Condensation Coefficient Modulation: An Unconventional Approach to the Fabrication of Transparent and Patterned Silver Electrodes for Photovoltaics and Beyond.

Silver is the metal of choice for the fabrication of highly transparent grid electrodes for photovoltaics because it has the highest electrical conductivity among metals together with high stability toward oxidation in air. Conventional methods for fabricating silver grid electrodes involve printing the metal grid from costly colloidal solutions of nanoparticles, selective removal of metal by etching using harmful chemicals, or electrochemical deposition of the silver, an inherently chemical intensive and slow process. This Spotlight highlights an emerging approach to the fabrication of transparent and patterned silver electrodes that can be applied to glass and flexible plastic substrates or directly on top of a device, based on spatial modulation of silver vapor condensation. This counterintuitive approach has been possible since the discovery in 2019 that thin films of perfluorinated organic compounds are highly resistant to the condensation of silver vapor, so silver condenses only where the perfluorinated layer is not. The beauty of this approach lies in its simplicity and versatility because vacuum evaporation is a well-established and widely available deposition method for silver and the shape and dimensions of metallized regions depend only on the method used to pattern the perfluorinated layer. The aim of this Spotlight is to describe this approach and summarize its electronic applications to date with particular emphasis on organic photovoltaics, a rapidly emerging class of thin-film photovoltaics that requires a flexible alternative to the conventional conducting oxide electrodes currently used to allow light into the device.

High Performance Transparent Silver Grid Electrodes for Organic Photovoltaics Fabricated by Selective Metal Condensation.

Silver grid electrodes on glass and flexible plastic substrates with performance that exceeds that of commercial indium-tin oxide (ITO) coated glass are reported and show their suitability as a drop-in replacement for ITO glass in solution-processed organic photovoltaics (OPVs). When supported on flexible plastic substrates these electrodes are stable toward repeated bending through a small radius of curvature over tens of thousands of cycles. The grid electrodes are fabricated by the unconventional approach of condensation coefficient modulation using a perfluorinated polymer shown to be far superior to the other compounds used for this purpose to date. The very narrow line width and small grid pitch that can be achieved also open the door to the possibility of using grid electrodes in OPVs without a conducting poly(3,4-ethylenedioxythiophene-poly(styrenesulfonate) (PEDOT: PSS) layer to span the gaps between grid lines.

Copper Substrate Electrode for Efficient Top-illuminated Organic Photovoltaics.

It is now recognized that for solution processed organic photovoltaics (OPVs) to be manufactured on a large scale the thickness of the photoactive layer must be substantially increased beyond the currently used ≤150 nm. We show that copper can replace silver as the reflective substrate electrode in high performance top-illuminated OPVs without compromising device power conversion efficiency when the photoactive layer is thick enough to absorb the majority of incident photons on the first pass through the photoactive layer. Copper is one hundredth of the cost of Ag, enabling a significant reduction in the bill of materials for OPV manufacture.

Assessing the suitability of copper thiocyanate as a hole-transport layer in inverted CsSnI3 perovskite photovoltaics.

We report the findings of a study into the suitability of copper (I) thiocyanate (CuSCN) as a hole-transport layer in inverted photovoltaic (PV) devices based on the black gamma phase (B-γ) of CsSnI3 perovskite. Remarkably, when B-γ-CsSnI3 perovskite is deposited from a dimethylformamide solution onto a 180-190 nm thick CuSCN film supported on an indium-tin oxide (ITO) electrode, the CuSCN layer is completely displaced leaving a perovskite layer with high uniformity and coverage of the underlying ITO electrode. This finding is confirmed by detailed analysis of the thickness and composition of the film that remains after perovskite deposition, together with photovoltaic device studies. The results of this study show that, whilst CuSCN has proved to be an excellent hole-extraction layer for high performance lead-perovskite and organic photovoltaics, it is unsuitable as a hole-transport layer in inverted B-γ-CsSnI3 perovskite photovoltaics processed from solution.

Stabilizing Lead-Free All-Inorganic Tin Halide Perovskites by Ion Exchange.

Because of its thermal stability, lead-free composition, and nearly ideal optical and electronic properties, the orthorhombic CsSnI3 perovskite is considered promising as a light absorber for lead-free all-inorganic perovskite solar cells. However, the susceptibility of this three-dimensional perovskite toward oxidation in air has limited the development of solar cells based on this material. Here, we report the findings of a computational study which identifies promising Rb y Cs1-y Sn(Br x I1-x )3 perovskites for solar cell applications, prepared by substituting cations (Rb for Cs) and anions (Br for I) in CsSnI3. We show the evolution of the material electronic structure as well as its thermal and structural stabilities upon gradual substitution. Importantly, we demonstrate how the unwanted yellow phase can be suppressed by substituting Br for I in CsSn(Br x I1-x )3 with x ≥ 1/3. We predict that substitution of Rb for Cs results in a highly homogeneous solid solution and therefore an improved film quality and applicability in solar cell devices.

Retarding oxidation of copper nanoparticles without electrical isolation and the size dependence of work function.

Copper nanoparticles (CuNPs) are attractive as a low-cost alternative to their gold and silver analogues for numerous applications, although their potential has hardly been explored due to their higher susceptibility to oxidation in air. Here we show the unexpected findings of an investigation into the correlation between the air-stability of CuNPs and the structure of the thiolate capping ligand; of the eight different ligands screened, those with the shortest alkyl chain, -(CH2)2-, and a hydrophilic carboxylic acid end group are found to be the most effective at retarding oxidation in air. We also show that CuNPs are not etched by thiol solutions as previously reported, and address the important fundamental question of how the work function of small supported metal particles scales with particle size. Together these findings set the stage for greater utility of CuNPs for emerging electronic applications.

High-Performance Silver Window Electrodes for Top-Illuminated Organic Photovoltaics Using an Organo-molybdenum Oxide Bronze Interlayer.

We report an organo-molybdenumn oxide bronze that enables the fabrication of high-performance silver window electrodes for top-illuminated solution processed organic photovoltaics without complicating the process of device fabrication. This hybrid material combines the function of wide-band-gap interlayer for efficient hole extraction with the role of metal electrode seed layer, enabling the fabrication of highly transparent, low-sheet-resistance silver window electrodes. Additionally it is also processed from ethanol, which ensures orthogonality with a large range of solution processed organic semiconductors. The key organic component is the low cost small molecule 3-mercaptopropionic acid, which (i) promotes metal film formation and imparts robustness at low metal thickness, (ii) reduces the contact resistance at the Ag/molybdenumn oxide bronze interface, (iii) and greatly improves the film forming properties. Silver electrodes with a thickness of 8 nm deposited by simple vacuum evaporation onto this hybrid interlayer have a sheet resistance as low as 9.7 Ohms per square and mean transparency ∼80% over the wavelength range 400-900 nm without the aid of an antireflecting layer, which makes them well-matched to the needs of organic photovoltaics and applicable to perovskite photovoltaics. The application of this hybrid material is demonstrated in two types of top-illuminated organic photovoltaic devices.

A silver-free, reflective substrate electrode for electron extraction in top-illuminated organic photovoltaics.

The choice of metals suitable as the reflective substrate electrode for top-illuminated organic photovoltaics (OPVs) is extremely limited. Herein, we report a novel substrate electrode for this class of OPV architecture based on an Al | Cu | AlOx triple-layer structure, which offers a reflectivity comparable to that of Al over the wavelength range 400-900 nm, a work function suitable for efficient electron extraction in OPVs and high stability towards oxidation. In addition to demonstrating the advantage of this composite electrode over Al in model top-illuminated OPVs, we also present the results of a photoelectron spectroscopy study, which show that an oxidised 0.8 nm Al layer deposited by thermal evaporation onto an Al | Cu reflective substrate electrode is sufficient to block oxidation of the underlying Cu by air or during deposition of a ZnO1-x electron-transport layer. This is remarkable given that the self-limiting oxide thickness on Al metal is greater than 2 nm.

A hybrid copper:tungsten suboxide window electrode for organic photovoltaics.

A new type of window electrode for organic photovoltaics (OPVs) based on an ultra-thin bilayer of copper and amorphous tungsten suboxide, which derives its remarkable optical and electrical properties from spontaneous diffusion of copper into the oxide layer. As the window electrode in efficient inverted OPVs, this unpatterned electrode is shown to perform as well as indium-tin oxide glass.

An indium-free low work function window electrode for organic photovoltaics which improves with in-situ oxidation.

A low-cost window electrode for organic photovoltaics that simultaneously removes the requirement for conducting oxide and conventional low work function electrodes and functions as a sink for oxygen/water in the heart of the device. Remarkably the functionality of this electrode, which is based on a 7.8 nm nanostructured Cu:Al film, improves upon in situ oxidation as demonstrated in bulk heterojunction organic photovoltaics.

Widely applicable coinage metal window electrodes on flexible polyester substrates applied to organic photovoltaics.

The fabrication, exceptional properties, and application of 8 nm thick Cu, Ag, Au, and Cu/Ag bilayer electrodes on flexible polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) substrates is reported. These electrodes are fabricated using a solvent free process in which the plastic surface is chemically modified with a molecular monolayer of thiol and amine terminated alkylsilanes prior to metal deposition. The resulting electrodes have a sheet resistance of ≤14 Ω sq⁻¹, are exceptionally robust and can be rapidly thermally annealed at 200 °C to reduce their sheet resistance to ≤9 Ω sq⁻¹. Notably, annealing Au electrodes briefly at 200 °C causes the surface to revert almost entirely to the {111} face, rendering it ideal as a model electrode for fundamental science and practical application alike. The power conversion efficiency of 1 cm² organic photovoltaics (OPVs) employing 8 nm Ag and Au films as the hole-extracting window electrode exhibit performance comparable to those on indium-tin oxide, with the advantage that they are resistant to repeated bending through a small radius of curvature and are chemically well-defined. OPVs employing Cu and bilayer Cu:Ag electrodes exhibit inferior performance due to a lower open-circuit voltage and fill factor. Measurements of the interfacial energetics made using the Kelvin probe technique provide insight into the physical reason for this difference. The results show how coinage metal electrodes offer a viable alternative to ITO on flexible substrates for OPVs and highlight the challenges associated with the use of Cu as an electrode material in this context.

Nanoscale geometric electric field enhancement in organic photovoltaics.

Generic design rules for electrode-organic semiconductor contacts that transcend specific materials are urgently required to guide the development of new electrodes and provide a framework for engineering this important class of interface. Herein a novel nanostructured window electrode is utilized in conjunction with three-dimensional electrostatic modeling to elucidate the importance of geometric electric field enhancement effects at the electrode interfaces in organic photovoltaics. The results of this study show that nanoscale protrusions at the electrode surfaces in organic photovoltaics dramatically improve the efficiency of photogenerated charge carrier extraction to the external circuit and that the origin of this improvement is the local amplification of the electrostatic field in the vicinity of said protrusions. This wholly geometric approach to engineering electrodes at the nanoscale is materials generic and can be employed to enhance the efficiency of charge carrier injection or extraction in a wide range of organic electronic devices.

Enhancing the open-circuit voltage of molecular photovoltaics using oxidized Au nanocrystals.

For organic photovoltaics (OPV) to realize applications effective strategies to maximize the open-circuit voltage must be developed. Herein we show that solution-processed surface-oxidized Au nanocrystals (o-AuNC) dramatically increase the open-circuit voltage (V(oc)) of OPV cells based on boron-subphthalocyanine chloride (SubPc)/C(60) and chloro-aluminum phthalocyanine (ClAlPc)/C(60) heterojunctions when incorporated at the interface between the hole-extracting electrode and the phthalocyanine donor layer. In addition, the cell-to-cell variation in V(oc) is reduced by up to 10-fold combined with a large reduction in the light intensity dependence of V(oc), both of which are important advantages for practical application. The largest increase in V(oc) is achieved for SubPc/C(60)-based cells which exhibit a 45% increase to 1.09 ± 0.01 V--an exceptionally high value for a single junction small molecule OPV. Remarkably these improvements are achieved using submonolayers of o-AuNC, which can be rationalized in terms of the exceptionally high work function of o-AuNC (∼5.9 eV) and geometric electric field enhancement effects.

Modification of charge transport in triphenyldiamine films induced by acid oxidized single-walled carbon nanotube interlayers.

We report the modification of the transport, optical and electrical properties of 200 nm thick N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'biphenyl-4,4'diamine (TPD) films on indium-tin oxide (ITO) when a low density of acid oxidized single-walled carbon nanotubes (o-SWCNTs) are present at the ITO/TPD interface. Most significantly, current-voltage measurements show strong evidence for a change from contact to bulk limited transport. We postulate that these observations result from a change in the structure of the TPD film seeded by the presence of o-SWCNTs at the ITO surface.

Enhancement of polymer luminescence by excitation-energy transfer from multi-walled carbon nanotubes.

Carbon nanotubes have been shown to efficiently quench luminescence from conjugated polymers when incorporated in a composite. However, shown here is an up to 100-fold increase in the visible photoluminescence signal from fluorescent chromophores in nylon 10,10 by incorporating multi-walled carbon nanotubes (MWCNTs). Using 325- and 488-nm excitation the optical absorption by MWCNTs embedded within the polymer matrix is demonstrated, followed by efficient excitation-energy transfer to emissive chromophores intrinsic to the polymer but only when the MWCNTs are acid functionalized. Furthermore, the MWCNTs are shown to significantly retard photobleaching of fluorescent centers in the nylon composites. These remarkable properties greatly advance the prospects of utilizing MWCNTs in organic solar cells and electroluminecent devices to improve performance.

Nanostructured copper phthalocyanine-sensitized multiwall carbon nanotube films.

We report a detailed study of the interaction between surface-oxidized multiwall carbon nanotubes (o-MWCNTs) and the molecular semiconductor tetrasulfonate copper phthalocyanine (TS-CuPc). Concentrated dispersions of o-MWCNT in aqueous solutions of TS-CuPc are stable toward nanotube flocculation and exhibit spontaneous nanostructuring upon rapid drying. In addition to hydrogen-bonding interactions, the compatibility between the two components is shown to result from a ground-state charge-transfer interaction with partial charge transfer from o-MWCNT to TS-CuPc molecules orientated such that the plane of the macrocycle is parallel to the nanotube surface. The electronegativity of TS-CuPc as compared to unsubsubtituted copper phthalocyanine is shown to result from the electron-withdrawing character of the sulfonate substituents, which increase the molecular ionization potential and promote cofacial molecular aggregation upon drying. Upon spin casting to form uniform thin films, the experimental evidence is consistent with an o-MWCNT scaffold decorated with phthalocyanine molecules self-assembled into extended aggregates reminiscent of 1-D linearly stacked phthalocyanine polymers. Remarkably, this self-organization occurs in a fraction of a second during the spin-coating process. To demonstrate the potential utility of this hybrid material, it is successfully incorporated into a model organic photovoltaic cell at the interface between a poly(3-hexylthiophene):[6,6]-phenyl-C61 butyric acid methyl ester bulk heterojunction layer and an indium-tin oxide-coated glass electrode to increase the light-harvesting capability of the device and facilitate hole extraction. The resulting enhancement in power conversion efficiency is rationalized in terms of the electronic, optical, and morphological properties of the nanostructured thin film.