Scalable PbS Quantum Dot Solar Cell Production by Blade Coating from Stable Inks.

The recent development of phase transfer ligand exchange methods for PbS quantum dots (QD) has enhanced the performance of quantum dots solar cells and greatly simplified the complexity of film deposition. However, the dispersions of PbS QDs (inks) used for film fabrication often suffer from colloidal instability, which hinders large-scale solar cell production. In addition, the wasteful spin-coating method is still the main technique for the deposition of QD layer in solar cells. Here, we report a strategy for scalable solar cell fabrication from highly stable PbS QD inks. By dispersing PbS QDs capped with CH3NH3PbI3 in 2,6-difluoropyridine (DFP), we obtained inks that are colloidally stable for more than 3 months. Furthermore, we demonstrated that DFP yields stable dispersions even of large diameter PbS QDs, which are of great practical relevance owing to the extended coverage of the near-infrared region. The optimization of blade-coating deposition of DFP-based inks enabled the fabrication of PbS QD solar cells with power conversion efficiencies of up to 8.7%. It is important to underline that this performance is commensurate with the devices made by spin coating of inks with the same ligands. A good shelf life-time of these inks manifests itself in the comparatively high photovoltaic efficiency of 5.8% obtained with inks stored for more than 120 days.

On the Colloidal Stability of PbS Quantum Dots Capped with Methylammonium Lead Iodide Ligands.

Phase-transfer exchange of pristine organic ligands for inorganic ones is essential for the integration of colloidal quantum dots (CQDs) in optoelectronic devices. This method results in a colloidal dispersion (ink) which can be directly deposited by various solution-processable techniques to fabricate conductive films. For PbS CQDs capped with methylammonium lead iodide ligands (MAPbI3), the most commonly employed solvent is butylamine, which enables only a short-term (hours) colloidal stability and thus brings concerns on the possibility of manufacturing CQD devices on a large scale in a reproducible manner. In this work, we studied the stability of alternative inks in two highly polar solvents which impart long-term colloidal stability of CQDs: propylene carbonate (PC) and 2,6-difluoropyridine (DFP). The aging and the loss of the ink's stability were monitored with optical, structural, and transport measurements. With these solvents, PbS CQDs capped with MAPbI3 ligands retain colloidal stability for more than 20 months, both in dilute and concentrated dispersions. After 17 months of ink storage, transistors with a maximum linear mobility for electrons of 8.5 × 10-3 cm2/V s are fabricated; this value is 17% of the one obtained with fresh solutions. Our results show that both PC- and DFP-based PbS CQD inks offer the needed shelf life to allow for the development of a CQD device technology.

Improved Reproducibility of PbS Colloidal Quantum Dots Solar Cells Using Atomic Layer-Deposited TiO2.

Thanks to their broadly tunable bandgap and strong absorption, colloidal lead chalcogenide quantum dots (QDs) are highly appealing as solution-processable active layers for third-generation solar cells. However, the modest reproducibility of this kind of solar cell is a pertinent issue, which inhibits the exploitation of this material class in optoelectronics. This issue is not necessarily imputable to the active layer but may originate from different constituents of the device structure. Herein, the deposition of TiO2 electron transport layer is focused on. Atomic layer deposition (ALD) greatly improves the reproducibility of PbS QD solar cells compared with the previously optimized sol-gel (SG) approach. Power conversion efficiency (PCE) of the solar cells using atomic layer-deposited TiO2 lies in the range between 5.5% and 7.2%, whereas solar cells with SG TiO2 have PCE ranging from 0.5% to 6.9% with a large portion of short-circuited devices. Investigations of TiO2 layers by atomic force microscopy and scanning electron microscopy reveal that these films have very different surface morphologies. Whereas the TiO2 films prepared by SG synthesis and deposited by spin coating are very smooth, TiO2 films made by ALD repeat the surface texture of the fluorine-doped tin oxide (FTO) substrate underneath.

Photophysical and electronic properties of bismuth-perovskite shelled lead sulfide quantum dots.

Metal halide perovskite shelled quantum dot solids have recently emerged as an interesting class of solution-processable materials that possess the desirable electronic properties of both quantum dots and perovskites. Recent reports have shown that lead sulfide quantum dots (PbS QDs) with perovskite ligand-shells can be successfully utilized in (opto)electronic devices such as solar cells, photoconductors, and field-effect transistors (FETs), a development attributed to the compatibility of lattice parameters between PbS and certain metal halide perovskites that results in the growth of the perovskite shell on the PbS QDs. Of several possible perovskite combinations used with PbS QDs, bismuth-based variants have been shown to have the lowest lattice mismatch and to display excellent performance in photoconductors. However, they also display photoluminescence (PL), which is highly sensitive to surface defects. In this work, we present an investigation of the transport and optical properties of two types of bismuth-based perovskite (MA3BiI6 and MA3Bi2I9) shelled PbS QDs. Our photophysical study using temperature-dependent PL spectroscopy between 5 and 290 K indicates that the PL efficiency of the reference oleic acid (OA) capped samples is much higher than that of the Bi-shelled ones, which suffer from traps, most likely formed at their surfaces during the phase-transfer ligand exchange process. Nevertheless, the results from electrical measurements on FETs show the successful removal of the native-OA ligands, displaying electron dominated transport with modest mobilities of around 10-3 cm2 [V s]-1 - comparable to the reported values for epitaxial Pb-based shelled samples. These findings advance our understanding of perovskite shelled QD-solids and point to the utility of these Bi-based variants as contenders for photovoltaic and other optoelectronic applications.

Bis{µ-2,2'-[(3,4-di-thia-hexane-1,6-di-yl)bis-(nitrilo-methanylyl-idene)]bis-(4-bromo-phenolato)-κ4O,N,N',O'}dicopper(II).

The crystal structure of the title compound, [Cu2(C18H12Br2N4O2S2)2], consists of binuclear complex units which lie across inversion centres and are connected by weak Cu-O coordination bonds forming chains along the b axis. The CuII ion is five-coordinated by two N atoms and two O atoms of the chelating ligand and one symmetry-related O atom forming a square-pyramidal coordination geometry. In the crystal, short S⋯Br contacts connect neighbouring chains into a two-dimensional network parallel to (101).

Comparing Halide Ligands in PbS Colloidal Quantum Dots for Field-Effect Transistors and Solar Cells.

Capping colloidal quantum dots (CQDs) with atomic ligands is a powerful approach to tune their properties and improve the charge carrier transport in CQD solids. Efficient passivation of the CQD surface, which can be achieved with halide ligands, is crucial for application in optoelectronic devices. Heavier halides, i.e., I- and Br-, have been thoroughly studied as capping ligands in the last years, but passivation with fluoride ions has not received sufficient consideration. In this work, effective coating of PbS CQDs with fluoride ligands is demonstrated and compared to the results obtained with other halides. The electron mobility in field-effect transistors of PbS CQDs treated with different halides shows an increase with the size of the atomic ligand (from 3.9 × 10-4 cm2/(V s) for fluoride-treated to 2.1 × 10-2 cm2/(V s) for iodide-treated), whereas the hole mobility remains unchanged in the range between 1 × 10-5 cm2/(V s) and 10-4cm2/(V s). This leads to a relatively more pronounced p-type behavior of the fluoride- and chloride-treated films compared to the iodide-treated ones. Cl-- and F--capped PbS CQDs solids were then implemented as p-type layer in solar cells; these devices showed similar performance to those prepared with 1,2-ethanedithiol in the same function. The relatively stronger p-type character of the fluoride- and chloride-treated PbS CQD films broadens the utility of such materials in optoelectronic devices.

Crystal structure of bis(µ2-4-bromo-2-[({2-[({2-[(5-bromo-2-oxidobenzylidene)amino]ethyl}sulfanyl)sulfonyl]ethyl}imino)methyl]phenolato)dicopper(II) dimethylformamide disolvate.

The title dinuclear copper(II) complex [Cu2(C18H16Br2N2O4S2)2] was prepared by direct synthesis of a dianionic Schiff base derived from 5-bromo-salicyl-aldehyde and cyste-amine. The discrete mol-ecules lie across inversion centers and crystallize with two di-methyl-formamide (DMF) mol-ecules of crystallization. The unique CuII ion is four-coordinated by two tetra-dentate Schiff base ligands in a distorted square-planar N2O2 environment. In the crystal, short inter-molecular S⋯Br contacts, weak C-H⋯O hydrogen bonds and intra- and inter-molecular π-π stacking inter-actions between rings of the ligand link the components into a two-dimensional network parallel to (010).