Nonradiative Recombination Of Excitons Research Articles

Shortwave-Infrared Silver Chalcogenide Quantum Dots for Optoelectronic Devices.

Silver chalcogenide (Ag2X, X = S, Se, Te) semiconductor quantum dots (QDs) have been extensively studied owing to their short-wave infrared (SWIR, 900-2500 nm) excitation and emission along with lower solubility product constant and environmentally benign nature. However, their unsatisfactory photoluminescence quantum yields (PLQYs) make it difficult to obtain optoelectronic devices with high performances. To tackle this challenge, researchers have made great efforts to develop valid strategies to improve the PLQYs of SWIR Ag2X QDs by suppressing their nonradiative recombination of excitons. In this Perspective, we summarize the significant approaches of heteroatom doping and surface passivation to enhance the PLQYs of SWIR Ag2X QDs, and we conclude their application in high-efficiency optoelectronic devices. Finally, we examine the future trends and promising opportunities of Ag2X QDs with regard to their optical properties and optoelectronics. We believe that this Perspective will serve as a valuable reference for future advancement in the synthesis and application of SWIR Ag2X QDs.

Photothermal-boosted S-scheme heterojunction of α-Fe2O3@NiOx for high-selective reduction of CO2 to CO

Self-heating photothermal catalysis, combining light promotion and thermal activation, offers unique advantages for CO2 conversion. The meticulous design of active sites and light-absorbing materials is crucial for high-performance photothermal catalysts. Herein, a S-Scheme heterostructure composed of NiOx subunits with abundant oxygen vacancies (Vo) bonded with α-Fe2O3 nanoplatelets has been fabricated for solar-driven photothermal catalytic CO2 reduction. Under continuous full-spectrum light irradiation (0.3 W·cm−2), the α-Fe2O3@NiOx hybrids exhibited a CO yield rate of 199.3 μmol∙g−1·h−1 in a gas–solid reaction models with near-unity selectivity. Additionally, the apparent quantum yield for CO production at 420 nm reaches 1.56 %. The prominent activity is attributed to three key factors: (1) The Vo-rich NiOx facilitates the accumulation of photogenerated electrons and activation of chemisorbed CO2. (2) The implemented S-Scheme heterostructures boost interfacial charge-transfer and provide spatially separated catalytic sites for efficient overall CO2 reduction. (3) The substantial photothermal effect of NiOx, which arises from nonradiative exciton recombination, induces local heating of the catalyst, thereby enhancing reaction kinetics. This work provides valuable insights into the utilization of a photothermal-photocatalytic S-Scheme heterojunction system for the photothermal catalytic CO2 reduction.

Full‐Spectral Response Perovskite Solar Cells Through Integration of MXene Modified Near‐Infrared Organic Heterojunction and Waveguide‐Structure Quantum‐Cutting Down‐Converter

AbstractTo date, lead‐based perovskite solar cells (PSCs) are optimized to the extreme and achieved an efficiency of as much as 26.1%. Expanding the spectral response is one of the most effective methods for achieving further efficiency breakthroughs. In this study, integrated PSCs are constructed by combining near‐infrared (NIR) organic bulk heterojunctions (BHJs) with perovskite layers to broaden the NIR spectral response range. Ultraviolet (UV)‐plasma‐treated MXene Nb2CTx ‐ quantum dots (QDs) are introduced to promote exciton dissociation inside the BHJ and to solve the problems of severe nonradiative exciton recombination and open‐circuit voltage (Voc) loss in IPSCs. In addition, CsPbCl3:Yb(7%),Li(2%) QDs with quantum‐cutting emission and photoluminescence quantum yield of up to 170% act as down‐converters to enhance the utilization of UV light. MgF2 is deposited on the quantum‐cutting layer to construct a waveguide‐structured anti‐reflection layer and further increase UV photon utilization. The champion device achieves superior photoelectric performance with a photoelectric conversion efficiency of 24.3%, Voc of 1.17 V, a short circuit current of 26.65 mA cm−2, and a fill factor of 77.95%. Champion devices exhibit excellent UV and long‐term stability. This study provides an instructive strategy for fabricating high‐performance full‐spectral‐response PSCs.

Exciton Dynamics and Optically Pumped Lasing in 1‐Naphthylmethylamine‐Based Quasi‐2D Perovskite Films

AbstractFilms of the quasi‐2D perovskite based on 1‐naphthylmethylamine (NMA) are promising as the gain medium for optically pumped lasing and future electrically pumped lasing because of its low lasing threshold and small electroluminescence efficiency rolloff. However, reasons for the low threshold and small efficiency rolloff are still unclear. Therefore, exciton dynamics are investigated in NMA‐based quasi‐2D perovskite films. It is found that quenching of bright excitons by other excitons or charge carriers is unlikely in NMA‐based quasi‐2D perovskite films, which is one reason for the low lasing threshold and small efficiency rolloff. Moreover, thermally stimulated current measurements reveal that the defect levels inside the band gap of the NMA‐based quasi‐2D perovskite are shallow, with a depth of ≈0.3 eV, causing a decrease in nonradiative exciton recombination through the defects. Therefore, population inversion can be easily achieved, leading to the low lasing threshold as well. For fabrication of NMA‐based quasi‐2D perovskite laser devices with even lower lasing thresholds, a circular‐shaped optical resonator, and small‐molecule‐based defect passivation are used. Optically pumped lasing can be obtained from these devices, with a threshold of ≈1 µJ cm−2, which is one of the lowest values ever reported in any perovskite lasers.

Space charge region recombination, non-radiative exciton recombination and the band-narrowing effect in high-efficiency silicon solar cells

An expression for finding the dependence of narrowing the bands in silicon ΔEg on the level of illumination from the intrinsic absorption band (or short-circuit current) has been proposed. This expression is used to find experimental values of ΔEg in high-efficient silicon solar cells. The dependence ΔEg (J) or dependence ΔEg (JI), where JI is the short-circuit current density, has been rebuilt into the ΔEg (ΔnOC) dependence, where ΔnOC is the excitation level in open-circuit conditions. With this aim, the generation-recombination balance equation was solved taking into account six recombination mechanisms in silicon, including Shockley–Reed–Hall recombination, radiative recombination, interband Auger recombination, surface recombination, non-radiative exciton recombination, and recombination in the space charge region. The latter two recombination terms are not taken into account in studies of the key parameters of silicon solar cells and in programs for simulating the characteristics of these solar cells. Therefore, in this work their correct definition was performed, their contribution was compared with the contribution of other recombination mechanisms, and it has been shown that the description of the characteristics and key parameters of silicon SC without taking them into account is insufficiently correct. The experimental dependences ΔEg (ΔnOC) obtained in the work were compared with Schenk’s theory. It has been shown that there is a good agreement between them.

Potassium Acetate Passivated SnO2 Interface for High‐Efficiency Two‐Step Deposited Perovskite Solar Cells

AbstractThe quality of the tin dioxide interface has an important impact on the performance of perovskite solar cells. Herein, a facile potassium acetate strategy to effectively treat the SnO2/perovskite interface and enhance the film quality of perovskite crystals is used. The defect density at the interface can be reduced, thereby suppressing the nonradiative recombination of excitons. Enhanced performance of the two‐step deposited perovskite device is obtained with an open‐circuit voltage (VOC) of 1.173 V, a fill factor of 78.31%, and a power conversion efficiency of 23.63%.

Modeling of characteristics of highly efficient textured solar cells based on c-silicon. The influence of recombination in the space charge region

Theoretical modeling of the optical and photovoltaic characteristics of highly efficient textured silicon solar cells (SC), including short-circuit current, open-circuit voltage and photoconversion efficiency, has been performed in this work. In the modeling, such recombination mechanisms as non-radiative exciton recombination relative to the Auger mechanism with the participation of a deep recombination level and recombination in the space charge region (SCR) was additionally taken into account. In a simple approximation, the external quantum efficiency of the photocurrent for the indicated SC in the long-wavelength absorption region has been simulated. A theory has been proposed for calculating the thickness dependences of short-circuit current, open-circuit voltage and photoconversion efficiency in them. The calculated dependences are carefully compared with the experimental results obtained for SC with the p+-i-α-Si:H/n-c-Si/i-n+-α-Si:H architecture and the photoconversion efficiency of about 23%. As a result of this comparison, good agreement between the theoretical and calculated dependences has been obtained. It has been ascertained that without taking into account recombination in SCR, a quantitative agreement between the experimental and theoretical light I V characteristics and the dependence of the output power in the SC load on the voltage on it cannot be obtained. The proposed approach and the obtained results can be used to optimize the characteristics of textured SC based on monocrystalline silicon.

Observation of Multi-Directional Energy Transfer in a Hybrid Plasmonic-Excitonic Nanostructure.

Hybrid plasmonic devices involve a nanostructured metal supporting localized surface plasmons to amplify light-matter interaction, and a non-plasmonic material to functionalize charge excitations. Application-relevant epitaxial heterostructures, however, give rise to ballistic ultrafast dynamics that challenge the conventional semiclassical understanding of unidirectional nanometal-to-substrate energy transfer. Epitaxial Au nanoislands are studied on WSe2 with time- and angle-resolved photoemission spectroscopy and femtosecond electron diffraction: this combination of techniques resolves material, energy, and momentum of charge-carriers and phonons excited in the heterostructure. A strong non-linear plasmon-exciton interaction that transfers the energy of sub-bandgap photons very efficiently to the semiconductor is observed, leaving the metal cold until non-radiative exciton recombination heats the nanoparticles on hundreds of femtoseconds timescales. The results resolve a multi-directional energy exchange on timescales shorter than the electronic thermalization of the nanometal. Electron-phonon coupling and diffusive charge-transfer determine the subsequent energy flow. This complex dynamics opens perspectives for optoelectronic and photocatalytic applications, while providing a constraining experimental testbed for state-of-the-artmodelling.

Experimental investigation and theoretical modeling of textured silicon solar cells with rear metallization

Crystalline Silicon (c-Si) remains a dominant photovoltaic material in solar cell industry. Currently, scientific and technological advances enable producing the c-Si solar cells (SCs) efficiency close to the fundamental limit. Therefore, combining the experimental results and those of modeling becomes crucial to further progress in improving the efficiency and reducing the cost of photovoltaic systems. We carried out the experimental characterization of the highly-efficient c-Si SCs and compared with the results of modeling. For this purpose, we developed and applied to the samples under investigation the improved theoretical model to optimize characteristics of highly efficient textured solar cells. The model accounts for all recombination mechanisms, including nonradiative exciton recombination by the Auger mechanism via a deep recombination centers and recombination in the space-charge region. To compare the theoretical results with those of experiments, we proposed empirical formula for the external quantum efficiency (EQE), which describes its experimental spectral dependence near the long-wave absorption edge. The proposed approach allows modeling of the short-circuit current and photoconversion efficiency in the textured crystalline silicon solar cells. It has been ascertained that the dependences of the short-circuit current on the open-circuit voltage and the dark current on the applied voltage at V < 0.6 V coincide with each other. The theoretical results, as compared to the experimental ones, allowed us to validate the developed formalism, and were used to optimize the key parameters of SCs, such as the base thickness, doping level and others. In this work, we have further generalized and refined the analytical approach proposed and used by us earlier to analyze high-efficiency solar cells and model their characteristics.

Enhancement of photoluminescence of monolayer transition metal dichalcogenide by subwavelength TiO<sub>2</sub> grating

Transition metal dichalcogenide (TMDC) monolayers have direct band gaps and can produce strong photoluminescence(PL), thereby possessing a wide application prospect in photoelectric devices and photoelectric detection fields. However, their PL efficiency needs further improving because they are of atomic thickness only, besides, they have non-radiative recombination of excitons. In this study, a combination structure of a gold film, titanium dioxide subwavelength gratings and TMDC monolayers is designed, which can greatly improve PL efficiency of the TMDC monolayers. The spontaneous emission rate can be controlled by the Purcell effect, and the maximum enhancement of photoluminescence is as high as 3.4 times. In this paper, the PL signals of monolayer WS<sub>2</sub> and monolayer WSe<sub>2</sub> on the designed structure are studied. The feasibility of the enhancement of PL of the TMDC monolayers on the subwavelength grating structure is verified experimentally, which provides a new idea for the application of two-dimensional materials to optoelectronic devices.

Ultrafast electron–hole relaxation dynamics in CdS nanocrystals

Surface traps significantly influence the charge carrier dynamics within semiconductor nanocrystals, introducing non-radiative exciton recombination channels which are detrimental for their applications. Understanding the nature of these trap states and modulating them synthetically bears immense potential in designing defect-free colloidal semiconductor nanocrystals for efficient optoelectronic devices. Thus, systems devoid of surface traps can be used to study the relaxation pathways of excitons generated within these nanocrystals. In this work, we study the ultrafast charge carrier relaxation dynamics upon near-edge resonance excitation and above-resonance excitation in CdS nanocrystals using ultrafast transient absorption spectroscopy, in order to understand intraband cooling and mid-gap trap states. The time-resolved studies reveal that the above bandgap excitation results in a three-step process, including instantaneous growth followed by a fast sub-picosecond decay and a long-lived (>1 ns) excited state or a trap state recombination. The large percentage of long-lived excitons in CdS nanocrystals elucidates the defect-free nature of the system arising from the absence of surface states.

Single photon sources with near unity collection efficiencies by deterministic placement of quantum dots in nanoantennas

Deterministic coupling between photonic nodes in a quantum network is an essential step toward implementing various quantum technologies. The omnidirectionality of free-standing emitters, however, makes this coupling highly inefficient, in particular if the distant nodes are coupled via low numerical aperture (NA) channels such as optical fibers. This limitation requires placing quantum emitters in nanoantennas that can direct the photons into the channels with very high efficiency. Moreover, to be able to scale such technologies to a large number of channels, the placing of the emitters should be deterministic. In this work, we present a method for directly locating single free-standing quantum emitters with high spatial accuracy at the center of highly directional bullseye metal–dielectric nanoantennas. We further employ non-blinking, high quantum yield colloidal quantum dots for on-demand single-photon emission that is uncompromised by instabilities or non-radiative exciton recombination processes. Taken together, this approach results in a record-high collection efficiency of 85% of the single photons into a low NA of 0.5, setting the stage for efficient coupling between on-chip, room temperature nanoantenna-emitter devices and a fiber or a remote free-space node without the need for additional optics.

Real-Time Blinking Suppression of Perovskite Quantum Dots by Halide Vacancy Filling.

Despite the excellent optoelectronic properties of halide perovskites, the ionic and electronic defects adversely affect the stability and durability of perovskites and their devices. These defects, intrinsic or produced by environmental factors such as oxygen, moisture, or light, not only cause chemical reactions that disintegrate the structure and properties of perovskites but also induce undesired photoluminescence blinking to perovskite quantum dots and nanocrystals. Blinking is also caused by the nonradiative Auger processes in the photocharged quantum dots or nanocrystals. Herein, we find real-time suppression of halide vacancy-assisted nonradiative exciton recombination and photoluminescence blinking in MAPbBr3 and MAPbI3 perovskite quantum dots by filling the vacancies using halide precursors (MABr and MAI). Also, halide vacancy filling increases the photoluminescence quantum efficiencies and lifetimes of the quantum dots. We estimate the rates of halide vacancy-assisted nonradiative recombination at 1 × 108 s-1 for MAPbBr3 and 1.9 × 109 s-1 for MAPbI3 quantum dots. The real-time blinking suppression using the halide precursors and statistical analysis of the ON/OFF blinking time reveal that the halide vacancies contribute to the type-A blinking through charging and discharging. Conversely, the blinking of the quantum dots after halide vacancy filling is dominated by the type-B mechanism.

Plasmon-assisted interaction of Si with light, for cancer hyperthermia and electromagnetic energy harvest

Metal-assisted chemical etching (MACE) is applied for fabrication of silicon nanowires (SiNWs). We have shown the effect of amorphous sheath of SiNWs by treating the nanowires with SF6 and the resulting reduction of absorption bandwidth, i.e. making SiNWs semi-transparent in near-infrared (IR). For the first time, by treating the fabricated SiNWs with copper containing HF∕H2O2∕H2O solution, we have generated crystalline nanowires with broader light absorption spectrum, up to λ = 1 μm. Both the absorption and photo-luminescence (PL) of the SiNWs are observed from visible to IR wavelengths. It is found that the SiNWs have PL at visible and near Infrared wavelengths, which may infer presence of mechanisms such as forbidden gap transitions other can involvement of plasmonic resonances. Non-radiative recombination of excitons is one of the reasons behind absorption of SiNWs. Also, on the dielectric metal interface, the absorption mechanism can be due to plasmonic dissipation or plasmon-assisted generation of excitons in the indirect band-gap material. Comparison between nanowires with and without metallic nanoparticles has revealed the effect of nanoparticles on absorption enhancement. The broader near IR absorption, paves the way for applications like hyperthermia of cancer while the optical transition in near IR also facilitates harvesting electromagnetic energy at a broad spectrum from visible to IR.

Correlation between excitons recombination dynamics and internal quantum efficiency of AlGaN-based UV-A multiple quantum wells

The correlation between the recombination dynamics of excitons and the internal quantum efficiency (IQE) of AlGaN-based UV-A multiple quantum wells (MQWs) was studied via photoluminescence (PL) and time-resolved PL (TRPL) spectroscopy. The probability ratio of the capture of excitons by nonradiative recombination centers (NRCs) and the radiative recombination of excitons was evaluated individually via two different experimental analyses. The IQE was evaluated via temperature- and excitation power density-dependent PL measurements and its dependence on excitation density was analyzed using a rate equation model based on the radiative and nonradiative recombination of excitons. Moreover, the radiative and nonradiative recombination lifetimes were evaluated via temperature-dependent TRPL measurements; furthermore, they were analyzed as functions of temperature and excitation energy density. The probability ratios obtained from the two individual analyses were in agreement. This quantitative agreement indicated that the analysis based on the radiative and nonradiative recombination processes of excitons, which included the process of filling NRCs, was valid for AlGaN-based UV-A MQWs.

Radiative and non-radiative exciton recombination rate constants in ZnSe clusters

Understanding the origin of photoluminescence intermittency and its correlation with microstructure is crucial for the design and preparation of quantum dots (QDs) with high fluorescence quantum yield. ZnSe clusters provide a typical model for studying the effect of their size, geometrical and electronic structures on their radiative and non-radiative process of II-VI QDs. The rate constants of radiative and non-radiative processes, kr and knr, of the (ZnSe)n clusters were computed by using first-principles calculations, Einstein spontaneous radiation theory and Fermi’s golden rule. The kr and knr variations with cluster size were analyzed in term of a number of quantities. Emission energy and reorganization energy were identified to play dominant roles in the determination of kr and knr for the studied clusters. Furthermore, a correlation between these two quantities and the geometric rigidity of the ZnSe clusters was revealed. The clusters with greater geometric rigidity tend to possess larger emission energy, and smaller reorganization energy. While radiative and non-radiative electron–hole recombination rates of the ZnSe clusters vary in a complicated way because of their diverse structures and prominent quantum size effect, our study highlights the correlation between recombination rate and cluster structure, which would be helpful for the design of QD materials with high fluorescence quantum yields.

Chain Coupling and Luminescence in High-Mobility, Low-Disorder Conjugated Polymers.

Optoelectronic devices based on conjugated polymers often rely on multilayer device architectures, as it is difficult to design all the different functional requirements, in particular the need for efficient luminescence and fast carrier transport, into a single polymer. Here we study the photophysics of a recently discovered class of conjugated polymers with high charge carrier mobility and low degree of energetic disorder and investigate whether it is possible in this system to achieve by molecular design a high photoluminescence quantum yield without sacrificing carrier mobility. Tracing exciton dynamics over femtosecond to microsecond time scales, we show that nearly all nonradiative exciton recombination arises from interactions between chromophores on different chains. We evaluate the temperature dependence and role of electron-phonon coupling leading to fast internal conversion in systems with strong interchain coupling and the extent to which this can be turned off by varying side chain substitution. By sterically decreasing interchain interaction, we present an effective approach to increase the fluorescence quantum yield of low-energy gap polymers. We present a red-NIR-emitting amorphous polymer with the highest reported film luminescence quantum efficiency of 18% whose mobility concurrently exceeds that of amorphous-Si. This is a key result toward the development of single-layer optoelectronic devices that require both properties.

Fluorescence Quantum Yield and Single-Particle Emission of CdSe Dot/CdS Rod Nanocrystals

The fluorescence quantum yield (QY) of CdSe dot/CdS rod (DR) nanoparticle ensembles is dependent on the Shell growth and excitation wavelength. We analyze the origin of this dependency by comparing the optical properties of DR ensembles to the results obtained in single-particle experiments. On the Ensemble level, we find that the QY of DRs with shell lengths shorter than 40 nm exhibits no dependence on the excitation wavelength, whereas for DRs with shell lengths longer than 50 nm, the QY significantly decreases for excitation above the CdS band gap. Upon excitation in the CdSe core, the ensemble QY, the fluorescence wavelength, and the fluorescence blinking behavior of individual particles are only dependent on the radial CdS shell thickness and not on the CDs shell length. If the photogenerated excitons can reach the CdSe core region, the fluorescence properties will be dependent only on the surface passivation in close vicinity to the CdSe core. The change in QY upon excitation above the band gap of CdS for longer DRs cannot be explained by nonradiative particles because the ratio of emitting DRs is found to be independent of the DR length. We propose a model after which the decrease in QY for longer CdS shells is due to an increasing fraction of nonradiative exciton recombination within the elongated shell. This is supported by an effective-mass-approximation-based calculation, which suggests an optimum length of DRs of about 40 nm, to combine the benefit of high CdS absorption cross section with a high fluorescence QY.

Approaching the Intrinsic Limit in Transition Metal Diselenides via Point Defect Control.

Two dimensional (2D) transition-metal dichalcogenide (TMD) based semiconductors have generated intense recent interest due to their novel optical and electronic properties and potential for applications. In this work, we characterize the atomic and electronic nature of intrinsic point defects found in single crystals of these materials synthesized by two different methods, chemical vapor transport and self-flux growth. Using a combination of scanning tunneling microscopy (STM) and scanning transmission electron microscopy (STEM), we show that the two major intrinsic defects in these materials are metal vacancies and chalcogen antisites. We show that by control of the synthetic conditions, we can reduce the defect concentration from above 1013/cm2 to below 1011/cm2. Because these point defects act as centers for nonradiative recombination of excitons, this improvement in material quality leads to a hundred-fold increase in the radiative recombination efficiency.

From Anhydrous Zinc Oxide Nanoparticle Powders to Aqueous Colloids: Impact of Water Condensation and Organic Salt Adsorption on Free Exciton Emission.

Variations in the composition and structure of ZnO nanoparticle interfaces have a key influence on the materials’ optoelectronic properties and are responsible for high number of discrepant results reported for ZnO-based nanomaterials. Here, we conduct a systematic study of the room-temperature photoluminescence of anhydrous ZnO nanocrystals, as synthesized in the gas phase and processed in water-free atmosphere, and of their colloidal derivatives in aqueous dispersions with varying amounts of organic salt admixtures. A free exciton band at hv = 3.3 eV is essentially absent in the anhydrous ZnO nanocrystal powders measured in vacuum or in oxygen atmosphere. Surface hydration of the nanoparticles during colloid formation leads to the emergence of the free exciton band at hv = 3.3 eV and induces a small but significant release in lattice strain as detected by X-ray diffraction. Most importantly, admixture of acetate or citrate ions to the aqueous colloidal dispersions not only allows for the control of the ζ-potential but also affects the intensity of the free exciton emission in a correlated manner. The buildup of negative charge at the solid—liquid interface, as produced by citrate adsorption, increases the free exciton emission. This effect is attributed to the suppression of electron trapping in the near-surface region, which counteracts nonradiative exciton recombination. Using well-defined ZnO nanoparticles as model systems for interface chemistry studies, our findings highlight water-induced key effects that depend on the composition of the aqueous solution shell around the semiconducting metal oxide nanoparticles.