Solid C60 Research Articles

Decomposition of solid C60–indene adducts by retro Diels Alder reaction – A kinetic and thermodynamic study

Diels-Alder cycloaddition is a common synthetic approach to functionalize fullerenes. However, the stability of such fullerene adducts is hampered by the existence of the Retro Diels-Alder (RDA) reaction. Herein, the RDA reactions in the solid phase of the mono and bisadducts of C60 with indene, IC60MA and IC60BA, were studied by differential scanning calorimetry and thermogravimetric analysis. The RDA reaction in solid IC60MA occurs at a higher temperature than in IC60BA. IC60MA decomposition follows a first-order rate law and in IC60BA it is described by two consecutive first-order reaction steps. The decomposition of both adducts yields a metastable C60 solid. The higher decomposition temperature of IC60MA is due to higher activation energy, Ea, and lower pre-exponential factor, A. The values of Ea for the RDA reactions differ due to crystal packing efficiency in the solids. The measured A values were found to reflect the statistical weight of C60–Indene bonds that can be broken. A reaction mechanism was proposed for the decomposition of the fullerene adducts. The enthalpies of sublimation of IC60MA and IC60BA were estimated based on the enthalpies of their respective RDA reactions. Additionally, the heat capacities of the solid fullerenes (C60, IC60MA, and IC60BA), at T = 298.15 K, were measured by high-precision heat capacity drop calorimetry, indicating that the rotational motion of C60 in the crystal increases its expected heat capacity.

On the nature of the Schottky anomaly in endohedral water.

In this work, we study the heat capacity contribution of a rigid water molecule encapsulated in C60 by performing six-dimensional eigenstate calculations with the inclusion of its quantized rotational and translational degrees of freedom. Two confinement model potentials are considered: in the first, confinement is described using distributed pairwise Lennard-Jones interactions, while in the second, the water molecule is trapped within an eccentric but isotropic 3D harmonic effective confinement potential [Wespiser et al., J. Chem. Phys. 156, 074304 (2022)]. Contributions to the heat capacity from both the ortho and para nuclear spin isomers of water are considered to enable the effects of their interconversion to be assessed. By including a symmetry-breaking quadrupolar potential energy term in the Hamiltonian, we can reproduce the experimentally observed Schottky anomaly at ∼2K [Suzuki et al., J. Phys. Chem. Lett. 10, 1306 (2019)]. Furthermore, our calculations predict a second Schottky anomaly at ∼0.1K resulting from the H configuration, a different orientational arrangement of the fullerene cages in crystalline solid C60. Contributions from the H configuration to CV also explain the second peak observed at ∼7K in the experimentally measured heat capacity.

Theoretical High Pressure Study of Phonon Density of State and Debye Temperature of Solid C60: Grüneisen Approximation Approach

A nanomaterial equation of state has been combined with Grüneisen approximation in present work to investigate the influence of high pressure on phonon density of state function of C60 through evaluating variations of lattice vibration frequencies and variation of mode density. Furthermore, the effect of high pressure on Debye temperature has been determined by using a formula of volume dependence of Debye temperature. Volume compression ratio in C60 has been computed, using a nanomaterial equation of state. Expressions of pressure dependence of phonon density of state and Debye temperature have been combined with volume compression ratio value. The evaluated result of volume compression ratio and phonon density of state have been compared with the experimental observations and good agreement can be seen.

Excitonic effects on the linear and nonlinear optical properties of solid C60 fullerene, insights from many-body first-principles calculations

We perform the many-body Bethe-Salpeter equation eigenstates based sum-over-states calculations for the linear and nonlinear optical properties of solid C60 fullerene. Excitonic and local field effects are included in the calculations. We calculate the one-photon absorption (OPA), third harmonic generation (THG), degenerate four-wave mixing (DFWM), and electric-field-induced second harmonic generation (ESHG) spectra of solid C60 fullerene. The overall agreement between the theoretical and experimental results is good for all calculated spectra. The OPA spectrum shows that the solid C60 fullerene has a large excitonic binding energy of 0.35 eV. The position and intensity of spectral peaks are modified significantly. By tracing the sum-over-states progress, we determine the type of nonlinear polarization resonances for the characteristic peaks of the THG process, which may clear up a discrepancy in two experimental results. The calculated DFWM spectrum is in excellent agreement with the available experimental results in terms of line shape and peak positions, and thus the two-photon absorption peaks can be well understood on the basis of the excitonic states of solid C60 fullerene. The dynamic ESHG spectrum is given as a reference for the future experiment.

Fullerite C60 optical constants in the C 1s NEXAFS region

Using data on the absorption cross sections the refraction coefficient spectral dependence n(E) and the spectra of the remaining optical coefficients (reflection coefficient, phase shift, and atomic form factor) in the fullerite C60 C 1s near edge X-ray absorption fine structure (NEXAFS) region (280–350 eV) were determined. For the n(E) calculations the Kramers-Kronig integral relations (KKRs) were used. The KKR computations were performed using data on atomic carbon absorption cross sections in the 10–30000 eV range and on solid and gaseous C60 – in the 0–120 eV. Absorption cross section spectrum in the fullerite C60 C 1s NEXAFS region were measured.

Excitonic Effects on the Linear and Nonlinear Optical Properties of Solid C60 Fullerene, Insights from Many-Body First-Principles Calculations

We perform the many-body Bethe-Salpeter equation eigenstates based sum-over-states calculations for the linear and nonlinear optical properties of solid C 60 fullerene. Excitonic and local field effects are included in the calculations. We calculate the one-photon absorption (OPA), third harmonic generation (THG), degenerate four-wave mixing (DFWM), and electric-field-induced second harmonic generation (ESHG) spectra of solid C 60 fullerene. The overall agreement between the theoretical and experimental results is good for all calculated spectra. The OPA spectrum shows that the solid C 60 fullerene has a large excitonic binding energy of 0.35 eV. The position and intensity of spectral peaks are modified significantly. By tracing the sum-over-states progress, we determine the type of nonlinear polarization resonances for the characteristic peaks of the THG process, which may clear up a discrepancy in two experimental results. The calculated DFWM spectrum is in excellent agreement with the available experimental results in terms of line shape and peak positions, and thus the two-photon absorption peaks can be well understood on the basis of the excitonic states of solid C 60 fullerene. The dynamic ESHG spectrum is given as a reference for the future experiment.

C60 self-orientation on hexagonal boron nitride induced by intermolecular coupling

A deep grasp of the properties of the interface between organic molecules and hexagonal boron nitride (h-BN) is essential for the full implementation of these two building blocks in the next generation of electronic devices. Here, using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS), we report on the geometric and electronic features of C60 evaporated on a single layer of h-BN grown on a Rh(110) surface under ultra-high vacuum. Two different molecular assemblies of C60 on the h-BN/Rh(110) surface were observed. The first STM study at room temperature (RT) and at low temperatures (40 K) looked at the molecular orientation of C60 on a two-dimensional layered material. Intramolecular-resolution images demonstrate the existence of a phase transition of C60 over the h-BN/Rh(110) surface similar to that found on bulk solid C60. At RT molecules exhibit random orientations, while at 40 K such rotational disorder vanishes and they adopt a common orientation over the h-BN/Rh(110) surface. The decrease in thermal energy allows recognition between C60 molecules, and they become equally oriented in the configuration at which the van der Waals intermolecular interactions are optimized. Bias-dependent submolecular features obtained by means of high-resolution STM images are interpreted as the highest occupied and lowest unoccupied molecular orbitals. STS data showed that fullerenes are electronically decoupled from the substrate, with a negligible charge transfer effect if any. Finally, the very early stages of multilayer growth were also investigated.

The Study of the Optical Properties of C60 Fullerene in Different Organic Solvents

AbstractC60 fullerene exhibits unique optical properties that have high potential for wide photo-optical applications. To analyze the optical properties of C60, its excitation and emission properties were studied using UV-Vis absorption and photoluminescence (PL) spectroscopy, which were performed in various, non-polar organic solvents such as toluene, xylene, and trichloroethylene (TCE). The C60 solutions in toluene, xylene, and TCE displayed similar excitation bands at 625, 591, 570, 535, and 404 nm corresponding to Ag → T1u and Ag → T1g transitions. However, these bands differed from the solid C60 observed by UV-Vis diffuse reflectance spectroscopy. The two emission band energies of C 60 solution in toluene and xylene were nearly the same (1.78 and 1.69 eV), whereas the C60 solution in TCE was shifted to 1.72 and 1.65 eV. Because the polarity of TCE is higher than that of toluene and xylene, the PL spectrum of the C 60 solution in TCE was red-shifted. The PL spectroscopy had a better capability than UV-Vis absorbance spectroscopy to distinguish the different interactions between C60 and the organic solvents due to their different solvent polarities.

Influence of the aggregate state on band structure and optical properties of C60 computed with different methods.

C60 and C60 based molecules are efficient acceptors and electron transport layers for planar perovskite solar cells. While properties of these molecules are well studied by ab initio methods, those of solid C60, specifically its optical absorption properties, are not. We present a combined density functional theory-Density Functional Tight Binding (DFTB) study of the effect of solid state packing on the band structure and optical absorption of C60. The valence and conduction band edge energies of solid C60 differ on the order of 0.1 eV from single molecule frontier orbital energies. We show that calculations of optical properties using linear response time dependent-DFT(B) or the imaginary part of the dielectric constant (dipole approximation) can result in unrealistically large redshifts in the presence of intermolecular interactions compared to available experimental data. We show that optical spectra computed from the frequency-dependent real polarizability can better reproduce the effect of C60 aggregation on optical absorption, specifically with a generalized gradient approximation functional, and may be more suited to study effects of molecular aggregation.

Intermolecular bonding in C70 at high pressure and temperature

Near-infrared (NIR) Raman spectroscopy has been used to analyze intermolecular bonding in solid C70, treated for 2 h under pressures in the range 0.8–2 GPa at temperatures between 350 and 600 K. The spectra obtained are analyzed in detail with the aim of finding spectral lines characteristic for the monomer C70, the dimer C140, and possibly for higher oligomers. In agreement with earlier studies, several new modes are observed in the NIR Raman spectra, in sharp contrast to what is found in Raman studies using visible light excitation. From the relative intensities of the characteristic dimer stretch line at 88 cm−1 and a mode at 457 cm−1, characteristic for the monomer, a semi-quantitative estimate for the dimer fraction in the material can be found as a function of pressure and temperature. From these results a reaction map, similar to that recently derived for C60, can be drawn. The data obtained indicate that C70 is almost completely polymerized into large, random oligomers (or polymers) after long-time treatment at elevated temperatures (>500 K) and pressures (>1.2 GPa). The phase diagram of C70 is updated and briefly discussed in the light of this and other recent high pressure studies.

Computational modelling and simulation of polycrystalline coherent inelastic neutron scattering

Inelastic neutron scattering is an experimental technique widely used to investigate the vibrational characteristics of materials in condensed matter research. While coherent inelastic neutron scattering is typically restricted to single-crystal samples, analysis of the complex datasets obtained on polycrystalline samples remains challenging, even for the simplest of structures. However, given the common availability of high performance computing platforms, it is becoming feasible to apply computationally intensive calculation methods that sample millions of q-points to the simulation of polycrystalline models of increasing complexity, a technique referred to as poly-CINS analysis. This approach allows the interpretation of experimental results by comparison and fitting against theoretical models. This paper describes a new high-performance implementation of the Scatter code, a modelling package developed for the General Utility Lattice Program (Gulp) for heterogenous CPU-GPU computing architectures. It provides the ability to generate theoretical poly-CINS data sets from semi-empirical and ab-initio models. We present the computational framework behind its implementation, applying an example of a semi-empirical model for the dynamics of a large unit-cell system, namely the two (low and ambient temperature) phases of solid C60 to illustrate the methodology and its scalability characteristics.

Quantitative first-principles calculations of valence and core excitation spectra of solid C60.

We present calculated valence and C 1s near-edge excitation spectra of solid C60 and experimental results measured with high-resolution electron energy-loss spectroscopy. The near-edge calculations are carried out using three different methods: solution of the Bethe-Salpeter equation (BSE) as implemented in the OCEAN suite (Obtaining Core Excitations with ab initio methods and the NIST BSE solver), the excited-electron core-hole approach (XCH), and the constrained-occupancy method using the Stockholm-Berlin core-excitation code, StoBe. The three methods give similar results and are in good agreement with experiment, though the BSE results are the most accurate. The BSE formalism is also used to carry out valence level calculations using the NIST Bethe-Salpeter Equation solver (NBSE). Theoretical results include self-energy corrections to the band gap and band widths, lifetime-damping effects, and Debye-Waller effects in the core-excitation case. A comparison of spectral features to those observed experimentally illustrates the sensitivity of certain features to computational details, such as self-energy corrections to the band structure and core-hole screening.

Incubation of solid state C60 fullerene under UV irradiation mimicking environmentally relevant conditions

Carbon-based nanomaterials, such as C60 fullerenes, are expected to accumulate in soil due to direct release and deposition from the atmosphere. However, little is known about the environmental fate of these nanoparticles which may be susceptible to photochemical and microbial degradation. In the present work, C60 was incubated for a period of 28 days and irradiated with UVA light. Three experiments were carried out where the fullerenes were either spiked onto a glass surface or added to quartz sand or sandy soil samples. At specific time intervals the samples were extracted and analysed by liquid chromatography coupled to UV or high resolution mass spectrometric (HRMS) detection. The fullerenes were degraded in all the treatments and the decay followed a pseudo-first-order rate law. In absence of a solid matrix, the half-life (t1⁄2) of the C60 was 13.1 days, with an overall degradation of 45.1% that was accompanied by the formation of functionalized C60-like structures. Furthermore, mass spectrometric analysis highlighted the presence of a large number of transformation products that were not directly related to the irradiation and presented opened cage and oxidized structures. When C60 was spiked into solid matrices the degradation occurred at a faster rate (t1⁄2 of 4.5 and 0.8 days for quartz sand and sandy soil, respectively). Minor but consistent losses were found in the non-irradiated samples, presumably due to biotic or chemical processes occurring in these samples. The results of this study suggest that light-mediated transformation of the fullerenes will occur in the environment.

Submolecular Electroluminescence Mapping of Organic Semiconductors.

The electroluminescence of organic films is the central aspect in organic light emitting diodes (OLEDs) and widely used in current display technology. However, its spatial variation on the molecular scale is essentially unexplored. Here, we address this issue by using scanning tunneling microscopy (STM) and present an in-depth study of the electroluminescence from thin C60 films (<10 monolayers) on Ag(111) and Au(111) surfaces. Similar to an OLED, the metal substrate and STM tip inject complementary charge carriers that may recombine within the molecular film; however, the atomically defined charge injection by the tip enables mapping of the local electroluminescence down to the submolecular scale. We show that the radiative recombination in solid C60 is restricted to various structural defects, whose emission characteristics can be addressed individually. The emission fine structure reveals a coupling to Jahn-Teller active vibrational modes of C60, which implies that its parity-forbidden lowest singlet transition becomes locally allowed at the emission centers. At lateral distances of a few nanometers, only a weak emission from tip-induced plasmons is detectable. Their excitation evidences the injection of both charge carrier types and confirms that they are unable to recombine radiatively at positions far from structural defects. Finally, we demonstrate that the molecular orbital pattern visible in electroluminescence maps enables an unambiguous discrimination between the intrinsic radiative recombination of electron-hole pairs in the organic film and the technique-related emission of tip-induced plasmons. This capability is essential to consolidate STM as a tool to explore the light generation from organic films on the nanoscale.

Explaining the symmetry breaking observed in the endofullerenes H2@C60, HF@C60, and H2O@C60.

Symmetry breaking has been recently observed in the endofullerenes M@C60 (M = H2, HF, H2O), manifesting in the splittings of the three-fold degenerate ground states of the endohedral ortho-H2, ortho-H2O and the j = 1 level of HF. The nature of the interaction causing the symmetry breaking is established in this study. A fragment of the solid C60 is considered, comprised of the central C60 molecule surrounded by twelve nearest-neighbor (NN) C60 molecules. The fullerenes have either P (major) or H (minor) orientational orderings, and are assumed to be rigid with Ih symmetry. Only the central C60 is occupied by the guest molecule M, while the NN fullerenes are all empty. The key proposition of the study is that the electrostatic interactions between the charge densities on the NN C60 molecules and that on M inside the central C60 give rise to the symmetry breaking responsible for the measured level splittings. Using this model, the M@C60 level splittings of interest are calculated variationally and using perturbation theory, for both the P and H orientations. Those obtained for the dominant P orientation are in excellent agreement with the experimental results, with respect to the splitting magnitudes and patterns, for all three M@C60 systems considered, pointing strongly to the quadrupolar M-NN interactions as the main cause of the symmetry breaking. The level splittings calculated for the H orientation are about 30 times smaller than the ones in the P orientation.

Phase evolution in mixture of cobalt and fullerene deposited from vapor

Recently we reported the evidence of solubility of Co in solid C60 found from magnetization of the CoxC60 mixture films (Phys. D: Appl. Phys. 48, 2015, 335002). In the present study we identified the Co solubility limit (xc = 2) and specified phase evolution in the CoxC60 mixtures in a wide interval of the Co concentrations (0 < x < 50) that was carried out through systematic characterization of the film surface morphology, chemical and phase composition. The effect of air exposure allowed us to recognize three intervals of x where phase evolution is controlled by rather different mechanisms. In the first interval (0 < x < 2, dilute mixtures) the phase evolution yields two separated phases, namely fcc-C60 and Co2C60. The dilute films do not include Co clusters and almost insensitive to the air exposure. Within the second and third intervals (supersaturated mixtures) designated as xc < x < xm and xm < x, respectively (xm = 10÷15), the formation of the Co clusters dominates in the phase evolution, which are found to be sensitive to the air exposure. The Co clustering in the mixtures from the second interval is completed by formation of critical nuclei. Within the third interval of x the phase evolution is controlled by growth of the Co clusters due to coalescence process.

Influence of CO molecular impurity on the structural and thermodynamic properties of fullerite C60, in a broad range of sorption temperatures

An x-ray diffraction study of how sorption of CO gas at a pressure of 30 atm in the temperature range of 150–600 °C influences the structural characteristics of polycrystalline and single crystal fullerite C60. The sorption kinetics are studied by constructing a dependence of the lattice parameter on the time it takes for fullerite to be saturated by CO molecules. At temperatures Tsorb > 300 °C there is an observed dissociation of carbon monoxide, accompanied by the precipitation of carbon powder and the chemical interaction of atomic oxygen with C60 and CO molecules, and possibly with the carbon condensate. These processes have a strong influence on the structural characteristics of fullerite, thus creating, in part, a nonmonotonic dependence of the parameter and lattice matrix volume on the impurity saturation temperature. The concentrations of solid solutions C60(CO)x poly- and single crystal samples are determined in the physisorption range for two modes (150 and 250 °C). It is found that the CO impurity has a linear effect on the lattice parameter and the temperature of the orientational transition of fullerite C60.

Capturing transiently charged states at the C60/TiO2(110) interface by time-resolved soft X-ray photoelectron spectroscopy

Time-resolved soft X-ray photoelectron spectroscopy is utilized to determine an energy level alignment and the photoexcited carrier dynamics at a C60/TiO2(110) interface. The interface electronic structure is characterized by a type II junction, which favors an injection of photoexcited electrons from C60 to TiO2. Ultraviolet (UV) laser pulse irradiation induces transient shifts of both C 1s and Ti 2p core levels towards the higher binding energies. These energy shifts are caused by a laser-induced charge transfer between the C60 layer and the TiO2(110) surface. Upon UV absorption, valence electrons of C60 are promoted to unoccupied levels, followed by a resonant transfer to TiO2, leaving C60 in a cationized state. On the TiO2(110) side, the electrons are injected into the conduction band to raise the carrier density so that downward bending of the TiO2 band is induced. The UV-excited states of C60 and TiO2 have sufficiently longer lifetime than the lifetime of the electron–hole pairs in solid C60. The C60/TiO2(110) interface is, thus, proved to be efficient for separating the electron–hole pairs generated within the C60 layer.

A new way to synthesize superconducting metal-intercalated C60 and FeSe.

Doping with the optimum concentration of carriers (electrons or holes) can modify the physical properties of materials. Therefore, improved ways to achieve carrier doping have been pursued extensively for more than 50 years. Metal-intercalation is one of the most important techniques for electron doping of organic / inorganic solids, and has produced superconductors from insulators and metallic solids. The most successful examples are metal-intercalated graphite and C60 superconductors. Metal intercalation has been performed using solid-reaction and liquid solvent techniques. However, precise control of the quantity of intercalants in the target solids can be difficult to achieve using these methods, as that quantity depends largely on the initial conditions. Here we report an electrochemical method for metal-intercalation, and demonstrate the preparation of superconductors using organic and inorganic materials (C60 and FeSe). The metal atoms are effectively intercalated into the spaces in C60 and FeSe solids by supplying an electric current between electrodes in a solvent that includes electrolytes. The recorded superconducting transition temperatures, Tc’s, were the same as those of metal-intercalated C60 and FeSe prepared using solid-reaction or liquid solvent techniques. This technique may open a new avenue in the search for organic / inorganic superconductors.

Exciton dynamics of C60-based single-photon emitters explored by Hanbury Brown-Twiss scanning tunnelling microscopy.

Exciton creation and annihilation by charges are crucial processes for technologies relying on charge-exciton-photon conversion. Improvement of organic light sources or dye-sensitized solar cells requires methods to address exciton dynamics at the molecular scale. Near-field techniques have been instrumental for this purpose; however, characterizing exciton recombination with molecular resolution remained a challenge. Here, we study exciton dynamics by using scanning tunnelling microscopy to inject current with sub-molecular precision and Hanbury Brown–Twiss interferometry to measure photon correlations in the far-field electroluminescence. Controlled injection allows us to generate excitons in solid C60 and let them interact with charges during their lifetime. We demonstrate electrically driven single-photon emission from localized structural defects and determine exciton lifetimes in the picosecond range. Monitoring lifetime shortening and luminescence saturation for increasing carrier injection rates provides access to charge-exciton annihilation dynamics. Our approach introduces a unique way to study single quasi-particle dynamics on the ultimate molecular scale.