Elucidating the Non-Covalent Interactions that Trigger Interdigitation in Lead-Halide Layered Hybrid Perovskites.

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.

Tailoring Interlayer Charge Transfer Dynamics in 2D Perovskites with Electroactive Spacer Molecules.

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-Ci molecules, where Ci indicates an alkylammonium chain and i indicates the number of CH2 units 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-Ci molecules, 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.

Finding the optimal exchange-correlation functional to describe the excited state properties of push-pull organic dyes designed for thermally activated delayed fluorescence.

To gauge the suitability of an organic dye for thermally activated delayed fluorescence (TADF), its excited state properties are often calculated using density functional theory. For this purpose, the choice of the exchange-correlation (XC) functional is crucial as it heavily influences the quality of the obtained results. In this work, 19 different XC functionals with various amounts of Hartree-Fock (HF) exchange and/or long-range correction parameters are benchmarked versus resolution-of-the-identity second-order coupled cluster (riCC2) calculations for a set of 10 prototype intramolecular donor-acceptor compounds. For the time-dependent density functional theory (TD-DFT) calculations, LC-BLYP(ω = 0.20) and M06-2X are the better performing XC functionals when looking at singlet and triplet excitation energies, respectively. For the singlet-triplet energy gap, LC-BLYP(ω = 0.17), LC-ωPBE(ω = 0.17) and a hybrid LC-BLYP(ω = 0.20)/M06-2X method give the smallest mean average errors (MAEs). Using the Tamm-Dancoff approximation (TD-DFT/TDA), the MAEs are further reduced for the triplet vertical excitation energies and the singlet-triplet energy gaps.

The Impact of Acceptor-Acceptor Homocoupling on the Optoelectronic Properties and Photovoltaic Performance of PDTSQxff Low Bandgap Polymers.

Push-pull-type conjugated polymers applied in organic electronics do not always contain a perfect alternation of donor and acceptor building blocks. Misscouplings can occur, which have a noticeable effect on the device performance. In this work, the influence of homocoupling on the optoelectronic properties and photovoltaic performance of PDTSQxff polymers is investigated, with a specific focus on the quinoxaline acceptor moieties. A homocoupled biquinoxaline segment is intentionally inserted in specific ratios during the polymerization. These homocoupled units cause a gradually blue-shifted absorption, while the highest occupied molecular orbital energy levels decrease only significantly upon the presence of 75-100% of homocouplings. Density functional theory calculations show that the homocoupled acceptor unit generates a twist in the polymer backbone, which leads to a decreased conjugation length and a reduced aggregation tendency. The virtually defect-free PDTSQxff affords a solar cell efficiency of 5.4%, which only decreases substantially upon incorporating a homocoupling degree over 50%.

PPV-Based Conjugated Polymer Nanoparticles as a Versatile Bioimaging Probe: A Closer Look at the Inherent Optical Properties and Nanoparticle-Cell Interactions.

Conjugated polymers have attracted significant interest in the bioimaging field due to their excellent optical properties and biocompatibility. Tailor-made poly(p-phenylenevinylene) (PPV) conjugated polymer nanoparticles (NPs) are in here described. Two different nanoparticle systems using poly[2-methoxy-5-(3',7'-dimethoxyoctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and a functional statistical copolymer 2-(5'-methoxycarbonylpentyloxy)-5-methoxy-1,4-phenylenevinylene (CPM-MDMO-PPV), containing ester groups on the alkoxy side chains, were synthesized by combining miniemulsion and solvent evaporation processes. The hydrolysis of ester groups into carboxylic acid groups on the CPM-MDMO-PPV NPs surface allows for biomolecule conjugation. The NPs exhibited excellent optical properties with a high fluorescent brightness and photostability. The NPs were in vitro tested as potential fluorescent nanoprobes for studying cell populations within the central nervous system. The cell studies demonstrated biocompatibility and surface charge dependent cellular uptake of the NPs. This study highlights that PPV-derivative based particles are a promising bioimaging probe and can cater potential applications in the field of nanomedicine.

Profluorescent PPV-Based Micellar System as a Versatile Probe for Bioimaging and Drug Delivery.

Although micelles are commonly used for drug delivery purposes, their long-term fate is often unknown due to photobleaching of the fluorescent labels or the use of toxic materials. Here, we present a metal-free, nontoxic, nonbleaching, fluorescent micelle that can address these shortcomings. A simple, yet versatile, profluorescent micellar system, built from amphiphilic poly(p-phenylenevinylene) (PPV) block copolymers, for use in drug delivery applications is introduced. Polymer micelles made from PPV show excellent stability for up to 1 year and are successfully loaded with anticancer drugs (curcumin or doxorubicin) without requiring introduction of physical or chemical cross-links. The micelles are taken up efficiently by the cells, which triggers disassembly, releasing the encapsulated material. Disassembly of the micelles and drug release is conveniently monitored as fluorescence of the single polymer chains appear, which enables not only to monitor the release of the payload, but in principle also the fate of the polymer over longer periods of time.

PPV Polymerization through the Gilch Route: Diradical Character of Monomers.

Despite various studies on the polymerization of poly(p-phenylene vinylene) (PPV) through different precursor routes, detailed mechanistic knowledge on the individual reaction steps and intermediates is still incomplete. The present study aims to gain more insight into the radical polymerization of PPV through the Gilch route. The initial steps of the polymerization involve the formation of a p-quinodimethane intermediate, which spontaneously self-initiates through a dimerization process leading to the formation of diradical species; chain propagation ensues on both sides of the diradical or chain termination occurs by the formation of side products, such as [2.2]paracyclophanes. Furthermore, different p-quinodimethane systems were assessed with respect to the size of their aromatic core as well as the presence of heteroatoms in/on the conjugated system. The nature of the aromatic core and the specific substituents alter the electronic structure of the p-quinodimethane monomers, affecting the mechanism of polymerization. The diradical character of the monomers has been investigated with several advanced methodologies, such as spin-projected UHF, CASSCF, CASPT2, and DMRG calculations. It was shown that larger aromatic cores led to a higher diradical character in the monomers, which in turn is proposed to cause rapid initiation.

Quinoxaline-Based Cyclo(oligophenylenes).

A series of fully conjugated quinoxaline-based oligophenylene macrocycles is synthesized by Ni(0)-mediated Yamamoto-type diaryl homocoupling of (fluorinated) 2,3-bis(4'-bromophenyl)quinoxaline precursors. Cyclotrimers and cyclotetramers are obtained as the dominant reaction products. The cyclooligomers are fully characterized, including single-crystal X-ray structures, and their optoelectronic properties are analyzed with respect to possible applications in host-guest chemistry and organic electronics.

Direct arylation as a versatile tool towards thiazolo[5,4-d]thiazole-based semiconducting materials.

A series of thiazolo[5,4-d]thiazole-based small molecule organic optoelectronic materials is synthesized via a straightforward microwave-activated Pd-catalyzed C-H arylation protocol. The procedure allows us to obtain extended 2,5-dithienylthiazolo[5,4-d]thiazole chromophores with tailor-made energy levels and absorption patterns, depending on the introduced (het)aryl moieties and the molecular (a)symmetry, by shortened sequences without organometallic intermediates. The synthesized materials can be applied as either electron donor or electron acceptor light-harvesting materials in molecular bulk heterojunction organic solar cells.

Electronic structure of positive and negative polarons in functionalized dithienylthiazolo[5,4-d]thiazoles: a combined EPR and DFT study.

2,5-Dithienylthiazolo[5,4-d]thiazole (DTTzTz) derivatives have high potential for solution-processed organic field-effect transistors and solar cells, both as electron acceptors and donors. Here, the electronic structure of positive and negative radicals (polarons) of two functionalized DTTzTz materials is studied using multi-frequency and multi-resonance electron paramagnetic resonance (EPR) in combination with density functional theory (DFT). It is shown that the negative and positive DTTzTz polarons can be distinguished on the basis of their characteristic EPR parameters. The chemically induced polarons are compared to light-generated states observed in a blend of one of the DTTzTz derivatives with a donor polymer. The study gives in-depth information about the spread of the electron or hole in the DTTzTz molecules.

Quinoxaline derivatives with broadened absorption patterns.

Quinoxaline-based semiconducting materials are currently of high interest in the field of organic photovoltaics. The number of structural variations employed has been, however, quite limited to date. In this paper we report on the synthesis of a series of quinoxaline monomers and triads with improved optical features. This was achieved by using conjugated linkers, i.e. ethenyl, butadienyl and/or aryl groups, to graft the solubilizing alkyl side chains onto the central quinoxaline core. The influence of the appended groups on the light-harvesting properties of the materials is briefly discussed.

Surface Modulation via Conjugated Bithiophene Ammonium Salt for Efficient Inverted Perovskite Solar Cells.

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.

3D Perovskite Passivation with a Benzotriazole-Based 2D Interlayer for High-Efficiency Solar Cells.

2H-Benzotriazol-2-ylethylammonium bromide and iodide and its difluorinated derivatives are synthesized and employed as interlayers for passivation of formamidinium lead triiodide (FAPbI3) solar cells. In combination with PbI2 and PbBr2, these benzotriazole derivatives form two-dimensional (2D) Ruddlesden-Popper perovskites (RPPs) as evidenced by their crystal structures and thin film characteristics. When used to passivate n-i-p FAPbI3 solar cells, the power conversion efficiency improves from 20% to close to 22% by enhancing the open-circuit voltage. Quasi-Fermi level splitting experiments and scanning electron microscopy cathodoluminescence hyperspectral imaging reveal that passivation provides a reduced nonradiative recombination at the interface between the perovskite and hole transport layer. Photoluminescence spectroscopy, angle-resolved grazing-incidence wide-angle X-ray scattering, and depth profiling X-ray photoelectron spectroscopy studies of the 2D/three-dimensional (3D) interface between the benzotriazole RPP and FAPbI3 show that a nonuniform layer of 2D perovskites is enough to passivate defects, enhance charge extraction, and decrease nonradiative recombination.

Living polymerization via anionic initiation for the synthesis of well-defined PPV materials.

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).

Charge transfer in the weak driving force limit in blends of MDMO-PPV and dithienylthiazolo[5,4-d]thiazoles towards organic photovoltaics with high V(OC).

A series of three 5'-aryl-2,5-dithienylthiazolo[5,4-d]thiazole (DTTzTz) semiconducting molecules with different aryl substituents has been investigated as alternative acceptor materials in combination with the donor polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) in order to evaluate the photoinduced charge transfer (CT) efficiency in the resulting blends, designed towards possible application in organic photovoltaics. Photoluminescence quenching together with polaron detection by electron paramagnetic resonance and photoinduced absorption (PIA) demonstrate an increasing charge transfer efficiency when the DTTzTz substituents are varied from thien-2-yl to 4-trifluoromethylphenyl and 4-cyanophenyl groups, correlating well with the increasing acceptor strength in this series of molecules. In line with this observation, there is a decrease in the effective optical bandgap relative to pure MDMO-PPV that becomes more pronounced along this series of acceptor compounds, reaching 0.12 eV in the blend with 4-CN-Ph-DTTzTz. Intermolecular interactions between the blend components lead to lower energy transitions which are found to contribute significantly to the device external quantum efficiency. The high V(OC) reached in devices based on MDMO-PPV:4-CN-Ph-DTTzTz blends meets the expectations for such a donor:acceptor combination. However, thermal activation of charge carrier recombination occurs because of the weak driving force for charge transfer, as shown by time-dependent PIA measurements, and this is suggested as a cause for the observed low photovoltaic performance.

On the stability of a variety of organic photovoltaic devices by IPCE and in situ IPCE analyses--the ISOS-3 inter-laboratory collaboration.

This work is part of the inter-laboratory collaboration to study the stability of seven distinct sets of state-of-the-art organic photovoltaic (OPV) devices prepared by leading research laboratories. All devices have been shipped to and degraded at RISØ-DTU up to 1830 hours in accordance with established ISOS-3 protocols under defined illumination conditions. In this work, we apply the Incident Photon-to-Electron Conversion Efficiency (IPCE) and the in situ IPCE techniques to determine the relation between solar cell performance and solar cell stability. Different ageing conditions were considered: accelerated full sun simulation, low level indoor fluorescent lighting and dark storage. The devices were also monitored under conditions of ambient and inert (N(2)) atmospheres, which allows for the identification of the solar cell materials more susceptible to degradation by ambient air (oxygen and moisture). The different OPVs configurations permitted the study of the intrinsic stability of the devices depending on: two different ITO-replacement alternatives, two different hole extraction layers (PEDOT:PSS and MoO(3)), and two different P3HT-based polymers. The response of un-encapsulated devices to ambient atmosphere offered insight into the importance of moisture in solar cell performance. Our results demonstrate that the IPCE and the in situ IPCE techniques are valuable analytical methods to understand device degradation and solar cell lifetime.

TOF-SIMS investigation of degradation pathways occurring in a variety of organic photovoltaic devices--the ISOS-3 inter-laboratory collaboration.

The present work is the fourth (and final) contribution to an inter-laboratory collaboration that was planned at the 3rd International Summit on Organic Photovoltaic Stability (ISOS-3). The collaboration involved six laboratories capable of producing seven distinct sets of OPV devices that were degraded under well-defined conditions in accordance with the ISOS-3 protocols. The degradation experiments lasted up to 1830 hours and involved more than 300 cells on more than 100 devices. The devices were analyzed and characterized at different points of their lifetimes by a large number of non-destructive and destructive techniques in order to identify specific degradation mechanisms responsible for the deterioration of the photovoltaic response. Work presented herein involves time-of-flight secondary ion mass spectrometry (TOF-SIMS) in order to study chemical degradation in-plane as well as in-depth in the organic solar cells. Various degradation mechanisms were investigated and correlated with cell performance. For example, photo-oxidation of the active material was quantitatively studied as a function of cell performance. The large variety of cell architectures used (some with and some without encapsulation) enabled valuable comparisons and important conclusions to be drawn on degradation behaviour. This comprehensive investigation of OPV stability has significantly advanced the understanding of degradation behaviour in OPV devices, which is an important step towards large scale application of organic solar cells.

Phase behavior of PCBM blends with different conjugated polymers.

In this work the phase behavior of [6,6]-phenyl C(61)-butyric acid methyl ester (PCBM) blends with different poly(phenylene vinylene) (PPV) samples is investigated by means of standard and modulated temperature differential scanning calorimetry (DSC and MTDSC) and rapid heat-cool calorimetry (RHC). The PPV conjugated polymers include poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene) (MDMO-PPV), High T(g)-PPV which is a copolymer, and poly((2-methoxy-5-phenethoxy)-1,4-phenylene vinylene) (MPE-PPV). Comparisons of these PPV:PCBM blends with regioregular poly(3-hexyl thiophene) (P3HT):PCBM blends are made to see the different component miscibilities among different blends. The occurrence of liquid-liquid phase separation in the molten state of MDMO-PPV:PCBM and High T(g)-PPV:PCBM blends is indicated by the coexistence of double glass transitions for blends with a PCBM weight fraction of around 80 wt%. This is in contrast to the P3HT:PCBM blends where no phase separation is observed. Due to its high cooling rate (about 2000 K min(-1)), RHC proves to be a useful tool to investigate the phase separation in PPV:PCBM blends through the glass transition of these crystallizable blends. P3HT is found to have much higher thermal stability than the PPV samples.

Description of the nanostructured morphology of [6,6]-phenyl-C61 -butyric acid methyl ester (PCBM) by XRD, DSC and solid-state NMR.

PCBM or [6,6]-phenyl-C(61)-butyric acid methyl ester is nowadays still one of the most successful electron acceptors for plastic bulk heterojunction (BHJ) photovoltaic devices. In this study, a set of complementary techniques, i.e. solid-state NMR, XRD and DSC, is proposed as a fast and sensitive tool to screen the morphology of PCBM specimens with different preparation histories. Based on proton NMR relaxation decay time values, an interval can be derived that situates the average crystal dimensions and which can further be refined on the basis of XRD patterns and DSC thermograms.

A three-step synthetic approach to asymmetrically functionalized 4H-cyclopenta[2,1-b:3,4-b']dithiophenes.

A convenient and efficient three-step route toward both symmetrically and asymmetrically functionalized 4H-cyclopenta[2,1-b:3,4-b']dithiophenes has been developed. Using this method a broad collection of functionalized bridged bithiophenes can smoothly be accessed. Starting from 3-bromo-2,2'-bithiophene, prepared by Kumada coupling of 2-thienylmagnesium bromide with 2,3-dibromothiophene under Pd(dppf)Cl(2) catalysis, lithiation and subsequent reaction with dialkyl ketones afforded (a)symmetrically dialkylated tertiary alcohol derivatives. By means of final Friedel-Crafts dehydration cyclization in sulfuric acid medium, these derivatives were converted to 4,4-dialkyl-4H-cyclopenta[2,1-b:3,4-b']dithiophenes. Upon replacement of the dialkyl ketone reagent by ethyl levulinate, an ester-functionalized 4H-cyclopenta[2,1-b:3,4-b']dithiophene was prepared, representing an attractive precursor for variously functionalized cyclopentadithiophene compounds.