materials that can be used for tribological applications or as protective coatings. In this work, 14 stable diamond-like phases based on fullerenes, carbon nanotubes, and graphene layers are studied via molecular dynamics simulation. The compliance constants, Young’s modulus, and Poisson’s ratio were calculated. Deformation behavior under tension is analyzed based on two deformation modes—bond rotation and bond elongation. The results show that some of the considered phases possess very high Young’s modulus ($E\ge 1$) TPa, even higher than that of diamond. Both Young’s modulus and Poisson’s ratio exhibit mechanical anisotropy. Half of the studied phases are partial auxetics possessing negative Poisson’s ratio with a minimum value of −0.8. The obtained critical values of applied tensile strain confirmed that diamond-like phases are high-strength structures with a promising application prospect. Interestingly, the critical limit is not a fracture but a phase transformation to the short-ordered crystal lattice. Overall, our results suggest that diamond-like phases have extraordinary mechanical properties, making them good materials for protective coatings. Full article

Metal cyanide clusterfullerenes (CYCFs) are formed via the encapsulation of a single metal atom and a cyanide unit inside fullerene cages, endowing them with excellent properties in various applications. In this work, we report the synthesis, isolation, and characterizations of the first cases of thulium (Tm)-based CYCFs with the popular C₈₂ carbon cages. The structural elucidation of the two TmCN@C₈₂ isomers was achieved via diverse analytical techniques, including mass spectrometry, Vis-NIR spectroscopy, single-crystal X-ray crystallography, and cyclic voltammetry. The crystallographic analyses unambiguously confirmed the molecular structures of the two TmCN@C₈₂ isomers as TmCN@C_s(6)-C₈₂ and TmCN@C_2v(9)-C₈₂. Both TmCN clusters adopt a well-established triangular configuration, with the Tm ion located on the symmetrical plane of the carbon cages. The electronic structures of both TmCN@C₈₂ isomers adopt a Tm³⁺(CN)⁻@(C₈₂)²⁻ configuration, exhibiting characteristic spectral and electrochemical properties reminiscent of divalent endohedral metallofullerenes (EMFs). Intriguingly, unlike the divalent Tm²⁺ ion observed in the mono-metallofullerenes Tm@C_2n, a higher oxidation state of Tm³⁺ is identified in the monometallic TmCN cluster due to bonding with the cyanide anion. This result provides valuable insight into the essential role of the non-metallic endo-units in governing the oxidation state of the metal ion and the electronic behaviors of EMFs. Full article

We have developed a highly efficient computation method based on density functional theory (DFT) within a set of fully symmetrized basis functions for the C₆₀ buckyball, which possesses the icosahedral ($I_h$) point-group symmetry with 120 symmetry operations. We demonstrate that our approach is much more efficient than the conventional approach based on three-dimensional plane waves. When applied to the calculation of optical transitions, our method is more than one order of magnitude faster than the existing DFT package with a conventional plane-wave basis. This makes it very convenient for modeling optical and transport properties of quantum devices related to buckyball crystals. The method introduced here can be easily extended to other fullerene-like materials. Full article

Macrocycles have attracted significant attention from academia due to their various applications in organic field-effect transistors, organic light-emitting diodes, organic photovoltaics, and dye-sensitized solar cells. Despite the existence of reports on the application of macrocycles in organic optoelectronic devices, these reports are mainly limited to analyzing the structure–property relationship of a particular type of macrocyclic structure, and a systematic discussion on the structure–property is still lacking. Herein, we conducted a comprehensive analysis of a series of macrocycle structures to identify the key factors that affect the structure–property relationship between macrocycles and their optoelectronic device properties, including energy level structure, structural stability, film-forming property, skeleton rigidity, inherent pore structure, spatial hindrance, exclusion of perturbing end-effects, macrocycle size-dependent effects, and fullerene-like charge transport characteristics. These macrocycles exhibit thin-film and single-crystal hole mobility up to 10 and 26.8 cm² V⁻¹ s⁻¹, respectively, as well as a unique macrocyclization-induced emission enhancement property. A clear understanding of the structure–property relationship between macrocycles and optoelectronic device performance, as well as the creation of novel macrocycle structures such as organic nanogridarenes, may pave the way for high-performance organic optoelectronic devices. Full article

Acute toxicity data are a necessary component of the general analysis of gaseous environments and the prediction of the possible consequences of exposure to a chemical substance on living organisms. One of the fastest ways to obtain such information is to use gas-phase chemical sensors with sensitive layers of biological origin. Here we report an experimental study of complex loadings for classical quartz crystal microbalances arising in closely packed protein layers of ovalbumin (OVA) on the surface of polycrystalline silver, silver coated with rigid carbon fullerene C₆₀, or a soft molecular-organic crystal of copper phthalocyanine (CuPc). OVA molecules are similarly immobilized on the silver and fullerene-decorated surfaces, while the response of the OVA-CuPc layer indicates an insignificant amount of protein on the surface. A systematic study of the kinetics of the responses of these layers to saturated vapors of volatile solvents shows that the QCM resonant frequency change correlates well with the toxicity of gaseous analytes. It has been observed that saturated vapors of water, ethanol, and their mixtures are classically adsorbed with a high adsorption capacity. Benzene and isobutanol showed only a non-monotonic anti-Sauerbrey behavior, while acetone and cyclohexane had a 10-fold smaller quasi-classical response. The possibility of a gaseous analyte changing not only the QCM loading but also the mechanical behavior of the protein mass associated with the surface opens up the possibility of observing nonspecific conformational changes in proteins, which can be the cause of general cytotoxicity. This effect, combined with the native conformation of OVA in densely packed protein films, allows the use of ovalbumin in creating sensitive bio-sniffer layers for fast toxicological assays—a new class of express tests for biosafety and environmental control. Full article

Soot-containing terbium (Tb)-embedded fullerenes were prepared by evaporation of Tb₄O₇-doped graphite rods in an electric arc discharge chamber. After 1,2,4-trichlorobenzene extraction of the soot and rotary evaporation of the extract, a solid product was obtained and then dissolved into toluene by ultrasonication. Through a three-stage high-pressure liquid chromatographic (HPLC) process, Tb@C₈₂ (I, II) isomers were isolated from the toluene solution of fullerenes and metallofullerenes. With the success of the growth of cocrystals of Tb@C₈₂ (I, II) with Ni(OEP), the molecular structures of Tb@C₈₂ (I) and Tb@C₈₂ (II) were confirmed to be Tb@C_2v(9)-C₈₂ and Tb@Cs(6)-C₈₂, respectively, based on crystallographic data from X-ray single-crystal diffraction. Moreover, it was found that Tb@C₈₂ (I, II) isomers demonstrated different packing behaviors in their cocrystals with Ni(OEP). Tb@C_2v(9)-C₈₂ forms a 1:1 cocrystal with Ni(OEP), in which Tb@C_2v(9)-C₈₂ is aligned diagonally between the Ni(OEP) bilayers to form zigzag chains. In sharp contrast, Tb@Cs(6)-C₈₂ forms a 2:2 cocrystal with Ni(OEP), in which Tb@Cs(6)-C₈₂ forms a centrosymmetric dimer that is aligned linearly with Ni(OEP) pairs to form one-dimensional structures in the a–c lattice plane. In addition, the distance of a Ni atom in Ni(OEP) to the Cs(6)-C₈₂ cage is much shorter than that to the C_2v(9)-C₈₂ one, indicative of a stronger π-π interaction between Ni(OEP) and the C₈₂ carbon cage in the cocrystal of Tb@C_S(6)-C₈₂ and Ni(OEP). Density functional theory calculations reveal that the regionally selective dimerization of Tb@C_S(6)-C₈₂ is the result of a dominant unpaired spin existing on a particular C atom of the C_S(6)-C₈₂ cage. Full article

A family of tribenzocoronene derivatives bearing various substituents (3) were constructed through the Diels–Alder reaction, followed by the Scholl oxidation, where the molecular structure of 3b was determined via single crystal X-ray diffraction analysis. The effect of substitution on the optical and electrochemical property was systematically investigated, with the assistance of theoretical calculations. Moreover, the thin films of the resulting molecules 3b and 3e complexed with fullerene produced strong photocurrent response upon irradiation of white light. In addition, 3b and 3e exhibit a positive nonlinear optical response resulting from the two-photon absorption and excited state absorption processes. Full article

As a newly synthesized two-dimensional carbon material, the stability study of monolayer fullerene networks or quasi-hexagonal phase fullerenes (qhp-C₆₀) is timely desirable. We have investigated the stabilities of qhp-C₆₀, including thermal, structural, mechanical, and thermodynamic stabilities, as well as the bonding characteristics, ductility, and mechanical properties, via first-principles calculations. The results show that qhp-C₆₀ is energetically, mechanically, and thermodynamically stable. The thermodynamic stability of qhp-C₆₀ at 300 K and 600 K is verified. The bonding characteristics of qhp-C₆₀ are analyzed from the bond length, and it has sp² and sp³ hybridization. The Pugh ratio (B/G) and Poisson’s ratio (v) indicate similar ductility with graphite and graphene. We also found that qhp-C₆₀ has the lowest hardness and the anisotropy of the material. In addition, the electronic characteristics, including electron localization function (ELF), crystal orbital Hamiltonian population (COHP), and density of states (DOS) at different temperatures, are analyzed to verify the thermal stability of the material. Our results might be helpful in the material design of qhp-C₆₀-related applications. Full article

The progress of modern electronics largely depends on the possible emergence of previously unknown materials in electronic technology. The search for and combination of new materials with extraordinary properties used for the production of new small-sized electronic devices and the improvement of the properties of existing materials due to improved technology for their manufacture and processing, in general, will determine the progress of highly promising electronics. In order to solve the problematic tasks of the miniaturization of electronic components with an increase in the level of connection of integrated circuits, new forms of electronic devices are being created using nanomaterials with controlled electrophysical characteristics. One of the unique properties of fullerene structures is that they can enclose one or several atoms inside their carbon framework. Such structures are usually called endohedral fullerenes. The electronic characteristics of endohedral fullerenes significantly depend on the properties of the encapsulated atom, which makes it possible to control them by choosing the encapsulated atom required by the property. Within the framework of the density functional theory in combination with the method of the nonequilibrium Green’s functions, the features of electron transport in fullerene nanojunctions were considered, which demonstrate “core–shell” nanoobjects, the “core” of which is an alkali halide crystal—KI—and the “shell” of which is an endohedral fullerene C₁₈₀ located between the gold electrodes (in the nanogap). The values of the total energy and the stability diagram of a single-electron transistor based on endohedral fullerene (KI)@C₁₈₀ were determined. The dependence of the total energy of fullerene molecules on the charge state is presented. The ranges of the Coulomb blockade, as well as their areas associated with the central Coulomb diamond were calculated. Full article

The movement of natural gas components through a crystalline fragment of C₆₀ fullerite in a simple cubic phase is numerically investigated. The methods of classical molecular physics, the Monte Carlo and Euler approaches, and a step-by-step numerical method of a high order of accuracy are used to study the effects arising from the passage of the particles through the C₆₀ fullerite. The influence of the characteristics of incoming particles on the permeability of fullerite was analyzed using the results of the performed calculations. The application of the fast integral approach based on the smoothed spherical potential is discussed and compared with the Monte Carlo method. Full article

Endohedral metallofullerenes (EMFs) are one type of intriguing metal/carbon hybrid molecule with the molecule configuration of sphere cavity-encapsulating metal ions/metal clusters due to their unique physicochemical properties and corresponding application in the fields of biological materials, single molecule magnet materials and energy conversion materials. Although the EMF family is growing, and versatile EMFs have been successfully synthesized and confirmed using crystal structures, some expected EMF members have not been observed using the conventional fullerene separation and purify strategy. These missing EMFs raise an interesting scientific issue as to whether this is due to the difficulty in separating them from the in situ formed carbon soot. Herein, we successfully captured a long-sought dysprosium-based EMF bearing a C_2v(5)-C₈₀ cage (Dy@C_2v(5)-C₈₀) in the form of Dy@C_2v(5)-C₈₀(CH₂Ph)(Ph = −C₆H₅) from carbon soot containing versatile EMFs using simple benzyl radical functionalization and unambiguously confirmed the molecule structure using single crystal X-ray diffraction characterization. Meanwhile, the crystal structure of Dy@C_2v(5)-C₈₀(CH₂Ph) showed that a single benzyl group was grafted onto the (5,6,6)-carbon, suggesting the open-shell electronic configuration of Dy@C_2v(5)-C₈₀. The theoretical calculations unveiled that the benzyl radical addition enables the modulation of the electronic configuration of Dy@C_2v(5)-C₈₀ and the corresponding stabilization of Dy@C_2v(5)-C₈₀ in conventional organic solvents. This facile stabilization strategy via benzyl radical addition exhibits the considerable capability to capture these missing EMFs, with the benefit of enriching the endohedral fullerene family. Full article