Metal-Solvent Complex Formation at the Surface of InP Colloidal Quantum Dots.

The surface chemistry of colloidal semiconductor nanocrystals (QDs) profoundly influences their physical and chemical attributes. The insulating organic shell ensuring colloidal stability impedes charge transfer, thus limiting optoelectronic applications. Exchanging these ligands with shorter inorganic ones enhances charge mobility and stability, which is pivotal for using these materials as active layers for LEDs, photodetectors, and transistors. Among those, InP QDs also serve as a model for surface chemistry investigations. This study focuses on group III metal salts as inorganic ligands for InP QDs. We explored the ligand exchange mechanism when metal halide, nitrate, and perchlorate salts of group III (Al, In Ga), common Lewis acids, are used as ligands for the conductive inks. Moreover, we compared the exchange mechanism for two starting model systems: InP QDs capped with myristate and oleylamine as X- and L-type native organic ligands, respectively. We found that all metal halide, nitrate, and perchlorate salts dissolved in polar solvents (such as n-methylformamide, dimethylformamide, dimethyl sulfoxide, H2O) with various polarity formed metal-solvent complex cations [M(Solvent)6]3+ (e.g., [Al(MFA)6]3+, [Ga(MFA)6]3+, [In(MFA)6]3+), which passivated the surface of InP QDs after the removal of the initial organic ligand. All metal halide capped InP/[M(Solvent)6]3+ QDs show excellent colloidal stability in polar solvents with high dielectric constant even after 6 months in concentrations up to 74 mg/mL. Our findings demonstrate the dominance of dissociation-complexation mechanisms in polar solvents, ensuring colloidal stability. This comprehensive understanding of InP QD surface chemistry paves the way for exploring more complex QD systems such as InAs and InSb QDs.

PbS Quantum Dots Ink with Months-Long Shelf-Lifetime Enabling Scalable and Efficient Short-Wavelength Infrared Photodetectors.

The phase-transfer ligand exchange of PbS quantum dots (QDs) has substantially simplified device fabrication giving hope for future industrial exploitation. However, this technique when applied to QDs of large size (>4 nm) gives rise to inks with poor colloidal stability, thus hindering the development of QDs photodetectors in short-wavelength infrared range. Here, it is demonstrated that methylammonium lead iodide ligands can provide sufficient passivation of PbS QDs of size up to 6.7 nm, enabling inks with a minimum of ten-week shelf-life time, as proven by optical absorption and solution-small angle X-ray scattering. Furthermore, the maximum linear electron mobility of 4.7 × 10-2 cm2 V-1 s-1 is measured in field-effect transistors fabricated with fresh inks, while transistors fabricated with the same solution after ten-week storage retain 74% of the average starting electron mobility, demonstrating the outstanding quality both of the fresh and aged inks. Finally, photodetectors fabricated via blade-coating exhibit 76% external quantum efficiency at 1300 nm and 1.8 × 1012 Jones specific detectivity, values comparable with devices fabricated using ink with lower stability and wasteful methods such as spin-coating.

Polaron Vibronic Progression Shapes the Optical Response of 2D Perovskites.

The optical response of 2D layered perovskites is composed of multiple equally-spaced spectral features, often interpreted as phonon replicas, separated by an energy Δ ≃ 12 - 40 meV, depending upon the compound. Here the authors show that the characteristic energy spacing, seen in both absorption and emission, is correlated with a substantial scattering response above ≃ 200 cm-1 (≃ 25 meV) observed in resonant Raman. This peculiar high-frequency signal, which dominates both Stokes and anti-Stokes regions of the scattering spectra, possesses the characteristic spectral fingerprints of polarons. Notably, its spectral position is shifted away from the Rayleigh line, with a tail on the high energy side. The internal structure of the polaron consists of a series of equidistant signals separated by 25-32 cm-1 (3-4 meV), depending upon the compound, forming a polaron vibronic progression. The observed progression is characterized by a large Huang-Rhys factor (S > 6) for all of the 2D layered perovskites investigated here, indicative of a strong charge carrier - lattice coupling. The polaron binding energy spans a range ≃ 20-35 meV, which is corroborated by the temperature-dependent Raman scattering data. The investigation provides a complete understanding of the optical response of 2D layered perovskites via the direct observation of polaron vibronic progression. The understanding of polaronic effects in perovskites is essential, as it directly influences the suitability of these materials for future opto-electronic applications.

Quasi-2D Lead-Tin Perovskite Memory Devices Fabricated by Blade Coating.

Two terminal passive devices are regarded as one of the promising candidates to solve the processor-memory bottleneck in the Von Neumann computing architectures. Many different materials are used to fabricate memory devices, which have the potential to act as synapses in future neuromorphic electronics. Metal halide perovskites are attractive for memory devices as they display high density of defects with a low migration barrier. However, to become promising for a future neuromorphic technology, attention should be paid on non-toxic materials and scalable deposition processes. Herein, it is reported for the first time the successful fabrication of resistive memory devices using quasi-2D tin-lead perovskite of composition (BA)2 MA4 (Pb0.5 Sn0.5 )5 I16 by blade coating. The devices show typical memory characteristics with excellent endurance (2000 cycles), retention (105  s), and storage stability (3 months). Importantly, the memory devices successfully emulate synaptic behaviors such as spike-timing-dependent plasticity, paired-pulse facilitation, short-term potentiation, and long-term potentiation. A mix of slow (ionic) transport and fast (electronic) transport (charge trapping and de-trapping) is proven to be responsible for the observed resistive switching behavior.

Solution-Processed Polymer Dielectric Interlayer for Low-Voltage, Unipolar n-Type Organic Field-Effect Transistors.

The integration of organic electronic circuits into real-life applications compels the fulfillment of a range of requirements, among which the ideal operation at a low voltage with reduced power consumption is paramount. Moreover, these performance factors should be achieved via solution-based fabrication schemes in order to comply with the promise of cost- and energy-efficient manufacturing offered by an organic, printed electronic technology. Here, we propose a solution-based route for the fabrication of low-voltage organic transistors, encompassing ideal device operation at voltages below 5 V and exhibiting n-type unipolarization. This process is widely applicable to a variety of semiconducting and dielectric materials. We achieved this through the use of a photo-cross-linked, low-k dielectric interlayer, which is used to fabricate multilayer dielectric stacks with areal capacitances of up to 40 nF/cm2 and leakage currents below 1 nA/cm2. Because of the chosen azide-based cross-linker, the dielectric promotes n-type unipolarization of the transistors and demonstrated to be compatible with different classes of semiconductors, from conjugated polymers to carbon nanotubes and low-temperature metal oxides. Our results demonstrate a general applicability of our unipolarizing dielectric, facilitating the implementation of complementary circuitry of emerging technologies with reduced power consumption.

Introduction to halide perovskite optoelectronics.

An introduction to the Nanoscale themed collection on halide perovskite nanomaterials for optoelectronic applications, featuring a variety of articles that highlight the latest developments to address ongoing challenges in the field.

On the Mechanism of Solvents Catalyzed Structural Transformation in Metal Halide Perovskites.

Metal halide perovskites show the capability of performing structural transformation, allowing the formation of functional heterostructures. Unfortunately, the elusive mechanism governing these transformations limits their technological application. Herein, the mechanism of 2D-3D structural transformation is unraveled as catalyzed by solvents. By combining a spatial-temporal cation interdiffusivity simulation with experimental findings, it is validated that, protic solvents foster the dissociation degree of formadinium iodide (FAI) via dynamic hydrogen bond, then the stronger hydrogen bond of phenylethylamine (PEA) cation with selected solvents compared to dissociated FA cation facilitates 2D-3D transformation from (PEA)2 PbI4 to FAPbI3 . It is discovered that, the energy barrier of PEA out-diffusion and the lateral transition barrier of inorganic slab are diminished. For 2D films the protic solvents catalyze grain centers (GCs) and grain boundaries (GBs) transforme into 3D phases and quasi-2D phases, respectively. While in the solvent-free case, GCs transform into 3D-2D heterostructures along the direction perpendicular to the substrate, and most GBs evolve into 3D phases. Finally, memristor devices fabricated using the transformed films uncover that, GBs composed of 3D phases are more prone to ion migration. This work elucidates the fundamental mechanism of structural transformation in metal halide perovskites, allowing their use to fabricate complex heterostructures.

Tuning the energy transfer in Ruddlesden-Popper perovskites phases through isopropylammonium addition - towards efficient blue emitters.

Here we demonstrate blue LEDs with a peak wavelength of 481 nm, with outstanding colour purity of up to 88% (CIE coordinates (0.1092, 0.1738)), an external quantum yield of 5.2% and a luminance of 8260 cd m-2. These devices are based on quasi-2D PEA2(Cs0.75MA0.25)Pb2Br7, which is cast from solutions containing isopropylammonium (iPAm). iPAm as additive assist in supressing the formation of bulk-like phases, as pointed out by both photophysical and structural characterization. Additionally, the study of the excitation dynamics demonstrates a hindering of the energy transfer to domains of lower energy that generally undermines the performance and emission characteristics of blue-emitting LEDs based on quasi-2D perovskites. The achieved narrow distribution of quantum well sizes and the hindered energy transfer result in a thin film photoluminescence quantum yield exceeding 60%. Our work demonstrates the great potential to tailor the composition and the structure of thin films based on Ruddlesden-Popper phases to boost performance of optoelectronic devices - specifically blue perovskite LEDs.

Approaching Bulk Mobility in PbSe Colloidal Quantum Dots 3D Superlattices.

3D superlattices made of colloidal quantum dots are a promising candidate for the next generation of optoelectronic devices as they are expected to exhibit a unique combination of tunable optical properties and coherent electrical transport through minibands. While most of the previous work was performed on 2D arrays, the control over the formation of these systems is lacking, where limited long-range order and energetical disorder have so far hindered the potential of these metamaterials, giving rise to disappointing transport properties. Here, it is reported that nanoscale-level controlled ordering of colloidal quantum dots in 3D and over large areas allows the achievement of outstanding transport properties. The measured electron mobilities are the highest ever reported for a self-assembled solid of fully quantum-confined objects. This ultimately demonstrates that optoelectronic metamaterials with highly tunable optical properties (in this case in the short-wavelength infrared spectral range) and charge mobilities approaching that of bulk semiconductor can be obtained. This finding paves the way toward a new generation of optoelectronic devices.

Efficient Selective Sorting of Semiconducting Carbon Nanotubes Using Ultra-Narrow-Band-Gap Polymers.

Conjugated polymers with narrow band gaps are particularly useful for sorting and discriminating semiconducting single-walled carbon nanotubes (s-SWCNT) due to the low charge carrier injection barrier for transport. In this paper, we report two newly synthesized narrow-band-gap conjugated polymers (PNDITEG-TVT and PNDIC8TEG-TVT) based on naphthalene diimide (NDI) and thienylennevinylene (TVT) building blocks, decorated with different polar side chains that can be used for dispersing and discriminating s-SWCNT. Compared with the mid-band-gap conjugated polymer PNDITEG-AH, which is composed of naphthalene diimide (NDI) and head-to-head bithiophene building blocks, the addition of a vinylene linker eliminates the steric congestion present in head-to-head bithiophene, which promotes backbone planarity, extending the π-conjugation length and narrowing the band gap. Cyclic voltammetry (CV) and density functional theory (DFT) calculations suggest that inserting a vinylene group in a head-to-head bithiophene efficiently lifts the highest occupied molecular orbital (HOMO) level (-5.60 eV for PNDITEG-AH, -5.02 eV for PNDITEG-TVT, and -5.09 eV for PNDIC8TEG-TVT). All three polymers are able to select for s-SWCNT, as evidenced by the sharp transitions in the absorption spectra. Field-effect transistors (FETs) fabricated with the polymer:SWCNT inks display p-dominant properties, with higher hole mobilities when using the NDI-TVT polymers as compared with PNDITEG-AH (0.6 cm2 V-1 s-1 for HiPCO:PNDITEG-AH, 1.5 cm2 V-1 s-1 for HiPCO:PNDITEG-TVT, and 2.3 cm2 V-1 s-1 for HiPCO:PNDIC8TEG-TVT). This improvement is due to the better alignment of the HOMO level of PNDITEG-TVT and PNDIC8TEG-TVT with that of the dominant SWCNT specie.

Tin Halide Perovskites: From Fundamental Properties to Solar Cells.

Metal halide perovskites have unique optical and electrical properties, which make them an excellent class of materials for a broad spectrum of optoelectronic applications. However, it is with photovoltaic devices that this class of materials has reached the apotheosis of popularity. High power conversion efficiencies are achieved with lead-based compounds, which are toxic to the environment. Tin-based perovskites are the most promising alternative because of their bandgap close to the optimal value for photovoltaic applications, the strong optical absorption, and good charge carrier mobilities. Nevertheless, the low defect tolerance, the fast crystallization, and the oxidative instability of tin halide perovskites currently limit their efficiency. The aim of this review is to give a detailed overview of the crystallographic, photophysical, and optoelectronic properties of tin-based perovskite compounds in their multiple forms from 3D to low-dimensional structures. At the end, recent progress in tin-based perovskite solar cells are reviewed, mainly focusing on the detail of the strategies adopted to improve the device performances. For each subtopic, the current challenges and the outlook are discussed, with the aim to stimulate the community to address the most important issues in a concerted manner.

Crystallization driven boost in fill factor and stability in additive-free organic solar cells.

The control of morphology and microstructure during and after the active layer processing of bulk-heterojunction solar cells is critical to obtain elevated fill factors and overall good device performance. With the recent development of non-fullerene acceptors, wide attention has been paid to improve miscibility, solubility and nanoscale separation by laborious molecular design processes and by the use of additives. Nonetheless, several post-processing strategies can equally contribute to obtain an optimum phase separation and even to an enhanced crystallinity, but their effect on performance and device lifetime of polymer/non-fullerene acceptor solar cells is still unclear. Herein, we report a systematic comparison between different post-processing treatments including thermal annealing (TA), vacuum drying (VD) and solvent vapor annealing (SVA) on the TPD-3F polymer and IT-4F non-fullerene acceptor, comparing their effects on device performance as well as on the morphology and optical and electrical properties. The optimized SVA treated devices exhibited power conversion efficiencies close to 14% with a remarkable 76% fill factor and superior short-circuit currents compared to the one of untreated devices. Moreover, SVA demonstrated improvements in device stability both under illumination and under ambient conditions. The induced phase separation and the increased crystallinity of the acceptor molecules, as revealed by GIWAXS measurements, led to increased photogenerated currents, with a more effective exciton dissociation and charge collection. The open-circuit voltage losses in the SVA and TA devices were explained by a bandgap reduction and a higher trap-assisted recombination, respectively. Overall, our study points to the role of post-processing in organic solar cell fabrication, and contributes towards a new generation of efficient and stable additive-free organic solar cells.

Brightening of dark excitons in 2D perovskites.

Optically inactive dark exciton states play an important role in light emission processes in semiconductors because they provide an efficient nonradiative recombination channel. Understanding the exciton fine structure in materials with potential applications in light-emitting devices is therefore critical. Here, we investigate the exciton fine structure in the family of two-dimensional (2D) perovskites (PEA)2SnI4, (PEA)2PbI4, and (PEA)2PbBr4. In-plane magnetic field mixes the bright and dark exciton states, brightening the otherwise optically inactive dark exciton. The bright-dark splitting increases with increasing exciton binding energy. Hot photoluminescence is observed, indicative of a non-Boltzmann distribution of the bright-dark exciton populations. We attribute this to the phonon bottleneck, which results from the weak exciton­acoustic phonon coupling in soft 2D perovskites. Hot photoluminescence is responsible for the strong emission observed in these materials, despite the substantial bright-dark exciton splitting.

Molecular Doping Directed by a Neutral Radical.

Molecular doping makes possible tunable electronic properties of organic semiconductors, yet a lack of control of the doping process narrows its scope for advancing organic electronics. Here, we demonstrate that the molecular doping process can be improved by introducing a neutral radical molecule, namely nitroxyl radical (2,2,6,6-teramethylpiperidin-i-yl) oxyl (TEMPO). Fullerene derivatives are used as the host and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazoles (DMBI-H) as the n-type dopant. TEMPO can abstract a hydrogen atom from DMBI-H and transform the latter into a much stronger reducing agent DMBI•, which efficiently dopes the fullerene derivative to yield an electrical conductivity of 4.4 S cm-1. However, without TEMPO, the fullerene derivative is only weakly doped likely by a hydride transfer following by an inefficient electron transfer. This work unambiguously identifies the doping pathway in fullerene derivative/DMBI-H systems in the presence of TEMPO as the transfer of a hydrogen atom accompanied by electron transfer. In the absence of TEMPO, the doping process inevitably leads to the formation of less symmetrical hydrogenated fullerene derivative anions or radicals, which adversely affect the molecular packing. By adding TEMPO we can exclude the formation of such species and, thus, improve charge transport. In addition, a lower temperature is sufficient to meet an efficient doping process in the presence of TEMPO. Thereby, we provide an extra control of the doping process, enabling enhanced thermoelectric performance at a low processing temperature.

The Fascinating Properties of Tin-Alloyed Halide Perovskites.

Tin-alloyed halide perovskites are progressively becoming more popular as slowly their optoelectronic properties start to rival those of the potentially risky pure lead analogues. However, to push this attractive semiconductor toward realistic applications, several major issues need to be solved. This Perspective will start with a description of the fundamental properties of tin-alloyed halide perovskites, continue discussing their weak points with special attention on the structural and electronic instabilities, and conclude examining the effects of the above-mentioned properties on devices. Finally we propose a plausible roadmap to further boost tin-alloyed halide perovskite devices to practical applications. We believe this roadmap should start from an understanding of this family of semiconductors from an atomistic viewpoint, proceeding to the control of thin-film fabrication, the structural properties, and finally the device optimization. We hope this Perspective can help to inject new enthusiasm and facilitate the progress in tin-alloyed halide perovskites, catalyzing their transition from the cradle of the laboratories to the reality of their fabrication.

Can Ferroelectricity Improve Organic Solar Cells?

Blends of semiconducting (SC) and ferroelectric (FE) polymers have been proposed for applications in resistive memories and organic photovoltaics (OPV). For OPV, the rationale is that the local electric field associated with the dipoles in a blend could aid exciton dissociation, thus improving power conversion efficiency. However, FE polymers either require solvents or processing steps that are incompatible with those required for SC polymers. To overcome this limitation, SC (poly(3-hexylthiophene)) and FE (poly(vinylidene fluoride-trifluoroethylene)) components are incorporated into a block copolymer and thus a path to a facile fabrication of smooth thin films from suitably chosen solvents is achieved. In this work, the photophysical properties and device performance of organic solar cells containing the aforementioned block copolymer consisting of poly(vinylidene fluoride-trifluoroethylene): P(VDF-TrFE), poly(3-hexylthiophene): P3HT and the electron acceptor phenyl-C61 -butyric acid methyl ester: [60]PCBM are explored. A decrease in photovoltaic performance is observed in blends of the copolymer with P3HT:[60]PCBM, which is attributed to a less favorable nanomorphology upon addition of the copolymer. The role of lithium fluoride (the cathode modification layer) is also clarified in devices containing the copolymer, and it is demonstrated that ferroelectric compensation prevents the ferroelectricity of the copolymer from improving photovoltaic performance in SC-FE blends.

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.

Scalable fabrication of high-quality crystalline and stable FAPbI3 thin films by combining doctor-blade coating and the cation exchange reaction.

Formamidinium lead iodide (FAPbI3) is one of the most extensively studied perovskite materials due to its narrow band gap and high absorption coefficient, which makes it highly suitable for optoelectronic applications. Deposition of a solution containing lead iodide (PbI2) and formamidinium iodide (FAI) or sequential deposition of PbI2 and FAI usually leads to the formation of films with a poor morphology and an unstable crystal structure that readily crystallize into two different polymorphs: the photoinactive yellow phase and the photoactive black phase. In this work, 2D 2-phenylethylammonium lead iodide (PEA2PbI4) thin films are deposited by a scalable doctor-blade coating technique and used as a growth template for the high-quality 3D FAPbI3 perovskite thin films which are obtained by organic cation exchange. We report the structural, morphological and optical properties of these converted 3D FAPbI3 perovskite films which we compare to the directly deposited 3D FAPbI3 films. The converted FAPbI3 thin films are compact, smooth, and highly oriented and exhibit better structural stability in comparison with the directly deposited 3D films. These results not only underscore the importance of the employed deposition techniques in fabricating highly crystalline and stable perovskite thin films but also provide a strategy to easily obtain very compact perovskite layers using doctor-blade coating.

Constructing the Electronic Structure of CH3NH3PbI3 and CH3NH3PbBr3 Perovskite Thin Films from Single-Crystal Band Structure Measurements.

Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced.