We developed a monolithic CdTe–PbS tandem solar cell architecture in which both the CdTe and PbS absorber layers are solution-processed from nanocrystal inks. Due to their tunable nature, PbS quantum ...dots (QDs), with a controllable band gap between 0.4 and ∼1.6 eV, are a promising candidate for a bottom absorber layer in tandem photovoltaics. In the detailed balance limit, the ideal configuration of a CdTe (E g = 1.5 eV)–PbS tandem structure assumes infinite thickness of the absorber layers and requires the PbS band gap to be 0.75 eV to theoretically achieve a power conversion efficiency (PCE) of 45%. However, modeling shows that by allowing the thickness of the CdTe layer to vary, a tandem with efficiency over 40% is achievable using bottom cell band gaps ranging from 0.68 and 1.16 eV. In a first step toward developing this technology, we explore CdTe–PbS tandem devices by developing a ZnTe–ZnO tunnel junction, which appropriately combines the two subcells in series. We examine the basic characteristics of the solar cells as a function of layer thickness and bottom-cell band gap and demonstrate open-circuit voltages in excess of 1.1 V with matched short circuit current density of 10 mA/cm2 in prototype devices.
A spin‐cast method is presented for the formation of phosphonic acid functionalized small molecule layers on solution‐processed ZnO substrates for use as electron collecting interlayers in organic ...photovoltaics. Phosphonic acid interlayers modify the ZnO work function and the charge carrier injection barrier at its interface, resulting in systematic control of V OC in inverted bulk heterojunction solar cells. Surface modification is shown to moderate the need for UV light‐soaking of the ZnO contact layers. Lifetime studies (30 days) indicate stable and improved OPV performance over the unmodified ZnO contact, which show significant increases in charge extraction barriers and series resistance. Results suggest that enhanced stability using small molecule modifiers is due to partial passivation of the oxide surface to molecular oxygen adsorption. Surface passivation while maintaining work function control of a selective interlayer can be employed to improve net efficiency and lifetime of organic photovoltaic devices. The modified cathode work function modulates V
OC via static energetic barriers and modulates contact conductivity by creating reversible and irreversible S‐shape current‐voltage characteristics as a result of kinetic barriers to charge transport.
Deposition of benzyl phosphonic acids and alkanethiol self‐assembled monolayers improve initial device performance, and have beneficial effect at mitigating the light‐soaking effect present after aging inverted architecture organic bulk heterojunction devices incorporating ZnO contact layers in air. The effect of a kinetic/transport barrier and a static energetic barrier resulting in formation of S‐shaped J–V curves is isolated.
Plasmonic metal nanoparticles have been used to enhance the performance of thin-film devices such as organic photovoltaics based on polymer/fullerene blends. We show that silver nanoprisms accumulate ...long-lived negative charges when they are in contact with a photoexcited bulk heterojunction blend composed of poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM). We report both the charge modulation and electroabsorption spectra of silver nanoprisms in solid-state devices and compare these spectra with the photoinduced absorption spectra of P3HT/PCBM blends containing silver nanoprisms. We assign a previously unidentified peak in the photoinduced absorption spectra to the presence of photoinduced electrons on the silver nanoprisms. We show that coating the nanoprisms with a 2.5 nm thick insulating layer can completely inhibit this charging. These results may inform methods for limiting metal-mediated losses in plasmonic solar cells.
Poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) is widely used as a semitransparent anode layer in organic light-emitting diodes and polymer photovoltaics. We use conductive atomic ...force microscopy (c-AFM) to map the electronic properties of PEDOT:PSS films during a variety of processing steps to better explain how the observed changes in macroscopic electronic properties arise from local changes in charge transport. We observe only small conductive regions, ∼20 nm in size, surrounded by more insulating regions in all of the films studied. We confirm that these features dominate the c-AFM measurements, independent of the substrate. We observe a marked increase in the density of the conductive regions with increasing annealing times, increasing applied bias (independent of polarity), and decreasing PSS concentration (achieved by altering PEDOT:PSS grades). We also find an increase in current flow following a chlorobenzene wash, suggesting the solvents used in processing the active semiconductor layers on top of PEDOT:PSS anodes may affect the quality of the interface and subsequently alter device performance.
The measured energy diagram for inverted cell architectures for perovskite photovoltaic devices is presented. Band offsets are determined in direct and inverse photoemission spectroscopy. The ...perovskite films assume a slightly p‐type characteristic on top of NiO and show good energetic alignment to adjacent organic electron transport layers. The finding explains the function of inverted devices and gives guidelines for optimization.
The p-type semiconductor GaInP2 has a nearly ideal bandgap (∼1.83 eV) for hydrogen fuel generation by photoelectrochemical water splitting but is unable to drive this reaction because of misalignment ...of the semiconductor band edges with the water redox half reactions. Here, we show that attachment of an appropriate conjugated phosphonic acid to the GaInP2 electrode surface improves the band edge alignment, closer to the desired overlap with the water redox potentials. We demonstrate that this surface modification approach is able to adjust the energetic position of the band edges by as much as 0.8 eV, showing that it may be possible to engineer the energetics at the semiconductor/electrolyte interface to allow for unbiased water splitting with a single photoelectrode having a bandgap of less than 2 eV.
We report a rapid method of depositing phosphonic acid molecular groups onto conductive metal oxide surfaces. Solutions of pentafluorobenzyl phosphonic acid (PFBPA) were deposited on indium tin ...oxide, indium zinc oxide, nickel oxide, and zinc oxide by spray coating substrates heated to temperatures between 25 and 150 °C using a 60 s exposure time. Comparisons of coverage and changes in work function were made to the more conventional dip-coating method utilizing a 1 h exposure time. The data show that the work function shifts and surface coverage by the phosphonic acid were similar to or greater than those obtained by the dip-coating method. When the deposition temperature was increased, the magnitude of the surface coverage and work function shift was also found to increase. The rapid exposure of the spray coating was found to result in less etching of zinc-containing oxides than the dip-coating method. Bulk heterojunction solar cells made of polyhexylthiophene (P3HT) and bis-indene-C60 (ICBA) were tested with PFBPA dip and spray-modified ITO substrates as well as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS)-modified ITO. The spray-modified ITO solar cells showed a similar open circuit voltage (VOC) and fill factor (FF) and a less than 5% lower short circuit current density (J SC) and power conversion efficiency (PCE) than the dip- and PEDOT:PSS-modified ITO. These results demonstrate a potential path to a scalable method to deposit phosphonic acid surface modifiers on metal oxides while overcoming the limitations of other techniques that require long exposure and post-processing times.
Enhanced power conversion efficiency is observed for inverted organic solar cells when a sol‐gel deposited MgZnO is used in place of ZnO. The enhanced fill factor and open‐circuit voltage suggest ...reduced recombination at the interface with bulk heterojunctions of poly(3‐hexylthiophene) (P3HT) blended with either 6,6‐phenyl‐C61‐butyric acid methyl ester (PCBM) or indene C60 bis‐adduct (ICBA).
We use electroabsorption spectroscopy to measure the change in built-in potential (V BI) across the polymer photoactive layer in diodes where indium tin oxide electrodes are systematically modified ...using dipolar phosphonic acid self-assembled monolayers (SAMs) with various dipole moments. We find that V BI scales linearly with the work function (Φ) of the SAM-modified electrode over a wide range when using a solution-coated poly(p-phenylenevinylene) derivative as the active layer. However, we measure an interfacial parameter of S = eΔV BI/ΔΦ < 1, suggesting that these ITO/SAM/polymer interfaces deviate from the Schottky–Mott limit, in contrast to what has previously been reported for a number of ambient-processed organic-on-electrode systems. Our results suggest that the energetics at these ITO/SAM/polymer interfaces behave more like metal/organic interfaces previously studied in UHV despite being processed from solution.
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