Linjun Wang

Theoretical predictions of size-dependent carrier mobility and polarity in graphene.

First-principles density functional theory coupled with deformation potential calculations indicate a strong width-dependent carrier mobility: for an armchair graphene ribbon whose width (i.e., number of carbons along the edge) is N = 3k, the room-temperature electron mobility is calculated to be approximately 10(6) cm(2) V(-1) s(-1) and the hole mobility approximately 10(4) cm(2) V(-1) s(-1), while for N = 3k + 1 or 3k + 2, the hole mobility is calculated to be 4-8 x 10(5) cm(2) V(-1) s(-1) and the electron mobility approximately 10(4) cm(2) V(-1) s(-1). Such alternating behavior is absent in zigzag-type graphene.

Charge separation in semicrystalline polymeric semiconductors by photoexcitation: is the mechanism intrinsic or extrinsic?

We probe charge photogeneration and subsequent recombination dynamics in neat regioregular poly(3-hexylthiophene) films over six decades in time by means of time-resolved photoluminescence spectroscopy. Exciton dissociation at 10K occurs extrinsically at interfaces between molecularly ordered and disordered domains. Polaron pairs thus produced recombine by tunnelling with distributed rates governed by the distribution of electron-hole radii. Quantum-chemical calculations suggest that hot-exciton dissociation at such interfaces results from a high charge-transfer character. PACS numbers: 72.20.Jv, 78.47.jd, 78.55.Kz, 78.66.Qn

Evaluation of Charge Mobility in Organic Materials: From Localized to Delocalized Descriptions at a First‐Principles Level

The carrier mobility for carbon electronic materials is an important parameter for optoelectronics. We report here some recently developed theoretical tools to predict the mobility without any free parameters. Carrier scatterings with phonons and traps are the key factors in evaluating the mobility. We consider three major scattering regimes: i) where the molecular internal vibration severely induces charge self-trapping and, thus, the hopping mechanism dominates; ii) where both intermolecular and intramolecular scatterings come to play roles, so the Holstein-Peierls polaron model is applied; and, iii) where charge is well delocalized with coherence length comparable with acoustic phonon wavelength, so that a deformation potential approach is more appropriate. We develop computational methods at the first-principles level for the three different cases that have extensive potential application in rationalizing material design.

Optical Properties of Oligothiophene Substituted Diketopyrrolopyrrole Derivatives in the Solid Phase: Joint J- and H-Type Aggregation

Photophysical properties of diketopyrrolopyrrole derivatives substituted with oligothiophenes are investigated. All compounds are found to be fluorescent both in solution and in the solid phase. At low temperature in the solid, fluorescence originates from excimer-like excited states. Comparison of absorption and fluorescence excitation spectra taken under matrix isolated conditions and on solid films show the presence of both J- and H-type absorption bands in the solid phase. Quantum-chemical calculations, including exciton-phonon coupling to account for deviations from the Born-Oppenheimer approximation, are performed to simulate the band shape of the lowest absorption band in the molecular solid. The joint presence of J- and H-bands is explained by the presence of two molecules in the unit cell. The Davydov splitting is substantial for molecules with linear alkyl substituents on the nitrogen atom (on the order of 0.2 eV) but can be reduced to almost zero by introducing branching at the β-carbon of the alkyl side chain.

Charge transfer rates in organic semiconductors beyond first-order perturbation: From weak to strong coupling regimes

Semiclassical Marcus electron transfer theory is often employed to investigate the charge transport properties of organic semiconductors. However, quite often the electronic couplings vary several orders of magnitude in organic crystals, which goes beyond the application scope of semiclassical Marcus theory with the first-order perturbative nature. In this work, we employ a generalized nonadiabatic transition state theory (GNTST) [Zhao et al., J. Phys. Chem. A 110, 8204 (2004)], which can evaluate the charge transfer rates from weak to strong couplings, to study charge transport properties in prototypical organic semiconductors: quaterthiophene and sexithiophene single crystals. By comparing with GNTST results, we find that the semiclassical Marcus theory is valid for the case of the coupling <10 meV for quaterthiophene and <5 meV for sexithiophene. It is shown that the present approach can be applied to design organic semiconductors with general electronic coupling terms. Taking oligothiophenes as examples, we find that our GNTST-calculated hole mobility is about three times as large as that from the semiclassical Marcus theory. The difference arises from the quantum nuclear tunneling and the nonperturbative effects.

Flexible Surface Hopping Approach to Model the Crossover from Hopping to Band-like Transport in Organic Crystals

Two distinct pictures are usually evoked when modeling charge transport in organic crystals, that is, band and hopping models, the signature of which is conveyed by a characteristic temperature dependence of mobility. Here, we present a novel flexible surface hopping approach compliant with general Hamiltonians that is able to grasp the crossover from hopping to band-like transport regimes. This approach is applied to solve a one-dimensional mixed quantum-classical model and to calculate the temperature dependence of charge mobility along with the degree of charge spatial localization. It is found that the roles of both local and nonlocal electron-phonon couplings strongly depend on the intrinsic charge localization strength.

Toward quantitative prediction of charge mobility in organic semiconductors: tunneling enabled hopping model.

A tunneling-enabled hopping mechanism is proposed, providing a pratical tool to quantitatively assess charge mobility in organic semiconductors. The paradoxical phenomena in TIPS-pentacene is well explained in that the optical probe indicates localized charges while transport measurements show bands of charge.

Maximizing Singlet Fission by Intermolecular Packing.

A novel nonadiabatic molecular dynamics scheme is applied to study the singlet fission (SF) process in pentacene dimers as a function of longitudinal and lateral displacements of the molecular backbones. Detailed two-dimensional mappings of both instantaneous and long-term triplet yields are obtained, characterizing the advantageous and unfavorable stacking arrangements, which can be achieved by chemical substitutions to the bare pentacene molecule. We show that the SF rate can be increased by more than an order of magnitude through tuning the intermolecular packing, most notably when going from cofacial to the slipped stacked arrangements encountered in some pentacene derivatives. The simulations indicate that the SF process is driven by thermal electron-phonon fluctuations at ambient and high temperatures, expected in solar cell applications. Although charge-transfer states are key to construct continuous channels for SF, a large charge-transfer character of the photoexcited state is found to be not essential for efficient SF. The reported time domain study mimics directly numerous laser experiments and provides novel guidelines for designing efficient photovoltaic systems exploiting the SF process with optimum intermolecular packing.

A Simple Solution to the Trivial Crossing Problem in Surface Hopping.

Surface hopping studies on supramolecular and nanoscale systems suffer severely from the trivial crossing problem, arising due to high density of adiabatic potential energy surfaces. We present a straightforward solution to the problem by introducing a self-consistency test to the well-known fewest switches surface hopping (FSSH) procedure. If the test is failed, the hopping probabilities are corrected with a simple procedure. The novel self-consistent fewest switches surface hopping (SC-FSSH) approach is applied to the Holstein Hamiltonian to study the time-dependence of the electron population. Already in the five-state system, SC-FSSH allows us to reduce the simulation time 10(4)-fold to achieve the FSSH accuracy. The reliable performance and simple formulation of SC-FSSH greatly expands the applicability range of the surface hopping method.

Photoactive Gate Dielectrics

[ ∗] Q. Shen , S. Liu , Cao , . Y L. Gan , Prof. X. Guo , Prof. Z. Liu Beijing National Laboratory for Molecular Sciences State Key Laboratory for Structural Chemistry of Unstable and Stable SpeciesCollege of Chemistry and Molecular Engineering Peking University, Beijing 100871 (P. R. China) E-mail: guoxf@pku.edu.cn ; zfl iu@pku.edu.cn L. Wang , Prof. Z. Shuai Department of ChemistryTsinghua University 100084 Beijing (P. R. China)E-mail: zgshuai@tsinghua.edu.cn Dr. M. L. Steigerwald , Prof. C. Nuckolls Department of Chemistry and the Columbia University Energy Frontiers Research Center Columbia University, New York, 10027 (USA)E-mail: cn37@columbia.edu