Recombination Of Free Carriers Research Articles

Monolayer-like Exciton Recombination Dynamics of Multilayer MoSe2 Observed by Pump-Probe Microscopy.

Transition metal dichalcogenides (TMDCs) have garnered considerable interest over the past decade as a class of semiconducting layered materials. Most studies on the carrier dynamics in these materials have focused on the monolayer due to its direct bandgap, strong photoluminescence, and strongly bound excitons. However, a comparative understanding of the carrier dynamics in multilayer (e.g., >10 layers) flakes is still absent. Recent computational studies have suggested that excitons in bulk TMDCs are confined to individual layers, leading to room-temperature stable exciton populations. Using this new context, we explore the carrier dynamics in MoSe2 flakes that are between ∼16 and ∼125 layers thick. We assign the kinetics to exciton-exciton annihilation (EEA) and Shockley-Read-Hall recombination of free carriers. Interestingly, the average observed EEA rate constant (0.003 cm2/s) is nearly independent of flake thickness and 2 orders of magnitude smaller than that of an unencapsulated monolayer (0.33 cm2/s) but very similar to values observed in encapsulated monolayers. Thus, we posit that strong intralayer interactions minimize the effect of layer thickness on recombination dynamics, causing the multilayer to behave like the monolayer and exhibit an apparent EEA rate intrinsic to MoSe2.

Sub-nanosecond free carrier recombination in an indirectly excited quantum-well heterostructure

Nanometer-thick quantum-well structures are quantum model systems offering a few discrete unoccupied energy states that can be impulsively filled and that relax back to equilibrium predominantly via spontaneous emission of light. Here we report on the response of an indirectly excited quantum-well heterostructure, probed by means of time and frequency resolved photoluminescence spectroscopy. This experiment provides access to the sub-nanosecond evolution of the free electron density, indirectly injected into the quantum wells. In particular, the modeling of the time-dependent photoluminescence spectra unveils the time evolution of the temperature and of the chemical potentials for electrons and holes, from which the sub-nanosecond time-dependent electron density is determined. This information allows to prove that the recombination of excited carriers is mainly radiative and bimolecular at early delays after excitation, while, as the carrier density decreases, a monomolecular and non-radiative recombination channel becomes relevant. Access to the sub-nanosecond chronology of the mechanisms responsible for the relaxation of charge carriers provides a wealth of information for designing novel luminescent devices with engineered spectral and temporal behavior.

(Invited) Signatures of Charge Carrier (De)Localization in Semiconducting Single-Walled Carbon Nanotubes

Semiconducting single-walled carbon nanotubes (s-SWCNTs) are attractive materials for a variety of opto-electronic devices and applications due their strong and energetically tunable optical absorption, and high charge carrier mobilities that result from the delocalized nature of the π-electron system. To realize the full potential of s-SWCNTs in these applications, it is critical to understand the generation, transport, interfacial transfer, and recombination of free charge carriers (electrons and holes). As with many pi-conjugated semiconductors, there remain uncertainties regarding the degree of (de)localization for charge carriers generated in s-SWCNTs either through photogenerated exciton dissociation or through charge injection by adsorbed redox dopants or gating. In this presentation, I will compare the various signatures of charge carrier localization and delocalization that appear in spectroscopic and transport studies of s-SWCNTs in a variety of different environments and over several decades of carrier density. These comparisons help to elucidate the important roles of intrinsic and extrinsic factors on carrier (de)localization and the information that spectroscopic signatures in the visible, near-IR, and mid-IR can provide on such (de)localization.

Resolving the Ultrafast Charge Carrier Dynamics of 2D and 3D Domains within a Mixed 2D/3D Lead‐Tin Perovskite

AbstractMixed 2D/3D perovskite materials are of particular interest to the photovoltaics and light‐ emitting diode (LED) communities due to their impressive opto‐electronic properties alongside improved moisture stability compared to conventional 3D perovskite absorbers. Here, a mixed lead‐tin perovskite containing distinct, self‐assembled domains of either 3D structures or highly phase‐pure Ruddlesden–Popper 2D structures is studied. The complex energy landscape of the material is revealed with ultrafast optical transient absorption measurements. It is shown that charge transfer between these microscale domains only occurs on nanosecond timescales, consistent with the large size of the domains. Using optical pump‐terahertz probe spectroscopy, the effective charge‐carrier mobility is shown to be an intermediary between analogous pure 2D and 3D perovskites. Furthermore, detailed analysis of the free carrier recombination dynamics is presented. By combining results from a range of excitation wavelengths within a full dynamic model of the photoexcited carrier population, it is shown that the 2D domains in the film exhibit remarkably similar carrier dynamics to the 3D domains, suggesting that long‐range charge‐transport should not be impeded by the heterogeneous structure of the material.

Self‐Doping of the Transport Layers Decreases the Bimolecular Recombination by Reducing Static Disorder

Electron‐transport layers (ETLs) have a crucial role in the solar cells’ performance. Generally, ETLs are characterized in terms of the interface properties and conductivity rather than their effect on the photoactive layer. Herein, two ETLs, 2,9‐bis(3‐((3‐(dimethylamino)propyl)amino)propyl)anthra[2,1,9‐def:6,5,10‐d′e′f′]diisoquinoline‐1,3,8,10(2H,9H)‐tetraone (PDINN) and 2,9‐bis[3‐(dimethyloxidoamino)propyl]anthra[2,1,9‐def:6,5,10‐d′e′f′]diisoquinoline‐1,3,8,10(2H,9H)‐tetrone, are compared in the conventional PM6:Y6 organic solar cell (OSC) structure and the influence of the ETL on the photoactive layer is shown. It is shown that a significant portion of the unpaired electrons of PDINN is mobile by combining electron paramagnetic resonance and Hall effect measurements. It is established that the high doping in PDINN ETL changes the dark electron concentration of the photoactive layer. The impacts of this change in the photoactive layer can be observed in the reduced static energetic disorder, and subsequently in the (nonradiative) recombination of free carriers. The results can be used to suppress nonradiative recombination in OSC, which can significantly boost their efficiency.

Understanding and Suppressing Non-Radiative Recombination Losses in Non-Fullerene Organic Solar Cells.

Organic solar cells benefit from non-fullerene acceptors (NFA) due to their high absorption coefficients, tunable frontier energy levels, and optical gaps, as well as their relatively high luminescence quantum efficiencies as compared to fullerenes. Those merits result in high yields of charge generation at a low or negligible energetic offset at the donor/NFA heterojunction, with efficiencies over 19% achieved for single-junction devices. Pushing this value significantly over 20% requires an increase in open-circuit voltage, which is currently still well below the thermodynamic limit. This can only be achieved by reducing non-radiative recombination, and hereby increasing the electroluminescence quantum efficiency of the photo-active layer. Here, current understanding of the origin of non-radiative decay, as well as an accurate quantification of the associated voltage losses are summarized. Promising strategies for suppressing these losses are highlighted, with focus on new material design, optimization of donor-acceptor combination, and blend morphology. This review aims at guiding researchers in their quest to find future solar harvesting donor-acceptor blends, which combine a high yield of exciton dissociation with a high yield of radiative free carrier recombination and low voltage losses, hereby closing the efficiency gap with inorganic and perovskite photovoltaics.

Charge Separation from Triplet Excited States in Nonfullerene Acceptor‐Based Organic Solar Cells

Suppressing charge recombination is pivotal for further improving the power conversion efficiency of organic solar cells (OSCs). The bimolecular recombination of free charge carriers leads to the formation of both singlet and triplet charge transfer (CT) states at a ratio of 1:3 when considering simple spin statistics, meaning that charge recombination via the triplet excited state is the main deactivation channel for OSCs. Although the formation of local triplet excitons through back charge transfer from triplet CT states is thought to be a terminal loss process, it is shown that charge separation from triplet excitons can occur in nonfullerene acceptor (NFA)‐based OSCs. To reveal the triplet exciton dynamics, a triplet sensitizer PtTPBP is doped into an OSC consisting of PM6 and Y6 as an electron donor and acceptor, respectively. Upon photoexcitation of PtTPBP, triplet excitons are formed, which subsequently transfer their energy to Y6, resulting in Y6 triplet excitons formation. Based on transient absorption and external quantum efficiency measurements, clear experimental evidence of charge photogeneration from Y6 triplet excitons at the PM6:Y6 interface is provided. This study highlights the importance of minimizing the energy difference between the singlet and triplet excited states of NFAs to suppress charge recombination.

Advancement of Physical and Photoelectrochemical Properties of Nanostructured CdS Thin Films toward Optoelectronic Applications.

CdS thin films were grown on an FTO substrate at different temperatures, employing the low-cost hydrothermal method. All the fabricated CdS thin films were studied using XRD, Raman spectroscopy, SEM, PL spectroscopy, a UV-Vis spectrophotometer, photocurrent, Electrochemical Impedance Spectroscopy (EIS), and Mott-Schottky measurements. According to the XRD results, all the CdS thin films were formed in a cubic (zinc blende) structure with a favorable (111) orientation at various temperatures. The Scherrer equation was used to determine the crystal size of the CdS thin films, which varied from 25 to 40 nm. The SEM results indicated that the morphology of thin films seems to be dense, uniform, and tightly attached to the substrates. PL measurements showed the typical green and red emission peaks of CdS films at 520 nm and 705 nm, and these are attributable to free-carrier recombination and sulfur vacancies or cadmium vacancies, respectively. The optical absorption edge of the thin films was positioned between 500 and 517 nm which related to the CdS band gap. For the fabricated thin films, the estimated Eg was found to be between 2.50 and 2.39 eV. According to the photocurrent measurements, the CdS thin films grown were n-type semiconductors. As indicated by EIS, resistivity to charge transfer (RCT) decreased with temperature, reaching its lowest level at 250 °C. Flat band potential and donor density were found to fluctuate with temperature, from 0.39 to 0.76 V and 4.41 × 1018 to 15.86 × 1018 cm-3, respectively, according to Mott-Schottky measurements. Our results indicate that CdS thin films are promising candidates for optoelectronic applications.

Exciton recombination in few‐layer MoS2 nanosheets: Role of free carriers and defects

A current obstacle to the development of extremely flexible and high‐performance optoelectronic devices using transition metal dichalcogenide nanosheets is the incomplete understanding of the exciton and free carrier recombination in the presence of defects. Here, taking liquid‐phase exfoliated few‐layer MoS2 nanosheets as a model system, we demonstrate the exciton and free carrier recombination mechanism by employing pump energy and fluence‐dependent ultrafast transient absorption spectroscopy. We demonstrate that 3.10 eV pump excitation, much above the lowest energy A exciton of four to six layers of MoS2 nanosheets (~1.84 eV), generates excitons and free carriers. The excitons decay quickly within ~3 ps due to the defect capture via the Shockley–Read–Hall mechanism. In contrast, free carriers show slower recombination (~1000 ps), which is an order of magnitude larger than the exciton recombination time. We verified this idea by exciting the sample with 1.94–2.22 eV pump excitations that predominantly generate excitons decaying within ~3 ps. Our systematic studies in few‐layer MoS2 nanosheets reveal crucial information on the unexplored domain of excitons and free carriers recombination in the presence of defects for several optoelectronic applications.

Metal oxide semiconductor nanowires enabled air-stable ultraviolet-driven synaptic transistors for artificial vision

The multi-terminal transistor can provide reliable platform to construct artificial synapses with various benefits. In particular, synaptic transistors based on wide-bandgap metal oxide semiconductors (MOSs) offer opportunities to realize ultraviolet (UV) artificial vision. In this work, via a low-cost electrospinning technique, we have fabricated bio-inspired synaptic transistors based on zinc tin oxide (ZnSnO) nanowires, which can be effectively tuned by UV laser to achieve air-stable synaptic characteristics, such as excitatory post-synaptic current, paired-pulse facilitation, and learning-forgetting process based on long-term potentiation. The adsorption/desorption of oxygen molecules governs the generation of free charge carriers in the ZnSnO nanowires. Via the combination of transmission electron microscopy and X-ray diffraction measurements, we found that the revealed SnO2/ZnO heterostructures can effectively mitigate the recombination of UV-induced free carriers in the ZnSnO nanowires. Furthermore, based on the synaptic characteristics obtained from ZnSnO nanowires, we present several applications relevant to the UV artificial vision. We believe this study can provide insights into importance of heterostructures in synaptic transistors based on low-dimension MOSs with superior environmental stability and various applications.

Polarization-Sensitive Nonlinear Optical Interaction of Ultrashort Laser Pulses with HPHT Diamond

The filamentation of focused 300 fs laser pulses with variable polarization azimuth in bulk of synthetic HPHT diamond demonstrates the possibility of polarization-dependent bandgap control for crystal dielectric photoexcitation. This directly affects the value of the filamentation threshold power, which exhibits the distinct dependence on the polarization azimuth angle. The nonlinear photoluminescence yield, when focusing ultrashort laser pulses with variable polarization in bulk of the synthetic diamond, indicates different polarization-dependent regimes in the dynamics of electron-hole plasma formation, arising due to different processes of photoexcitation and recombination of free carriers during the filamentation process. Thus, at the onset of the filamentation process, at relatively low intensities, the photoluminescence yield rate depends on polarization azimuth controlling bandgap, while at high intensities the resulting dense absorbing plasma exhibits isotropy with respect to laser radiation polarization, and photoluminescence yield weakly depends on polarization azimuth.

Relationship between Energetic Disorder and Reduced Recombination of Free Carriers in Organic Solar Cells

AbstractReducing non‐radiative recombination is key to achieve high fill factors (FFs) in organic solar cells. While it is generally accepted that recombination proceeds via charge transfer (CT) states at the donor:acceptor interface, the underlying principles that dictate the decay kinetics of these CT states are not yet well understood. Here, a study on the effect of energetic disorder is presented. Based on a data set of 10 representative donor:acceptor blends, clear correlations between disorder, the recombination coefficient of free charge carriers, and the non‐radiative voltage loss are found. It is suggested that a narrower distribution of CT energies leads to a longer CT decay time and thus reduces non‐radiative losses. This leads to a simultaneous improvement of the FF and open circuit voltage and highlights the importance of having materials with low energetic disorder on the way to the commercialisation of organic photovoltaics.

Terahertz Modulation and Ultrafast Characteristic of Two-Dimensional Lead Halide Perovskites.

In recent years, two-dimensional (2D) halide perovskites have been widely used in solar cells and photoelectric devices due to their excellent photoelectric properties and high environmental stability. However, the terahertz (THz) and ultrafast responses of the 2D halide perovskites are seldom studied, limiting the developments and applications of tunable terahertz devices based on 2D perovskites. Here, 2D R-P type (PEA)2(MA)2Pb3I10 perovskite films are fabricated on quartz substrates by a one-step spin-coating process to study their THz and ultrafast characteristics. Based on our homemade ultrafast optical pump–THz probe (OPTP) system, the 2D perovskite film shows an intensity modulation depth of about 10% and an ultrafast relaxation time of about 3 ps at a pump power of 100 mW due to the quantum confinement effect. To further analyze the recombination mechanisms of the photogenerated carriers, a three-exponential function is used to fit the carrier decay processes, obtaining three different decay channels, originating from free carrier recombination, exciton recombination, and trap-assisted recombination, respectively. In addition, the photoconductor changes (∆σ) at different pump–probe delay times are also investigated using the Drude-Smith model, and a maximum difference of 600 S/m is obtained at τp = 0 ps for a pump power of 100 mW. Therefore, these results show that the 2D (PEA)2(MA)2Pb3I10 film has potential applications in high-performance tunable and ultrafast THz devices.

Light emitters based on CdTe doped with isovalent impurities

The problems of developing light-emitting structures based on CdTe with an extended range of operating temperatures and radiation-resistant parameters are studied. A technique for obtaining heterostructures has been mastered, technological modes of isovalent substitution have been determined, and radiation sources with a high quantum efficiency η = 7–20% at 300 K in a wide spectral region have been obtained. The design of devices has been developed and light emitters based on CdTe, whose radiation is determined by the interband recombination of free charge carriers and the dominant annihilation of bound excitons, have been fabricated by doping with isovalent impurities Mg, Ca.

Charge Carrier and Exciton Dynamics in Perovskites Revealed by Time‐Integrated Photoluminescence after Double‐Pulse Excitation

AbstractThe rate constants that describe the decays of excited states (free charge carriers, excitons) are important parameters for perovskite materials. Typically, these rates are determined using detectors with high time‐resolution to record the time‐dependent photoluminescence on the nanosecond scale. Herein, a method is applied that uses two excitation pulses with a variable delay and an inexpensive detector capable of measuring only the quasisteady state photoluminescence. Based on how the time‐integrated photoluminescence varies as a function of the delay time between the two excitation pulses, the rate constants for exciton–exciton annihilation, monomolecular exciton decay, bimolecular free charge carrier recombination, and monomolecular trapping of free charge carriers can be extracted. To demonstrate the method quasi‐2D perovskites are investigated as they are known to exhibit excited‐state populations that can be exciton dominated, free charge carrier dominated, or a mixture of the two. The method leads to unique curves and accurate extracted parameters in all cases. The introduced method of determining excited‐state lifetimes can be used with detectors that only have a low temporal resolution. This opens the path to the spatial mapping of excited‐state dynamics using standard cameras which would be attractive for quality control of photovoltaic layers.

Thermally Activated Reverse Electron Transfer Limits Carrier Generation Efficiency in PM6:Y6 Non‐Fullerene Organic Solar Cells

Transient absorption and time‐resolved fluorescence measurements in a wide temperature range are used to investigate the mechanism of charge carrier generation in efficient organic solar cells based on a PM6:Y6 donor–acceptor blend. The generation mechanisms differ significantly under excitation of a donor or acceptor. The investigations reveal a temperature‐dependent interplay between the formation of interfacial charge transfer (CT) states and intra‐moiety CT states of the acceptor, their separation into free charge carriers and carrier recombination. The efficient charge carrier generation is ensured by the carrier separation over a small energy barrier, which is easily surmountable at room temperature. However, the overall yield of charge carrier generation at room temperature is reduced by the recombination of charge carriers due to the thermally activated back transfer of electrons from the acceptor to the donor via the highest occupied molecular orbit (HOMO) levels, which is enabled by the small energy offset between HOMO levels of the donor and the acceptor.

Monitoring of Dose Dependent Damage in MeV Energy Hydrogen Implanted Silicon by Photo-Modulated Reflectance Measurements

High-energy low-mass proton implantation achieved considerable interest in semiconductor technology, due to much deeper penetration of hydrogen ions into silicon as compared to common dopants, boron, phosphorous, and arsenic. Accordingly, monitoring the accumulation kinetics and stability of proton-implantation induced defects and their influence on the optical and electrical properties of Si achieved increased attention both in technological process control and scientific research. We show that photo-modulated-reflectance (PMR) is effective technique to measure very low defect concentrations in the ppb-ppm range in high energy proton implanted silicon. After ion irradiation, the as-implanted dilute damage structure may lead to long term changes of the defect distribution and the formation of defect compounds due to mobility of point defects at room temperature. Moreover, low-mass hydrogen atoms may move significantly faster at room temperature compared to heavier dopants. We show that PMR is capable to detect differences in implanted proton dose with high sensitivity in a wide dose range, and, on a longer time scale, allows to follow changes in free carrier generation and recombination processes through the measurement of the long term decay of the PMR signal which is related to the sample response based on electro-optic and thermo-optic effects. Our experiments may pave the way toward high precision process control of device structure fabrication which utilizes the high-energy hydrogen implantation step. Also, our aim is to gain insight into the main processes underlying the dose dependent change and long-term decay of the PMR signal in high energy proton implanted Si.

Charge carrier dynamics in different crystal phases of CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> perovskite

Despite that organic-inorganic lead halide perovskites have attracted enormous scientific attention for energy conversion applications over the recent years, the influence of temperature and the type of the employed hole transport layer (HTL) on the charge carrier dynamics and recombination processes in perovskite photovoltaic devices is still largely unexplored. In particular, significant knowledge is missing on how these crucial parameters for radiative and non-radiative recombinations, as well as for efficient charge extraction vary among different perovskite crystalline phases that are induced by temperature variation. Herein, we perform micro photoluminescence (μPL) and ultrafast time resolved transient absorption spectroscopy (TAS) in Glass/Perovskite and two different Glass/ITO/HTL/Perovskite configurations at temperatures below room temperature, in order to probe the charge carrier dynamics of different perovskite crystalline phases, while considering also the effect of the employed HTL polymer. Namely, CH₃NH₃PbI₃ films were deposited on Glass, PEDOT:PSS and PTAA polymers, and the developed Glass/CH₃NH₃PbI₃ and Glass/ITO/HTL/CH₃NH₃PbI₃ architectures were studied from 85 K up to 215 K in order to explore the charge extraction dynamics of the CH₃NH₃PbI₃ orthorhombic and tetragonal crystalline phases. It is observed an unusual blueshift of the bandgap with temperature and the dual emission at temperature below of 100 K and also, that the charge carrier dynamics, as expressed by hole injection times and free carrier recombination rates, are strongly depended on the actual pervoskite crystal phase, as well as, from the selected hole transport material.

Interpreting the Time‐Resolved Photoluminescence of Quasi‐2D Perovskites

AbstractOptical excitation of quasi‐2D perovskites leads to excited‐state populations of excitons, free charge carriers, or a mixture of both, depending on the type and amount of 2D spacer used. The fluence dependence of three quantities: 1) the time‐resolved photoluminescence decay, 2) the photoluminescence quantum yield (PLQY) after pulsed excitation, and 3) the initial rate of photon emission, allow the mixture of excited states present to be determined. These can be described by a simple model considering noninteracting populations of excitons and charge carriers in separate subvolumes of the film. The model reproduces all unique features of the data, such as the anomalous peak of the PLQY at intermediate fluences, due to bimolecular free carrier emission gaining efficiency before exciton–exciton annihilation reduces the exciton emission efficiency. The excited state population varies from 100% excitons in films made from high concentrations of butylamine spacers to ≈7% excitons and 93% free carriers for low concentrations of 1‐naphthylmethylamine spacers. The effective rates of free carrier recombination and exciton–exciton annihilation are high, often on the order of 1 × 10−9 cm3 s−1. The implications for the different excited‐state populations and their dynamics in terms of device engineering are discussed.

Orders of Recombination in Complete Perovskite Solar Cells – Linking Time‐Resolved and Steady‐State Measurements

AbstractIdeally, the charge carrier lifetime in a solar cell is limited by the radiative free carrier recombination in the absorber which is a second‐order process. Yet, real‐life cells suffer from severe nonradiative recombination in the bulk of the absorber, at interfaces, or within other functional layers. Here, the dynamics of photogenerated charge carriers are probed directly in pin‐type mixed halide perovskite solar cells with an efficiency >20%, using time‐resolved optical absorption spectroscopy and optoelectronic techniques. The charge carrier dynamics in complete devices is fully consistent with a superposition of first‐, second‐, and third‐order recombination processes, with no admixture of recombination pathways with non‐integer order. Under solar illumination, recombination in the studied solar cells proceeds predominantly through nonradiative first‐order recombination with a lifetime of 250 ns, which competes with second‐order free charge recombination which is mostly if not entirely radiative. Results from the transient experiments are further employed to successfully explain the steady‐state solar cell properties over a wide range of illumination intensities. It is concluded that improving carrier lifetimes to >3 µs will take perovskite devices into the radiative regime, where their performance will benefit from photon‐recycling.