Theoretical design of azaacene-based non-fullerene electron transport material used in inverted perovskite solar cells

ABSTRACT

Inverted perovskite solar cells (PSCs) have attracted much attention due to their low-temperature and solution-based process. Electron transport layers are important components in inverted PSCs. Non-fullerene n-type organic small molecules seem to be more attractive as electron transport layers, because their structures are easy to be synthesised and modified. In this paper, density functional theory and semi-classical Marcus electron transfer theory were used to explore the electron transport properties in three azaacene derivatives, including one experimentally reported molecule, 1,4,9,16-tetrakis((triisopropylsilyl)ethynyl)quinoxalino[2^?,3^?:4^″,5^″]cyclopenta[1^″,2^″,3^″:5^′,6^′]acenaphtho[1^′,2^′:5,6]pyrazino[2,3-b]phenazine (1), and two theoretically designed molecules (2 and 3). Compound 2 is formed by substituting i-Pr groups in compound 1 with H atoms, which is designed to evaluate the effect of i-Pr groups on the electron transport properties. Compound 3 is designed by adding one more benzopyrazine group to the conjugation structure of compound 1. It shows that i-Pr group can increase HOMO and LUMO energy levels and improve solubility in organic solvent and hydrophobicity. Enlarging conjugation can not only decrease LUMO energy level and electron reorganisation energy, but also can increase solubility and electron mobility. So our designed compound 3 is expected to be a potential electron transport material in inverted PSCs.     

Influence of the Coulomb forces on the thermodynamic and transport properties of non stoichiometric cerium dioxide

Abstract

In this study, it is demonstrated that the Coulomb interactions explains the essential of experimental thermodynamic and transport thermodynamic results.     

Transport Equation Evaluation of Coupled Continuous Time Random Walks

The transport behavior of a migrating particle in a disordered medium is exhibited in the solution of a transport equation derived from a coupled continuous time random walk (CTRW). A core aspect of CTRW is the spectrum of transitions in displacement s and time t, ψ(s,t), that characterizes the disordered system, which determine the transport. In many applications the CTRW approach has successfully accounted for the anomalous or non-Fickian nature of the particle plume propagation based on a power-law dependence ψ(t) in a decoupled p(s)ψ(t) approximation to ψ(s,t). For example, this power-law dependence in t derives from the complex Darcy flow fields in geological formations. Recently, the fully coupled CTRW was analyzed using a particle tracking approach, demonstrating that the decoupled approximation is valid only for a compact distribution of s. In this paper we solve the nonlocal-in-time transport equation with a ψ(s,t) containing a power-law dependence in both s (a Lévy-like distribution) and t, which necessitates the strong s,t coupling. We show enhanced transport behavior (relative to the plume propagation behavior reported in the literature) that derives from the rare large displacements in s (limited by the transition t). The interplay between the two coupled power laws is clearly shown in the changes in the breakthrough curves in the arrival times, dispersion and dependence on the velocity (v=s/t) distribution. Similar enhancements are exhibited in the particle tracking results.     

DFT/TDDFT investigation on the photophysical properties of a series of phosphorescent cyclometalated complexes based on the benchmark complex FIrpic

The photophysical properties of four Ir(III) complexes have been investigated by means of the density functional theory/time-dependent density functional theory (DFT/TDDFT). The effect of the electron-withdrawing and electron-donating substituents on charge injection, transport, absorption and phosphorescent properties has been studied. The theoretical calculation shows that the lowest-lying singlet absorptions for complexes 1–4 are located at 387, 385, 418 and 386 nm, respectively. For 1–4, the phosphorescence at 465, 485, 494 and 478 nm is mainly attributed to the LUMO → HOMO and LUMO → HOMO-1 transition configurations characteristics. In addition, ionisation potential (IP), electron affinities (EAs) and reorganisation energy have been investigated to evaluate the charge transfer and balance properties between hole and electron. The balance of the reorganisation energies for complex 3 is better than others. The difference between hole transport and electron transport for complex 3 is the smallest among these complexes, which is beneficial to achieve the hole and electron transfer balance in emitting layer.     

Integrable Structure of Conformal Field Theory II. Q-operator and DDV equation

This paper is a direct continuation of [1] where we began the study of the integrable structures in Conformal Field Theory. We show here how to construct the operators ${\bf Q}_{\pm}(\lambda)$ which act in the highest weight Virasoro module and commute for different values of the parameter λ. These operators appear to be the CFT analogs of the Q - matrix of Baxter [2], in particular they satisfy Baxter's famous T- Q equation. We also show that under natural assumptions about analytic properties of the operators as the functions of λ the Baxter's relation allows one to derive the nonlinear integral equations of Destri-de Vega (DDV) [3] for the eigenvalues of the Q-operators. We then use the DDV equation to obtain the asymptotic expansions of the Q - operators at large λ; it is remarkable that unlike the expansions of the T operators of [1], the asymptotic series for Q(λ) contains the “dual” nonlocal Integrals of Motion along with the local ones. We also discuss an intriguing relation between the vacuum eigenvalues of the Q - operators and the stationary transport properties in the boundary sine-Gordon model. On this basis we propose a number of new exact results about finite voltage charge transport through the point contact in the quantum Hall system. Received: 2 December 1996 / Accepted: 11 March 1997     

Absence of Transport Under a Slowly Varying Potential in Disordered Systems

In the tight-binding random Hamiltonian on Z ^d , we consider the charge transport induced by an electric potential which varies sufficiently slowly in time, and prove that it is almost surely equal to zero at high disorder. In order to compute the charge transport, we adopt the adiabatic approximation and prove a weak form of adiabatic theorem while there is no spectral gap at the Fermi energy.     

Application of Fiber-Optical Techniques in the Access Transmission and Backbone Transport of Mobile Networks

Abstract

Fixed access networks widely employ fiber-optical techniques due to the extremely wide bandwidth offered to subscribers. In the last decade, there has also been an enormous increase of user data visible in mobile systems. The importance of fiber-optical techniques within the fixed transmission/transport networks of mobile systems is therefore inevitably increasing. This article summarizes a few reasons and gives examples why and how fiber-optic techniques are employed efficiently in second-generation networks.     

H-mode in tokamaks attributed to absence of trapped ions in poloidally rotating plasma

It is proposed that the suppression of transport in the H-mode in tokamaks is caused by the absence of trapped ions in the transport barrier. If the poloidal Mach number M=v _θ B/(v _TiB_θ) is large there are exponentially few trapped ions. This criterion agrees with experimental observations of H-mode plasmas. The recently observed transport suppression by reversed shear also points to the dominant role of trapped particles in turbulent transport. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 6, 427–430 (25 March 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Chemical Substitutions in Tl 2 Mn 2 O 7 Pyrochlore,Synthesized Under High Pressure: Effects on the Colossal Magnetoresistance

Tl 2 Mn 2 O 7 pyrochlore has recently been described as a half-metallic ferromagnet showing colossal magnetoresistance (CMR) properties. New series of Tl 2 Mn 2 O 7 derivatives have been prepared under high pressure conditions. We have replaced Tl 3+ cations by Bi 3+ and Cd 2+ , leading to different modifications of the physical properties, with dramatic improvements of CMR. The Mn 4+ cations have also been partially replaced by Sb 5+ and Te 6+ . In particular, moderate Sb substitution leads to significant increments of T C . In this work we discuss on the effects of the different chemical substitutions on the structural, magnetic and transport properties.     

Charge ordering-disordering in the Th-doped CaMnO3

The structural transitions that appear in the manganites Ca_1-xTh_xMnO₃ versus temperature are studied in connection with their magnetic and transport properties, and compared to those of the Ca_1-xLn_xMnO₃ manganites. An orthorhombic to monoclinic transition is observed for low x values (;this structural distortion, also observed for Ln-doped oxides, is related to the magnetoresistance properties. For higher x values (), modulated commensurate and incommensurate phases are obtained at low temperature, with , b =2 a p and , which are related to Mn³⁺/Mn⁴⁺ charge ordering (CO) phenomena. T values, determined from electron diffraction, are in agreement with those determined from the M ( T ) curves. The low temperature electron microscopy shows that the CO in those oxides is more complex than in Ln-doped manganites. In particular, the destabilisation of CO and consequently of the antiferromagnetic interactions is evidenced as the thorium content increases which may explain the appearance of a spin-glass like behavior for higher x values not seen for Ca_1-xSm_xMnO₃ phases . Received 2 November 1998     

Microwave transport approach to the coherence of interchain hopping in (TMTSF)2PF6

We report a microwave study of the longitudinal and transverse transport properties of the quasi-one-dimensional organic conductor (TMTSF)₂PF₆ in its normal phase. The contactless technique have provided a direct measurement of the temperature profile of the resistivity along the b' direction and in magnetic fields up to 14 T. A characteristic energy scale ( K) has been observed which delimits a transient regime from an insulating to a metallic behavior. This anomalous profile is discussed in terms of the onset of coherent transport properties along the b' direction below 40 K. This is also supported by the observation of a finite longitudinal and transverse magnetoresistances only below 40 K, indicative of a two-dimensional regime. Below T_x, however, strong deviations with respect to a Fermi liquid behavior are evidenced. Received 27 January 1999     

Single voxel vascular transport functions of arteries,capillaries and veins; and the associated arterial input function in dynamic susceptibility contrast magnetic resonance brain perfusion imaging

PurposeThe composite vascular transport function of a brain voxel consists of one convolutional component for the arteries, one for the capillaries and one for the veins in the voxel of interest. Here, the goal is to find each of these three convolutional components and the associated arterial input function.Pharmacokinetic modellingThe single voxel vascular transport functions for arteries, capillaries and veins were all modelled as causal exponential functions. Each observed multipass tissue contrast function was as a first approximation modelled as the resulting parametric composite vascular transport function convolved with a nonparametric and voxel specific multipass arterial input function. Subsequently, the residue function was used in the true perfusion equation to optimize the three parameters of the exponential functions.Deconvolution methodsFor each voxel, the parameters of the three exponential functions were estimated by successive iterative blind deconvolutions using versions of the Lucy-Richardson algorithm. The final multipass arterial input function was then computed by nonblind deconvolution using the Lucy-Richardson algorithm and the estimated composite vascular transport function.ResultsSimulations showed that the algorithm worked. The estimated mean transit time of arteries, capillaries and veins of the simulated data agreed with the known input values. For real data, the estimated capillary mean transit times agreed with known values for this parameter. The nonparametric multipass arterial input functions were used to derive the associated map of the arrival time. The arrival time map of a healthy volunteer agreed with known arterial anatomy and physiology.ConclusionClinically important new voxelwise hemodynamic information for arteries, capillaries and veins separately can be estimated using multipass tissue contrast functions and the iterative blind Lucy-Richardson deconvolution algorithm.     

DFT-based study of the impact of transition metal coordination on the charge transport and nonlinear optical (NLO) properties of 2-{[5-(4-nitrophenyl)-1,3,4-thiadiazol-2-ylimino]methyl}phenol

Theoretical investigations of the impact of transition metal chelation on the electron/hole-transport and nonlinear optical (NLO) properties of 2-{[5-(4-nitrophenyl)-1,3,4-thiadiazol-2-ylimino]methyl}phenol (L) are reported herein. Calculations were carried out via density functional theory (DFT)-based methods, employing exchange–correlation functionals and basis sets of different qualities. Results have shown that free L is a moderate electron/hole-transporter, but that its Pd(II) and Pt(II) complexes are excellent hole- and electron-transport materials respectively, owing to their very small reorganisation energies and relatively large electronic coupling matrix elements or transfer integrals. These results indicate that the complexes are potentially suitable charge transport materials for the construction of organic light emitting diodes (OLEDs). Nevertheless, the results also revealed a higher NLO activity for L than its metal complexes. Interestingly, the first and second hyperpolarizabilities, along with some computed NLO properties of both L and its complexes are found to be remarkably higher than those of the prototypical push–pull molecule, para-nitroaniline. Accordingly, these compounds are potential candidates for the fabrication of optoelectronic and photonic devices for second- and third-order NLO applications. Summarily, metal chelation is found to enhance the charge transport properties in some cases, and to slightly diminish NLO response of L in all cases investigated.     

On the question of short-period oscillations of the collector voltage during transverse electron focusing

Giant short-period oscillations during transverse electron focusing at high emitter voltages have been observed in bismuth samples with a superlattice on the surface. A model is proposed which explains the onset of the oscillations, their position on the magnetic-field scale, and their intensification and shift along the magnetic-field scale with increasing current (this shift depending on the direction of current flow) and which can also account for the absence of oscillations in fields which are multiples of the field of the first oscillation. In this model the oscillations are attributed to the appearance of resonant surface (edge) states and their contribution to the electron transport. Pis'ma Zh. éksp. Teor. Fiz. 68, No. 12, 887–892 (25 December 1998)     

Resilience of public transport networks against attacks

The behavior of complex networks under failure or attack depends strongly on the specific scenario. Of special interest are scale-free networks, which are usually seen as robust under random failure but appear to be especially vulnerable to targeted attacks. In recent studies of public transport networks of fourteen major cities of the world it was shown that these systems when represented by appropriate graphs may exhibit scale-free behavior [Physica A 380, 585 (2007); Eur. Phys. J. B 68, 261 (2009)]. Our present analysis focuses on the effects that defunct or removed nodes have on the properties of public transport networks. Simulating different directed attack strategies, we derive vulnerability criteria that result in minimal strategies with high impact on these systems.     

Numerical solutions of matrix Riccati equations for radiative transfer in a plane-parallel geometry

Abstract

In this paper, we conduct numerical experiments with matrix Riccati equations (MREs) which describe the reflection (R) and transmission (T) matrices of the specific intensities in a layer containing randomly distributed scattering particles. The theoretical formulation of MREs is discussed in our previous paper where we show that R and T for a thick layer can be efficiently computed by successively doubling R and T matrices for a thin layer (with small optical thickness τ_Δ). We can compute R(τ_Δ) and T(τ_Δ) very accurately using either a fourth-order Runge–Kutta scheme or the fourth-order iterative solution. The differences between these results and those computed by the eigenmode expansion technique (EMET) are very small (<0.1%). Although the MRE formulation cannot be extended to handle the inhomogeneous term (source term) in the differential equation, we show that the force term can be reformulated as an equivalent boundary condition which is consistent with MRE methods. MRE methods offer an alternative way of solving plane-parallel radiative transport problems. For large problems that do not fit into computer memory, the MRE method provides a significant reduction in computer memory and computational time.     

Pressure-driven molecular dynamics simulations of water transport through a hydrophilic nanochannel

ABSTRACT

Transport of fluids inside porous materials is relevant to many fields of application. Non-equilibrium molecular dynamics simulation is a powerful technique to explore fluid transport through porous media at the molecular scale. In this work, we compared two commonly used methods for studying pressure-driven transport. The first method was based on the application of an external force field on each fluid particle. The second method made use of two movable walls, acting as pistons, so as to generate transport. These two methods were used to study water transport inside a cylindrical hydrophilic silica nanopore. Several pressure differences were considered from 20 bar to 1000 bar. The results were compared to the theoretical Poiseuille fluid flow. No significant difference was found between the two methods. However, a substantial water flow enhancement was observed compared with the theoretical flow. Both the structural and dynamical properties of water remained unaffected by the applied pressure difference.     

Effect of evanescent channels on position-dependent diffusion in disordered waveguides

Abstract

We employ ab initio simulations of wave transport in disordered waveguides to demonstrate explicitly that although accounting for evanescent channels manifests itself in the renormalization of the transport mean free path, the position-dependent diffusion coefficient, as well as distributions of angular transmission, total transmission and conductance, all remain universal.     

Transport and heating of electrons in semiconductors with a one-dimensional superlattice

On the basis of the Boltzmann equation with a new model collision integral that takes into account the redistribution of energy and momentum of all degrees of freedom of the electron, we have constructed and investigated a three-dimensional model of electron transport in one-dimensional semiconductor superlattices (SL’s). The current-voltage curves (CVC), mean energies, and effective temperatures of the electrons have been found for vertical and longitudinal transport. In contrast to one-dimensional models, the approach developed here allows one to take into account and describe not only longitudinal electron heating, but also electron heating transverse to the current. For vertical transport, transverse heating substantially alters the position, magnitude, and width of the current maximum. For longitudinal transport, electron heating that is non-quadratic in the field arises along the superlattice axis even in the approximation of a linear current-voltage characteristic. The possibility of describing electron transport in a superlattice using a mixed Fermi distribution with an isotropic temperature is analyzed. Fiz. Tverd. Tela (St. Petersburg) 41, 1698–1706 (September 1999)     

Predictability of ion transport properties from the structure of solid electrolytes

The concept of bond valence (BV) is widely used in crystal chemical considerations, e.g. to assess equilibrium positions of atoms in crystal structures from an empirical relationship between bond lengthR _M−X and bond valenceS _A−X =exp [(R ₀ −R _M−X ) /b] as sites where the BV sumV(A)=∑ s _M−X equals the formal valenceV _id of the cationM ⁺ . Our modified BV approach that systematically accounts for the softness of the bond may then be effectively used to study the interplay between structure and properties of solid electrolytes. This is exemplified for correlations to experimental data from IR, NMR, and impedance spectroscopy. Combining the bond valence approach with reverse Monte Carlo (RMC) modeling or molecular dynamics (MD) simulations provides a deeper understanding of ion transport mechanisms, especially in highly disordered or amorphous solids. Local structure models for crystalline electrolytes are derived by combining crystallographic structure information with simulations. A method for the prediction of the activation energy of the ionic conductivity from the bond valence analysis of the crystal structure is proposed. Taking into account the mass dependence of the conversion factor from bond valence mismatch into an activation energy scale, we could establish a correlation that holds for different types of mobile ions. The strong coupling of the H⁺ transfer to the anion motion in proton conductors requires a special treatment. For glassy solid electrolytes RMC structure models are BV-analyzed to assess the total number of equilibrium sites and to identify transport pathways for the mobile ions. Recently, we have reported a correlation between the pathway volume fraction and the transport properties that permits to predict both absolute value and activation energy of the dc ionic conductivities of disordered solids (including mixed alkali glasses) directly from their structural models. Here we discuss a corresponding BV analysis of molecular dynamics simulation trajectories that allows quantifying the evolution of pathways in time and the influence of temperature on the transport pathways. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 — 18, 2004.