Using the density functional theory calculations, we studied the ferroelectric, electrical and optical properties of series of bias-controllable endohedral fullerenes (TM@C28, TM= Ti-Ni). The important finding is that Cr@C28 has a large electric dipole moment and an appropriate bandgap (~1.2eV) as building blocks for ferroelectric-photovoltaic materials. By sandwiching Cr@C28 molecules between two van der Waals layers, e.g., graphene or transition metal dichalcogenides, the heterostructures may have exotic ferroelectric and photovoltaic properties with high tunability and performance.
Density-functional theory based global geometry optimization is used to scrutinize the possibility of endohedral doping of hydrogenated Si fullerenes as a route to Si nanostructures with high magnetic moments. In contrast to previous suggestions, our unbiased sampling finds the smallest Si16H16 endohedral cage generally too small to encapsulate 3d metal dopant atoms. For the next larger fullerene-like cage though, we identify perfectly symmetric MSi20H20 (M = Co, Ti, V, Cr) cage structures as ground states. These structures conserve the high spin moment of the dopant atom and therewith undersc…
In this paper, we discuss the results of our study of the synthesis of endohedral iron-fullerenes. A low energy Fe+ ion beam was irradiated to C60 thin film by using a deceleration system. Fe+-irradiated C60 thin film was analyzed by high performance liquid chromatography and laser desorption/ionization time-of-flight mass spectrometry. We investigated the performance of the deceleration system for using a Fe+ beam with low energy. In addition, we attempted to isolate the synthesized material from a Fe+-irradiated C60 thin film by high performance liquid chromatography.
Well-protected magnetization, tunable quantum states and long coherence time are desired for the use of magnetic molecules in spintronics and quantum information technologies. In this work, endohedral fullerene molecules M@C28 with different transition metal cores were explored through systematic first-principles calculations and spin dynamics analyses. Many of them have stable magnetization, giant magnetic anisotropy energy and bias-tunable structure. In particular, some of them may have coherence time up to several milliseconds for their quantum spin states at high temperature (~10K) after f…
We report the results of molecular dynamics simulations of the release of five species of noble gas atoms trapped inside a small cluster of fullerenes in the temperature range 4000K < T < 5000K. We find that larger noble gas atoms are generally released at a slower rate and that helium is released considerably more rapidly than any of the other noble gases. The differing release rates are due not only to the differences in the size and mass of a given endohedral species but also because larger trapped atoms tend to stabilize the fullerene cage against thermal fluctuations. Unlike with the case…
The model of endofullerenes M@C60 with M=Li,Na,Cs,Cu,Ag are proposed for study an effect of the nature of endoatoms upon features of the minimum energy structures. They were calculated by SCF Hartree-Fock method with ECP (Ag and Cs) and all-electronic basis sets assuming arbitrary symmetry distortion (C1 point group). All models display the off-center position for the endoatoms and the charge transfer between M and the carbon cage strongly dependent on the nature of endoatoms. Ionization potentials and atomic radii are proposed as the basic factors providing the properties of endofullerenes
Molecular Dynamics (MD) computer simulations are utilized to better understand the escape of neon from small (N=5) endohedral Ne@C60 clusters. Multiple runs at various temperatures are used to increase the reliability of our statistics. The cluster holds together until somewhere between T = 1150K and T = 1200K, where it dissociates, showing no intermediate sign of melting or fullerene disintegration. When the temperature is increased to around T = 4000K, the encapsulated neon atoms begin to leave the cluster, with the fullerene molecules still remaining intact. At temperatures near T = 4400K, …
We measure 13C and 45Sc NMR lineshapes and spin-lattice relaxation times (T1) to probe the orientational dynamics of the endohedral metallofullerene Sc3N@C80. The measurements show an activated behavior for molecular reorientations over the full temperature range with a similar behavior for the temperature dependence of the 13C and 45Sc data. Combined with spectral data from Magic Angle Spinning (MAS) NMR, the measurements can be interpreted to mean the motion of the encapsulated Sc3N molecule is independent of that of the C80 cage, although this requires the similar temperature dependence of …
A new multifunctional 2D material is theoretically predicted based on systematic ab-initio calculations and model simulations for the honeycomb lattice of endohedral fullerene W@C28 molecules. It has structural bistability, ferroelectricity, multiple magnetic phases, and excellent valley characters and can be easily functionalized by the proximity effect with magnetic isolators such as MnTiO3. Furthermore, we may also manipulate the valley Hall and spin transport properties by selectively switch a few W@C28 molecules to the metastable phase. These findings pave a new way in integrate different…
Endohedral Derivatives of the Recently Synthesized Two-Dimensional Fullerene Networks: Electronic and Optical Insights from First-Principles Calculations
Organic bulk-heterojunctions (BHJ) and solar cells containing the trimetallic nitride endohedral fullerene 1-[3-(2-ethyl)hexoxy carbonyl]propyl-1-phenyl-Lu3N@C80 (Lu3N@C80-PCBEH) show an open circuit voltage (VOC) 0.3 V higher than similar devices with [6,6]-phenyl-C[61]-butyric acid methyl ester (PC61BM). To fully exploit the potential of this acceptor molecule with respect to the power conversion efficiency (PCE) of solar cells, the short circuit current (JSC) should be improved to become competitive with the state of the art solar cells. Here, we address factors influencing the JSC in blend…
Our ability to understand and tailor metal-organic interfaces is mandatory to functionalize organic complexes for next generation electronic and spintronic devices. For magnetic data storage applications, metal-carrying organic molecules, so called single molecular magnets (SMM) are of particular interest as they yield the possibility to store information on the molecular scale. In this work, we focus on the adsorption properties of the prototypical SMM Sc3N@C80 grown in a monolayer film on the Ag(111) substrate. We provide clear evidence of a pyramidal distortion of the otherwise planar Sc3N …
Using density functional theory, we examine a nitrogen-doped anionic golden cage (NAu$_{16}^-$). For the exohedral adsorption that is more stable than the endohedral doping, the bridge and hollow sites have larger binding energies than the atop sites by ~1 eV. When the N atom is adsorbed on the cage, electrons are transferred from Au$_{16}^-$ to the N atom. The transition between the exohedral and endohedral adsorption may occur thermally through a bridge site. In the infrared active vibrational spectra, exohedral doping causes greater intensities at higher frequencies than endohedral doping.
In three out of five cases considered in our work, DFT calculations presented by Xu and Hou in their Comment give the same ground state confirmations. On the other hand, depending on the choice of the exchange-correlation functional, the geometry optimization within DFT results in different ground state confirmations for B@C60 and B60, Table I of the Comment. Therefore, the energy balance between nearest confirmations in these molecular complexes is subtle, and various methods can give different ground state structures. Consequently, the results of our method - the Hartree-Fock (HF) approach w…
Any single molecular magnets (SMM) perspective for application is as good as its magnetization stability in ambient conditions. Endohedral metallofullerenes (EMFs) provide a solid basis for promising SMMs. In this study, we investigated the behavior of functionalized EMFs on a gold surface (EMF-L-Au). Having followed the systems molecular dynamics paths, we observed that the chemically locked inner cluster inside fullerene cage will remain locked even at room temperature due to the ligand-effect. We have located multiple possible minima with different charge arrangements between EMF-L-Au fragm…
In this article, the stability of p-i-n perovskite solar cells is studied under accelerated heat lifetime conditions (60 oC ,85oC and N2 atmosphere). By using a combination of buffer layer engineering, impedance spectroscopy and other characterization techniques, we propose the interaction of the perovskite active layer with the top Al metal electrode through diffusion mechanisms as the major thermal degradation pathway for planar inverted perovskite photovoltaics (PVs) under 85oC heat conditions. We show that by using thick solution processed fullerene buffer layer the perovskite active layer…
The time dependence of device performance has been measured for photocells using blends containing the conjugated polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) with two different functionalized C60 electron acceptor molecules: commercially available [6,6]-phenyl C61 butyric acid methyl ester (PCBM) or [6,6]-phenyl C61 butyric acid octadecyl ester (PCBOD) produced in this laboratory. Performance was characterized by the short-circuit current output of the devices, with the time dependence of PCBM samples typically degrading exponentially. Variations in the charact…
For many years the faith of organic photovoltaics has been linked to the one of fullerene, since fullerene has been considered the electron-acceptor of choice in bulk heterojunctions solar cells. In the last years, the number of molecules that can be very competitive in replacing fullerene has increased significantly. In this work, we study by means of different theoretical methods five molecules that have demonstrated to work effectively as acceptors in organic heterojunctions. We discuss the comparison of simulated absorption spectra with the experimental spectra.
We present a first-principles investigation of the excited-state properties of electron acceptors in organic photovoltaics including C$_{60}$, C$_{70}$, [6,6]-phenyl-C$_{61}$-butyric-acid-methyl-ester ([C$_{60}$]PCBM), and bis-[C$_{60}$]PCBM using many-body perturbation theory within the Hedin's $G_0W_0$ approximation and an efficient Lanczos approach. Calculated vertical ionization potentials (VIP) and vertical electron affinities (VEA) of C$_{60}$ and C$_{70}$ agree very well with experimental values measured in gas phase. The density of states of all three molecules is also compared to phot…
We evaluate the performances of ab initio GW calculations for the ionization energies and HOMO-LUMO gaps of thirteen gas phase molecules of interest for organic electronic and photovoltaic applications, including the C60 fullerene, pentacene, free-base porphyrins and phtalocyanine, PTCDA, and standard monomers such as thiophene, fluorene, benzothiazole or thiadiazole. Standard G0W0 calculations, that is starting from eigenstates obtained with local or semilocal functionals, significantly improve the ionization energy and band gap as compared to density functional theory Kohn-Sham results, but …
We investigate the mechanical properties of $π$-conjugated polymeric materials composed of regioregular poly(3-hexylthiophene) (P3HT) and fullerene C$_{60}$ using coarse-grained molecular dynamics simulations. Specifically, we perform tensile simulations of P3HT:C$_{60}$ composites with varied degrees of polymerization and C$_{60}$ mass fractions to obtain their stress-strain responses. Decomposition of stress tensor into kinetic energy and virial contributions indicates that the tensile moduli of the pure P3HT samples are greatly dependent on non-bonded interactions and on bonded interactions…
We present a neutron spectroscopy based method to study quantitatively the partial miscibility and phase behaviour of an organic photovoltaic active layer made of conjugated polymer:small molecule blends, presently illustrated with the regio-random poly(3-hexylthiophene-2,5-diyl) and fullerene [6,6]-Phenyl C$_{61}$ butyric acid methyl ester (RRa-P3HT:PCBM) system. We perform both inelastic neutron scattering and quasi-elastic neutron scattering measurements to study the structural dynamics of blends of different compositions enabling us to resolve the phase behaviour. The difference of neutron…
Non-fullerene acceptors (NFAs) are excellent light harvesters, yet the origin of such high optical extinction is not well understood. In this work, we investigate the absorption strength of NFAs by building a database of time-dependent density functional theory (TDDFT) calculations of ~500 pi-conjugated molecules. The calculations are first validated by comparison with experimental measurements on liquid and solid state using common fullerene and non-fullerene acceptors. We find that the molar extinction coefficient (ε_(d,max)) shows reasonable agreement between calculation in vacuum and exper…
Multilayers of fullerenes with and without endohedral Ar units, C60 and Ar@C60, were investigated by photoemission and density functional theory. The stoichiometry and the endohedral nature of Ar is checked by x-ray photoelectron spectroscopy and x-ray photoelectron diffraction. Valence band ultraviolet photoemission spectra show a strong hybridisation of the Ar 3p valence shell with the 6T1u molecular orbital of C60. A hybridisation gap of 1.6 +/- 0.2 eV is found. This is in agreement with density functional theory (DFT) that predicts 1.47 eV, and indicates Ar@C60 to be a noble gas compound w…
In the last three decades, zero-dimensional, one-dimensional, and two-dimensional carbon nanomaterials (i.e., fullerenes, carbon nanotubes, and graphene, respectively) have attracted significant attention from the scientific community due to their unique electronic, optical, thermal, mechanical, and chemical properties. While early work showed that these properties could enable high performance in selected applications, issues surrounding structural inhomogeneity and imprecise assembly have impeded robust and reliable implementation of carbon nanomaterials in widespread technologies. However, …
Hybrid conjugated polymer/fullerene filaments based on MEH-PPV/PVP/PCBM are prepared by electrospinning, and their properties assessed by scanning electron, atomic and lateral force, tunnelling, and confocal microscopy, as well as by attenuated total reflection Fourier transform-infrared spectroscopy, photoluminescence quantum yield and spatially-resolved fluorescence. Highlighted features include ribbon-shape of the realized fibers, and the persistence of a network serving as a template for heterogeneous active layers in solar cell devices. A set of favorable characteristics is evidenced in t…
Endohedral fullerenes are perfect nanolaboratories for the study of magnetism. The substitution of a diamagnetic scandium atom in Dy2ScN@C80 with gadolinium decreases the stability of a given magnetization and demonstrates Gd to act as a single atom catalyst that accelerates the reaching of thermal equilibrium. X-ray magnetic circular dichroism at the M4,5 edges of Gd and Dy shows that the Gd magnetic moment follows the sum of the external and the dipolar magnetic field of the two Dy ions and compared to Dy2ScN@C80 a lower exchange barrier is found between the ferromagnetic and the antiferroma…
Understanding of degradation mechanisms in polymer:fullerene bulk-heterojunctions on the microscopic level aimed at improving their intrinsic stability is crucial for the breakthrough of organic photovoltaics. These materials are vulnerable to exposure to light and/or oxygen, hence they involve electronic excitations. To unambiguously probe the excited states of various multiplicities and their reactions with oxygen, we applied combined magneto-optical methods based on multifrequency (9 and 275 GHz) electron paramagnetic resonance (EPR), photoluminescence (PL), and PL-detected magnetic resonan…
Photovoltaic potential of tin perovskites revealed through layer-by-layer investigation of optoelectronic and charge transport properties
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH（亥姆霍兹柏林材料与能源有限公司）；Egyptian Petroleum Research Institute（埃及石油研究所）；IPVF, Institut Photovoltaïque d'Ile-de-France（法兰西岛光伏研究所）；University of Naples Federico II（那不勒斯费德里科二世大学）；Henan University（河南大学）；University of the Basque Country UPV/EHU（巴斯克国立大学）；Bielefeld University（比勒费尔德大学）
