We present a theoretical model to compute the efficiency of the generation of two or more electron-hole pairs in a semiconductor by the absorption of one photon via the process of carrier multiplication (CM). The photogeneration quantum yield of electron-hole pairs is calculated from the number of possible CM decay pathways of the electron and the hole. We apply our model to investigate the underlying cause of the high efficiency of CM in bulk 2H-MoTe2, as compared to bulk PbS and PbSe. Electronic band structures were calculated with density functional theory, from which the number of possible CM decay pathways was calculated for all initial electron and hole states that can be produced at a given photon energy. The variation of the number of CM pathways with photon energy reflects the dependence of experimental CM quantum yields on the photon energy and material composition. We quantitatively reproduce experimental CM quantum yields for MoTe2, PbS, and PbSe from the calculated number of CM pathways and one adjustable fit parameter. This parameter is related to the ratio of Coulomb coupling matrix elements and the cooling rate of the electrons and holes. Large variations of this fit parameter result in small changes in the modeled quantum yield for MoTe2, which confirms that its high CM efficiency can be mainly attributed to its extraordinary large number of CM pathways. The methodology of this work can be applied to analyze or predict the CM efficiency of other materials.@en

InP and InZnP colloidal quantum dots (QDs) are promising materials for application in light-emitting devices, transistors, photovoltaics, and photocatalytic cells. In addition to possessing an appropriate bandgap, high absorption coefficient, and high bulk carrier mobilities, the intrinsic toxicity of InP and InZnP is much lower than for competing QDs that contain Cd or Pb–providing a potentially safer commercial product. However, compared to other colloidal QDs, InP QDs remain sparsely used in devices and their electronic transport properties are largely unexplored. Here, we use time-resolved microwave conductivity measurements to study charge transport in films of InP and InZnP colloidal quantum dots capped with a variety of short ligands. We find that transport in InP QDs is dominated by trapping effects, which are mitigated in InZnP QDs. We improve charge carrier mobilities with a range of ligand-exchange treatments and for the best treatments reach mobilities and lifetimes on par with those of PbS QD films used in efficient solar cells. To demonstrate the device-grade quality of these films, we construct solar cells based on InP & InZnP QDs with power conversion efficiencies of 0.65 and 1.2%, respectively. This represents a large step forward in developing Cd- and Pb-free next-generation optoelectronic devices.@en

Carrier multiplication (CM) is the process in which multiple electron–hole pairs are created upon absorption of a single photon in a semiconductor. CM by an initially hot charge carrier occurs in competition with cooling by phonon emission, with the respective rates determining the CM efficiency. Up until now, CM rates have only been calculated theoretically. We show for the first time how to extract a distinct CM rate constant from experimental data of the relaxation time of hot charge carriers and the yield of CM. We illustrate this method for PbSe quantum dots. Additionally, we provide a simplified method using an estimated energy loss rate to estimate the CM rate constant just above the onset of CM, when detailed experimental data of the relaxation time is missing.@en

Two-dimensional (2D) semiconductors hold high potential for the implementation of efficient ultrathin electronics (e.g. field-effect transistors, light emitting diodes and solar cell devices). In recent years, colloidal methods to synthesize ultrathin 2D materials have been developed that offer alternatives (like the production of non-layered 2D materials and upscaling) to mechanical exfoliation methods. By focusing on optoelectronic applications, it is important to characterize the nature and dynamics of photoexcited states in these materials. In this paper, we use ultrafast transient absorption (TA) and terahertz (THz) spectroscopy as optimal tools for such a characterization. We choose recently synthesized ultrathin colloidal 2D InSe nanosheets (inorganic layer thickness 0.8-1.7 nm; ≤5 nm including ligands) for discussing TA and THz spectroscopic studies and elucidate their charge carrier dynamics under photoexcitation with TA. THz spectroscopy is then used to extract contactless AC mobilities as high as 20±2 cm²/Vs in single InSe layers. The obtained results underpin the general applicability of TA and THz spectroscopy for characterizing photoexcited states in 2D semiconductors.

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Singlet fission in tetracene generates two triplet excitons per absorbed photon. If these triplet excitons can be effectively transferred into silicon (Si), then additional photocurrent can be generated from photons above the bandgap of Si. This could alleviate the thermalization loss and increase the efficiency of conventional Si solar cells. Here, we show that a change in the polymorphism of tetracene deposited on Si due to air exposure facilitates triplet transfer from tetracene into Si. Magnetic field-dependent photocurrent measurements confirm that triplet excitons contribute to the photocurrent. The decay of tetracene delayed photoluminescence was used to determine a transfer efficiency of ∼36% into Si. Our study suggests that control over the morphology of tetracene during the deposition will be of great importance to boost the triplet transfer yield further.

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Indium antimonide (InSb) quantum dots (QDs) have unique and interesting photophysical properties, but widespread experimentation with InSb QDs is lacking due to the difficulty in synthesizing this material. The key experimental challenge in fabricating InSb QDs is preparing a suitable Sb-precursor in the correct oxidation state that reacts with the In-precursor in a controllable manner. Here, we review and discuss the synthetic strategies for making colloidal InSb QDs and present a new reaction scheme yielding small (∼1 nm diameter) InSb QDs. This was accomplished by employing Sb(NMe₂)₃ as the antimony precursor and by screening different reducing agents that can selectively reduce it to stibine in situ. The released SbH₃, subsequently, reacts with In carboxylate to form small InSb clusters. The absorption features are moderately tunable (from 400 nm to 660 nm) by the amount and rate of reductant addition as well as the temperature of injection and subsequent annealing. Optical properties were probed with transient absorption spectroscopy and show complex time and spectral dependencies.

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In this work, we investigate the occurrence of localized surface plasmon resonances (LSPRs) in different nickel sulfide nanostructures. Therefore, spherical and anisotropic nickel sulfide nanoparticles (NPs) are synthesized and analyzed regarding their optical properties by UV/vis/NIR and transient absorption spectroscopy. Furthermore, new pathways for the synthesis of spherical Ni₃S₂ nanodots with an extremely narrow size distribution, as well as Au-Ni₃S₂ core-shell NPs with controllable shell thickness, are presented. Our results show that NPs of different metallic nickel sulfide phases like Ni₃S₂ and Ni₃S₄ exhibit LSPR bands in the visible regime of the electromagnetic spectrum, which possibly makes them a comparably cheaper alternative to NPs consisting of noble metals like Au and Ag. In case of the presented plasmonic core-shell particles, the resonance frequency of the plasmon can be tuned between those of pure gold and pure Ni₃S₂ NPs by varying the Ni₃S₂ shell thickness.

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