Bimolecular Recombination Coefficient Research Articles

Elucidating How Low Energy Offset Matters to Performance of Nonfullerene Acceptor-Based Solar Cells

The energetic offset between the highest occupied molecular orbitals of the donor and acceptor components of organic photovoltaic blends is well-known to affect the device efficiency. It is well-established that a decreasing offset increases the open-circuit voltage but reduces the short-circuit current, which has been explained by insufficient exciton dissociation. However, the impact of the offset on the fill factor and underlying processes is less clear. Here, we study free charge generation and recombination in three different nonfullerene acceptors, Y6, ITIC, and o-IDBTR, blended with the same donor polymer PM6. We demonstrate that a diminishing offset results in field-dependent charge generation related to field-assisted exciton dissociation. On the other hand, reformation of excitons from free charges is identified as an additional channel for charge recombination, which goes along with a substantial rise in the bimolecular recombination coefficient. In combination of these two effects, the fill factor drops considerably with a decreasing energy offset. Using the comparison between PM6:ITIC and PM6:o-IDBTR, we show that bulk properties such as morphology and carrier mobilities can not fully explain the observed difference in performance, highlighting the importance of interfacial kinetics and thermodynamics in controlling the device efficiency, both through generation and recombination of charge carriers.

Device Modelling and Optimization of Nanomaterial-Based Planar Heterojunction Solar Cell (by Varying the Device Dimensions and Material Parameters).

The objective of this work is to model a multi-disciplinary (multi-physics) organic photovoltaic (OPV) using mathematical modeling and analyzing the behavior of a standard planar heterojunction (PHJ) or bi-layer thin-film photovoltaic device, supporting the optimization of an efficient device for future production and assisting in evaluating and choosing the materials required for the efficient device. In order to increase photodiode performance, the device structure and geometrical properties have also been optimized and evaluated. In this work, the effects of varying the device size and transport parameters on the performance parameters of a PHJ OPV structure comprised of Indium Tin Oxide as the anode (ITO), semiconducting single-wall carbon nanotube (s-SWCNT) as the donor, fullerene C70 as the acceptor, and Aluminium (Al) as the cathode have been analyzed. The conclusion suggests that a highly effective ITO/s-SWCNT/C70/Al PHJ solar cell may be fabricated if the suggested device is appropriately built with a thin layer and a high exciton diffusion length, bi-molecular recombination coefficient, and improved mobility charge carriers, in particular hole mobility in the cell’s donor layer. In addition, the displayed current–voltage (I–V) characteristics of the proposed PHJ device are clearly indicated, with the ITO/s-SWCNT/C70/Al combination having the greatest short-circuit current density (Jsc) value of 5.61 mA/cm2, open-circuit voltage (Voc) of 0.7 V, fill factor (FF) of 79% and efficiency (ɳ) of 3.1%. Results show that the electrical performance of organic solar cells is sensitive to the thickness of the photoactive substance. These results open the path for developing inexpensive and highly efficient solar cells.

Revealing Charge Transfer Dynamics in Methylammonium Lead Bromide Perovskites via Transient Photoluminescence Characterization.

It is an important but difficult issue to identify charge and energy transfer processes in materials where multiple band gaps coexist. Conventional methods using transient absorption and optoelectrical characterization based on devices could not provide a clear picture of transfer dynamics. According to the bimolecular and monomolecular nature of each process, the carrier dynamics is supposed to solve this issue. In this work, we established a novel, convenient and universal strategy based on the calculation of carrier dynamics to distinguish energy/charge transfer and reveal their transfer dynamics in methylammonium lead bromide (MAPbBr3) films with mixing wide-band gap small grains and narrow-band gap large grains. A highly efficient charge transfer process is confirmed with a high negative nonradiative bimolecular recombination coefficient of −2.12 × 10–7 cm–3 s–1, indicating that free carriers within small grains are efficiently transferred from small grains to large grains. As a result, emission from large grains becomes dominant when increasing the photoexcitation intensity. In addition, current-density-dependent electroluminescence results in emission only from large grains, further verifying the charge transfer process. Moreover, it is interesting to find that when decreasing the size of small grains, the charge transfer process is facilitated, leading to an increased nonradiative bimolecular recombination coefficient from −2.12 × 10–7 to −4.01 × 10–7 cm–3 s–1 in large grains. Our work provides a convenient strategy to identify and quantify energy and charge transfer in metal halide perovskites, which can be used to enrich our understanding of perovskite photophysics.

An Instantaneous Recombination Rate Method for the Analysis of Interband Recombination Processes in ZnO Crystals.

Time-resolved photoluminescence (TRPL) analysis is often performed to assess the qualitative features of semiconductor crystals using predetermined functions (e.g., double- or multi-exponentials) to fit the decays of PL intensity. However, in many cases—including the notable case of interband PL in direct gap semiconductors—this approach just provides phenomenological parameters and not fundamental physical quantities. In the present work, we highlight that within a properly chosen range of laser excitation, the TRPL of zinc oxide (ZnO) bulk crystals can be described with excellent precision with second-order kinetics for the total recombination rate. We show that this allows us to define an original method for data analysis, based on evaluating the “instantaneous” recombination rate that drives the initial slope of the decay curves, acquired as a function of the excitation laser fluence. The method is used to fit experimental data, determining useful information on fundamental quantities that appear in the second-order recombination rate, namely the PL (unimolecular) lifetime, the bimolecular recombination coefficient, the non-radiative lifetime and the equilibrium free-carrier concentration. Results reasonably close to those typically obtained in direct gap semiconductors are extracted. The method may represent a useful tool for gaining insight into the recombination processes of a charge carrier in ZnO, and for obtaining quantitative information on ZnO excitonic dynamics.

Chain aggregation dictates bimolecular charge recombination and fill factor of all-polymer blend solar cells

Small bimolecular charge recombination coefficients resulted in all-polymer blend solar cells with high fill factors. The preferred blend morphology was characterized by a well-ordered local structure, exhibiting chain aggregation by both the polymer donor and acceptor.

Investigation of charge carrier mobility and recombination in PBDTTPD thin layer structures

Abstract In this paper we present investigation of hole transport properties in sandwich and OFET structures with single active layer of PBDTTPD (Poly[(5,6-dihydro-5-octyl-4,6-dioxo-4H-thieno[3,4-c]pyrrole-1,3-diyl)[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]]). Sandwich structures were investigated by photo-CELIV and TOF techniques, obtained results showed strongly time dependent hole mobility and non-Gaussian DOS tail. Photogenerated charge carrier decay experiment demonstrated that bimolecular recombination coefficient is smaller than calculated Langevin recombination coefficient and this was explained by faster holes escaping recombination area and not participating in Langevin recombination process. Organic field-effect transistor structure was investigated by current transients technique to find hole mobility near the dielectric layer and to study OTS treatment influence on hole transport. The study of hole mobility dependence on temperature was performed in order to evaluate energetic disorder of interface DOS in the channel of OFET structures.

On the recombination order of surface recombination under open circuit conditions

Understanding the recombination dynamics of organic and perovskite solar cells has been a crucial prerequisite in the steadily increasing performance of these promising new types of photovoltaics. Surface recombination in particular has turned out to be one of the last remaining roadblocks, which specifically reduces the open circuit voltage. In this study, the relationship between the rate of surface recombination and the density of charge carriers is analyzed, revealing a cubic dependence between these two parameters. This hypothesis is then tested and verified with the recombination dynamics of an organic solar cell known to exhibit significant surface recombination and a high energy proton irradiated CH 3 NH 3 PbI 3 perovskite solar cell during white light illumination. Incidentally, these results can also explain recombination orders exceeding the commonly known threshold for bimolecular recombination that have been observed in some studies without the need for a charge carrier dependent bimolecular recombination coefficient. • Surface recombination specifically reduces the open circuit voltage in organic and perovskite solar cells. • A cubic relationship between the rate of surface recombination and the charge carrier density has been derived. • This hypothesis has been successfully tested for organic and perovskite solar cells. • Recombination orders β > 2 can now be explained without charge carrier density dependent k bm .

Probing photoelectrical transport in lead halide perovskites with van der Waals contacts.

Lead halide perovskites have attracted increasing interest for their exciting potential in diverse optoelectronic devices. However, their charge transport properties remain elusive, plagued by the issues of excessive contact resistance and large hysteresis in ambient conditions. Here we report a van der Waals integration approach for creating high-performance contacts on monocrystalline halide perovskite thin films with minimum interfacial damage and an atomically clean interface. Compared to the deposited contacts, our van der Waals contacts exhibit two to three orders of magnitude lower contact resistance, enabling systematic transport studies in a wide temperature range. We report a Hall mobility exceeding 2,000 cm2 V-1 s-1 at around 80 K, an ultralow bimolecular recombination coefficient of 3.5 × 10-15 cm3 s-1 and a photocurrent gain >106 in the perovskite thin films. Furthermore, magnetotransport studies reveal a quantum-interference-induced weak localization behaviour with a phase coherence length up to 49 nm at 3.5 K. Our results lay the foundation for exploring new physics in this class of 'soft-lattice' materials.

Carrier recombination mechanism in CsPbBr3 revealed by time-resolved photoluminescence spectroscopy

We systematically investigate the recombination mechanism of photogenerated charge carriers in bulk $\mathrm{CsPbB}{\mathrm{r}}_{3}$ by means of time-resolved photoluminescence (TR-PL) spectroscopy at low temperature and various laser excitation powers. A dynamic recombination model is proposed to describe the TR-PL that predicts the time-dependent exciton and free-charge populations. It provides a clear representation of competing mono- and bimolecular recombination processes. A decrease in carrier lifetime with increasing laser intensity was observed that was attributed to exciton-exciton scattering. A bimolecular recombination coefficient of $\ensuremath{\sim}{10}^{\ensuremath{-}7}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{3}/\mathrm{s}$ was obtained for exciton recombination. As the concentration of photoexcited carriers increases, stronger exciton-exciton annihilation occurs. The exciton-exciton annihilation rate for $\mathrm{CsPbB}{\mathrm{r}}_{3}$ is $3.63\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{3}\phantom{\rule{0.16em}{0ex}}{\mathrm{s}}^{\ensuremath{-}1}$ at 10-mW laser power. Notably, the exciton-exciton annihilation rate in bulk material is comparable to that obtained for photoexcited $\mathrm{CsPbB}{\mathrm{r}}_{3}$ nanoscale quantum dots.

Reliability of charge carrier recombination data determined with charge extraction methods

Charge extraction methods are popular for measuring the charge carrier density in thin film organic solar cells and to draw conclusions about the order and coefficient of nongeminate charge recombination. However, results from such studies may be falsified by inhomogeneous steady state carrier profiles or surface recombination. Here, we present a detailed drift-diffusion study of two charge extraction methods, bias-assisted charge extraction (BACE) and time-delayed collection field (TDCF). Simulations are performed over a wide range of the relevant parameters. Our simulations reveal that both charge extraction methods provide reliable information about the recombination order and coefficient if the measurements are performed under appropriate conditions. However, results from BACE measurements may be easily affected by surface recombination, in particular for small active layer thicknesses and low illumination densities. TDCF, on the other hand, is more robust against surface recombination due to its transient nature but also because it allows for a homogeneous high carrier density to be inserted into the active layer. Therefore, TDCF is capable to provide meaningful information on the order and coefficient of recombination even if the model conditions are not exactly fulfilled. We demonstrate this for an only 100 nm thick layer of a highly efficient nonfullerene acceptor (NFA) blend, comprising the donor polymer PM6 and the NFA Y6. TDCF measurements were performed as a function of delay time for different laser fluences and bias conditions. The full set of data could be consistently fitted by a strict second order recombination process, with a bias- and fluence-independent bimolecular recombination coefficient k2 = 1.7 × 10−17 m3 s−1. BACE measurements performed on the very same layer yielded the identical result, despite the very different excitation conditions. This proves that recombination in this blend is mostly through processes in the bulk and that surface recombination is of minor importance despite the small active layer thickness.

Room-temperature stability of excitons and transverse-electric polarized deep-ultraviolet luminescence in atomically thin GaN quantum wells

We apply first-principles calculations to study the effects of extreme quantum confinement on the electronic, excitonic, and radiative properties of atomically thin (1–4 atomic monolayers) GaN quantum wells embedded in AlN. We determine the quasiparticle bandgaps, exciton energies and wave functions, radiative lifetimes, and Mott critical densities as a function of well and barrier thickness. Our results show that quantum confinement in GaN monolayers increases the bandgap up to 5.44 eV and the exciton binding energy up to 215 meV, indicating the thermal stability of excitons at room temperature. Exciton radiative lifetimes range from 1 to 3 ns at room temperature, while the Mott critical density for exciton dissociation is approximately 1013 cm−2. The luminescence is transverse-electric polarized, which facilitates light extraction from c-plane heterostructures. We also introduce a simple approximate model for calculating the exciton radiative lifetime based on the free-carrier bimolecular radiative recombination coefficient and the exciton radius, which agrees well with our results obtained with the Bethe–Salpeter equation predictions. Our results demonstrate that atomically thin GaN quantum wells exhibit stable excitons at room temperature for potential applications in efficient light emitters in the deep ultraviolet as well as room-temperature excitonic devices.

Determination of bimolecular recombination constants in organic double-injection devices using impedance spectroscopy

A method for determination of the bimolecular recombination constant in working double-injection diodes such as organic light-emitting diodes (OLEDs) and organic photovoltaics (OPVs) using impedance spectroscopy is proposed. The proposed method is based on the theory that was developed to interpret the negative capacitance that has previously been observed in both OLEDs and OPVs. The determination of the bimolecular recombination constants is demonstrated using working polymer light-emitting diodes based on poly(9,9-dioctylfluorene-alt-benzothiadiazole). These impedance spectroscopy measurements thus allow us to determine the required bimolecular recombination coefficients along with the electron and hole drift mobilities in working organic double-injection diodes.

Apparent Field‐Dependence of the Charge Carrier Generation in Organic Solar Cells as a Result of (Bimolecular) Recombination

Charge carrier generation in organic solar cells is often reported to depend on the electric field. This is, however, not measured directly but derived from transient charge carrier extraction experiments based on the time delayed collection field (TDCF) method. In this work, numerical simulations of TDCF experiments are presented which – when analyzed in the same way as reported in literature – result in a field‐dependence of charge carrier generation despite the fact that a field‐independent generation is used. This discrepancy is shown to be caused by recombination of photogenerated charge carriers occurring in the time range prior to and during extraction. This apparent field‐dependence becomes more pronounced for larger recombination coefficients and decreasing charge carrier mobilities, very much in accordance with experimental TDCF data from literature. Even an apparent voltage‐ and time‐dependence of the bimolecular recombination coefficient is reproduced in the simulations although a constant, voltage‐independent one is used. These findings strongly question whether TDCF is an appropriate method to detect a potential field‐dependence of the photocurrent generation and the recombination coefficient. Our study shows that all experimental results can consistently be explained without the assumption of a field‐dependence of the charge carrier generation and the bimolecular recombination coefficient.

High open-circuit voltage in perovskite solar cells: The role of hole transport layer

Abstract Using the drift-diffusion model, a new expression for the open-circuit voltage ( V o c ) in perovskite solar cells is derived. The V o c increases with the ratio of the charge carrier mobilities ( μ e / μ h ) and by lowering the HOMO energy level of the hole transport layer (HTL). Using the derived V o c , we have found an analytical expression for the bimolecular recombination coefficient which decreases exponentially with increasing temperature. We have shown that the recombination coefficient thus derived is reduced by the formation of polarons, which may be expected to increase the photocurrent and hence power conversion efficiency in perovskite solar cells.

Effect of Low Temperature on Charge Transport in Operational Planar and Mesoporous Perovskite Solar Cells.

Low-temperature optoelectrical studies of perovskite solar cells using MAPbI3 and mixed-perovskite absorbers implemented into planar and mesoporous architectures reveal fundamental charge transporting properties in fully assembled devices operating under light bias. Both types of devices exhibit inverse correlation of charge carrier lifetime as a function of temperature, extending carrier lifetimes upon temperature reduction, especially after exposure to high optical biases. Contribution of bimolecular channels to the overall recombination process should not be overlooked because the density of generated charge surpasses trap-filling concentration requirements. Bimolecular charge recombination coefficient in both device types is smaller than Langevin theory prediction, and its mean value is independent of the applied illumination intensity. In planar devices, charge extraction declines upon MAPbI3 transition from a tetragonal to an orthorhombic phase, indicating a connection between the trapping/detrapping mechanism and temperature. Studies on charge extraction by linearly increasing voltage further support this assertion, as charge carrier mobility dependence on temperature follows multiple-trapping predictions for both device structures. The monotonously increasing trend following the rise in temperature opposes the behavior observed in neat perovskite films and indicates the importance of transporting layers and the effect they have on charge transport in fully assembled solar cells. Low-temperature phase transition shows no pattern of influence on thermally activated electron/hole transport.

Charge transport in quantum dot organic solar cells with Si quantum dots sandwiched between poly(3-hexylthiophene) (P3HT) absorber and bathocuproine (BCP) transport layers

We have modeled a multilayer quantum dot organic solar cell that explores the current-voltage characteristic of the solar cell whose characteristics can be tuned by varying the fabrication parameters of the quantum dots (QDs). The modeled device consists of a hole transport layer (HTL) which doubles up as photon absorbing layer, several quantum dot layers, and an electron transport layer (ETL). The conduction of charge carriers in HTL and ETL has been modeled by the drift-diffusion transport mechanism. The conduction and recombination in the quantum dot layers are described by a system of coupled rate equations incorporating tunneling and bimolecular recombination. Analysis of QD-solar cells shows improved device performance compared to the similar bilayer and trilayer device structures without QDs. Keeping other design parameters constant, solar cell characteristics can be controlled by the quantum dot layers. Bimolecular recombination coefficient of quantum dots is a prime factor which controls the open circuit voltage (VOC) without any significant reduction in short circuit current (JSC).

Manipulating the Net Radiative Recombination Rate in Lead Halide Perovskite Films by Modification of Light Outcoupling.

Photon recycling is a fundamental physical process that becomes especially important for photovoltaic devices that operate close to the radiative limit. This implies that the externally measured radiative decay rate deviates from the internal radiative recombination rate of the material. In the present Letter, the probability of photon recycling in organic lead halide perovskite films is manipulated by modifying the underlying layer stacks. We observe recombination kinetics by time-resolved photoluminescence that is controlled by the optical design of the chosen layer structure. Quantitative simulations of decay rates and emission spectra show excellent agreement with experimental results if we assume that the internal bimolecular recombination coefficient is ∼66% radiative.

Photon Reabsorption Masks Intrinsic Bimolecular Charge-Carrier Recombination in CH3NH3PbI3 Perovskite.

An understanding of charge-carrier recombination processes is essential for the development of hybrid metal halide perovskites for photovoltaic applications. We show that typical measurements of the radiative bimolecular recombination constant in CH3NH3PbI3 are strongly affected by photon reabsorption that masks a much larger intrinsic bimolecular recombination rate constant. By investigating a set of films whose thickness varies between 50 and 533 nm, we find that the bimolecular charge recombination rate appears to slow by an order of magnitude as the film thickness increases. However, by using a dynamical model that accounts for photon reabsorption and charge-carrier diffusion we determine that a single intrinsic bimolecular recombination coefficient of value 6.8 × 10-10 cm3s-1 is common to all samples irrespective of film thickness. Hence, we postulate that the wide range of literature values reported for such coefficients is partly to blame on differences in photon out-coupling between samples with crystal grains or mesoporous scaffolds of different sizes influencing light scattering, whereas thinner films or index-matched surrounding layers can reduce the possibility for photon reabsorption. We discuss the critical role of photon confinement on free charge-carrier retention in thin photovoltaic layers and highlight an approach to assess the success of such schemes from transient spectroscopic measurement.

Structural Order: The Dominant Factor for Nongeminate Recombination in Organic Photovoltaic Devices

Reducing nongeminate recombination (NGR) will provide a major boost to the performance of bulk heterojunction (BHJ) organic photovoltaic (OPV) devices. It is therefore critical to identify the dominant factor(s) that determines NGR. While substantial research effects have been made and various factors have been considered, the determining factor has not been ascertained. After comprehensively evaluating the impact of deep defect states, donor–acceptor interfacial area, and mobility, here we demonstrate that the structural order is the dominant factor that determines NGR in OPV devices. Intensity modulated photovoltage spectroscopy in conjunction with the charge extraction technique is applied to quantitatively measure bimolecular recombination coefficients. A model P3HT:PCBM system with varying composition and annealing temperature, which removes uncontrolled variables yet resembles the behaviors of different polymer donor OPV systems, enables us to reach the unambiguous conclusion. Our findings shed ligh...

Carrier-density-dependent recombination dynamics of excitons and electron-hole plasma in m -plane InGaN/GaN quantum wells

We study the carrier-density-dependent recombination dynamics in $m$-plane InGaN/GaN multiple quantum wells in the presence of $n$-type background doping by time-resolved photoluminescence. Based on Fermi's golden rule and Saha's equation, we decompose the radiative recombination channel into an excitonic and an electron-hole pair contribution, and extract the injected carrier-density-dependent bimolecular recombination coefficients. Contrary to the standard electron-hole picture, our results confirm the strong influence of excitons even at room temperature. Indeed, at 300 K, excitons represent up to 63 \ifmmode\pm\else\textpm\fi{} 6% of the photoexcited carriers. In addition, following the Shockley-Read-Hall model, we extract the electron and hole capture rates by deep levels and demonstrate that the increase in the effective lifetime with injected carrier density is due to asymmetric capture rates in presence of an $n$-type background doping. Thanks to the proper determination of the density-dependent recombination coefficients up to high injection densities, our method provides a way to evaluate the importance of Auger recombination.