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Silver-bismuth double perovskites are promising replacement materials for lead-based ones in photovoltaic (PV) devices due to the lower toxicity and enhanced stability to environmental factors. In addition, they might even be more suitable for indoor PV, due to the size of their bandgap better matching white LEDs emission. Unfortunately, their optoelectronic performance does not reach that of the lead-based counterparts, because of the indirect nature of the band gap and the high exciton binding energy. One strategy to improve the electronic properties is the dimensional reduction from the 3D to the 2D perovskite structure, which features a direct band gap, as it has been reported for 2D monolayer derivates of Cs2AgBiBr6 obtained by substituting Cs+ cations with bulky alkylammonium cations. However, a similar dimensional reduction also brings to a band gap opening, limiting light absorption in the visible. In this work, we report on the achievement of a bathochromic shift in the absorption features of a butylammonium-based silver-bismuth bromide monolayer double perovskite through doping with iodide and study the optical properties and stability of the resulting thin films in environmental conditions. These species might constitute the starting point to design future sustainable materials to implement as active components in indoor photovoltaic devices used to power the IoT.

We report the introduction of distinct optical properties into organotin sulfide clusters by the attachment of extended polycyclic aromatic organic molecules. This was realized by the reactions of [(R

We report the syntheses of two new organotin sulfide clusters with heteroaromatic substituents. A phenanthroline-functionalized tin sulfide cluster [(RPhenSn)4S6] (1; RPhen = CMe2CH2C(Me)N-NC(H)C12H7N2) and a bipyridyl-terminated cluster [(R4-bipySn)4S6] (2; R4-bipy = CMe2CH2C(Me)N-NC(H)-4-C10H7N2) were obtained from reactions of the hydrazone-functionalized organotin sulfide cluster [(RNSn)4S6] (RN = CMe2CH2C(Me)N-NH2) with 1,10-phenanthroline-5-carboxaldehyde or 2,2'-bipyridine-4-carbaldehyde. 1 and 2 were tested towards their capability of trapping metal ions by means of the terminal chelating ligands. The reaction of 2 with ZnCl2 afforded the cluster compound [(R4-bipyZnCl2Sn)4S6] (5), in which four ZnCl2 units are coordinated by the heteroaromatic organic groups. We discuss the structures and demonstrate the effect of ZnCl2 trapping on optical absorption and luminescence properties.

Bismuth halides represent an emergent class of materials that combines semiconductor properties with non-toxic constituents. However, many simple bismuth halide compounds feature bandgaps that are significantly higher than those of the lead halide perovskites, which they are supposed to replace. One way to address this issue is the preparation of multinary metal halide materials that feature an additional metal ion. Here, we report on the synthesis and properties of (HPy)2(Py)CuBi3I12 (1) a new copper iodido bismuthate, a photoconductor, which shows a low band gap of 1.59 eV and good thermal and air stability.

Fundmental comprehension of light-induced processes in perovskites are still scarce. One active debate surrounds the influence of excess lead iodide (PbI2) on device performance, as well as optoelectronic properties, where both beneficial and detrimental traits have been reported. Here, we study its impact on charge carrier recombination kinetics by simultaneously acquiring the photoluminescence quantum yield and time-resolved photoluminescence as a function of excitation wavelength (450-780 nm). The presence of PbI2 in the perovskite film is identified via a unique spectroscopic signature in the PLQY spectrum. Probing the recombination in the presence and absence of this signature, we detect a radiative bimolecular recombination mechanism induced by PbI2. Spatially resolving the photoluminescence, we determine that this radiative process occurs in a small volume at the PbI2/perovskite interface, which is only active when charge carriers are generated in PbI2, and therefore provide deeper insight into how excess PbI2 may improve the properties of perovskite-based devices.

The fate of excited charge carriers in metal halide perovskite semiconductors is influenced by energetic disorder and defects. Here, photoluminescence (PL) blinking is used to probe metastable nonradiative (NR) centers and the nanoscale energy landscape. Temporal activation of an NR center creates a local region with increased NR recombination. Activation and deactivation of this local PL quenching does not only lead to PL blinking, but also to fluctuations of the PL spectra, if the crystal is inhomogeneous in the sense that the PL emission spectrum is slightly different from one location to another. It resembles the spectral hole-burning technique; however, here the eliminated excited states are chosen by their spatial localization close to the quencher. In MAPbI3, PL spectral fluctuations at low temperature reveal energetic inhomogeneities on the order of 5 to 10 meV. Quenching of the main PL band is often found to correlate with an increase of the low-energetic tail of the PL spectra, which is attributed to partially radiative recombination of charges captured by the NR center. The transition energy of the NR center is found to be only ≈80 meV smaller than the bandgap, implying that the underlying defect cannot be a single mid-bandgap state. (Less)

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUG Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research. Ministerio de Ciencia e Innovación | Ref. RYC2018-026103-I Agencia Estatal de Investigación | Ref. CTQ2017-82711-P Ministerio de Economía y Competitividad | Ref. MDM-2015-0538 Agencia Estatal de Investigación | Ref. PID2019-107314RB-I00

Herein, we present the synthesis of two pyrene‐functionalized clusters, [(RpyrSn)4S6]⋅2 CH2Cl2 (4) and [(RpyrSn)4Sn2S10]⋅n CH2Cl2 (n=4, 5 a; n=2, 5 b; Rpyr=CMe2CH2C(Me)N‐NC(H)C16H9), both of which form in reactions of the organotin sulfide cluster [(RNSn)4S6] (C; RN=CMe2CH2C(Me)N‐NH2) with the well‐known fluorescent dye 1‐pyrenecarboxaldehyde (B). In contrast, reactions using an organotin sulfide cluster with another core structure, [(RNSn)3S4Cl] (A), leads to formation of small molecular fragments, [(RpyrCl2Sn)2S] (1), (pyren‐1‐ylmethylene)hydrazine (2), and 1,2‐bis(pyren‐1‐ylmethylene)hydrazine (3). Besides synthesis and structures of the new compounds, we report the influence of the inorganic core on the optical properties of the dye, which was analyzed exemplarily for compound 5 a via absorption and fluorescence spectroscopy. This cluster was also used for exploring the potential of such non‐volatile clusters for deposition on a metal surface under vacuum conditions., A first series of pyrene‐terminated organotin sulfide compounds and unprecedented side products, [(RpyrCl2Sn)2S] (1), (pyren‐1‐ylmethylene)hydrazine (2), 1,2‐bis(pyren‐1‐ylmethylene)hydrazine (3), [(RpyrSn)4S6]⋅2 CH2Cl2 (4), and [(RpyrSn)4Sn2S10] (5), were synthesized. The combination of inorganic Sn/S moieties with the pyrene units affects optical absorption and fluorescence properties as well as the deposition on a metal surface.

Bismuth halides represent an emergent class of materials that combines semiconductor properties with non-toxic constituents. However, many simple bismuth halide compounds feature bandgaps that are significantly higher than those of the lead halide perovskites, which they are supposed to replace. One way to address this issue is the preparation of multinary metal halide materials that feature an additional metal ion. Here, we report on the synthesis and properties of (HPy)2(Py)CuBi3I12 (1) a new copper iodido bismuthate, a photoconductor, which shows a low band gap of 1.59 eV and good thermal and air stability.

We measure both nonlinear absorption and nonlinear refraction in a ${{\rm CH}_3}{{\rm NH}_3}{{\rm PbBr}_3}$CH

We report the syntheses of two new organotin sulfide clusters with heteroaromatic substituents. A phenanthroline-functionalized tin sulfide cluster [(RPhenSn)4S6] (1; RPhen = CMe2CH2C(Me)N-NC(H)C12H7N2) and a bipyridyl-terminated cluster [(R4-bipySn)4S6] (2; R4-bipy = CMe2CH2C(Me)N-NC(H)-4-C10H7N2) were obtained from reactions of the hydrazone-functionalized organotin sulfide cluster [(RNSn)4S6] (RN = CMe2CH2C(Me)N-NH2) with 1,10-phenanthroline-5-carboxaldehyde or 2,2'-bipyridine-4-carbaldehyde. 1 and 2 were tested towards their capability of trapping metal ions by means of the terminal chelating ligands. The reaction of 2 with ZnCl2 afforded the cluster compound [(R4-bipyZnCl2Sn)4S6] (5), in which four ZnCl2 units are coordinated by the heteroaromatic organic groups. We discuss the structures and demonstrate the effect of ZnCl2 trapping on optical absorption and luminescence properties.

Studying optoelectronic properties in FAPb$_{1-x}$Sn$_x$I$_3$ perovskites as a function of the lead:tin content, Parrott et al. observed the broadest luminescence linewidth and the largest luminescence Stokes shift in mixed compositions with Sn $ < 25$% and with $> 0.85$%. Since the largest effects of alloy disorder were expected for the 50:50 composition, it was concluded that the revealed disorder effects might arise from extrinsic factors that can be eliminated upon further crystal growth optimization. This comment shows that the largest effects of alloy disorder for perfectly random fluctuations in FAPb$_{1-x}$Sn$_x$I$_3$ perovskite are, in fact, expected for $x < 0.25$ and for $x > 0.85$. Therefore, further crystal growth optimization is futile., 2 pages, one figure

We present a comprehensive investigation of the charge-transfer (CT) effect in weakly interacting organic semiconductor mixtures. The donor–acceptor pair diindenoperylene (DIP) and N,N′-bis(2-ethylhexyl)-1,7-dicyanoperylene-3,4/9,10-bis(dicarboxyimide) (PDIR–CN2) has been chosen as a model system. A wide range of experimental methods was used in order to characterize the structural, optical, electronic, and device properties of the intermolecular interactions. By detailed analysis, we demonstrate that the partial CT in this weakly interacting mixture does not have a strong effect on the ground state and does not generate a hybrid orbital. We also find a strong CT transition in light absorption as well as in photo- and electroluminescence. By using different layer sequences and compositions, we are able to distinguish electronic coupling in-plane vs out-of-plane and, thus, characterize the anisotropy of the CT state. Finally, we discuss the impact of CT exciton generation on charge-carrier transport and on...

We measure nonlinear refraction and absorption of a CH3NH3PbBr3 single crystal with the Z-scan technique. Our results provide the first reference of the intrinsic, ultrafast nonlinear refractive index in the metal halide perovskite material class.

Organo-metal halide perovskites are promising solution-processed semiconductors, however, they possess diverse and largely not understood non-radiative mechanisms. Here, we resolve contributions of individual non-radiative recombination centers (quenchers) in nanocrystals of methylammonium lead iodide by studying their photoluminescence blinking caused by random switching of quenchers between active and passive states. We propose a model to describe the observed reduction of blinking upon cooling and determine energetic barriers of 0.2 to 0.8 eV for enabling the switching process, which points to ion migration as the underlying mechanism. Moreover, due to the strong influence of individual quenchers, the crystals show very individually-shaped photoluminescence enhancement upon cooling, suggesting that the high variety of activation energies of the PL enhancement reported in literature is not related to intrinsic properties but rather to the defect chemistry. Stabilizing the fluctuating quenchers in their passive states thus appears to be a promising strategy for improving the material quality., The mechanism of the non-radiative recombination in halide perovskite nanocrystals has not been fully understood. Here Gerhard et al. resolve the contributions of individual recombination centers by photoluminescence blinking measurements and identify ion migration as the underlying mechanism.

We investigate the time-resolved photoluminescence (PL) polarization anisotropy of the organic photovoltaic model systems P3HT:PC61BM and PTB7:PC71BM, and their corresponding neat polymer films. Both blends show a strong emission from interfacial charge-transfer states (CTSs); the CTS emission can be uniquely identified by its negative polarization anisotropy, which is indicative of a significant rotation of the transition dipole moment upon charge transfer at the donor–acceptor interface. We also observe a spectral region showing negative anisotropy in the PL of the neat PTB7 film; this spectral region is at slightly higher energy than the blend CTS emission. This negative anisotropy is not observed in the emission spectrum of the polymer in solution. This suggests that some emissive states in the pristine PTB7 film have transition dipole moments rotated relative to the absorbing states; we interpret these to be states with a significant interchain charge-transfer character.

A big challenge of the 21st century is to cope with the huge amounts of plastic waste on Earth. Especially the oceans are heavily polluted with plastics. To counteract this issue, biological (enzymatic) plastic decomposition is increasingly gaining attention. Recently it was shown that polyethylene terephthalate (PET) can be degraded in a saltwater-based environment using bacterial PETase produced by a marine diatom. At moderate temperatures, plastic biodegradation is slow and requires sensitive methods for detection, at least at initial stages. However, conventional methods for verifying the plastic degradation are either complex, expensive, time-consuming or they interfere with the degradation process. Here, we adapt lensless digital holographic microscopy (LDHM) as a new application for efficiently monitoring enzymatic degradation of a PET glycol copolymer (PETG). LDHM is a cost-effective, compact and sensitive optical method. We demonstrate enzymatic PETG degradation over a time course of 43 days employing numerical analysis of LDHM images.

We measure both nonlinear absorption and nonlinear refraction in a C H 3 N H 3 P b B r 3 single crystal using the Z-scan technique with femtosecond laser pulses. At 1000 nm, we obtain values of 5.2 cm/GW and + 9.5 ⋅ 10 − 14 c m 2 / W for nonlinear absorption and nonlinear refraction, respectively. The sign and magnitude of the observed refractive nonlinearity are reproduced well by the two-band model. Our results suggest that the large nonlinear refractive index measured in perovskite nanostructures cannot be explained by an intrinsically high bound-electronic nonlinear refractive index in this emerging material class but is possibly caused by free carriers or quantum confinement effects.

A decisive factor for the performance of organic bulk heterojunction solar cells is the competition between charge separation and geminate electron–hole recombination through a charge-transfer (CT) state after exciton separation across the heterointerface. By time-resolving the near-infrared emission of the high-performance low-bandgap PTB7:PC71BM material system, we selectively study the properties of CT states formed after optical excitation with a femtosecond laser pulse. We observe that the CT emission yield is higher after 705 nm excitation of the polymer rather than after 400 nm excitation of the fullerene, which can be attributed to better charge separation for excitons generated in fullerene aggregates. Additionally, the CT states are weakly bound with their emission not far red-shifted from that of the exciton. Examining the time-resolved CT emission from room temperature to 10 K, we observe changes in CT state lifetime with energy and temperature, indicative of CT state separation effectively co...

Charge-transfer (CT) states across organic heterojunctions play an important role in determining the efficiency of organic solar cells. These states can be the precursors of free charges or lead to geminate recombination losses. Here, we use time-resolved photoluminescence measurements to study charge-transfer states in a sequence of polythiophene:fullerene derivative blends with different mixing ratios, over the temperature range from 10 to 290 K, and after excitation with various photon energies. Our results show that (1) excess fullerene leads to a higher probability of CT state formation per absorbed photon and (2) the CT emission intensity is temperature-dependent whereas its emission lifetime is temperature-independent. Observation 1 cannot be explained solely by the increased fraction of excitations formed on fullerene-derivatives in the fullerene-rich blends, suggesting that disruption of the polymer packing at high fullerene loadings can negatively influence charge separation. Observation 2 sugge...

We fabricate photodetectors based on solution-processed single CH3NH3PbBr3 microcrystals (MCs) and map the two-photon absorption (TPA) excited photocurrent (PC) with spatial resolution of 1 μm. We find that the charge carrier transport length in the MCs depends on the applied electric field, and increases from 5.7 μm for 0.02 V bias (dominated by carrier diffusion) to 23.2 μm for 2 V bias (dominated by carrier drift). Furthermore, PC shows strong spatial variations. Combining the PC mapping results with time-resolved photoluminescence microscopy, we demonstrate that the spatial distribution of PC mainly originates from the inhomogeneous distribution of trap-states across perovskite MCs. This suggests that there is still large margin for improvement of perovskite single crystal devices by better controlling of the traps.

The microscopic mechanisms of exciton and charge-transfer-state dissociation in organic semiconductors play a major role for the efficiencies of organic solar cells [1]. One of the most direct experiments for probing the dynamics of these processes is luminescence quenching. Here, we present a comprehensive experimental and simulative study of the field and temperature dependence of the dissociation of singlet excitons in PTB7 and PC71BM, and from charge-transfer states generated across interfaces in PTB7/PC71BM bulk heterojunction solar cells. We deduce the relevant data from time-resolving the near infrared emission of the states from 10K to room temperature and for electric fields ranging from 0 to 2.5 MV/cm. To draw qualitative conclusions from our data, we use an analytical field-assisted hopping model in the presence of disorder [2]. We conclude that singlet excitons can be split by high fields, and that disorder plays a large role in broadening the critical threshold field for which singlet excitons are separated. Charge-transfer (CT) state dissociation can be induced by both field and temperature, and the data imply that a strong reduction of the Coulomb binding potential at the interface facilitates their separation. The observations provided herein of the field dependent separation of CT states as a function of temperature offer a rich dataset against which theoretical models of charge separation can be rigorously tested. References: [1] H. Bassler and A. Kohler, Phys. Chem. Chem. Phys. 17, 28451 (2015) [2] O. Rubel, S. D. Baranovskii, W. Stolz, and F. Gebhard, Phys. Rev. Lett. 100, 196602 (2008).

The physics of charge separation in organic semiconductors is a topic of ongoing research of relevance to material and device engineering. Herein, we present experimental observations of the field and temperature dependence of charge separation from singlet excitons in PTB7 and ${\mathrm{PC}}_{71}\mathrm{BM}$, and from charge-transfer states created across interfaces in $\mathrm{PTB}7/{\mathrm{PC}}_{71}\mathrm{BM}$ bulk heterojunction solar cells. We obtain this experimental data by time-resolving the near infrared emission of the states from 10 K to room temperature and electric fields from 0 to $2.5\phantom{\rule{4pt}{0ex}}{\mathrm{MV}\phantom{\rule{0.16em}{0ex}}\mathrm{cm}}^{\ensuremath{-}1}$. Examining how the luminescence is quenched by field and temperature gives direct insight into the underlying physics. We observe that singlet excitons can be split by high fields, and that disorder broadens the high threshold fields needed to split the excitons. Charge-transfer (CT) states, on the other hand, can be separated by both field and temperature. Also, the data imply a strong reduction of the activation barrier for charge splitting from the CT state relative to the exciton state. The observations provided herein of the field-dependent separation of CT states as a function of temperature offer a rich data set against which theoretical models of charge separation can be rigorously tested; it should be useful for developing the more advanced theoretical models of charge separation.

Metal halide perovskites are promising optoelectronic materials. Their electronic properties however are rather unstable which is often assigned to ion migration. Ion migration can be readily influenced by an electric field (EF). Here, the response of photoluminescence (PL) of individual MAPbX3 (MA = CH3NH3, X = I, Br) sub-micrometer-sized polycrystals to EF is studied. Alternating EF with frequency higher than 10 Hz is found to reversibly quench PL. It is proposed that an alternating EF when applied together with light increases ion migration. This leads to a shift in the equilibrium between creation and annihilation of defects toward higher concentration of nonradiative recombination centers. The PL quenching is found to increase with increasing frequency of the field. This can be rationalized by the frequency dependence of the dielectric constant, leading to stronger internal fields for high modulation frequencies compared to, e.g., a constant EF with the same external amplitude. PL quenching and enhancement observed under constant EF are hypothesized to be due to a reconfiguration of already existing nonradiative recombination centers situated on grain boundaries. The control of perovskite PL by alternating EF reported here can find applications in optoelectronic devices. (Less)

Charge transfer (CT) states play evidently an important role at the interface of organic heterostructures but their identification and characterization is often experimentally less obvious and challenging. We studied two exemplary material systems which both represented a benchmark within the research of organic photovoltaics at their time: the homopolymer P3HT blended with PC61BM and the copolymer PTB7 blended with PC71BM. In both heterostructures, we could identify a distinct CT state emission by the use of NIR time-resolved photoluminescence (PL) [1], [2]. The selectivity of this technique enables us to clearly probe the energetics and dynamics of weak emitting interfacial states and therefore to prove differences in the CT state characteristics between the two systems. We went beyond this previous work and investigated the time and temperature dependent emission anisotropy as well as the electric field dependence of the time-resolved PL for both blends and the pristine polymers, respectively. In both cases the CT state emission clearly deviates from the one of the primarily excited singlet excitons: the emission anisotropy reveals an additional relaxation pathway for the exciton which is connected with a change of the transition dipole moment of the emission, and under applied bias different quenching thresholds can give access to varying binding energies of the emissive excitons involved. Finally, we think that our findings demonstrate how interfacial CT state emission can be clearly identified as such and how it can be unambiguously distinguished from singlet exciton emission.

In organic photovoltaics (OPV), perylene diimide (PDI) acceptor materials are promising candidates to replace the commonly used, but more expensive fullerene derivatives. The use of alternative acceptor materials however implies new design guidelines for OPV devices. It is therefore important to understand the underlying photophysical processes, which either lead to charge generation or geminate recombination. In this contribution, we investigate radiative losses in a series of OPV materials based on two polymers, P3HT and PTB7, respectively, which were blended with different PDI derivatives. Our time-resolved photoluminescence measurements (TRPL) allow us to identify different loss mechanisms by the decay characteristics of several excitonic species. In particular, we find evidence for unfavorable morphologies in terms of large-scale pure domains, inhibited exciton transport and incomplete charge transfer. Furthermore, in one of the P3HT-blends, an interfacial emissive charge transfer (CT) state with strong trapping character is identified.

We present a multimode continuous wave terahertz spectrometer driven by a compact laser diode with a tunable spectrum. An external feedback based on two optical gratings into the diode allows us to shape the laser emission spectrum, and hence the temporal shape of the terahertz signals. In particular, we show a power enhancement of a factor of ten for individual regions of the spectrum to gain a signal-to-noise ratio in the frequency range of interest.

We investigate the NIR time-resolved photoluminescence of a series of P3HT:PC61BM solar cells with varying blend ratios after preferential excitation of the PC61BM and P3HT components respectively. Besides the rapid and diffusion-limited quenching of singlet excitons we resolve a weak emission feature in the near-infrared that our measurements confirm comes from interfacial charge-transfer (CT) states. This CT state emission becomes stronger for samples with an excess of PC61BM, and also after selective excitation of the PC61BM component. In this way, we show that these NIR time-resolved photoluminescence measurements provide an accurate method of observing subtle changes in the formation and dynamics of CT states at organic heterojunctions due to its high selectivity, and suggest that PC61BM excitons are more likely to lead to geminately recombining CT states than are the excitons created on P3HT. We also measure the temperature dependence of the transient NIR photoluminescence and find that while the intensity of the NIR emission is temperature dependent, its lifetime is not. This interesting observation suggests that the CT states we observe are formed through a precursor state which can either form separated charges or CT states, and that the relative yield of these two pools is temperature dependent. Furthermore, it indicates that charges within these relaxed CT states are trapped at the donor-acceptor interface and cannot contribute to free-charge generation via thermal activation anymore.

Geminate recombination of photo-generated excitons represents a considerable loss mechanism in polymer solar cells. We apply time-resolved photoluminescence (TRPL) to study the radiative recombination which accompanies the process of charge generation. A streak camera is used, which is sensitive for both the photoluminescence (PL) from the initially excited singlet excitons and the weaker emission from charge transfer (CT) states. The latter are formed at internal interfaces when the polymer is blended with a fullerene acceptor. We draw a comparison between our results for two polymers, P3HT and PTB7, respectively, which were studied in blends with the fullerene derivative PCBM. In addition, pristine films were investigated, allowing for the identification of interfacial features in the blends. For both polymers, the PL of the singlet states was rapidly quenched in blends with PCBM. In P3HT, time constants of about 40 ps were recorded for the singlet exciton decay and related to exciton diffusion, whereas the PL of PTB7 was almost completely quenched within the first 3 ps. The decay rates of the emissive CT excitons were 2-3 orders of magnitude smaller than those of the singlet state. Yet, due to their slower dynamics (~ 500 ps), they could be separated from the superimposed singlet emission. The CT decay times in blends with P3HT exhibited no significant temperature dependence, indicating that thermally driven dissociation of emissive excitons is unlikely. For blends with PTB7, however, a faster decay of the CT emission was obtained at room temperature.

The efficiency droop in nitride LEDs is currently attributed to either carrier-density-dependent nonradiative recombination or to carrier leakage, both being discussed in terms of a single-particle picture. Our time-resolved photoluminescence results show that the radiative lifetime is independent of carrier density, while the nonradiative lifetime scales with the inverse of the carrier density. This can not be understood in a single-particle model. By means of a many-particle theory approach we obtain a consistent picture with both radiative and Auger recombination enhanced by excitonic electron-hole correlation. In the high carrier density limit single-particle radiative and Auger recombination are recovered.

Room-temperature electronic properties of semiconductors, especially in the case of higher charge densities, are commonly discussed in terms of single-particle excitations -- free electrons and holes. Many-particle effects, such as the formation of excitons (Coulomb-bound electron-hole pairs), are usually seen as low-temperature and low-density phenomena. In this paper, using ultrafast terahertz and photoluminescence measurements, the authors find that under certain conditions typical for wide-band-gap semiconductors, the radiative excitons can be efficiently formed at high charge density and at room temperature. This effect is believed to contribute to the extraordinarily high quantum efficiency of group III nitride light emitters.

Charge transfer states in blends of organic semiconductors have significant importance for the functioning of organic optoelectronic devices, but are also interesting from the perspective of fundamental research as many of their properties as well as their influence on the photophysics of the material are not yet completely understood. We report on a time-resolved photoluminescence study of the photophysics of the charge transfer state in the prototypical donor–acceptor system pentacene mixed with its perfluorinated counterpart. We find indications for the existence of two distinct charge-transfer states, one of them formed in the bulk of the mixed phase, the other one formed at the interface to phase-separated pentacene domains. We discuss the implications of the difference in temperature dependence of the emission intensity and the lifetime observed for these charge transfer states.

We measured pulsed THz emission from high-mobility MBE grown InGaAs/InAlAs multi-nanolayer structures. The detected average THz power was 32 μW at 32 mW optical excitation power. The bandwidth of the THz pulses exceeds 4 THz.

Financial support from the Tunisian General Directorate of Scientific and Technical Research (DGRST) is gratefully acknowledged. The authors are very grateful to Prof. Dr. Martin Koch of the Physics department of the Philipp University of Marburg for giving the opportunity to perform time-resolved photoluminescence measurements in his laboratories. The authors would like to thank the CRHEA CNRS Sophia-Antipolis for SEM analysis.

We present first results on photoconductive THz emitters for 1.55µm excitation. The emitters are based on MBE grown In0.53Ga0.47As/In0.52Al0.48As multilayer heterostructures (MLHS) with high carrier mobility. The high mobility is achieved by spatial separation of photoconductive and trapping regions. Photoconductive antennas made of these MLHS are evaluated as THz emitters in a THz time domain spectrometer (THz TDS). The high carrier mobility and effective absorption significantly increases the optical-to-THz conversion efficiency with THz bandwidth in excess of 3 THz.

We present first results on photoconductive switches based on MBE grown InGaAs/InAlAs multi-nanolayer structures with separated trapping and photoconductive layers, the later exhibiting high carrier mobility. The high mobility significantly increases the optical power-to-THz conversion efficiency, while the emitted THz bandwidth exceeds 3 THz.

We propose a hybrid architecture for continuous wave terahertz spectroscopy employing a conventional two color photomixing system combined with a quasi time domain spectrometer, driven by a multimode laser diode. This approach fuses high spectral intensity with broadband frequency information and overcomes the ambiguity of standard continuous wave thickness measurements.

The dependence of radiative and nonradiative lifetimes on the excess carrier density in GaInN/GaN quantum wells is studied via time-resolved photoluminescence spectroscopy over a wide range of excitation densities. Our results differ from the predictions of simple free-carrier models: density independent radiative lifetimes clearly evidence the excitonic nature even at room temperature. At high densities, nonradiative lifetimes are weakly temperature dependent and proportional to the inverse of the density, implying an excitonic, threshold-less Auger process. Furthermore, in the intermediate density regime between low and high injection, an increase of the nonradiative lifetimes is observed, which is typical for Shockley-Read-Hall-type recombination.

We present results on optimized growth temperatures and layer structure design of high mobility photoconductive Terahertz (THz) emitters based on molecular beam epitaxy grown In0.53Ga0.47As/In0.52Al0.48As multilayer heterostructures (MLHS). The photoconductive antennas made of these MLHS are evaluated as THz emitters in a THz time domain spectrometer and with a Golay cell. We measured a THz bandwidth in excess of 4 THz and average THz powers of up to 64 μW corresponding to an optical power-to-THz power conversion efficiency of up to 2 × 10−3.