Exciton Dissociation Mechanism Research Articles

Trap‐Assisted Exciton Dissociation Through Continuous Trapping/Detrapping in Lithium Ions Inserted Crystalline Carbon Nitride

AbstractHere, lithium ions inserted crystalline carbon nitrides (LCCN) with different defect concentrations are prepared by elaborately regulating the mass transfer process in thermal polymerization. It is revealed that there is no conventional exciton–polarons‐induced exciton dissociation mechanism in LCCN due to the weak coupling between excitons and phonons. On the contrary, excitons continue to trap/detrap through defect‐induced traps, which weakens the Coulomb force between electron–hole pairs, thereby accelerating exciton dissociation. It is worth emphasizing that this is the first systematic research on the exciton dissociation characteristics and photocatalytic activity of LCCN of poly(heptazine imide) structure. A strategy of assisting exciton dissociation through defect‐induced traps to address the inherently high exciton binding energy and low exciton dissociation efficiency issues in polymer photocatalysts is proposed.

Squaraine Dyes for Single‐Component Shortwave Infrared‐Sensitive Photodiodes and Upconversion Photodetectors

AbstractSensitive detection of shortwave infrared (SWIR) light using organic dyes will be a significant advance toward many applications in industry and research. Furthermore, from a fabrication and optimization view, photogeneration of charges in diodes consisting of a single dye layer will be highly attractive. However, SWIR dyes are scarce and organic photodiodes usually utilize a donor–acceptor materials combination to split excitons into charges. Here, it is demonstrated that single‐component layers of several SWIR squaraine dyes operate as efficient photodetectors, with peak external quantum efficiency > 40% beyond 1000 nm and sensitivity out to 1300 nm. Photocurrents show a superlinear dependence on reverse bias. It is shown that this results from a field‐assisted exciton dissociation mechanism, and not from field‐dependent charge injection or extraction. SWIR photodiodes are combined with organic light‐emitting diodes to fabricate upconversion photodetectors – devices that convert SWIR photons directly into visible light. Upconverters are characterized by a low turn‐on voltage (1.5 V) and a high luminance contrast (on‐off ratio 16 000) and SWIR‐to‐visible (λ = 575 nm) photon conversion efficiency (1.85%). Upconversion photodetectors emerge as a promising alternative to the current inorganic‐based imaging technology.

Insights into the Charge-Transfer Mechanism and Stacking Structures in a Large Sample of Donor/Acceptor Models of a Non-Fullerene Organic Solar Cell

Non-fullerene acceptors (NFAs) have boomed in the field of organic solar cells (OSCs); however, the charge generation mechanism remains elusive owing to the complex molecular stacking patterns in the active layer and numerous selections of the donor and acceptor for practical OSCs. Herein, we built 178 interfacial models consisting of molecules M-Phs and BTP-eC9 as the donor (D) and acceptor (A), respectively, to reveal the relationship between the molecular stacking patterns and charge-transfer (CT) mechanisms. After obtaining the optimized D/A structures, we divided the 178 D/A dimers into different groups (T-S, C-S, N-N groups) based on the molecular stacking pattern by positional parameters (i.e., centroid distance and angle) and calculated their interfacial properties. The results indicate that multichannel exciton dissociation mechanisms exist in the M-Phs/BTP-eC9 active layer (i.e., hot exciton and direct excitation mechanisms, the intermolecular electric field (IEF) mechanism, and hole transfer) and the different CT mechanisms are mainly attributed to changes in the stacking patterns caused by the different portions of the acceptor approaching the skeleton of the donor. We further classified the group with the terminal unit of the acceptor inclined to approach different portions of the donor skeleton in detail by a molecular orientation (face-on, edge-on, and slipped), and we found a strong correlation between the energy of the lowest charge-transfer state (ECT) and the distance of the centroid between the terminal unit of the acceptor and the π bridge of the donor. This work provides a robust description of the relationship between molecular stackings and CT mechanisms, suggesting the crucial role of D and A arrangements in the NFA-based active layer.

Elucidating the Chain-Extension Effect on the Exciton-Dissociation Mechanism through an Intra- or Interchain Polaron-Pair State in Push–Pull Conjugated Polymers

We elucidated chain-extension effects of a benzodithiophene (BDT) and thienopyrroledione-based push–pull conjugated polymer (CP) on its exciton-dissociation mechanism within aggregate systems using transient absoption spectroscopy. The side-group extension CP with benzothiophene on the BDT unit induced H-type excitons with excess energy owing to decreased chain stiffness. This led to interchain polaron-pair (PP)-mediated exciton dissociation. The stiff side-group extended with thienothiophene on the BDT unit also induced H-type excitons, but the decreased energy and breadth of the density of states suppressed the interchain PP-mediated exciton dissociation. The main-chain-extension CP with two thiophenes on either side of the BDT unit has a curved structure disturbing the interchain packing. Thus, the driving force of exciton dissociation between the chains decreased, leading to intrachain PP-mediated exciton dissociation. Our findings can facilitate the development of novel CPs to further increase the efficiencies of polymer solar cells.

The Role of Entropy Gains in the Exciton Separation in Organic Solar Cells.

In organic solar cells (OSCs), the lower dielectric constant of organic semiconductor material induces a strong Coulomb attraction between electron-hole pairs, which leads to a low exciton separation efficiency, especially the charge transfer (CT) state. The CT state formed at the electron-donor (D) and electron-acceptor (A) interface is regarded as an unfavorable property of organic photovoltaic devices. Since the OSC works in a nonzero temperature condition, the entropy effect would be one of the main reasons to overcome the Coulomb energy barrier and must be taken into account. In this review, the present understanding of the entropy-driven charge separation is reviewed and how factors such as the dimensionality of the organic semiconductor, energy disorder effect, the morphology of the active layer, are described, as well as how the nonequilibrium effect affects the entropy contribution in compensating the Coulomb dissociation barrier for CT exciton separation and charge generation process. The investigation of the entropy effect on exciton dissociation mechanism from both theoretical and experimental aspects is focused on, which provides pathways for understanding the underlying mechanisms of exciton separation and further enhancing the efficiency of OSCs.

Transient coexistence of excitons and charge carriers in high-purity diamond

We investigate the transient coexistence state of the excitons and charge carriers in highly-pure diamond after an impulsive injection of excitons, by probing free electrons until the relaxation of carriers with the nanosecond time-resolved cyclotron resonance (TRCR) method. By analyzing the time profiles of the TRCR signal with a numerical solution of rate equations for exciton and charge carrier densities over a wide temperature range from 10 K to 261 K, the temperature dependence of the coefficient of two-body (Auger) collision of excitons, the rate of thermal dissociation of excitons, and exciton and electron lifetimes was extracted. The shift of exciton dissociation mechanisms from the Auger process below 40 K to the thermal ionization above 80 K was revealed for an initial density of excitons in the order of 1015 cm−3. We also found that the equilibrium between electrons and excitons is established within 100 ns above 80 K, when the thermal ionization of excitons dominates the dissociation process. These results provide fundamental understandings of transient carrier correlation in optoelectronic devices.

Study of photogenerated exciton dissociation in transition metal dichalcogenide van der Waals heterojunction A2-MWS4: a first-principles study.

In order to explore the photocatalytic hydrogen production efficiency of the MoS2/WSe2 heterostructure (A2-MWS4) as a photocatalyst, it is highly desirable to study the photogenerated exciton dissociation related to photocatalysis. The electronic properties, optical absorption, and lattice dynamic properties of A2-MWS4 were investigated using a first-principles approach. The results show that the type II energy band alignment of A2-MWS4 facilitates the dissociation of photogenerated excitons (electrons and holes). The highly localized d-state electrons of A2-MWS4 induce the formation of internal potentials that promote the dissociation of photogenerated excitons. The hot carrier diffuses its extra energy into the lattice by scattering with phonons and forms a hot spot in the lattice while releasing phonons, which are dragged away from the hot spot by Ridley decay to promote exciton dissociation. These findings could provide insights for research studies on photochemical reactions and photovoltaic devices.

Field Effect versus Driving Force: Charge Generation in Small‐Molecule Organic Solar Cells

AbstractEfficient charge generation in organic semiconductors usually requires an interface with an energetic gradient between an electron donor and an electron acceptor in order to dissociate the photogenerated excitons. However, single‐component organic solar cells based on chloroboron subnaphthalocyanine (SubNc) have been reported to provide considerable photocurrents despite the absence of an energy gradient at the interface with an acceptor. In this work, it is shown that this is not due to direct free carrier generation upon illumination of SubNc, but due to a field‐assisted exciton dissociation mechanism specific to the device configuration. Subsequently, the implications of this effect in bilayer organic solar cells with SubNc as the donor are demonstrated, showing that the external and internal quantum efficiencies in such cells are independent of the donor‐acceptor interface energetics. This previously unexplored mechanism results in efficient photocurrent generation even though the driving force is minimized and the open‐circuit voltage is maximized.

Dissociation of two-dimensional excitons in monolayer WSe2

Two-dimensional (2D) semiconducting materials are promising building blocks for optoelectronic applications, many of which require efficient dissociation of excitons into free electrons and holes. However, the strongly bound excitons arising from the enhanced Coulomb interaction in these monolayers suppresses the creation of free carriers. Here, we identify the main exciton dissociation mechanism through time and spectrally resolved photocurrent measurements in a monolayer WSe2p–n junction. We find that under static in-plane electric field, excitons dissociate at a rate corresponding to the one predicted for tunnel ionization of 2D Wannier–Mott excitons. This study is essential for understanding the photoresponse of 2D semiconductors and offers design rules for the realization of efficient photodetectors, valley dependent optoelectronics, and novel quantum coherent phases.

Visualization of channel formation of organic field-effect transistors by scanning photocurrent microscopy

Abstract Scanning modulated photocurrent microscopy by means of chopped red laser light for local excitation is employed in organic field-effect transistors having pentacene as active layer. The spatial modulated photoresponse presents a gradual increase from the source-to drain-side with increasing the negative gate-source voltage and undergoes enhancement under additional full device blue bias-bandgap illumination. The electric field-assisted exciton dissociation mechanism alone cannot explain the photoresponse enhancement under blue bias-light. This enhancement can be explained by considering that the electrons from the laser light-created triplet excitons have a large probability to be transferred to trapped holes accumulated at the pentacene-insulator interface creating mobile holes. In the framework of this interpretation, an increased local photoresponse reveals the channel region with upwards band bending and accumulated trapped holes from holes injected and extra holes created in case where an additional blue bias-light bandgap excitation is employed. Taking advantage of this property, the gradual increase of the spatial photoresponse along the channel, observed during turning-on the transistor with increasing the negative gate voltage, can be used to visualize the growing accumulation channel region from the source-to drain-side against the pinch-off depletion region. Moreover, the spatial photoresponse changes observed during transition from the linear to the saturation regime with increasing the negative drain voltage, can be used to monitor the suppression of the accumulation region and the increase of the electric field in the drain-side.

Origin of the Excited-State Absorption Spectrum of Polythiophene.

The excited states of conjugated polymers play a central role in their applications in organic solar photovoltaics. The delocalized excited states of conjugated polymers are short-lived (τ < 40 fs) but are imperative in the photovoltaic properties of these materials. Photoexcitation of poly(3-hexylthiophene) (P3HT) induces an excited-state absorption band, but the transitions that are involved are not well understood. In this work, calculations have been performed on P3HT analogues using nonlinear response time-dependent density functional theory to show that an increase in the oligomer length correlates with the dominance of the S1 → S3 transition. Furthermore, the predicted transition energy shows an excellent agreement with experiment. The calculations also yielded results on intramolecular charge transfer in P3HT due to the S1 → S3 transition, providing insight into the mechanism of exciton dissociation to form charge carriers.

A Multidimensional View of Charge Transfer Excitons at Organic Donor-Acceptor Interfaces.

How tightly bound charge transfer (CT) excitons dissociate at organic donor-acceptor interfaces has been a long-standing question in the organic photovoltaics community. Recently, it has been proposed that exciton delocalization reduces the exciton binding energy and promotes exciton dissociation. In order to understand this mechanism, it is critical to resolve the evolution of the exciton's binding energy and coherent size with femtosecond time resolution. However, because the coherent size is just a few nanometers, it presents a major experimental challenge to capture the CT process simultaneously in the energy, spatial, and temporal domains. In this work, the challenge is overcome by using time-resolved photoemission spectroscopy. The spatial size and electronic energy of a manifold of CT states are resolved at the zinc phthalocyanine (ZnPc)-fullerene (C60) donor-acceptor interface. It is found that CT at the interface first populates delocalized CT excitons with a coherent size of 4 nm. Then, this delocalized CT exciton relaxes in energy to produce CT states with delocalization sizes in the range of 1-3 nm. While the CT process from ZnPc to C60 occurs in about 150 fs after photoexcitation, the localization and energy relaxation occur in 2 ps. The multidimensional view on how CT excitons evolve in time, space, and energy provides key information to understand the exciton dissociation mechanism and to design nanostructures for effective charge separation.

High Conversion Efficiency Carbon Nanotube-Based Barrier-Free Bipolar-Diode Photodetector.

Conversion efficiency (CE) is the most important figure of merit for photodetectors. For carbon nanotubes (CNT) based photodetectors, the CE is mainly determined by excitons dissociation and transport of free carriers toward contacts. While phonon-assisted exciton dissociation mechanism is effective in split-gate CNT p-n diodes, the CE is typically low in these devices, approximately 1-5%. Here, we evaluate the performance of a barrier-free bipolar diode (BFBD), which is basically a semiconducting CNT asymmetrically contacted by perfect n-type ohmic contact (Sc) and p-type ohmic contact (Pd) at the two ends of the diode. We show that the CE in short channel BFBD devices (e.g., 60 nm) is over 60%, and it reduces rapidly with increasing channel length. We find that the electric-field-assisted mechanism dominates the dissociation rate of excitons in BFBD devices at zero bias and thus the photocurrent generation process. By performing a time-resolved and spatial-resolved Monte Carlo simulation, we find that there exists an effective electron (hole)-rich region near the n-type (p-type) electrode in the asymmetrically contacted BFBD device, where the electric-field strength is larger than 17 V/μm and exciton dissociation is extremely fast (<0.1 ps), leading to very high CE in the BFBD devices.

Organic Photovoltaics: Elucidating the Ultra‐Fast Exciton Dissociation Mechanism in Disordered Materials

AbstractOrganic photovoltaics (OPVs) offer the opportunity for cheap, lightweight and mass‐producible devices. However, an incomplete understanding of the charge generation process, in particular the timescale of dynamics and role of exciton diffusion, has slowed further progress in the field. We report a new Kinetic Monte Carlo model for the exciton dissociation mechanism in OPVs that addresses the origin of ultra‐fast (&lt;1 ps) dissociation by incorporating exciton delocalization. The model reproduces experimental results, such as the diminished rapid dissociation with increasing domain size, and also lends insight into the interplay between mixed domains, domain geometry, and exciton delocalization. Additionally, the model addresses the recent dispute on the origin of ultra‐fast exciton dissociation by comparing the effects of exciton delocalization and impure domains on the photo‐dynamics.This model provides insight into exciton dynamics that can advance our understanding of OPV structure–function relationships.

Organic Photovoltaics: Elucidating the Ultra‐Fast Exciton Dissociation Mechanism in Disordered Materials

Organic photovoltaics (OPVs) offer the opportunity for cheap, lightweight and mass-producible devices. However, an incomplete understanding of the charge generation process, in particular the timescale of dynamics and role of exciton diffusion, has slowed further progress in the field. We report a new Kinetic Monte Carlo model for the exciton dissociation mechanism in OPVs that addresses the origin of ultra-fast (<1 ps) dissociation by incorporating exciton delocalization. The model reproduces experimental results, such as the diminished rapid dissociation with increasing domain size, and also lends insight into the interplay between mixed domains, domain geometry, and exciton delocalization. Additionally, the model addresses the recent dispute on the origin of ultra-fast exciton dissociation by comparing the effects of exciton delocalization and impure domains on the photo-dynamics.This model provides insight into exciton dynamics that can advance our understanding of OPV structure-function relationships.

High Photoresponse in Hybrid Graphene–Carbon Nanotube Infrared Detectors

Efficient exciton dissociation is crucial to obtaining high photonic response in photodetectors. This work explores implementation of a novel exciton dissociation mechanism through heterojunctions self-assembled at the graphene/MWCNT (multiwall carbon nanotube) interfaces in graphene/MWCNT nanohybrids. Significantly enhanced near-infrared photoresponsivity by nearly an order of magnitude has been achieved on the graphene/MWCNT nanohybrids as compared to the best achieved so far on carbon nanotube (CNT) only infrared (IR) detectors. This leads to a high detectivity up to 1.5 × 10(7) cm·Hz(1/2)·W(-1) in the graphene/MWCNT nanohybrid, which represents a 500% improvement over the best D* achieved on MWCNT film IR detectors and may be further improved with optimization on the interfacial heterojunctions. This approach of the self-assembly of graphene/CNT nanohybrids provides a pathway toward high-performance and low-cost carbon nanostructure IR detectors.

Relaxation Dynamics of Photoexcited Excitons in Rubrene Single Crystals Using Femtosecond Absorption Spectroscopy

The relaxation dynamics of an exciton in rubrene was investigated by femtosecond absorption spectroscopy. Exciton relaxation to a self-trapped state occurs via the coherent oscillation with 78 cm(-1) due to a coupled mode of molecular deformations with phenyl-side-group motions and molecular displacements. From the temperature dependence of the decay time of excitons, the energy necessary for an exciton to escape from a self-trapped state is evaluated to be ~35 meV (~400 K). As a result, a self-trapped exciton is stable at low temperatures. At room temperature, excitons can escape from a self-trapped state and, subsequently, they are dissociated to charged species. The exciton dissociation mechanism is discussed on the basis of the results.

Organic photovoltaic cells based on unconventional electron donor fullerene and electron acceptor copper hexadecafluorophthalocyanine

We demonstrate organic discrete heterojunction photovoltaic cells based on fullerene (C60) and copper hexadecafluorophthalocyanine (F16CuPc), in which the C60 and F16CuPc act as the electron donor and the electron acceptor, respectively. The C60/F16CuPc cells fabricated with conventional and inverted architectures both exhibit comparable power conversion efficiencies. Furthermore, we show that the photocurrent in both cells is generated by a conventional exciton dissociation mechanism rather than the exciton recombination mechanism recently proposed for a similar C60/F16ZnPc system [Song et al., J. Am. Chem. Soc. 132, 4554 (2010)]. These results demonstrate that new unconventional material systems are a potential way to fabricate organic photovoltaic cells with inverted as well as conventional architectures.

Merocyanine/C60 Planar Heterojunction Solar Cells: Effect of Dye Orientation on Exciton Dissociation and Solar Cell Performance

AbstractIn this study the charge dissociation at the donor/acceptor heterointerface of thermally evaporated planar heterojunction merocyanine/C60 organic solar cells is investigated. Deposition of the donor material on a heated substrate as well as post‐annealing of the complete devices at temperatures above the glass transition temperature of the donor material results in a twofold increase of the fill factor. An analytical model employing an electric‐field‐dependent exciton dissociation mechanism reveals that geminate recombination is limiting the performance of as‐deposited cells. Fourier‐transform infrared ellipsometry shows that, at temperatures above the glass transition temperature of the donor material, the orientation of the dye molecules in the donor films undergoes changes upon annealing. Based on this finding, the influence of the dye molecules’ orientations on the charge‐transfer state energies is calculated by quantum mechanical/molecular mechanics methods. The results of these detailed studies provide new insight into the exciton dissociation process in organic photovoltaic devices, and thus valuable guidelines for designing new donor materials.

Nonadiabatic Simulations of Exciton Dissociation in Poly-p-phenylenevinylene Oligomers

We present simulations of exciton dissociation and charge separation processes in the prototypical conjugated polymer, poly-p-phenylenevinylene. Our mixed quantum/classical simulations focus on the nonadiabatic excited state dynamics of single and pi-stacked oligomers of varying length. By applying a constant external electric field, our simulations reveal the details and time scale for exciton dissociation and fluorescence quenching and suggest how those processes relate to charge carrier (polaron) formation in polymer systems. We find that, in such a polarizing environment, sufficiently long chromophores (either single or interacting chains) can form polaron pairs via a delayed exciton dissociation mechanism or nearly instantaneously following photoexcitation. However, we find that these processes are mechanically essentially the same, being highly nonadiabatic in character and requiring transitions through "gateway" states to reach the completely charge separated electronic states. Finally, we observe thermally driven polaron hopping dynamics between chains, similar to the energy transfer dynamics we had described previously (J. Phys. Chem. A 2009, 113 (15), 3427). Our results are consistent with a range of apparently conflicting experiments, resolving some controversies regarding the molecular mechanism for charge carrier photogeneration in conjugated polymers.