Indium Tin Oxide (ITO) thin films are commonly used as transparent conductive layers in the production of solar cells. ITO films are typically heat-treated at temperatures exceeding 200 degrees C after magnetron sputtering to optimize the physical, optical, and electrical characteristics for photovoltaic devices. This high temperature heating procedure greatly limits the use of potential substrates, particularly those comprised of low-temperature-rated polymers. Herein, we examine the physical, optical, and electrical transport effects of oxygen:argon plasmas during radio frequency magnetron sputtering of ITO on glass and flexible polymer surfaces without subsequent heat treatment. ITO thin films were characterized via sheet resistance testing, UV-Vis spectroscopy, X-ray diffraction, and scanning electron microscopy imaging. Sheet resistance measurements revealed an increase in surface resistance with increasing oxygen concentration during sputtering. UV-Vis optical transmittance measurements demonstrated an improvement in optical transmittance with an increase in oxygen concentration reaching a maximum transmittance at an oxygen concentration of 1-2%. Most importantly, it was discovered that producing bilayers of ITO with pure argon sputtered plasmas followed by oxygen:argon plasmas produced ITO thin films with suitable resistance and transmittance without the need for high temperature post annealing. These results highlight a methodology for the deposition of ITO thin films on temperature sensitive substrates for flexible photovoltaics and low-cost module production.

Metal ion linked multilayers offer a means of controlling interfacial energy and electron transfer for a range of applications including solar energy conversion, catalysis, sensing, and more. Despite the importance of structure to these interlayer transfer processes, little is known about the distance and orientation between the molecules/surface of these multilayer films. Here we gain structural insights into these assemblies using a combination of UV-Vis polarized visible attenuated total reflectance (p-ATR) and F & ouml;rster Resonance Energy Transfer (FRET) measurements. The bilayer of interest is composed of a metal oxide surface, phosphonated anthracene molecule, Zn(ii) linking ion, and a platinum porphyrin with one (P1), two (P2), or three (P3) phenylene spacers between the chromophoric core and the metal ion binding carboxylate group. As observed by both time-resolved emission and transient absorption, the FRET rate and efficiency decreases with an increasing number of phenylene spacers (P1 > P2 > P3). However, from p-ATR measurements we observe a change in orientation of porphyrins in the bilayer, which inhibits a uniform determination of the orientation factor (kappa(2)) across the series. Instead, we narrow the scope of viable structures by determining the best agreement between experimental and calculated FRET efficiencies. Additionally, we provide evidence that suggests, for the first time, that the bilayer structure is similar on both planar and mesoporous substrates.

In this work, a two-step hydrothermal/solvothermal process was developed to generate highly fluorescent lawsone polymer dots (LPDs) utilizing an inexpensive and abundant starting material, 2-hydroxy-1,4-napththoquinone (lawsone). This hydrothermal/solvothermal process produces LPDs that have excitation independent emission with well-defined electronic transitions. This two-step protocol provides a straightforward approach to remove unwanted small molecular fluorescence, which has plagued carbon dot systems, without the need for advanced chromatographic purification methods or steps. A series of spectroscopic, electrochemical, and theoretical experiments suggest that this process proceeds via a sequential dehydration and dehydrogenation pathway to cross-link the lawsone into a carbon dot structure. This polymerization process helps to stabilize and favor certain electronic transitions inherently present in the lawsone monomer. The generation of the LPDs results in a 2 order of magnitude increase in the emission intensity and a quantum yield of 37%. This behavior is likely the result of the cross-linked structure shielding these electronic states from deactivation caused by nonradiative processes such as vibrational coupling and excited state quenching from thermal deactivation and solvent collisions. This finding is consistent with a cross-linked enhanced emission (CEE) mechanism, as previously observed for other similar systems. The LPDs were then incorporated into a TiO2 photoanode and utilized as a photosensitizer in a dye-sensitized solar cell (DSSC) which showed an enhancement in photocurrent density over pure TiO2. We also prepared a derivative of the LPDs utilizing a diethylene triamine additive (nitrogen-doped lawsone polymer dots (N-LPDs)) using the same two-step protocol and demonstrated its potential as a fluorescence microscopy dye for imaging MDA-MB-231 cancer cells.

Modification of transparent metal oxide (MOx) surfaces with organic monolayers is widely employed to tailor the properties of interfaces in organic electronic devices, and MOx substrates modified with light-absorbing chromophores are a key component of dye-sensitized solar cells (DSSCs). The effects of an organic modifier on the performance of a MOx-based device are frequently assessed by performing experiments on model monolayer|MOx interfaces, where an "inert" MOx (e.g., Al2O3) is used as a control for an "active" MOx (e.g., TiO2). An underlying assumption in these studies is that the structure of the MOx-monolayer complex is similar between different metal oxides. The validity of this assumption was examined in the present study. Using UV-Vis attenuated total reflection spectroscopy, we measured the mean dipole tilt angle of 4,4'-(anthracene-9,10-diyl)bis(4,1-phenylene)diphosphonic acid (A1P) adsorbed on indium tin oxide (ITO), TiO2, ZrO2, and Al2O3. When the surface roughness of the MOx substrate and the surface coverage (𝛤) of the A1P film were constant, the molecular orientation of A1P was the same on these substrates. The study was extended to 4,4'-(anthracene-9,10-diyl)bis(4,1-phenylene)dicarboxylic acid (A1C) adsorbed on the same group of MOx substrates. The mean tilt angle of A1C and A1P films on ITO was the same, which is likely due the intermolecular interactions resulting from the high and approximately equal 𝛤 of both films. Comparing A1C films at the same 𝛤 on TiO2 and Al2O3 having the same surface roughness, there was no difference in the mean tilt angle. MD simulations of A1C and A1P on TiO2 produced nearly identical tilt angle distributions, which supports the experimental findings. This study provides first experimental support for the assumption that the structure of the MOx-modifer film is the same on an "active" substrate vs. a "inert" control substrate.

Perovskite light-emitting diodes (PeLEDs) have received great attention for their potential as next-generation display technology. While remarkable progress has been achieved in green, red, and near-infrared PeLEDs with external quantum efficiencies (EQEs) exceeding 20%, obtaining high performance blue PeLEDs remains a challenge. Poor charge balance due to large charge injection barriers in blue PeLEDs has been identified as one of the major roadblocks to achieve high efficiency. Here band edge control of perovskite emitting layers for blue PeLEDs with enhanced charge balance and device performance is reported. By using organic spacer cations with different dipole moments, that is, phenethyl ammonium (PEA), methoxy phenethyl ammonium (MePEA), and 4-fluoro phenethyl ammonium (4FPEA), the band edges of quasi-2D perovskites are tuned without affecting their band gaps. Detailed characterization and computational studies have confirmed the effect of dipole moment modification to be mostly electrostatic, resulting in changes in the ionization energies of approximate to 0.45 eV for MePEA and approximate to -0.65 eV for 4FPEA based thin films relative to PEA-based thin films. With improved charge balance, blue PeLEDs based on MePEA quasi-2D perovskites show twofold increase of the EQE as compared to the control PEA based devices.

The incorporation of dye-electron donor motifs on metal oxide surfaces is a common strategy to increase dye regeneration rate, slow recombination, and improve overall dye-sensitized device performance. Here we used zinc ion linked multilayer assembly of a dye (N3) and a cobalt polypyridyl electron donor (Co) on TiO2 as an alternative to traditional covalently linked dye-donor systems. The formation of the TiO2-N3-Zn-Co multilayer was monitored using UV–Vis and ATR-IR and we introduced inductively coupled plasma mass spectrometry as a means of quantifying the surface loading of spectroscopically obscured molecules like Co. Interestingly, and contrary to the original intent, the addition of Co electron donor impeded the dye-sensitized device in nearly every performance metric. Transient absorption measurements indicate that both excited state quenching of N3 by Co and Co to N3+ electron transfer are slower than the intrinsic excited state decay and recombination, respectively. We suggest that the geometric restriction imposed by the metal ion linked architecture sufficiently slows electron transfer such that Co is effectively inert in this assembly. While this bilayer did not improve device performance, these insights may guide new design strategies that will improve performance and/or will be of use in other applications where electron transfer is not desired but say communication of spin and/or magnetic moment is needed.

Metal ion linked multilayers on mesoporous, semiconducting surfaces have recently emerged as a simple but effective strategy to facilitate photoinduced energy and electron transfer events at organic-inorganic interfaces. In this manuscript, we recount our group's work in understanding, controlling, and harnessing photoinduced processes in these multilayer assemblies. This includes, 1) manipulating interfacial electron transfer rates at dye-semiconductor interfaces, 2) generating directional energy and electron cascade solar cells, and 3) facilitating and harnessing molecular photon upconversion via triplet-triplet annihilation. We then close with a brief summary of the progress to date, general limitations with the current films/work, and an outlook as to what the future may hold for these multilayer films.

Metal ion-linked multilayers offer an easily prepared and modular architecture for controlling energy and electron transfer events on nanoparticle, metal oxide films. However, unlike with planar electrodes, the mesoporous nature of the films inherently limits both the thickness of the multilayer and subsequent diffusion through the pores. Here, we systematically investigated the role of TiO2 nanoparticle film porosity and metal ion-linked multilayer thickness in surface loading, through-pore diffusion, and overall device performance. The TiO2 porosity was controlled by varying TiO2 sintering times. Molecular multilayer thickness was controlled through assembling ZnII-linked bridging molecules (B = p-terphenyl diphosphonic acid) between the metal oxide and the Ru(bpy)2((4,4'-PO3H2)2bpy)]Cl2 dye (RuP), thus producing TiO2-(Bn)-RuP films. Using attenuated total reflectance infrared absorption and UV-vis spectroscopy, we observed that at least two molecular layers (i.e., TiO2-B2 or TiO2-B1-RuP) could be formed on all films but subsequent loading was dependent on the porosity of the TiO2. Rough estimates indicate that in a film with 34 nm average pore diameter, the maximum multilayer film thickness is on the order of 4.6-6 nm, which decreases with decreasing pore size. These films were then incorporated as the photoanodes in dye-sensitized solar cells with cobalt(II/III)tris(4,4'-di-tert-butyl-2,2'-bipyridine) as a redox mediator. In agreement with the surface-loading studies, electrochemical impedance spectroscopy measurements indicate that mediator diffusion is significantly hindered in films with thicker multilayers and less porous TiO2. Collectively, these results show that care must be taken to balance multilayer thickness, substrate porosity, and size of the mediator in designing and maximizing the performance of new multilayer energy and electron management architectures.

Surface passivation of perovskite solar cells (PSCs) using a low-cost industrial organic pigment quinacridone (QA) is presented. The procedure involves solution processing a soluble derivative of QA, N , N -bis(tert-butyloxycarbonyl)-quinacridone (TBOC-QA), followed by thermal annealing to convert TBOC-QA into insoluble QA. With halide perovskite thin films coated by QA, PSCs based on methylammonium lead iodide (MAPbI 3 ) showed significantly improved performance with remarkable stability. A PCE of 21.1 % was achieved, which is much higher than 18.9 % recorded for the unmodified devices. The QA coating with exceptional insolubility and hydrophobicity also led to greatly enhanced contact angle from 35.6° for the pristine MAPbI 3 thin films to 77.2° for QA coated MAPbI 3 thin films. The stability of QA passivated MAPbI 3 perovskite thin films and PSCs were significantly enhanced, retaining about 90 % of the initial efficiencies after more than 1000 hours storage under ambient conditions.

In this report, the synthesis and characterization of two bis-cyclometalated iridium(III) complexes are presented. Single-crystal X-ray diffraction shows that [Ir(ppy)2(4,4'-bis(diethylphosphonomethyl)-2,2'-bipyridine)]PF6 adopts a pseudooctahedral geometry. The complexes have an absorption feature in the near-visible-UV region and emit green light with excited-state lifetimes in hundreds of nanoseconds. The redox properties of these complexes show reversible behavior for both oxidative and reductive events. [Ir(ppy)2(4,4'-bis(phosphonomethyl)-2,2'-bipyridine)]PF6 readily binds to metal oxide supports, like nanostructured SnIV-doped In2O3 and TiO2, while still retaining reversible redox chemistry. When incorporated as the photoanode in dye-sensitized solar cells, the devices exhibit open-circuit voltages of >1 V, which is a testament to their strength of these iridium(III) complexes as photochemical oxidants.

Photon upconversion via triplet–triplet annihilation (TTA-UC) is a promising strategy for increasing maximum theoretical solar cell efficiencies by a factor of 1.3. However, one factor limiting integrated TTA-UC solar cell performance is the transmission window between sensitizer and acceptor molecule absorption. Here we demonstrate that the incorporation of a singlet sensitizer (SS) into a self-assembled trilayer is an effective means of harnessing that previously transmitted light. A record TTA-UC photocurrent density of 0.315 mA cm–2 under 1 sun irradiation was achieved and is attributed to directional SS-to-sensitizer singlet energy transfer and sensitizer-to-acceptor triplet energy transfer, followed by TTA, excited-state electron transfer into TiO2, and regeneration by a redox mediator in solution. These results demonstrate that singlet sensitization-enhanced self-assembled trilayers are a promising strategy for enhancing broad-band light absorption and improving the performance of TTA-UC solar cells.

The interfaces between perovskite and charge transport layers greatly impact the device efficiency and stability of perovskite solar cells (PSCs). Inserting an ultrathin wide-band-gap layer between perovskite and hole transport layers (HTLs) has recently been shown as an effective strategy to enhance device performance. Herein, a small amount of an organic halide salt, N,N'-dimethylethylene-1,2-diammonium iodide, is used to create two-dimensional (2D)-three-dimensional (3D) heterojunctions on MAPbI3 thin film surfaces by facile solution processing. The formation of an ultrathin wide-band-gap 2D perovskite layer on top of 3D MAPbI3 changes the morphological and photophysical properties of perovskite thin films, effectively reduces the surface defects, and suppresses the charge recombination in the interfaces between perovskite and HTL. As a result, a power conversion efficiency of ∼20.2%, with an open-circuit voltage of 1.14 V, a short-circuit current density of 22.57 mA cm-2, and a fill factor of 0.78, is achieved for PSCs with enhanced stability.

A simple electrochemical assay to monitor the dispersion of Pseudomonas aeruginosa PA01 biofilm is described. Pyrolytic graphite (PG) electrodes were modified with P. aeruginosa PA01 using layer-by-layer (LbL) methods. The presence of the bacteria on the electrodes was directly monitored using square wave voltammetry (SWV) via the electrochemical reduction of electroactive phenazine compounds expressed by the bacteria, which indicate the presence of biofilm. Upon treatment of bacteria-modified electrodes with a 2-aminoimidazole (2-AI) derivative with known Pseudomonas anti-biofilm properties, the bacteria-related electrochemical reduction peaks decreased in a concentration dependent manner, indicating dispersal of the biofilm on the electrode surface. A similar 2-AI compound with negligible anti-biofilm activity was used as a comparative control and produced muted electrochemical results. Electrochemical responses mirrored previously established bioassay-derived half maximal inhibition concentration (IC50) and half maximal effective concentration (EC50) values.. Biofilm dispersal detection via the electrochemical response was validated by monitoring crystal violet absorbance after its release from electrode confined P. aeruginosa biofilm. Mass spectrometry data showing multiple redox active phenazine compounds are presented to provide insight into the surface reaction complexity. Overall, we present a very simple assay to monitor the anti-biofilm activity of compounds of interest.

Maximizing regeneration and minimizing recombination rates at dye–semiconductor interfaces is crucial for the realization of efficient dye-sensitized solar and photoelectrosynthesis cells. Previously it has been shown that simply coordinating the metal ion to the nonsurface bound carboxylate groups of a dye molecule can slow recombination rates and increase open-circuit voltages. However, it was unclear if the additional steric effects or charge of the metal ion were the cause of this behavior. Here we use three different redox mediators, (1) I–/I3–, (2) [tris(1,10-phenanthroline)cobalt]3+/2+, and (3) [Co(4,4′,4″-tritert-butyl-2,2′:6′,2″-terpyridine)(NCS)3]0/1– to elucidate the role, if any, of electrostatic interactions between the coordinated metal ion and mediator in dictating these interfacial electron transfer events. Using a combination of spectroscopy, electrochemistry, and solar cell measurements, we demonstrate that while electrostatic interactions may influence dye regeneration rates, for exampl...