The design of vacuum-processed organic solar cells requires a balance between optimizing energetic and morphological properties for efficient photovoltaic performance. In this study, we investigate two structurally similar molecular donors, DCV-iPr and DCV-Me, which exhibit stark differences in photovoltaic performance despite their minimal chemical differences. Through a combined experimental and theoretical approach-including crystal structure prediction, vapor deposition simulations, GIWAXS measurements, and advanced electronic structure calculations-we establish how molecular packing influences optical absorption and photovoltaic efficiency. Our findings show that steric effects introduced by the isopropyl group in DCV-iPr lead to a brick-wall molecular arrangement, favoring J-like excitonic interactions and resulting in sharp optical absorption with a reduced Stokes shift. In contrast, DCV-Me forms a more H-like aggregation, leading to broadened absorption and higher voltage losses. While DCV-iPr demonstrates enhanced photovoltaic performance, we identify substantial remaining voltage losses associated with charge-transfer excitations at the donor-acceptor interface. This work provides key design guidelines linking molecular packing to optical absorption properties and highlights the need for alternative acceptor materials with steeper absorption onsets to further optimize vacuum-processed organic solar cells.

The aggregation behavior of dipyrrolonaphthyridinedione (DPND) chromophores in the solid state critically determines their optoelectronic properties. Here, we investigate how systematic variation in the side-chain geometry-specifically the branching point and steric profile-governs molecular packing and excitonic coupling. Using crystal structure prediction (CSP) combined with experimental GIWAXS and solid-state NMR, we obtain the packing geometry and crystal structure for three DPND derivatives (DPND-iPr, DPND-EtPr, and DPND-iBu). The results reveal that side-chain branching at the first carbon atom promotes herringbone packing and J-type behavior, while branching at the second carbon induces brick-wall stacking and H-type behavior in the solid state. Optical simulations based on the Holstein exciton-vibrational Hamiltonian reproduce experimental absorption and photoluminescence spectra, confirming the transition from J-like to H-like photophysics as the side-chain branching position shifts. This study demonstrates that fine-tuning alkyl side-chain geometry enables rational control of aggregation and excitonic behavior in cross-conjugated DPNDs, providing new design principles for functional organic semiconductors.

We introduce a new computational approach for predicting organic crystalline structures on flat surfaces, an essential step in designing and optimizing thin-film systems for electronic devices. Based on molecular mechanics and molecular dynamics simulations, and implemented in a user-friendly Python program, this method enables a sequential layer-by-layer analysis of crystalline formation, thus allowing to identify surface-induced polymorphs (SIPs) and to study the transition between surface and bulk structures. A validation against six diverse test cases demonstrated a good match with experimental crystalline parameters and arrangements, underscoring the reliability of the method in identifying the most relevant polymorphs for a given molecule.

The density of states (DOS) is fundamentally important for understanding physical processes in organic disordered semiconductors, yet hard to determine experimentally. We evaluated the DOS by considering recombination via tail states and using the temperature and open-circuit voltage (Voc) dependence of the ideality factor. By performing Suns-Voc measurements, we find that the energetic disorder increases deeper into the band gap, which is not expected for a Gaussian or exponential DOS. The linear dependence of the disorder on energy reveals the power-law DOS in organic solar cells.

Photovoltaics (PVs) are a critical technology for curbing growing levels of anthropogenic greenhouse gas emissions, and meeting increases in future demand for low-carbon electricity. In order to fulfil ambitions for net-zero carbon dioxide equivalent (CO2eq) emissions worldwide, the global cumulative capacity of solar PVs must increase by an order of magnitude from 0.9 TWp in 2021 to 8.5 TWp by 2050 according to the International Renewable Energy Agency, which is considered to be a highly conservative estimate. In 2020, the Henry Royce Institute brought together the UK PV community to discuss the critical technological and infrastructure challenges that need to be overcome to address the vast challenges in accelerating PV deployment. Herein, we examine the key developments in the global community, especially the progress made in the field since this earlier roadmap, bringing together experts primarily from the UK across the breadth of the photovoltaics community. The focus is both on the challenges in improving the efficiency, stability and levelized cost of electricity of current technologies for utility-scale PVs, as well as the fundamental questions in novel technologies that can have a significant impact on emerging markets, such as indoor PVs, space PVs, and agrivoltaics. We discuss challenges in advanced metrology and computational tools, as well as the growing synergies between PVs and solar fuels, and offer a perspective on the environmental sustainability of the PV industry. Through this roadmap, we emphasize promising pathways forward in both the short- and long-term, and for communities working on technologies across a range of maturity levels to learn from each other.

Structural templating with homogeneous template layers is one of the strategies for controlling the orientation of small molecular absorbers in the photoactive layer of an organic solar cell to increase its power conversion efficiency. A main challenge thereby is the energetic alignment of the template molecules to the photoactive and charge-transporting materials. In the present study, the effects of a cluster-like template layer of ellagic acid (EA) on the morphology and optical properties of side-chain-substituted dicyanovinyl quaterthiophene (DCV4T-Et-2) thin films are discussed. In the monolayer regime, J-aggregation of DCV4T-Et-2 is confirmed. Insertion of the EA template layer leads to an improved aggregation behavior and formation of J-aggregates in DCV4T-Et-2 films near the EA interface. The orientation of DCV4T-Et-2 molecules in 30 nm thick films changes from "edge-on" to "face-on" due to a pi-pi interaction between the flat-lying EA molecules and the DCV4T-Et-2 molecules. The face-on orientation by templating is preserved in blend layers with C-60, and a considerable increase in the crystallinity of the DCV4T-Et-2 phase in the blend is induced. Organic solar cells based on templated DCV4T-Et-2:C-60 active layers exhibit more than a 50% increase in the efficiency compared to nontemplated active layers. The short-circuit current density and the fill factor are significantly improved. Although the energetic alignment of EA is not ideal, no additional open-circuit voltage losses were observed with templating, due to the cluster-like morphology of the EA layer. Our results demonstrate a cluster-like templating approach with the novel template molecule EA to tailor the molecular orientation, crystallinity, and consequently optical properties of organic semiconducting molecules without significant energetic losses favorable for use in organic electronics.

π-Conjugated push-pull molecules based on triphenylamine and 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) have been functionalized with different terminal arene units. In solution, these highly TCBD-twisted systems showed a strong internal charge transfer band in the visible spectrum and no detectable photoluminescence (PL). Photophysical and theoretical investigations revealed very short singlet excited state deactivation time of ≈10 ps resulting from significant conformational changes of the TCBD-arene moiety upon photoexcitation, opening a pathway for non-radiative decay. The PL was recovered in vacuum-processed films or when the molecules were dispersed in a PMMA matrix leading to a significant increase of the excited state deactivation time. As shown by cyclic voltammetry, these molecules can act as electron donors compared to C60 . Hence, vacuum-processed planar heterojunction organic solar cells were fabricated leading to a maximum power conversion efficiency of ca. 1.9 % which decreases with the increase of the arene size.

Ellagic acid (EA), an antioxidant from fruits or other plants, has recently evoked interest in the field of organic electronics because of its weak electron donor properties. In this work, the preparation of uniaxial pi-stacked EA films by thermal evaporation on different surfaces is reported for the first time. The (102) lattice plane of the pi-electron system was confirmed as the contact plane for one monolayer equivalent on Ag(111) by low-electron energy diffraction. X-ray and atomic force microscopy measurements revealed nanocrystalline grains with an average inplane size of 50 nm and considerably smaller average out-of-plane crystallite sizes (16-25 nm) in films of 16-75 nm thickness. The influence of different substrates was minor compared to the effect of the film thickness. An increase in the in-plane density of grains at larger film thicknesses was deduced from the trend in their uniaxial optical properties. Weak and strong intermolecular H-bonding interactions were identified in the EA crystal lattice, while a surplus of weak H-bonding was observed for the nanocrystallites in thin films, as compared to bulk EA. Finally, EA was coevaporated with the semiconducting thiophene molecule DCV4T-Et-2 to demonstrate principle interactions with a guest molecule by H-bonding analysis. Our results illustrate the feasibility of applying EA films as alignment layers for templating other semiconducting organic films used in organic electronic devices.

The synthesis of two N,N-bis(4-biphenylyl)aniline (BPA) based push–pull is reported herein. Evaluation as donor materials in all-small-molecule planar-heterojunction organic solar cells lead to impressive fill factor (>73%) and promising power conversion efficiencies.

The first successful example of vacuum‐deposited organic photovoltaic (OPV) cells based on a fullerene derivative and a small‐molecule donor is reported. A series of thermally robust fluorous fullerene acceptors with experimental gas‐phase electron affinities ranging from 2.8 to 3.3 eV are paired with a new dicyanovinyl thiophene‐based molecular donor to enable direct comparison of their performance in planar and bulk heterojunction architectures in the cells fabricated by vacuum deposition. Unprecedented insights into the role of the acceptor intrinsic molecular and electronic structures are obtained, which are not obscured by solvent and additive effects as in the typical solution‐processed fullerene‐based OPV cells.

Acceptor-substituted S,N-heteropentacenes with systematically varied alkyl side chains were prepared and implemented as donors in vacuum-processed OSCs giving devices with efficiencies in the range of 4–6%. An odd–even effect with respect to the length of the alkyl side chains is noted.

A new class of A–D–A molecular donor materials based on planarS,N-heterohexacenes is developed for vacuum-processed planar and bulk-heterojunction solar cells providing promising power conversion efficiencies up to 7.1%.

A series of novel acceptor–donor–acceptor oligothiophenes terminally substituted with the 1‐(1,1‐dicyanomethylene)‐cyclohex‐2‐ene (DCC) acceptor has been synthesized. Structural, thermal, optoelectronic, and photovoltaic properties of the π‐extended DCCnTs (n = 1–4) are characterized and contrasted to the trends found for the series of parent dicyanovinyl (DCV)‐substituted oligothiophenes DCVnT. The optoelectronic properties reveal the influence of the additional exocyclic, sterically fixed double bonds in trans‐configuration in the novel DCCnT derivatives. A close correspondence for derivatives with equal number of double bonds, that is, DCCnTs and DCV(n + 1)Ts, is identified. Despite having the same energy gap, the energy levels of the frontier orbitals, HOMO and LUMO, for the DCC‐derivatives are raised and more destabilized due to the aromatization energy of a thiophene ring versus two exocyclic double bonds indicating improved donor and reduced acceptor strength. DCC‐terthiophenes give good photovoltaic performance as donor materials in vacuum‐processed solar cells (power conversion efficiencies ≤ 4.4%) clearly outperforming all comparable DCV4T derivatives.

The fast growing market of organic electronics, including organic photovoltaics (OPV), stimulates the development of versatile technologies for structuring thin-film materials. Ultraviolet lasers have proven their full potential for patterning single organic layers, but in a multilayer organic device the obtained layer selectivity is limited as all organic layers show high UV absorption. In this paper, we introduce mid-infrared (IR) resonant ablation as an alternative approach, in which a short pulse mid-infrared laser can be wavelength tuned to one of the molecular vibrational transitions of the organic material to be ablated. As a result, the technique is selective in respect of processing a diversity of organics, which usually have different infrared absorption bands. Mid-IR resonant ablation is demonstrated for a variety of organic thin films, employing both nanosecond (15 ns) and picosecond (250 ps) laser pulses tunable between 3 and 4 microns. The nanosecond experimental set-up is based on a commercial laser at 1064 nm pumping a singly resonant Optical Parametric Oscillator (OPO) built around a Periodically-Poled Lithium Niobate (PPLN) crystal with several Quasi-Phase Matching (QPM) periods, delivering more than 0.3 W of mid-IR power, corresponding to 15 μJ pulses. The picosecond laser set-up is based on Optical Parametric Amplification (OPA) in a similar crystal, allowing for a comparison between both pulse length regimes. The wavelength of the mid-infrared laser can be tuned to one of the molecular vibrational transitions of the organic material to be ablated. For that reason, the IR absorption spectra of the organic materials used in a typical OPV device were characterized in the wavelength region that can be reached by the laser setups. Focus was on OPV substrate materials, transparent conductive materials, hole transport materials, and absorber materials. The process has been successfully demonstrated for selective thin film patterning, and the influence of the various laser parameters is discussed.

A new class of acceptor-substituted S,N-heteropentacenes is developed for vacuum-processed organic solar cells, providing encouraging power conversion efficiencies of up to 6.5%. Atomic force microscopy (AFM) investigations give a direct correlation between the blend film morphology and the photovoltaic parameters, such as short-circuit current density (JSC ) and fill factor (FF).

In this work we apply a joint experimental and theoretical approach to investigate thin films of side chain substituted dicyanovinyl quaterthiophenes (DCV4T-Et2) and DCV4T-Et2:C60 blends, prototypic absorbers for small molecule organic solar cells. Structural characterization of the morphology of thin films thermally deposited at different substrate temperatures on a silica surface was performed by variable angle spectroscopic ellipsometry, grazing incidence X-ray diffraction, and atomic force microscopy measurements. These methods, combined with full-atomistic molecular dynamic (MD) simulation, provide detailed information about thin film morphology, namely about molecular orientation, absorption, phase separation, and crystallinity, i.e., factors that affect the efficiency of organic solar cells. Using molecular dynamics simulation, we can constitute why the DCV4T-Et2 molecules arrange strongly tilted in pristine (69 degrees to 70 degrees tilt angle to the substrate normal) and DCV4T-Et2:C60 blend films (tilt angle of 65 degrees to 69 degrees).

Enhancement of the efficiency of organic solar cell devices requires knowledge about the structure of the organic layers involved. Films of the donor material dicyanovinyl-sexithiophene bearing four ethyl side-chains at thiophenes two and five DCV6T-Et(2,2,5,5) (DCV6T-Et) are prepared by thermal evaporation in high vacuum at various thicknesses and substrate temperatures. Infrared spectroscopic ellipsometry is used for determination of the molecular orientation in the thin films grown on room temperature (RT) substrate. From simulation of the IR ellipsometric data, the film thickness and the anisotropic optical constants of the DCV6T-Et films are determined. It is found that the optical constants strongly depend on the film thickness. Different average molecular orientations are determined for a few molecules thin (4 nm) and somewhat thicker (20 nm) films. Furthermore, the evolution of the surface morphology of films deposited at elevated substrate temperatures (80 °C, 100 °C) is studied in comparison to the thick RT-film. Atomic force microscopy images indicate that the growth on heated substrate is accompanied by an increase in grain size and surface roughness of the films. Simultaneously, the measured optical absorption spectra display structured and increased absorption in the red spectral region for the DCV6T-Et films deposited at higher substrate temperatures. The changes in surface topography and optical response relate to improved molecular arrangement induced by the substrate heating. To demonstrate the morphological influence on solar cell performance, we finally discuss DCV6T-Et/C60 planar heterojunction solar cells composed of DCV6T-Et films deposited at different substrate temperatures.