Precursor-Engineered Volatile Inks Enable Reliable Blade-Coating of Cesium-Formamidinium Perovskites Toward Fully Printed Solar Modules.

Reliable fabrication of large-area perovskite films with antisolvent-free printing techniques requires high-volatility solvents, such as 2-methoxyethanol (2ME), to formulate precursor inks. However, the fabrication of high-quality cesium-formamidinium (Cs-FA) perovskites has been hampered using volatile solvents due to their poor coordination with the perovskite precursors. Here, this issue is resolved by re-formulating a 2ME-based Cs0.05FA0.95PbI3 ink using pre-synthesized single crystals as the precursor instead of the conventional mixture of raw powders. The key to obtaining high-quality Cs-FA films lies in the removal of colloidal particles from the ink and hence the suppression of colloid-induced heterogeneous nucleation, which kinetically facilitates the growth of as-formed crystals toward larger grains and improved film crystallinity. Employing the precursor-engineered volatile ink in the vacuum-free, fully printing processing of solar cells (with carbon electrode), a power conversion efficiency (PCE) of 19.3%, a T80 (80% of initial PCE) of 1000 h in ISOS-L-2I (85 °C/1 Sun) aging test and a substantially reduced bill of materials are obtained. The reliable coating methodology ultimately enables the fabrication of carbon-electrode mini solar modules with a stabilized PCE of 16.2% (average 15.6%) representing the record value among the fully printed counterparts and a key milestone toward meeting the objectives for a scalable photovoltaic technology.

Ligand Tuning of Localized Surface Plasmon Resonances in Antimony-Doped Tin Oxide Nanocrystals.

Aliovalent-doped metal oxide nanocrystals exhibiting localized surface plasmons (LSPRs) are applied in systems that require reflection/scattering/absorption in infrared and optical transparency in visible. Indium tin oxide (ITO) is currently leading the field, but indium resources are known to be very restricted. Antimony-doped tin oxide (ATO) is a cheap candidate to substitute the ITO, but it exhibits less advantageous electronic properties and limited control of the LSPRs. To date, LSPR tuning in ATO NCs has been achieved electrochemically and by aliovalent doping, with a significant decrease in doping efficiency with an increasing doping level. Here, we synthesize plasmonic ATO nanocrystals (NCs) via a solvothermal route and demonstrate ligand exchange to tune the LSPR energies. Attachment of ligands acting as Lewis acids and bases results in LSPR peak shifts with a doping efficiency overcoming those by aliovalent doping. Thus, this strategy is of potential interest for plasmon implementations, which are of potential interest for infrared upconversion, smart glazing, heat absorbers, or thermal barriers.

The Fine-Structure Constant as a Ruler for the Band-Edge Light Absorption Strength of Bulk and Quantum-Confined Semiconductors.

Low-dimensional semiconductors have found numerous applications in optoelectronics. However, a quantitative comparison of the absorption strength of low-dimensional versus bulk semiconductors has remained elusive. Here, we report generality in the band-edge light absorptance of semiconductors, independent of their dimensions. First, we provide atomistic tight-binding calculations that show that the absorptance of semiconductor quantum wells equals mπα (m = 1 or 2 with α as the fine-structure constant), in agreement with reported experimental results. Then, we show experimentally that a monolayer (superlattice) of quantum dots has similar absorptance, suggesting an absorptance quantum of mπα per (confined) exciton diameter. Extending this idea to bulk semiconductors, we experimentally demonstrate that an absorptance quantum equal to mπα per exciton Bohr diameter explains their widely varying absorption coefficients. We thus provided compelling evidence that the absorptance quantum πα per exciton diameter rules the band-edge absorption of all direct semiconductors, regardless of their dimension.

Micron Thick Colloidal Quantum Dot Solids.

Shortwave infrared colloidal quantum dots (SWIR-CQDs) are semiconductors capable of harvesting across the AM1.5G solar spectrum. Today's SWIR-CQD solar cells rely on spin-coating; however, these films exhibit cracking once thickness exceeds ∼500 nm. We posited that a blade-coating strategy could enable thick QD films. We developed a ligand exchange with an additional resolvation step that enabled the dispersion of SWIR-CQDs. We then engineered a quaternary ink that combined high-viscosity solvents with short QD stabilizing ligands. This ink, blade-coated over a mild heating bed, formed micron-thick SWIR-CQD films. These SWIR-CQD solar cells achieved short-circuit current densities (Jsc) that reach 39 mA cm-2, corresponding to the harvest of 60% of total photons incident under AM1.5G illumination. External quantum efficiency measurements reveal both the first exciton peak and the closest Fabry-Perot resonance peak reaching approximately 80%-this is the highest unbiased EQE reported beyond 1400 nm in a solution-processed semiconductor.

Looking beyond the Surface: The Band Gap of Bulk Methylammonium Lead Iodide.

Despite the intense research on photovoltaic lead halide perovskites, reported optical properties as basic as the absorption onset and the optical band gap vary significantly. To unambiguously answer the question whether the discrepancies are a result of differences between bulk and "near-surface" material, we perform two nonlinear spectroscopies with drastically different information depths on single crystals of the prototypical (CH3NH3)PbI3 methylammonium lead iodide. Two-photon absorption, detected via the resulting generation of carriers and photocurrents (2PI-PC), probes the interband transitions with an information depth in the millimeter range relevant for bulk (single-crystal) material. In contrast, the transient magneto-optical Kerr effect (trMOKE) measured in a reflection geometry determines the excitonic transition energies in the region near (hundreds of nm) the surface which also determine the optical properties in typical thin films. To identify differences between structural phases, we sweep the sample temperature across the orthorhombic-tetragonal phase transition temperature. In the application-relevant room-temperature tetragonal phase (at 170 K), we find a bulk band gap of 1.55 ± 0.01 eV, whereas in the near-surface region excitonic transitions occur at 1.59 ± 0.01 eV. The latter value is consistent with previous reflectance measurements by other groups and considerably higher than the bulk band gap. The small band gap of the bulk material explains the extended infrared absorption of crystalline perovskite solar cells, the low-energy bands which carry optically driven spin-polarized currents, and the narrow bandwidth of crystalline perovskite photodetectors making use of the spectral filtering at the surface.

Exfoliated CrPS4 with Promising Photoconductivity.

Layered semiconductors have attracted significant attention due to their diverse physical properties controlled by composition and the number of stacked layers. Herein, large crystals of the ternary layered semiconductor chromium thiophosphate (CrPS4 ) are prepared by a vapor transport synthesis. Optical properties are determined using photoconduction, absorption, photoreflectance, and photoacoustic spectroscopy exposing the semiconducting properties of the material. A simple, one-step protocol for mechanical exfoliation onto a transmission electron microscope grid is developed, and multiple layers are characterized by advanced electron microscopy methods, including atomic resolution elemental mapping confirming the structure by directly showing the positions of the columns of different elements' atoms. CrPS4 is also liquid exfoliated, and in combination with colloidal graphene, an ink-jet-printed photodetector is created. This all-printed graphene/CrPS4 /graphene heterostructure detector demonstrates a specific detectivity of 8.3 × 108 (D*). This study shows a potential application of both bulk crystal and individual flakes of CrPS4 as active components in light detection, when introduced as ink-printable moieties with a large benefit for manufacturing.

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.

Fully Printed Infrared Photodetectors from PbS Nanocrystals with Perovskite Ligands.

Colloidal nanocrystals from PbS are successfully applied in highly sensitive infrared photodetectors with various device architectures. Here, we demonstrate all-printed devices with high detectivity (∼1012 cm Hz1/2/W) and a cut-off frequency of >3 kHz. The low material consumption (<0.3 mg per detector) and short processing time (14 s per detector) enabled by the automated printing promises extremely low device costs. To enable all-printed devices, an ink formulation was developed based on nanocrystals stabilized by perovskite-like methylammonium iodobismuthate ligands, which are dispersed in a ternary solvent. Fully inkjet printed devices based on this solvent were achieved with printed silver electrodes and a ZnO interlayer. Considerable improvements were obtained by the addition of small amounts of the polymer poly(vinylpyrrolidone) to the ink. The polymer improved the colloidal stability of the ink and its film-formation properties and thus enabled the scalable printing of single detectors and detector arrays. While photoconductors were shown here, the developed ink will certainly find application in a series of further electronic devices based on nanocrystals from a broad range of materials.

A Shape-Induced Orientation Phase within 3D Nanocrystal Solids.

When nanocrystals self assemble into ordered superstructures they form functional solids that may inherit the electronical properties of the single nanocrystals. To what extent these properties are enhanced depends on the positional and orientational order of the nanocrystals within the superstructure. Here, the formation of micrometer-sized free-standing supercrystals of faceted 20 nm Bi nanocrystals is investigated. The self-assembly process, induced by nonsolvent into solvent diffusion, is probed in situ by synchrotron X-ray scattering. The diffusion-gradient is identified as the critical parameter for controlling the supercrystal-structure as well as the alignment of the supercrystals with respect to the substrate. Monte Carlo simulations confirm the positional order of the nanocrystals within these superstructures and reveal a unique orientation phase: the nanocrystal shape, determined by the atomic Bi crystal structure, induces a total of 6 global orientations based on facet-to-facet alignment. This parallel alignment of facets is a prerequisite for optimized electronic and optical properties within designed nanocrystal solids.

General Observation of Photocatalytic Oxygen Reduction to Hydrogen Peroxide by Organic Semiconductor Thin Films and Colloidal Crystals.

Low-cost semiconductor photocatalysts offer unique possibilities for industrial chemical transformations and energy conversion applications. We report that a range of organic semiconductors are capable of efficient photocatalytic oxygen reduction to H2O2 in aqueous conditions. These semiconductors, in the form of thin films, support a 2-electron/2-proton redox cycle involving photoreduction of dissolved O2 to H2O2, with the concurrent photooxidation of organic substrates: formate, oxalate, and phenol. Photochemical oxygen reduction is observed in a pH range from 2 to 12. In cases where valence band energy of the semiconductor is energetically high, autoxidation competes with oxidation of the donors, and thus turnover numbers are low. Materials with deeper valence band energies afford higher stability and also oxidation of H2O to O2. We found increased H2O2 evolution rate for surfactant-stabilized nanoparticles versus planar thin films. These results evidence that photochemical O2 reduction may be a widespread feature of organic semiconductors, and open potential avenues for organic semiconductors for catalytic applications.

Cellular interfaces with hydrogen-bonded organic semiconductor hierarchical nanocrystals.

Successful formation of electronic interfaces between living cells and semiconductors hinges on being able to obtain an extremely close and high surface-area contact, which preserves both cell viability and semiconductor performance. To accomplish this, we introduce organic semiconductor assemblies consisting of a hierarchical arrangement of nanocrystals. These are synthesised via a colloidal chemical route that transforms the nontoxic commercial pigment quinacridone into various biomimetic three-dimensional arrangements of nanocrystals. Through a tuning of parameters such as precursor concentration, ligands and additives, we obtain complex size and shape control at room temperature. We elaborate hedgehog-shaped crystals comprising nanoscale needles or daggers that form intimate interfaces with the cell membrane, minimising the cleft with single cells without apparent detriment to viability. Excitation of such interfaces with light leads to effective cellular photostimulation. We find reversible light-induced conductance changes in ion-selective or temperature-gated channels.Nanomaterials that form a bioelectronic interface with cells are fascinating tools for controlling cellular behavior. Here, the authors photostimulate single cells with spiky assemblies of semiconducting quinacridone nanocrystals, whose nanoscale needles maximize electronic contact with the cells.

Enabling Ambipolar to Heavy n-Type Transport in PbS Quantum Dot Solids through Doping with Organic Molecules.

PbS quantum dots (QDs) are remarkable semiconducting materials, which are compatible with low-cost solution-processed electronic device fabrication. Understanding the doping of these materials is one of the great research interests, as it is a necessary step to improve the device performance as well as to enhance the applicability of this system for diverse optoelectronic applications. Here, we report the efficient doping of the PbS QD films with the use of solution-processable organic molecules. By engineering the energy levels of the donor molecules and the PbS QDs through the use of different cross-linking ligands, we are able to control the characteristics of PbS field-effect transistors (FETs) from ambipolar to strongly n-type. Because the doping promotes trap filling, the charge carrier mobility is improved up to 0.64 cm2 V-1 s-1, which is the highest mobility reported for low-temperature processed PbS FETs employing SiO2 as the gate dielectric. The doping also reduces the contact resistance of the devices, which can also explain the origin of the increased mobility.

Broadening of Distribution of Trap States in PbS Quantum Dot Field-Effect Transistors with High-k Dielectrics.

We perform a quantitative analysis of the trap density of states (trap DOS) in PbS quantum dot field-effect transistors (QD-FETs), which utilize several polymer gate insulators with a wide range of dielectric constants. With increasing gate dielectric constant, we observe increasing trap DOS close to the lowest unoccupied molecular orbital (LUMO) of the QDs. In addition, this increase is also consistently followed by broadening of the trap DOS. We rationalize that the increase and broadening of the spectral trap distribution originate from dipolar disorder as well as polaronic interactions, which are appearing at strong dielectric polarization. Interestingly, the increased polaron-induced traps do not show any negative effect on the charge carrier mobility in our QD devices at the highest applied gate voltage, giving the possibility to fabricate efficient low-voltage QD devices without suppressing carrier transport.

Quasi-epitaxial Metal-Halide Perovskite Ligand Shells on PbS Nanocrystals.

Epitaxial growth techniques enable nearly defect free heterostructures with coherent interfaces, which are of utmost importance for high performance electronic devices. While high-vacuum technology-based growth techniques are state-of-the art, here we pursue a purely solution processed approach to obtain nanocrystals with eptaxially coherent and quasi-lattice matched inorganic ligand shells. Octahedral metal-halide clusters, respectively 0-dimensional perovskites, were employed as ligands to match the coordination geometry of the PbS cubic rock-salt lattice. Different clusters (CH3NH3+)(6-x)[M(x+)Hal6](6-x)- (Mx+ = Pb(II), Bi(III), Mn(II), In(III), Hal = Cl, I) were attached to the nanocrystal surfaces via a scalable phase transfer procedure. The ligand attachment and coherence of the formed PbS/ligand core/shell interface was confirmed by combining the results from transmission electron microscopy, small-angle X-ray scattering, nuclear magnetic resonance spectroscopy and powder X-ray diffraction. The lattice mismatch between ligand shell and nanocrystal core plays a key role in performance. In photoconducting devices the best performance (detectivity of 2 × 1011 cm Hz 1/2/W with > 110 kHz bandwidth) was obtained with (CH3NH3)3BiI6 ligands, providing the smallest relative lattice mismatch of ca. -1%. PbS nanocrystals with such ligands exhibited in millimeter sized bulk samples in the form of pressed pellets a relatively high carrier mobility for nanocrystal solids of ∼1.3 cm2/(V s), a carrier lifetime of ∼70 µs, and a low residual carrier concentration of 2.6 × 1013 cm-3. Thus, by selection of ligands with appropriate geometry and bond lengths optimized quasi-epitaxial ligand shells were formed on nanocrystals, which are beneficial for applications in optoelectronics.

Galvanic Exchange in Colloidal Metal/Metal-Oxide Core/Shell Nanocrystals.

While galvanic exchange is commonly applied to metallic nanoparticles, recently its applicability was expanded to metal-oxides. Here the galvanic exchange is studied in metal/metal-oxide core/shell nanocrystals. In particular Sn/SnO2 is treated by Ag+, Pt2+, Pt4+, and Pd2+. The conversion dynamics is monitored by in situ synchrotron X-ray diffraction. The Ag+ treatment converts the Sn cores to the intermetallic Ag x Sn (x ∼ 4) phase, by changing the core's crystal structure. For the analogous treatment by Pt2+, Pt4+, and Pd2+, such a galvanic exchange is not observed. This different behavior is caused by the semipermeability of the naturally formed SnO2 shell, which allows diffusion of Ag+ but protects the nanocrystal cores from oxidation by Pt and Pd ions.

Random Lasing with Systematic Threshold Behavior in Films of CdSe/CdS Core/Thick-Shell Colloidal Quantum Dots.

While over the past years the syntheses of colloidal quantum dots (CQDs) with core/shell structures were continuously improved to obtain highly efficient emission, it has remained a challenge to use them as active materials in laser devices. Here, we report random lasing at room temperature in films of CdSe/CdS CQDs with different core/shell band alignments and extra thick shells. Even though the lasing process is based on random scattering, we find systematic dependencies of the laser thresholds on morphology and laser spot size. To minimize laser thresholds, optimizing the film-forming properties of the CQDs, proven by small-angle X-ray scattering, was found to be more important than the optical parameters of the CQDs, such as biexciton lifetime and binding energy or fluorescence decay time. Furthermore, the observed systematic behavior turned out to be highly reproducible after storing the samples in air for more than 1 year. These highly reproducible systematic dependencies suggest that random lasing experiments are a valuable tool for testing nanocrystal materials, providing a direct and simple feedback for further development of colloidal gain materials toward lasing in continuous wave operation.

Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites.

Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ∼10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440-700 nm) with low pump thresholds down to 5±1 µJ cm(-2) and high values of modal net gain of at least 450±30 cm(-1). Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX3 nanocrystals and random lasing in films of CsPbX3 nanocrystals.

High mobility and low density of trap states in dual-solid-gated PbS nanocrystal field-effect transistors.

Dual-gated PbS nanocrystal field-effect transistors employing SiO2 and Cytop as gate dielectrics are fabricated. The obtained electron mobility (0.2 cm(2) V(-1) s(-1) ) and the high on/off ratio (10(5) -10(6) ), show that the controlled nanocrystal assembly (obtained with self-assembled monolayers), as well as the trap density reduction (using Cytop as dielectric), are crucial steps for the future application of nanocrystals.

Iodide-capped PbS quantum dots: full optical characterization of a versatile absorber.

Lead sulfide quantum dots represent an emerging photovoltaic absorber material. While their associated optical qualities are true for the colloidal solution phase, they change upon processing into thin-films. A detailed view to the optical key-parameters during solid-film development is presented and the limits and outlooks for this versatile and promising absorber are discussed.