With chlorinated solvents unlikely to be permitted for use in solution-processed organic solar cells in industry, there must be a focus on developing nonchlorinated solvent systems. Here we report high-efficiency devices utilizing a low-bandgap donor polymer (PffBT4T-2DT) and a nonfullerene acceptor (EH-IDTBR) from hydrocarbon solvents and without using additives. When mesitylene was used as the solvent, rather than chlorobenzene, an improved power conversion efficiency (11.1%) was achieved without the need for pre- or post-treatments. Despite altering the processing conditions to environmentally friendly solvents and room-temperature coating, grazing incident X-ray measurements confirmed that active layers processed from hydrocarbon solvents retained the robust nanomorphology obtained with hot-processed chlorinated solvents. The main advantages of hydrocarbon solvent-processed devices, besides the improved efficiencies, were the reproducibility and storage lifetime of devices. Mesitylene devices showed better reproducibility and shelf life up to 4000 h with PCE dropping by only 8% of its initial value.

Two intermediate-sized donor molecules, BBTz-X and BDT-X, have been synthesized by the Stille coupling between 4-(4,4-bis(2-ethylhexyl)-6-(trimethylstannyl)-4H-silolo[3,2-b:4,5-b′]dithiophen-2-yl)-7-(5′-hexyl-[2,2′-bithiophen]-5-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine and either 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-2,6-diiodobenzo[1,2-d:4,5-d′]bis(thiazole) or 2,6-dibromo-4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene, respectively. Both oxidation and reduction potentials for BBTz-X are anodically shifted relative to those for BDT-X, but the oxidation potential is more sensitive to the identity of the core; this is consistent with what is seen for DFT-calculated HOMO and LUMO energies and with a slightly blue-shifted absorption maximum for BBTz-X. Although DFT calculations, along with crystal structures of related compounds, suggest more planar molecular structures for BBTz-X than for BDT-X, film structures and the effects of various annealing processes on these films, as revealed by GIWAXS, are similar. The performance of BDT-X:PC61BM bulk-heterojunction solar cells is more sensitive to annealing conditions than that of BBTz-X:PC61BM cells, but under appropriate conditions, both yield power conversion efficiencies of >7%.

Employment of thin perovskite shells and metal halides as surface-passivants for colloidal quantum dots (CQDs) have been important, recent developments in CQD optoelectronics. These have opened the route to single-step deposited high-performing CQD solar cells. These promising architectures employ a QD hole-transporting layer (HTL) whose intrinsically shallow Fermi level (EF) restricts band-bending at maximum power-point during solar cell operation limiting charge collection. Here, we demonstrate a generalized approach to effectively balance band-edge energy levels of the main CQD absorber and charge-transport layer for these high-performance solar cells. Briefly soaking the QD HTL in a solution of the metal-organic p-dopant, molybdenum tris(1-(trifluoroacetyl)-2-(trifluoromethyl)ethane-1,2-dithiolene), effectively deepens its Fermi level, resulting in enhanced band bending at the HTL:absorber junction. This blocks the back-flow of photo-generated electrons, leading to enhanced photocurrent and fill factor compared to undoped devices. We demonstrate 9.0% perovskite-shelled and 9.5% metal-halide-passivated CQD solar cells, both achieving ca. 10% relative enhancements over undoped baselines.

Planar perovskite solar cells can be prepared without high temperature processing steps typically associated with mesoporous device architectures; however, their efficiency has been lower and producing high quality perovskite films in planar devices has been challenging. Here, we report a modified two-step interdiffusion protocol suitable to prepare pin-hole free perovskite films with greatly improved morphology. This is achieved by simple addition of small amounts of glycol ethers to the preparation protocol. We unravel the impact the glycol ethers have on the perovskite film formation using in-situ UV-Vis absorbance and GIWAXS experiments. From these experiments we conclude: addition of glycol ethers changes the lead iodide to perovskite conversion dynamics and enhances the conversion efficiency, resulting in more compact polycrystalline films, and it creates micrometer-sized perovskite crystals vertically-aligned across the photoactive layer. Consequently, the average photovoltaic performance increases from 13.5% to 15.9% and reproduciability is enhanced, specifically when 2-methoxyethanol is used as additive.

In this work, we investigated the effects of high operating temperature and thermal cycling on the photovoltaic performance of perovskite solar cells (PSCs) with a typical mesostructured (m)-TiO2-CH3NH3PbI3-xClx-spiro-OMeTAD architecture. After carrying out temperature-dependent grazing incidence wide-angle X-ray scattering (GIWAXS), in-situ X-ray diffraction (XRD) and optical absorption experiments, thermal durability of PSCs was tested by subjecting the devices to repetitive heating to 70 °C and cooling to room temperature (20 °C). An unexpected regenerative effect was observed after the first thermal cycle; the average power conversion efficiency (PCE) increased by approximately 10 % in reference to the as-prepared device. This increase of PCE was attributed to the heating-induced improvement of crystallinity and p-doping in the hole-transporter, Spiro-OMeTAD, which promotes the efficient extraction of photo-generated carriers. However, further thermal cycles produced a detrimental effect on the photovoltaic performance of PSCs with short-circuit current and fill factor degrading faster than the open-circuit voltage. Similarly, the photovoltaic performance of PSCs degraded at high operation temperatures; both short-circuit current and open-circuit voltage decreased with increasing temperature, but the temperature-dependent trend of fill factor was opposite. Our impedance spectroscopy analysis revealed a monotonous increase of charge transfer resistance and a concurrent decrease of charge recombination resistance with increasing temperature, indicating high recombination of charge carriers. Our results revealed that both thermal cycling and high temperatures produce irreversible detrimental effects on the PSC performance due to the deteriorated interfacial photo-carrier extraction. The present findings suggest that development of robust charge transporters and proper interface engineering are critical for the deployment of perovskite photovoltaics in harsh thermal environments.

Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a widely studied model system. Underlying structure–property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm–1 for P3HT:F4TCNQ. We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10–4 mol cm–3 is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders of magnitude can be attributed to an increase in charge-carrier mobility to more than 10–1 cm2 V–1 s–1. Surprisingly, in contrast to charge transport in undoped P3HT, we find that the molecular weight of the polymer does not strongly influence the electrical conductivity, which highlights the need for studies that elucidate structure–property relationships of strongly doped conjugated polymers.

Chemical bath deposition (CBD) of tin oxide (SnO) thin films as an electron-transport layer (ETL) in a planar-heterojunction n-i-p organohalide lead perovskite and organic bulk-heterojunction (BHJ) solar cells is reported. The amorphous SnO (a-SnO) films are grown from a nontoxic aqueous bath of tin chloride at a very low temperature (55 °C) and do not require postannealing treatment to work very effectively as an ETL in a planar-heterojunction n-i-p organohalide lead perovskite or organic BHJ solar cells, in lieu of the commonly used ETL materials titanium oxide (TiO) and zinc oxide (ZnO), respectively. Ultraviolet photoelectron spectroscopy measurements on the glass/indium-tin oxide (ITO)/SnO/methylammonium lead iodide (MAPbI)/2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene device stack indicate that extraction of photogenerated electrons is facilitated by a perfect alignment of the conduction bands at the SnO/MAPbI interface, while the deep valence band of SnO ensures strong hole-blocking properties. Despite exhibiting very low electron mobility, the excellent interfacial energetics combined with high transparency (E > 4 eV) and uniform substrate coverage make the a-SnO ETL prepared by CBD an excellent candidate for the potentially low-cost and large-scale fabrication of organohalide lead perovskite and organic photovoltaics.

Surface molecular doping of graphene has been shown to modify its work function and increase its conductivity. However, the associated shifts in work function and increases in carrier concentration are highly coupled and limited by the surface coverage of dopant molecules on graphene. Here we show that few-layer graphene (FLG) can be doped using a hybrid approach, effectively combining surface doping by larger (metal-)organic molecules, while smaller molecules, such as Br2 and FeCl3, intercalate into the bulk. Intercalation tunes the carrier concentration more effectively, whereas surface doping of intercalated FLG can be used to tune its work function without reducing the carrier mobility. This multi-modal doping approach yields a very high carrier density and tunable work function for FLG, demonstrating a new versatile platform for fabricating graphene-based contacts for electronic, optoelectronic and photovoltaic applications.

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

Solution-processed organic films are a facile route to high-speed, low cost, large-area deposition of electrically functional components (transistors, solar cells, emitters, etc.) that can enable a diversity of emerging technologies, from Industry 4.0, to the Internet of things, to point-of-use heath care and elder care. The extreme sensitivity of the functional performance of organic films to structure and the general nonequilibrium nature of solution drying result in extreme processing-performance correlations. In this Review, we highlight insights into the fundamentals of solution-based film deposition afforded by recent state-of-the-art in situ measurements of functional film drying. Emphasis is placed on multimodal studies that combine surface-sensitive X-ray scattering (GIWAXS or GISAXS) with optical characterization to clearly define the evolution of solute structure (aggregation, crystallinity, and morphology) with film thickness.