Direct observation and evolution of electronic coupling between organic semiconductors

The electronic wavefunctions of an atom or molecule are affected by its interactions with its environment. These interactions dictate electronic and optical processes at interfaces, and is especially relevant in the case of thin film optoelectronic devices such as organic solar cells. In these devices, charge transport and interfaces between multiple layers occur along the thickness or vertical direction, and thus such electronic interactions are crucial in determining the device properties. Here, we introduce a new in-situ spectroscopic ellipsometry data analysis method called DART with the ability to directly probe electronic coupling due to intermolecular interactions along the thickness direction using vacuum-deposited organic semiconductor thin films as a model system. The analysis, which does not require any model fitting, reveals direct observations of electronic coupling between frontier orbitals under optical excitations leading to delocalization of the corresponding electronic wavefunctions with thickness or, equivalently, number of molecules away from the interface in C60 and MeO-TPD deposited on an insulating substrate (SiO2). Applying the same methodology for C60 deposited on phthalocyanine thin films, the analyses shows strong, anomalous features - in comparison to C60 deposited on SiO2 - of the electronic wavefunctions corresponding to specific excitation energies in C60 and phthalocyanines. Translation of such interactions in terms of dielectric constants reveals plasmonic type resonance absorptions resulting from oscillations of the excited state wavefunctions between the two materials across the interface. Finally, reproducibility, angstrom-level sensitivity and simplicity of the method are highlighted showcasing its applicability for studying electronic coupling between any vapor-deposited material systems where real-time measurements during deposition are possible.Comment: 12 pages, 6 figures, Supplementary informatio

Studying the effect of high substrate temperature on the microstructure of vacuum evaporated TAPC: C60 organic solar thin films

Organic solar cells (OSCs), also known as organic photovoltaics (OPVs), are an emerging solar cell technology composed of carbon-based, organic molecules, which convert energy from the sun into electricity. Key for their performance is the microstructure of the light-absorbing organic bulk heterojunction. To study this, organic solar films composed of both fullerene C60 as electron acceptor and different mole percentages of di-[4-(N,N-di-p-tolyl-amino)-phenyl]-cyclohexane (TAPC) as electron donor were evaporated in vacuum in different mixing ratios (5, 50 and 95 mol%) on an ITO-coated glass substrate held at room temperature and at 110 °C. The microstructure of the C60: TAPC heterojunction was studied by grazing incidence wide angle X-ray scattering to understand the effect of substrate heating. By increasing the substrate temperature from ambient to 110 °C, it was found that no significant change was observed in the crystal size for the C60: TAPC concentrations investigated in this study. In addition to the variation done in the substrate temperature, the variation of the mole percent of the donor (TAPC) was studied to conclude the effect of both the substrate temperature and the donor concentration on the microstructure of the OSC films. Bragg peaks were attributed to C60 in the pure C60 sample and in the blend with low donor mole percentage (5%), but the C60 peaks became nondiscernible when the donor mole percentage was increased to 50% and above, showing that TAPC interrupted the formation of C60 crystals

Probing the energy levels of organic bulk heterojunctions by varying the donor content

The performance of organic solar cells is strongly governed by the properties of the photovoltaic active layer. In particular, the energetics at the donor (D)–acceptor (A) interface dictate the properties of charge transfer (CT) states and limit the open-circuit voltage. More generally, energetic landscapes in thin films are affected by intermolecular, e.g., van der Waals, dipole, and quadrupole, interactions that vary with D:A mixing ratio and impact energy levels of free charges (ionization energy, electron affinity) and excitons (singlet, CT states). Disentangling how different intermolecular interactions impact energy levels and support or hinder free charge generation is still a major challenge. In this work, we investigate interface energetics of bulk heterojunctions via sensitive external quantum efficiency measurements and by varying the D:A mixing ratios of ZnPc or its fluorinated derivatives and C60. With increasing donor fluorination, the energetic offset between FxZnPc and C60 reduces. Moving from large to low offset systems, we find qualitatively different trends in device performances with D:C60 mixing ratios. We rationalize the performance trends via changes in the energy levels that govern exciton separation and voltage losses. We do so by carefully analyzing shifts and broadening sEQE spectra on a linear and logarithmic scale. Linking this analysis with molecular properties and device performance, we comment on the impact of charge–quadrupole interactions for CT dissociation and free charge generation in our D:C60 blends. With this, our work (1) demonstrates how relatively accessible characterization techniques can be used to probe energy levels and (2) addresses ongoing discussions on future molecular design and optimal D–A pairing for efficient CT formation and dissociation

Vacuum-deposited donors for low-voltage-loss nonfullerene organic solar cells

The advent of nonfullerene acceptors (NFAs) enabled records of organic photovoltaics (OPVs) exceeding 19% power conversion efficiency in the laboratory. However, high-efficiency NFAs have so far only been realized in solution-processed blends. Due to its proven track record in upscaled industrial production, vacuum thermal evaporation (VTE) is of prime interest for real-world OPV commercialization. Here, we combine the benchmark solution-processed NFA Y6 with three different evaporated donors in a bilayer (planar heterojunction) architecture. We find that voltage losses decrease by hundreds of millivolts when VTE donors are paired with the NFA instead of the fullerene C60, the current standard acceptor in VTE OPVs. By showing that evaporated small-molecule donors behave much like solution-processed donor polymers in terms of voltage loss when combined with NFAs, we highlight the immense potential for evaporable NFAs and the urgent need to direct synthesis efforts toward making smaller, evaporable compounds

Studying the kinetic parameters of BaTi5O11 by using the thermoluminescence technique

The present study discusses the thermoluminescence (TL) characteristics of monoclinic barium titanate (BaTi5O11) which is chemically prepared using the sol–gel technique. The crystallinity is confirmed by X-ray diffraction, and the oxidation state of each element, morphology, and particle size of the prepared powder are chemically probed by different spectroscopic tools including X-ray Photoelectron Spectroscopy and Energy dispersive X-Ray spectroscopy. The sample is irradiated by a beta (β)-source with different applied doses in the range of 1.1––385 Gy. The kinetic parameters which correspond to the charge carrier traps were determined. The analysis methods indicated that the TL glow curve of BaTi5O11 consists of 6 overlapped peaks corresponding to 6 electron traps. The values for the trap depth are found to be in the range 0.94–1.40 eV and the TL glow peaks are located between 380.4 and 560.5 K. The study confirms the potential of BaTi5O11 for β-dosimetry

Vacuum deposited organic solar cells with BTIC-H as A–D–A non-fullerene acceptor

The record power conversion efficiency of solution-processed organic solar cells (OSCs) has almost doubled since non-fullerene acceptors (NFAs) replaced fullerene derivatives as the best-performing acceptor molecules. The successful transition from C60 to NFAs is still pending for vacuum-thermal evaporated (VTE) OSCs, not least because most NFAs are too large to be evaporated without breaking. Due to VTE’s relevance in terms of industrial manufacturing, discovering high-performing VTE NFAs is a major opportunity for OSCs. Here, we fabricate evaporated OSCs based on the NFA BTIC-H known from solution processing. This A–D–A molecule has an unfused bithiophene core, 1,1-dicyanomethylene-3-indanone end groups, and hexyl side chains, making it small enough to be evaporated well. We pair BTIC-H with four commonly used evaporated donors—DCV5T-Me(3,3), DTDCPB, HB194, and SubNc—in planar heterojunctions. We observe appreciable photocurrents and a voltage loss of ∼0.8 V, matching that of corresponding C60 devices. Donor:BTIC-H bulk heterojunctions likely face charge collection issues due to unfavorable microstructure. Our work demonstrates one of few NFA based evaporated OSCs with encouraging performance results and gives one potential starting point for molecule design of further NFAs suitable for VTE

Emissive brightening in molecular graphene nanoribbons by twilight states

Carbon nanomaterials are expected to be bright and efficient emitters, but structural disorder, intermolecular interactions and the intrinsic presence of dark states suppress their photoluminescence. Here, we study synthetically-made graphene nanoribbons with atomically precise edges and which are designed to suppress intermolecular interactions to demonstrate strong photoluminescence in both solutions and thin films. The resulting high spectral resolution reveals strong vibron-electron coupling from the radial-breathing-like mode of the ribbons. In addition, their cove-edge structure produces inter-valley mixing, which brightens conventionally-dark states to generate hitherto-unrecognised twilight states as predicted by theory. The coupling of these states to the nanoribbon phonon modes affects absorption and emission differently, suggesting a complex interaction with both Herzberg–Teller and Franck– Condon coupling present. Detailed understanding of the fundamental electronic processes governing the optical response will help the tailored chemical design of nanocarbon optical devices, via gap tuning and side-chain functionalisation

Interfacial rearrangements and strain evolution in the thin film growth of ZnPc on glass

We report on the characterization of the growth of vacuum-deposited zinc phthalocyanine (ZnPc) thin films on glass through a combination of in situ grazing incidence x-ray scattering, x-ray reflectivity, and atomic force microscopy. We found that the growth at room temperature proceeds via the formation of two structurally unique substrate-induced interfacial layers, followed by the growth of the γ-ZnPc polymorph thereafter (thickness ≈1.0 nm). As the growth of the bulk γ-ZnPc progresses, a substantial out-of-plane lattice strain (≈15% relative to γ-ZnPc powder) is continually relaxed during the thin film growth. The rate of strain relaxation was slowed after a thickness of ≈13 nm, corresponding to the transition from layer growth to island growth. The findings reveal the real-time microstructural evolution of ZnPc and highlight the importance of substrate-induced strain on thin film growth