Light emitters based on CdTe doped with isovalent impurities

The optical and luminescent properties of hexagonal α-ZnSe heterolayers, obtained by isovalent substitution for α-CdSe have been investigated. For the first time defined the parameters of the band structure – Δcr = 0,07 еV і Δso = 0,37 еV. It was found that α-ZnSe luminescence is high temperature up to 550 K, determined by the dominant radiation of excitons bounded on Cd isovalent impurity and interband recombination of free charge carriers. The high quantum efficiency η=8-10 % of heterolayers α-ZnSe luminescence allows to use them as a source of stable radiation, as well as sensors that registered the temperature changes.

Досліджено оптичне поглинання, відбивання і люмінесценцію CdTe:Ca. Встановлено, що отримані леговані Ca поверхневі шари характеризуються інтенсивною фотолюмінесценцією з η = 8-10% у крайовій області. Випромінювання формується внаслідок міжзонної рекомбінації вільних носіїв заряду і анігіляцією зв’язаних на ізовалентних домішках Ca екситонів. Зазначені складові спостерігаються у диференційних спектрах оптичного відбивання Ŕω у приповерхневому шарі отриманому при легування ізовалентною домішкою Ca підкладинок CdTe. Встановлено, що легування обумовлює утворення p-типу провідності.

Intermolecular charge transfer (CT) states at the interface between electron-donating (D) and electron-accepting (A) materials in organic thin films are characterized by absorption and emission bands within the optical gap of the interfacing materials. CT states efficiently generate charge carriers for some D-A combinations, and others show high fluorescence quantum efficiencies. These properties are exploited in organic solar cells, photodetectors, and light-emitting diodes. This review summarizes experimental and theoretical work on the electronic structure and interfacial energy landscape at condensed matter D-A interfaces. Recent findings on photogeneration and recombination of free charge carriers via CT states are discussed, and relations between CT state properties and optoelectronic device parameters are clarified.

Photo‐generation and recombination of free charge carriers in poly‐3 (hexylthiophene) (P3HT) and [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) blend films has been studied at different PCBM concentrations by means of fluorescence spectroscopy and transient photocurrent methods. We show that more than 80% of excitons form charge transfer (CT) states at PCBM concentrations above 4%. Efficiency of the CT state dissociation into free charge carries strongly depends on the PCBM concentration; the dissociation efficiency increases more than 30 times when PCBM concentration increases from 1 to 32%. We attribute the strong concentration dependence to formation of PCBM clusters facilitating electron migration and/or delocalization. Reduced charge carrier recombination coefficient has also been observed at high PCBM concentrations. We suggest that this may be partly caused by the reduced stability of reformed Coulombicaly bound charge pairs.

The influence of the generation and recombination of free charge carriers in the p-i-n structure in strong electric fields on the stationary volt-ampere characteristics is considered. The issues of the stability of stationary solutions are investigated. It is shown that a form of the stationary volt-ampere characteristics and their stability depend on ratios between free electrons and holes in the current injected into the i-layer and in the current outflowing from the layer. When the structure is forward biased, the oscillations may occur.

The optimal modes of isovalent substitution and the CdTe/CdS/ZnS heterostructure obtained for the first time were established, the main parameters of the band structure of the constituent heterolayers and the characteristics of the obtained radiation sources were determined. The high quantum efficiency η ≈ 12-14 % of surface ZnS is caused by isovalent impurities. The band structure parameters of the obtained isovalently substituted CdS layers of atypical cubic modification and their luminescence efficiency of η ≈ 7-8 % were established. The emission of the resulting layers is localized in the edge region of the material and is formed by interband emitting transitions and the dominant annihilation of bound excitons.

Photorefractive and photoconductivity steady-state as well as time-resolved measurements have been performed in strongly reduced KNbO3. The recorded photorefractive gratings show a nonexponential dark decay and an intensity-dependent two-wave mixing gain. The measured photoconductivity depends sublinearly on light intensity. The observed behavior is interpreted in terms of a band transport model that uses a single donor level with only electrons as free charge carriers, taking the nonlinear recombination of free charge carriers (owing to variation of the trap density) and the time dependence of the free-charge-carrier density into account. An analytical solution for the nonexponential dark decay of the photorefractive grating is derived. As an application of this model the results of the photorefractive and the stationary and transient photoconductivity experiments are used to determine the model parameters (thermal excitation rate, photoexcitation cross section, recombination coefficient, acceptor and donor densities, and electron mobility).

We develop an empirically based optoelectronic model to accurately simulate the photocurrent in organic photovoltaic (OPV) devices with novel materials including bulk heterojunction OPV devices based on a new low band gap dithienothiophene-DPP donor polymer, P(TBT-DPP), blended with PC70BM at various donor-acceptor weight ratios and solvent compositions. Our devices exhibit power conversion efficiencies ranging from 1.8% to 4.7% at AM 1.5G. Electron and hole mobilities are determined using space-charge limited current measurements. Bimolecular recombination coefficients are both analytically calculated using slowest-carrier limited Langevin recombination and measured using an electro-optical pump-probe technique. Exciton quenching efficiencies in the donor and acceptor domains are determined from photoluminescence spectroscopy. In addition, dielectric and optical constants are experimentally determined. The photocurrent and its bias-dependence that we simulate using the optoelectronic model we develop, which takes into account these physically measured parameters, shows less than 7% error with respect to the experimental photocurrent (when both experimentally and semi-analytically determined recombination coefficient is used). Free carrier generation and recombination rates of the photocurrent are modeled as a function of the position in the active layer at various applied biases. These results show that while free carrier generation is maximized in the center of the device, free carrier recombination is most dominant near the electrodes even in high performance devices. Such knowledge of carrier activity is essential for the optimization of the active layer by enhancing light trapping and minimizing recombination. Our simulation program is intended to be freely distributed for use in laboratories fabricating OPV devices.

Semiconducting single-walled carbon nanotubes (s-SWCNTs) are promising for solution-processed, thin film photovoltaics due to their strong near-infrared absorptivity and excellent transport properties. We report on the generation yield and recombination kinetics of free charge carriers in photoexcited thin films of polymer-wrapped s-SWCNTs with and without an overlying electron-accepting C60 layer, using time-resolved microwave photoconductivity (TRMC). Free carriers are generated in neat s-SWCNT films, even without an obvious driving force for exciton dissociation. However, most carriers recombine in <10 ns. Adding C60 increases the yield and extends the lifetime of a significant fraction of free carriers to ≫100 ns via interfacial charge separation. Spectral dependencies indicate that the driving force for interfacial electron transfer vanishes for large-diameter SWCNTs, from which we approximate (9,7) s-SWCNT energetics. We estimate a free carrier generation yield of ∼6% in neat s-SWCNT films and 9 GHz...

The precise mechanism and dynamics of charge generation and recombination in bulk heterojunction polymer:fullerene blend films typically used in organic photovoltaic devices have been intensively studied by many research groups, but nonetheless remain debated. In particular the role of interfacial charge-transfer (CT) states in the generation of free charge carriers, an important step for the understanding of device function, is still under active discussion. In this article we present direct optical probes of the exciton dynamics in pristine films of a prototypic polycarbazole-based photovoltaic donor polymer, namely poly[N-11''-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), as well as the charge generation and recombination dynamics in as-cast and annealed photovoltaic blend films using methanofullerene (PC(61)BM) as electron acceptor. In contrast to earlier studies we use broadband (500-1100 nm) transient absorption spectroscopy including the previously unobserved but very important time range between 2 ns and 1 ms, which allows us not only to observe the entire charge carrier recombination dynamics but also to quantify the existing decay channels. We determine that ultrafast exciton dissociation occurs in blends and leads to two separate pools of products, namely Coulombically bound charge-transfer (CT) states and unbound (free) charge carriers. The recombination dynamics are analyzed within the framework of a previously reported model for poly(3-hexylthiophene):PCBM (Howard, I. A. J. Am. Chem. Soc. 2010, 132, 14866) based on concomitant geminate recombination of CT states and nongeminate recombination of free charge carriers. The results reveal that only ~11% of the initial photoexcitations generate interfacial CT states that recombine exclusively by fast nanosecond geminate recombination and thus do not contribute to the photocurrent, whereas ~89% of excitons create free charge carriers on an ultrafast time scale that then contribute to the extracted photocurrent. Despite the high yield of free charges the power conversion efficiency of devices remains moderate at about 3.0%. This is largely a consequence of the low fill factor of devices. We relate the low fill factor to significant energetic disorder present in the pristine polymer and in the polymer:fullerene blends. In the former we observed a significant spectral relaxation of exciton emission (fluorescence) and in the latter of the polaron-induced ground-state bleaching, implying that the density of states (DOS) for both excitons and charge carriers is significantly broadened by energetic disorder in pristine PCDTBT and in its blend with PCBM. This disorder leads to charge trapping in solar cells, which in turn causes higher carrier concentrations and more significant nongeminate recombination. The nongeminate recombination has a significant impact on the IV curves of devices, namely its competition with charge carrier extraction causes a stronger bias dependence of the photocurrent of devices, in turn leading to the poor device fill factor. In addition our results demonstrate the importance of ultrafast free carrier generation and suppression of interfacial CT-state formation and question the applicability of the often used Braun-Onsager model to describe the bias dependence of the photocurrent in polymer:fullerene organic photovoltaic devices.

The in‐depth understanding of charge carrier photogeneration and recombination mechanisms in organic solar cells is still an ongoing effort. In donor:acceptor (bulk) heterojunction organic solar cells, charge photogeneration and recombination are inter‐related via the kinetics of charge transfer states—being singlet or triplet states. Although high‐charge‐photogeneration quantum yields are achieved in many donor:acceptor systems, only very few systems show significantly reduced bimolecular recombination relative to the rate of free carrier encounters, in low‐mobility systems. This is a serious limitation for the industrialization of organic solar cells, in particular when aiming at thick active layers. Herein, a meta‐analysis of the device performance of numerous bulk heterojunction organic solar cells is presented for which field‐dependent photogeneration, charge carrier mobility, and fill factor are determined. Herein, a “spin‐related factor” that is dependent on the ratio of back electron transfer of the triplet charge transfer (CT) states to the decay rate of the singlet CT states is introduced. It is shown that this factor links the recombination reduction factor to charge‐generation efficiency. As a consequence, it is only in the systems with very efficient charge generation and very fast CT dissociation that free carrier recombination is strongly suppressed, regardless of the spin‐related factor.

Among perovskite semiconductors, quasi-two-dimensional (2D) materials are attractive for the pursuit of electrically driven lasing given their excellent performance in light-emitting diodes (LEDs) and their recent success in continuous-wave optically pumped lasing. We investigate the spontaneous photoluminescence emission and amplified spontaneous emission (ASE) of a series of quasi-2D emitters, and their directly analogous 3D materials formed by removing the 2D organic spacer by annealing. Although the PL photoluminescence (PL) (at low optical excitation power) from quasi-2D films with high 2D spacer fractions can be much brighter than that from their 3D counterparts, the ASE thresholds of these quasi-2D materials tend to be higher. This counter-intuitive behavior is investigated through time-resolved photophysical studies, which reveal the emission in the high-spacer-content quasi-2D perovskite can be exclusively excitonic, and the exciton–exciton annihilation of quasi-2D perovskite starts to take over the exciton dynamics at a low exciton density (<1016 cm−3). To lower ASE thresholds in quasi-2D materials it is necessary to increase the volume fraction of thick quantum wells, which we achieve by decreasing the spacer content or by utilizing 1-naphthylmethylamine (NMA) linkers. The increase of the volume fraction of thick quantum wells correlates with an increased contribution of free carrier recombination to the emission process of the quasi-2D materials. These results suggest that material development of quasi-2D materials for gain applications should target fast free charge carrier recombination rates by engineering the well thickness and size and not maximum photoluminescence quantum yields under low power excitation.

Charge carrier balance and recombination are essential factors relating to the performance of white organic light-emitting devices (WOLEDs). In this study, we discussed the contribution of charge carrier balance in the interlayer-based WOLEDs. By varying the interlayer thickness, the mechanisms of electroluminescent spectral alteration, energy transfer, and especially, charge carrier transport and balance in the devices were investigated and revealed in detail. With a 5 nm thick interlayer tailoring charge carrier transport and recombination, WOLEDs yielded a high power efficiency, current efficiency and external quantum efficiency of 36.1 lm W−1, 47.1 cd A−1 and 18.3%, respectively. Additionally, single-carrier devices and quantitative analysis were subsequently carried out, demonstrating that the enhancement of carrier recombination efficiency corresponds to the optimization of device performance.

There are various methods to produce hydrogen from water splitting as a substitute energy resource for fossil fuels in accordance with the global environmental crisis. Among these, water photocatalysis is considered one of the most renewable and sustainable processes simulated the solar energy utilized system in nature. During a half century, different kinds of photocatalysts were developed to convert photon energy into chemical energy to induce redox potential under visible light irradiation condition. In the beginning step, semiconductor materials, such as transition metal oxides, were explored extensively to use as a photocatalyst for hydrogen generation. However, semiconductor has limitations to act as an effective photocatalyst for water splitting due to the large band gap and recombination of charge carriers. Therefore, several kinds of modifications of structure or components have been studied to design visible light active photocatalysts for water splitting to generate hydrogen. Their performance was improved substantially by adding a noble metal or sensitizer to adjust the band gap and reduce the recombination of photoinduced charge carriers. Considering solar light-induced photocatalytic hydrogen generation, various visible light active photocatalysts have been derived from carbon chain organic compounds and lattice crystals. This review classifies the visible light active photocatalysts as follows: (a) structural and chemical components of modified graphitic carbon nitride (g-C3N4), (b) exfoliated perovskites, and (c) π-bond conjugated polymers to produce hydrogen from water splitting. The hydrogen evolution efficiency of photocatalysts shows a great difference under visible light (λ > 400 nm) irradiation according to the three-dimensional structure and electron transfer pathway. This is because the capability of restricting the recombination of photoinduced charge carriers and the band gap between the valence band and the conduction band of photocatalysts is dependent on the morphology and electrostatic interactions among components. This paper reviews visible light photocatalysts, that is, g-C3N4 based materials, layered perovskites, and conjugated polymers, to provide integrated insight into photocatalytic water splitting to obtain hydrogen.

Exciton localization phenomena are considered here to comprehend the high internal quantum efficiency in InGaN/GaN multiple-quantum-well structures having discrete quantum dots (QDs) prepared by metal–organic-chemical-vapor deposition method on c-sapphire substrates. Spectroscopic results from the variable-temperature steady-state-photoluminescence and time-resolved photoluminescence (TRPL) are investigated. While the exciton localization is enhanced by strong localized states within the InGaN/GaN QDs–the impact of free carrier recombination cannot be ignored. The observed non-exponential decay in TRPL measurements is explained using a model by meticulously including localized exciton, non-radiative and free carrier recombination rates. A new method is proposed to calculate the internal quantum efficiency, which is supplementary to the traditional approach based on temperature-dependent photoluminescence measurement.