Photocatalytic doping of organic semiconductors.

Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)1-3 and ultimately enhances device performance4-7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants8-10, which are consumed during the doping process. Achieving efficient doping with weak and/or widely accessible dopants under mild conditions remains a considerable challenge. Here, we report a previously undescribed concept for the photocatalytic doping of OSCs that uses air as a weak oxidant (p-dopant) and operates at room temperature. This is a general approach that can be applied to various OSCs and photocatalysts, yielding electrical conductivities that exceed 3,000 S cm-1. We also demonstrate the successful photocatalytic reduction (n-doping) and simultaneous p-doping and n-doping of OSCs in which the organic salt used to maintain charge neutrality is the only chemical consumed. Our photocatalytic doping method offers great potential for advancing OSC doping and developing next-generation organic electronic devices.

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.

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.

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.

Polymer-Nanocarbon Topological and Electronic Interface.

The electronic structure of semiconducting carbon nanotubes selected through polymer functionalization is routinely verified by measuring the spectral van Hove singularity signature under ultraclean vacuum conditions. Interpreting the effect of unperturbed polymer adsorption on the nanotube energetic bands in solvent media is experimentally challenging owing to solvent molecular crowding around the hybrid complex. Here, a liquid-based scanning tunneling microscope and spectroscope operating in a noise-free laboratory is used to resolve the polymer-semiconducting carbon-nanotube-underlying graphene heterostructure in the presence of encompassing solvent molecules. The spectroscopic measurements highlight the role of polymer packing and graphene landscape on the electronic shifts induced in the nanotube energy bands. Together with molecular dynamics simulations, our experimental findings emphasize the necessity of recording physicochemical and electronic properties of liquid-phase solubilized hybrid materials in their native state.

Exciton Recombination in Formamidinium Lead Triiodide: Nanocrystals versus Thin Films.

The optical properties of the newly developed near-infrared emitting formamidinium lead triiodide (FAPbI3 ) nanocrystals (NCs) and their polycrystalline thin film counterpart are comparatively investigated by means of steady-state and time-resolved photoluminescence. The excitonic emission is dominant in NC ensemble because of the localization of electron-hole pairs. A promisingly high quantum yield above 70%, and a large absorption cross-section (5.2 × 10-13 cm-2 ) are measured. At high pump fluence, biexcitonic recombination is observed, featuring a slow recombination lifetime of 0.4 ns. In polycrystalline thin films, the quantum efficiency is limited by nonradiative trap-assisted recombination that turns to bimolecular at high pump fluences. From the temperature-dependent photoluminescence (PL) spectra, a phase transition is clearly observed in both NC ensemble and polycrystalline thin film. It is interesting to note that NC ensemble shows PL temperature antiquenching, in contrast to the strong PL quenching displayed by polycrystalline thin films. This difference is explained in terms of thermal activation of trapped carriers at the nanocrystal's surface, as opposed to the exciton thermal dissociation and trap-mediated recombination, which occur in thin films at higher temperatures.

Probing photoinduced electron-transfer in graphene-dye hybrid materials for DSSC.

We investigated the photophysical properties of a newly synthesized hybrid material composed of a triphenylamine dye covalently bound to reduced graphene oxide, potentially relevant as a stable photosensitizer in dye-sensitized solar cells. The photophysical characterization has been carried out by means of fluorescence quenching and fluorescence lifetime measurements, complemented by Electron Paramagnetic Resonance (EPR) spectroscopy, aimed at the detailed description of the photoinduced processes occurring in the hybrid and in the mixed hybrid/N-doped TiO2 material. The combined optical/magnetic study unequivocally demonstrates a fast quenching of the dye excited state in the isolated hybrid and an efficient electron transfer to N-doped titania nanopowders. In the latter case, a metastable radical cation on the dye moiety is photogenerated and the corresponding negative charge, an electron, is trapped in defect sites of the doped semiconductor oxide. The spin distribution in the stable radical has been determined by EPR spectroscopy and correlated with DFT calculations.

Filling the Green Gap of a Megadalton Photosystem I Complex by Conjugation of Organic Dyes.

Photosynthesis is Nature's major process for converting solar into chemical energy. One of the key players in this process is the multiprotein complex photosystem I (PSI) that through absorption of incident photons enables electron transfer, which makes this protein attractive for applications in bioinspired photoactive hybrid materials. However, the efficiency of PSI is still limited by its poor absorption in the green part of the solar spectrum. Inspired by the existence of natural phycobilisome light-harvesting antennae, we have widened the absorption spectrum of PSI by covalent attachment of synthetic dyes to the protein backbone. Steady-state and time-resolved photoluminescence reveal that energy transfer occurs from these dyes to PSI. It is shown by oxygen-consumption measurements that subsequent charge generation is substantially enhanced under broad and narrow band excitation. Ultimately, surface photovoltage (SPV) experiments prove the enhanced activity of dye-modified PSI even in the solid state.

Conjugated polymer-assisted dispersion of single-wall carbon nanotubes: the power of polymer wrapping.

The future application of single-walled carbon nanotubes (SWNTs) in electronic (nano)devices is closely coupled to the availability of pure, semiconducting SWNTs and preferably, their defined positioning on suited substrates. Commercial carbon nanotube raw mixtures contain metallic as well as semiconducting tubes of different diameter and chirality. Although many techniques such as density gradient ultracentrifugation, dielectrophoresis, and dispersion by surfactants or polar biopolymers have been developed, so-called conjugated polymer wrapping is one of the most promising and powerful purification and discrimination strategies. The procedure involves debundling and dispersion of SWNTs by wrapping semiflexible conjugated polymers, such as poly(9,9-dialkylfluorene)s (PFx) or regioregular poly(3-alkylthiophene)s (P3AT), around the SWNTs, and is accompanied by SWNT discrimination by diameter and chirality. Thereby, the π-conjugated backbone of the conjugated polymers interacts with the two-dimensional, graphene-like π-electron surface of the nanotubes and the solubilizing alkyl side chains of optimal length support debundling and dispersion in organic solvents. Careful structural design of the conjugated polymers allows for a selective and preferential dispersion of both small and large diameter SWNTs or SWNTs of specific chirality. As an example, with polyfluorenes as dispersing agents, it was shown that alkyl chain length of eight carbons are favored for the dispersion of SWNTs with diameters of 0.8-1.2 nm and longer alkyls with 12-15 carbons can efficiently interact with nanotubes of increased diameter up to 1.5 nm. Polar side chains at the PF backbone produce dispersions with increased SWNT concentration but, unfortunately, cause reduction in selectivity. The selectivity of the dispersion process can be monitored by a combination of absorption, photoluminescence, and photoluminescence excitation spectroscopy, allowing identification of nanotubes with specific coordinates [(n,m) indices]. The polymer wrapping strategy enables the generation of SWNT dispersions containing exclusively semiconducting nanotubes. Toward the applications in electronic devices, until now most applied approach is a direct processing of such SWNT dispersions into the active layer of network-type thin film field effect transistors. However, to achieve promising transistor performance (high mobility and on-off ratio) careful removal of the wrapping polymer chains seems crucial, for example, by washing or ultracentrifugation. More defined positioning of the SWNTs can be accomplished in directed self-assembly procedures. One possible strategy uses diblock copolymers containing a conjugated polymer block as dispersing moiety and a second block for directed self-assembly, for example, a DNA block for specific interaction with complementary DNA strands. Another strategy utilizes reactive side chains for controlled anchoring onto patterned surfaces (e.g., by interaction of thiol-terminated alkyl side chains with gold surfaces). A further promising application of purified SWNT dispersions is the field of organic (all-carbon) or hybrid solar cell devices.

Localization and dynamics of amylose-lipophilic molecules inclusion complex formation in starch granules.

Inclusion complex formation between lipophilic dye molecules and amylose polymers in starch granules is investigated using laser spectroscopy and microscopy. By combining confocal laser scanning microscopy (CLSM) with spatial resolved photoluminescence (PL) spectroscopy, we are able to discriminate the presence of amylose in the peripheral region of regular and waxy granules from potato and corn starch, associating a clear optical fingerprint with the interaction between starch granules and lipophilic dye molecules. We show in particular that in the case of regular starch the polar head of the lipophilic dye molecules remains outside the amylose helix experiencing a water-based environment. The measurements performed on samples that have been extensively washed provide a strong proof of the specific interaction between lipid dye molecules and amylose chains in regular starch. These measurements also confirm the tendency of longer amylopectin chains, located in the hilum of waxy starch granules, to form inclusion complexes with ligands. Through real-time recording of CLSM micrographs, within a time frame of tens of seconds, we measured the dynamics of occurrence of the inclusion process between lipids and amylose located at the periphery of starch granules.

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.

PbI2 Passivation of Three Dimensional PbS Quantum Dot Superlattices Toward Optoelectronic Metamaterials.

Lead chalcogenide colloidal quantum dots are one of the most promising materials to revolutionize the field of short-wavelength infrared optoelectronics due to their bandgap tunability and strong absorption. By self-assembling these quantum dots into ordered superlattices, mobilities approaching those of the bulk counterparts can be achieved while still retaining their original optical properties. The recent literature focused mostly on PbSe-based superlattices, but PbS quantum dots have several advantages, including higher stability. In this work, we demonstrate highly ordered 3D superlattices of PbS quantum dots with tunable thickness up to 200 nm and high coherent ordering, both in-plane and along the thickness. We show that we can successfully exchange the ligands throughout the film without compromising the ordering. The superlattices as the active material of an ion gel-gated field-effect transistor achieve electron mobilities up to 220 cm2 V-1 s-1. To further improve the device performance, we performed a postdeposition passivation with PbI2, which noticeably reduced the subthreshold swing making it reach the Boltzmann limit. We believe this is an important proof of concept showing that it is possible to overcome the problem of high trap densities in quantum dot superlattices enabling their application in optoelectronic devices.

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.

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.

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.

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.

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.

Direct measurement of the triplet exciton diffusion length in organic semiconductors.

We present a new method to measure the triplet exciton diffusion length in organic semiconductors. N,N'-di-[(1-naphthyl)-N,N'-diphenyl]-1,1'-biphenyl)-4,4'-diamine (NPD) has been used as a model system. Triplet excitons are injected into a thin film of NPD by a phosphorescent thin film, which is optically excited and forms a sharp interface with the NPD layer. The penetration profile of the triplet excitons density is recorded by measuring the emission intensity of another phosphorescent material (detector), which is doped into the NPD film at variable distances from the injecting interface. From the obtained triplet penetration profile we extracted a triplet exciton diffusion length of 87±2.7 nm. For excitation power densities >1 mW/mm(2) triplet-triplet annihilation processes can significantly limit the triplet penetration depth into organic semiconductor. The proposed sample structure can be further used to study excitonic spin degree of freedom.