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Two-dimensional (2D) perovskites are well-known for the broad tunability of their optoelectronic properties. One of the prime methods is templating the inorganic sublattice via a selection of organic spacers. Here, with the use of magneto-optical spectroscopy, we demonstrate the remarkable potential of distortion engineering to tune the effective mass in 2D perovskites. We show that the 2D perovskites containing benzotriazole-based organic cations are characterized by the lowest reduced effective mass that has been measured for a lead iodide 2D perovskite. This stems directly from the very low degree of octahedral distortion in this material system. The practically flat structure of inorganic sublattice with no measurable out-of-plane corrugation results in the reduction of reduced effective mass by 12% with respect to the reference structure of (PEA)2PbI4. The reduction in the mass is naturally accompanied by a lower 1s exciton binding energy of ∼200 meV.

Two-dimensional (2D) hybrid organic–inorganic perovskites constitute a versatile class of materials applied to a variety of optoelectronic devices. These materials are composed of alternating layers of inorganic lead halide octahedra and organic ammonium cations. Most perovskite research studies so far have focused on organic sublattices based on phenethylammonium and alkylammonium cations, which are packed by van der Waals cohesive forces. Here, we report a more complex organic sublattice containing benzotriazole-based ammonium cations packed through interdigitated π–π stacking and hydrogen bonding. Single crystals and thin films of four perovskite derivatives are studied in depth with optical spectroscopy and X-ray diffraction, supported by density-functional theory calculations. We quantify the lattice stabilization of interdigitation, dipole–dipole interactions, and inter- as well as intramolecular hydrogen bonding. Furthermore, we investigate the driving force behind interdigitation by defining a steric occupancy factor σ and tuning the composition of the organic and inorganic sublattice. We relate the phenomenon of interdigitation to the available lattice space and to weakened hydrogen bonding to the inorganic octahedra. Finally, we find that the stabilizing interactions in the organic sublattice slightly improve the thermal stability of the perovskite. This work sheds light on the design rules and structure–property relationships of 2D layered hybrid perovskites.

The metal halide perovskite absorbers are prone to surface defects, which severely limit the power conversion efficiencies (PCEs) and the operational stability of the perovskite solar cells (PSCs). Herein, trace amounts of bithiophene propylammonium iodide (bi-TPAI) are applied to modulate the surface properties of the gas-quenched perovskite. It is found that the bi-TPAI surface treatment has negligible impact on the perovskite morphology, but it can induce a defect passivation effect and facilitate the charge carrier extraction, contributing to the gain in the open-circuit voltage (Voc) and fill factor. As a result, the PCE of the gas-quenched sputtered NiOx-based inverted PSCs is enhanced from the initial 20.0% to 22.0%. Most importantly, the bi-TPAI treatment can largely alleviate or even eliminate the burn-in process during the maximum power point tracking measurement, improving the operational stability of the devices.

The family of hybrid organic–inorganic lead-halide perovskites are the subject of intense interest for optoelectronic applications, from light-emitting diodes to photovoltaics to X-ray detectors. Due to the inert nature of most organic molecules, the inorganic sublattice generally dominates the electronic structure and therefore the optoelectronic properties of perovskites. Here, we use optically and electronically active carbazole-based Cz-Cimolecules, where Ciindicates an alkylammonium chain and iindicates the number of CH2units in the chain, varying from 3 to 5, as cations in the two-dimensional (2D) perovskite structure. By investigating the photophysics and charge transport characteristics of (Cz-Ci)2PbI4, we demonstrate a tunable electronic coupling between the inorganic lead-halide and organic layers. The strongest interlayer electronic coupling was found for (Cz-C3)2PbI4, where photothermal deflection spectroscopy results remarkably reveal an organic–inorganic charge transfer state. Ultrafast transient absorption spectroscopy measurements demonstrate ultrafast hole transfer from the photoexcited lead-halide layer to the Cz-Cimolecules, the efficiency of which increases by varying the chain length from i= 5 to i= 3. The charge transfer results in long-lived carriers (10–100 ns) and quenched emission, in stark contrast to the fast (sub-ns) and efficient radiative decay of bound excitons in the more conventional 2D perovskite (PEA)2PbI4, in which phenylethylammonium (PEA) acts as an inert spacer. Electrical charge transport measurements further support enhanced interlayer coupling, showing increased out-of-plane carrier mobility from i= 5 to i= 3. This study paves the way for the rational design of 2D perovskites with combined inorganic–organic electronic properties through the wide range of functionalities available in the world of organics.

Organic semiconductors can afford detection at wavelengths beyond commercial silicon photodetectors. However, for each targeted near-infrared wavelength range, this requires individually optimized materials, which adds to the complexity and costs. Moreover, finding molecules with strong absorption beyond 1 μm that perform well in organic photodetectors remains a challenge. In microcavity devices, the detection window can be extended to wavelengths inaccessible for silicon without the need for new materials by adopting an intelligent design. Previous work has demonstrated the applicability of a dithienopyrrole-based donor polymer (PDTPQx) in such a cavity photodetector device, with a photoresponse up to 1200 nm. In this work, the π-conjugated backbone of the polymer is extended, affording higher hole mobility and better donor:acceptor intermixing. This leads to enhanced peak external quantum efficiencies up to 1450 nm. The (thermal noise limited) detectivities achieved with the PTTPQxpolymer (1.07 × 1012to 1.82 × 1010Jones) are among the very best in the 900–1400 nm wavelength regime.

At present, two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs) are drawing significant interest because of their potential use in different optoelectronic applications, that is, photovoltaics and photodetectors. Here, we report on a series of 2D layered HOIPs (Bit-C3)2PbX4(with X = Cl, Br, and I) containing a 2,2′-bithiophene chromophore functionalized with a propylammonium tethering chain as a model molecule. The optical properties, crystal structure, and phase behavior of the 2D layered HOIPs are studied in depth. The crystal structures with the chemical formula (Bit-C3)2PbX4(with X = Cl, and Br) are successfully obtained. Contrastingly, different crystal structures with an inorganic framework containing face- and corner-sharing octahedra were identified for the iodide-based HOIP. The phase diversity and thermal stability of the (Bit-C3)2PbX4(with X = Cl, Br, and I) thin films were investigated via in situmeasurements. Here, the presence of lower-dimensional hybrids with reduced electronic dimensionality within the iodide-based thin film is demonstrated. Additionally, we show that the 2D hybrid thermal stability is dependent on the type of lead(II)halide framework employed. We suggest that, via halide substitution from iodide to bromide and chloride, the molecular degrees of freedom of the Bit-C3 ammonium cations are reduced by spatial confinement of a smaller inorganic framework, therefore, limiting the formation of lower-dimensional hybrids besides the targeted 2D layered HOIP. This study illustrates the importance of efficiently utilizing the space supplied by the inorganic framework in which the organic ammonium cations can reside within a 2D layered HOIP. This, in turn, dictates how the organic ammonium cations arrange themselves within the organic layer and influences the adopted crystal structure of the hybrid.

Low-dimensional lead halide hybrid perovskites are nowadays in the spotlight because of their improved stability and extensive chemical flexibility compared to their 3D perovskite counterparts, the current challenge being to design functionalized organic cations. Here, we report on the synthesis and full characterization of a perovskite-like hybrid (a perovskitoid) where the 1D lead iodide layout is patterned with a donor–acceptor charge transfer complex (CTC) between pyrene and tetracyanoquinodimethane, with a chemical formula of (C20H17NH3)PbI3·(C12H4N4). By combining multiple structural analysis and spectroscopic techniques with ab initio modeling, we show that the electronic, optical, and charge-transport properties of the hybrid materials are dominated by the organic CTC, with the inorganic backbone primarily acting as a template for the organization of the donor and acceptor molecules. Interestingly, time-resolved microwave conductivity (TRMC) measurements show an enhanced photocurrent generation in the 1D hybrid compared to the pure organic charge-transfer salt, likely associated with transient localization of the holes on the lead-iodide octahedra. This observation is in line with the close energy resonance between the valence crystal orbitals of the lead-iodide lattice and the frontier occupied molecular orbitals of pyrene predicted by the DFT calculations. Therefore, it paves the way toward the design of new hybrid low-dimensionality perovskites offering a synergic combination of organic and inorganic functionalities.

Fluorescent conjugated polymers formulated in nanoparticles show attractive properties to be used as bioimaging probes. However, their fluorescence brightness is generally limited by quenching phenomena due to interchain aggregation in the confined nanoparticle space. In this work, branched conjugated polymer networks are investigated as a way to enhance the photoluminescence quantum yield of the resulting conjugated polymer nanoparticles (CPNs). 1,3,5-Tribromobenzene and 2,2′,7,7′-tetrabromo-9,9′-spirobifluorene are chosen as branching moieties and are added in 3 or 5 mol % to the poly(p-phenylene ethynylene) (PPE) conjugated polymer synthesis. Nanoparticles of all samples are prepared via the combined miniemulsion/solvent evaporation technique. The optical properties of the branched polymers in solution and in nanoparticle form are then compared to those of the linear PPE counterpart. The fluorescence quantum yield of the CPNs increases from 5 to 11% for the samples containing 1,3,5-tribromobenzene. Furthermore, when 5 mol % of either branching molecule is used, the one-photon fluorescence brightness doubles. The nanoparticles show low cytotoxicity in A549 human lung carcinoma cells up to a concentration of 100 μg/mL for 24 h. They also exhibit good particle uptake into cells and compatibility with two-photon imaging.

The highest efficiency in perovskite solar cells is currently achieved with mixed-cation hybrid perovskites. The ratio in which the cations are present in the perovskite structure has an important effect on the optical properties and the stability of these materials. At present, the formamidinium cation is an integral part of many of the highest efficiency perovskite systems. In this work, we introduce a nuclear magnetic resonance (NMR) spectroscopy protocol for the identification and differentiation of mixed perovskite phases and of a secondary phase due to formamidinium degradation. The influence of the cooling rate used in a precipitation method on the FA/MA ratio in formamidinium–methylammonium lead iodide perovskites (FAxMA1–xPbI3) was investigated and compared to the FA/MA ratio in thin films. In order to obtain the FA/MA ratio from fast and accessible liquid-state 1H NMR spectra, the influence of the acidity of the solution on the line width of the resonances was elucidated. The ratio of the organic cations incorporated into the perovskite structure could be reliably quantified in the presence of the secondary phase through a combination of liquid-state 1H NMR and solid-state 13C NMR spectroscopic analysis.

The commercial uptake of (polymer-based) organic solar cells is among others hindered by poor reproducibility of the device performance, arising from the variability in molar mass distribution and the presence of structural defects in push–pull conjugated polymers. Traditional “in-flask” synthesis methods and commonly used catalysts contribute to these issues. Flow chemistry has been proposed to provide consistent molar masses, while a recently applied Buchwald catalyst shows promise for reduced structural defect formation. However, this catalyst has not been used for donor polymers affording state-of-the-art efficiencies in organic solar cells, such as PM6 and D18. In this work, we utilize these two polymers as model systems to probe the effect of different synthetic conditions and examine the precise chemical structures, including any homocoupled defects present, by matrix-assisted laser desorption/ionization time-of-flight (MALDI–ToF) mass spectrometry. Additionally, we analyze how these structural factors impact the material and device properties. By combining droplet-flow chemistry and defect-free synthesis, we demonstrate a reproducible and scalable protocol for the synthesis of donor polymers with a tailorable molar mass for high-efficiency organic photovoltaics.

Conjugated polyelectrolyte (CPE) interfacial layers present a powerful way to boost the I–Vcharacteristics of organic photovoltaics. Nevertheless, clear guidelines with respect to the structure of high-performance interlayers are still lacking. In this work, impedance spectroscopy is applied to probe the dielectric permittivity of a series of polythiophene-based CPEs. The presence of ionic pendant groups grants the formation of a capacitive double layer, boosting the charge extraction and device efficiency. A counteracting effect is the diminishing affinity with the underlying photoactive layer. To balance these two effects, we found copolymer structures containing nonionic side chains to be beneficial.

In this work, the synthesis of N,N′-dialkyl-6,6′-dibromoisoindigo derivatives by continuous-flow chemistry is explored as a means to enhance material availability and structural diversity, in particular toward the application of isoindigo-based semiconductors in high-performance organic photovoltaic devices. The individual steps in the conventional batch synthesis protocol are evaluated and, when needed, adapted to flow reactors. To overcome the low solubility of nonalkylated 6,6′-dibromoisoindigo in common organic solvents, the flow condensation reaction between the 6-bromo-isatin and 6-bromo-oxindole precursors is evaluated in polar aprotic solvents. Dialkylation of 6,6′-dibromoisoindigo is readily performed in flow using a solid-phase reactor packed with potassium carbonate. In an alternative strategy, solubility is ensured by first introducing the N-alkyl side chains on 6-bromo-isatin and 6-bromo-oxindole (accessible via a highyielding flow reduction of alkylated 6-bromo-isatin), followed by condensation using the conventional method in acetic-hydrochloric acid medium. The N,N′-dialkylated 6,6′-dibromoisoindigo derivatives indeed show enhanced solubility in the hot reaction mixture compared to the non-alkylated material but eventually precipitate when the reaction mixture is cooled down. Nevertheless, the condensation between both alkylated starting materials is achieved in flow without any blockages by keeping the outlet from the reactor heated and as short as possible. The latter strategy allows the preparation of both symmetrically and asymmetrically N-substituted isoindigo compounds.

Long alkyl chain ligands such as oleic acid (OLA) which cover the as-prepared PbS nanodots act as an insulating layer that impedes efficient charge transfer in PbS nanodots:polymer hybrid solar cells. The replacement of OLA with tailored ligands of an appropriate chain length is needed to achieve a noticeable enhancement of photovoltaic performance. Several studies have centered on the ligand exchange prior to casting the PbS film1,2,3. However, this post synthesis approach requires careful consideration for the choice of a ligand as clustering of the nanodots has to be avoided. Recently, a new approach that allows direct chemical ligand replacement in a blended mixture of PbS:P3HT has been demonstrated 4,5,6. In this contribution, the latter approach (post-fabrication) was compared with the post-synthesis ligand exchange. We investigated the effect of the ligand exchange processes to the charge separation dynamics in the P3HT:PbS blends by steady-state and time-resolved photoluminescence (PL). Hexanoic acid and acetic acid were used as a short-length ligand for the post fabrication approach while decylamine, octylamine and butylamine were used for the post-synthesis approach. As expected, decreasing the chain length of the ligand led to an increase of the P3HT fluorescence quenching. The absence of enhancement of PbS luminescence due to energy transfer from P3HT and the dependence of the quenching efficiency on the bulkiness of the ligands coating the QDs suggest that the quenching of the P3HT fluorescence is dominated by electron transfer to PbS quantum dots (QDs). In addition, the fluorescence quenching is also less prominent in the P3HT with higher regioregularity (RR) suggesting an enhanced phase separation in the blend due to more densely packed nature of conjugated polymer with higher RR.

The anionic polymerization of PPV via the sulfinyl precursor route is further investigated. When LHMDS is employed as the base to form the actively propagating quinodimethane system and THF as the solvent, anionic polymerizations can be observed. With the use of tert‐ butyl‐substituted anionic initiators, specific functional groups can be built in the polymer chain and the chain length can be efficiently controlled, which is demonstrated here for the first time. With introduction of branched side chains on the aromatic core, soluble conjugated PPV material can be obtained with molecular weights in the range of 5000–16 000 g mol−1.

The use of nanostructured non-conventional semiconductors such as conjugated polymers and metal oxides (e.g. TiO2), opens promising perspectives towards a new generation of solar cells based on the concept of donor:acceptor bulk heterojunctions. In this concept donor material and acceptor material form interpenetrating networks allowing light absorption, charge transfer and charge transport throughout the entire bulk of the thin film. Since nanomorphology is of crucial importance for this type of solar cells, in this contribution the use of nanofibers in bulk heterojunction solar cells is explored in order to obtain highways for charge transport. We investigate in particular the use of P3AT (poly(3-alkylthiophene)) nanofibers and show that the polymer fraction aggregated into fibers can be easily controlled by temperature. We find an optimal efficiency at intermediate fiber fraction and show that it can be linked to the morphology of the active layer.

The influence of fullerene side chain functionalization on both the morphology and electro-optical properties of bulk-heterojunction polymer:fullerene solar cells is discussed through a systematic investigation of material blends consisting of the conjugated polymer poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) as donor and fullerene molecules with different side chains as the acceptor. The varying side chain of the fullerenes was found to induce morphological changes as confirmed by different analytical techniques such as Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), and Nuclear Magnetic Resonance (NMR). The fullerene with the shorter side chain, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), forms crystalline nanophases in the blend, while this is not the case for the alternative diphenylmethanofullerene acceptor, [6,6]-1,1-bis(4,4′-dodecyloxyphenyl)methanofullerene (DPM-12). The introduction of NMR allows us to estimate the fraction of crystalline fullerene. The morphological changes have a profound effect on the characteristics of charge transfer states (CT) formed at the polymer:fullerene interfaces. Crystallization of fullerene molecules shifts the energy of the CT state. This shift in energy is directly manifested in the open-circuit voltage of solar cells based on the fullerene acceptors under investigation.

The field‐effect transistor (FET) and diode characteristics of poly(3‐alkylthiophene) (P3AT) nanofiber layers deposited from nanofiber dispersions are presented and compared with those of layers deposited from molecularly dissolved polymer solutions in chlorobenzene. The P3AT n‐alkyl‐side‐chain length was varied from 4 to 9 carbon atoms. The hole mobilities are correlated with the interface and bulk morphology of the layers as determined by UV–vis spectroscopy, transmission electron microscopy (TEM) with selected area electron diffraction (SAED), atomic force microscopy (AFM), and polarized carbon K‐edge near edge X‐ray absorption fine structure (NEXAFS) spectroscopy. The latter technique reveals the average polymer orientation in the accumulation region of the FET at the interface with the SiO2gate dielectric. The previously observed alkyl‐chain‐length‐dependence of the FET mobility in P3AT films results from differences in molecular ordering and orientation at the dielectric/semiconductor interface, and it is concluded that side‐chain length does not determine the intrinsic mobility of P3ATs, but rather the alkyl chain length of P3ATs influences FET diode mobility only through changes in interfacial bulk ordering in solution processed films.

The mass production technique of gravure contact printing is used to fabricate state‐of‐the art polymer field‐effect transistors (FETs). Using plastic substrates with prepatterned indium tin oxide source and drain contacts as required for display applications, four different layers are sequentially gravure‐printed: the semiconductor poly(3‐hexylthiophene‐2,5‐diyl) (P3HT), two insulator layers, and an Ag gate. A crosslinkable insulator and an Ag ink are developed which are both printable and highly robust. Printing in ambient and using this bottom‐contact/top‐gate geometry, an on/off ratio of >104and a mobility of 0.04 cm2V−1s−1are achieved. This rivals the best top‐gate polymer FETs fabricated with these materials. Printing using low concentration, low viscosity ink formulations, and different P3HT molecular weights is demonstrated. The printing speed of 40 m min−1on a flexible polymer substrate demonstrates that very high‐volume, reel‐to‐reel production of organic electronic devices is possible.

The morphological, bipolar charge‐carrier transport, and photovoltaic characteristics of poly(3‐alkylthiophene) (P3AT):[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) blends are studied as a function of alkyl side‐chain length m, where mequals the number of alkyl carbon atoms. The P3ATs studied are poly(3‐butylthiophene) (P3BT, m= 4), poly(3‐pentylthiophene) (P3PT, m= 5), and poly(3‐hexylthiophene) (P3HT, m= 6). Solar cells with these blends deliver similar order of photo‐current yield (exceeding 10 mA cm−2) irrespective of side‐chain length. Power conversion efficiencies of 3.2, 4.3, and 4.6% are within reach using solar cells with active layers of P3BT:PCBM (1:0.8), P3PT:PCBM (1:1), and P3HT:PCBM (1:1), respectively. A difference in fill factor values is found to be the main source of efficiency difference. Morphological studies reveal an increase in the degree of phase separation with increasing alkyl chain length. Moreover, while P3PT:PCBM and P3HT:PCBM films have similar hole mobility, measured by hole‐only diodes, the hole mobility in P3BT:PCBM lowers by nearly a factor of four. Bipolar measurements made by field‐effect transistor showed a decrease in the hole mobility and an increase in the electron mobility with increasing alkyl chain length. Balanced charge transport is only achieved in the P3HT:PCBM blend. This, together with better processing properties, explains the superior properties of P3HT as a solar cell material. P3PT is proved to be a potentially competitive material. The optoelectronic and charge transport properties observed in the different P3AT:PCBM bulk heterojunction (BHJ) blends provide useful information for understanding the physics of BHJ films and the working principles of the corresponding solar cells.

Photocurrent generation by charge‐transfer (CT) absorption is detected in a range of conjugated polymer–[6,6]‐phenyl C61butyric acid methyl ester (PCBM) based solar cells. The low intensity CT absorption bands are observed using a highly sensitive measurement of the external quantum efficiency (EQE) spectrum by means of Fourier‐transform photocurrent spectroscopy (FTPS). The presence of these CT bands implies the formation of weak ground‐state charge‐transfer complexes in the studied polymer–fullerene blends. The effective band gap (Eg) of the material blends used in these photovoltaic devices is determined from the energetic onset of the photocurrent generated by CT absorption. It is shown that for all devices, under various preparation conditions, the open‐circuit voltage (Voc) scales linearly with Eg. The redshift of the CT band upon thermal annealing of regioregular poly(3‐hexylthiophene):PCBM and thermal aging of poly(phenylenevinylene)(PPV):PCBM photovoltaic devices correlates with the observed drop in open‐circuit voltage of high‐temperature treated versus untreated devices. Increasing the weight fraction of PCBM also results in a redshift of Eg, proportional with the observed changes in Vocfor different PPV:PCBM ratios. As Egcorresponds with the effective bandgap of the material blends, a measurement of the EQEspectrum by FTPS allows us to measure this energy directly on photovoltaic devices, and makes it a valuable technique in the study of organic bulk heterojunction solar cells.

Three 2,5-substituted polar PPV derivatives have been prepared using the sulfinyl precursor route and compared to the apolar MDMO‐PPV. All polymers were obtained in excellent yield and with improved purity as compared to other methods. The influence of the polarity of the side chains, i.e. oligo(oxyethylene) and alkyl substituents, on the optical and electronic properties were investigated. In thin films, the oligo(oxyethylene) substituents do not significantly alter the optical properties of the conjugated backbone and the field effect mobility. In contrast, other thin film electrical properties, such as relative permittivity and conductivity, are markedly affected by the polar substituents. This is also the case for their solubility and solution properties. The polar PPV‐derivatives are not only soluble in a wide range of solvents, but also exhibit aggregation phenomena.

The reduction of phthalic thioanhydrides with NaBH4 at between 0 and −20 °C leads to the selective formation of 3-hydroxy-2-thiophthalides, whereas higher temperatures favour the formation of the corresponding phthalide derivatives. A mechanism is proposed that can explain these observations. Kinetic control at low temperatures leads to an improved stability of the intermediate alkoxide, thus allowing isolation of the γ-hydroxythiolactone after subsequent acidification of the reaction mixture. In this way the formation of the thermodynamically favoured phthalide derivative is avoided. Further reduction of the γ-hydroxythiolactone with AcOH/57% aqueous HI yields 2-thiophthalides, useful precursors for conducting polymers. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

A new and convenient route to an unsymmetrically substituted sulfinyl monomer of precursor polymer toward poly[2-methyl-5-(3,7-dimethyloctyloxy)-p-phenylenevinylene] (OC1C10) is described. OC1C10 is a commercial polymer used as the active layer in LEDs. Therefore, the optimization of the reaction conditions of the monomer synthesis was of some importance for a possible commercialization of this new process. It was possible to increase the overall yield by a factor of 1.5, as compared to the route previously used to obtain these compounds.

Block copolymers of poly(methylphenylsilylene) and poly(methyl methacrylate) have been synthesized by condensation of α,ω-dichloropoly(methylphenylsilylene) with poly(methyl methacrylate)-lithium. The α,ω-dichloropoly(methylphenylsilylene) was synthesized by the Wurtz‐type reductive coupling of dichloromethylphenylsilane using sodium in boiling toluene and poly(methyl methacrylate)-lithium was prepared by anionic polymerization of methyl methacrylate in tetrahydrofuran initiated by α-methylstyrene‐lithium/LiCl. The structures of the block copolymers have been confirmed using size exclusion chromatography and NMR spectroscopy. © 1998 SCI.

2D hybrid perovskites consisting of layers of lead halide octahedra separated by long organic linker cations have great potential for functional material design toward tailored optical and electronic properties. Here, we report the first direct observation of light-induced charge transfer (CT) in a series of novel 2D perovskites incorporating conjugated linkers based on the carbazole molecule. Dedicated electron paramagnetic resonance experiments and supporting quantum-chemical calculations reveal that excitons generated in the lead halide layer undergo CT at the organic–inorganic interface, resulting in a positive polaron delocalized over several carbazole moieties and a partner electron residing in the inorganic layer. The occurrence of such CT processes in these materials not only offers interesting new perspectives for the functionalization of future 2D perovskites but could also lead to a better understanding of the unusual broadband emission reported for this material class, which has been directly related to polaronic effects.