Publications

In n–i–p-type conventional perovskite solar cells (PSCs) using a doped 2,2′,7,7′-tetrakis (N,N′-di-p-methoxyphenylamine)-9,9′-spirofluorene (spiro-OMeTAD) hole transport layer (HTL), the issues of reproducibility and stability are closely associated with the redox-inactive additives lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) and 4-tert-butylpyridine (tBP). Instead of these additives, copper(II) di[bis(trifluoromethylsulfonyl)imide] (Cu(TFSI)2) is demonstrated as a direct and efficient p-dopant for spiro-OMeTAD. With the adoption of the technologically relevant coevaporation technique, highly uniform, pinhole-free doped HTLs are achieved with controlled amounts of Cu(TFSI)2 and are spectroscopically and electrically characterized. Using these highly conducting doped HTLs, CH3NH3PbI3-based planar PSCs are realized, which exhibit high photoconversion efficiency (>13% with merely 4 mol % dopant) and excellent reproducibility. Also, by taking advantage of the coevaporation technique, the Cu(TFSI)2-doped HTL thickness impact on PSCs is investigated. It is observed that devices with even the thinnest (40 nm) HTL perform very similarly to the ones with a 100 nm thick HTL, which opens up cost-effective preparation strategies. Moreover, a remarkable storage stability over 218 days is observed for devices with a coevaporated Cu(TFSI)2-doped HTL, suggesting that this approach of controlled direct doping is a viable alternative to the existing arbitrarily p-doped HTL in perovskite solar cells.

Herein, we analyze charge carrier mobility and morphology of the active blend layer in thin film organic solar cells and correlate them with device parameters. A low band gap donor-acceptor copolymer in combination with phenyl-C61-butyric acid methyl ester (PCBM) or two bis-adduct fullerenes, bis-PCBM and bis-o-quino-dimethane C60 (bis-oQDMC), is investigated. We study the charge transport of polymer:fullerene blends in hole- and electron-only devices using the space-charge limited current method. Lower electron mobilities are observed in both bis-adduct fullerene blends. Hole mobility, however, is decreased only in the blend containing bis-oQDMC. Both bis-adduct fullerene blends show very high open circuit voltage in solar cell devices, but poor photocurrent compared to the standard PCBM blend for an active layer thickness of 200 nm. Therefore, a higher short circuit current is feasible for the polymer:bis-PCBM blend by reducing the active layer thickness in order to compensate for the low electron mobility, which results in a PCE of 4.3%. For the polymer:bis-oQDMC blend, no such improvement is achieved due to an unfavorable morphology in this particular blend system. The results are supported by external quantum efficiency measurements, atomic force microscopy, transmission electron microscopy and UV/vis spectroscopy. Based on these results, the investigations presented herein give a more scientific basis for the optimization of solar cells.

We report a highly transparent, low resistance Ag metal network templated by a cracked polymer thin film and its incorporation in an organic solar cell. The performance of this scalable metallic network is comparable to that of conventional ITO electrodes. This is a general approach to replace ITO in diverse thin film devices.

Seven novel polyesters with sidechain diester groups are synthesized, electrochemically characterized, and compared to polybutylacrylate and polycaprolactone. As “beyond PEO” SPEs, they show high capacity retention even at high C rate and low T.

In this contribution, the optical losses and gains attributed to periodic nanohole array electrodes in polymer solar cells are systematically studied. For this, thin gold nanomeshes with hexagonally ordered holes and periodicities (P) ranging from 202 nm to 2560 nm are prepared by colloidal lithography. In combination with two different active layer materials (P3HT:PC₆₁BM and PTB7:PC₇₁BM), the optical properties are correlated with the power conversion efficiency (PCE) of the solar cells. A cavity mode is identified at the absorption edge of the active layer material. The resonance wavelength of this cavity mode is hardly defined by the nanomesh periodicity but rather by the absorption of the photoactive layer. This constitutes a fundamental dilemma when using nanomeshes as ITO replacement. The highest plasmonic enhancement requires small periodicities. This is accompanied by an overall low transmittance and high parasitic absorption losses. Consequently, larger periodicities with a less efficient cavity mode, yet lower absorptive losses were found to yield the highest PCE. Nevertheless, ITO-free solar cells reaching ~77% PCE compared to ITO reference devices are fabricated. Concomitantly, the benefits and drawbacks of this transparent nanomesh electrode are identified, which is of high relevance for future ITO replacement strategies.

Vide infra: Two boron-dipyrromethene (BODIPY)-type infrared sensitizers are investigated for use in titania-based dye-sensitized solar cells (DSCs). The DSCs use a solution of dimethylferrocene (Me2 Fc) in nitromethane as electrolyte. The titania conduction band edge is fine-tuned by adding lithium ions from LiTFSI, while the choice of dimethylferrocene as redox shuttle provides the ideal driving force for dye regeneration, allowing the BODIPY-based DSCs to reach unprecedented quantum efficiencies in the near-infrared.

Metal halide perovskites are the first solution processed semiconductors that can compete in their functionality with conventional semiconductors, such as silicon. Over the past several years, perovskite semiconductors have reported breakthroughs in various optoelectronic devices, such as solar cells, photodetectors, light emitting and memory devices, and so on. Until now, perovskite semiconductors face challenges regarding their stability, reproducibility, and toxicity. In this Roadmap, we combine the expertise of chemistry, physics, and device engineering from leading experts in the perovskite research community to focus on the fundamental material properties, the fabrication methods, characterization and photophysical properties, perovskite devices, and current challenges in this field. We develop a comprehensive overview of the current state-of-the-art and offer readers an informed perspective of where this field is heading and what challenges we have to overcome to get to successful commercialization.

We present a photophysical and device-based investigation of a new bipyridyl−NCS ruthenium complex sensitizer with an extended π system, in both sensitized TiO2 and incorporated into solid-state dye-sensitized solar cells. We compare this new sensitizer to an analog dye without the extended π system. We observe very similar excited-state absorption spectra and charge recombination kinetics for the two systems. However, the π-extended senstizer has a phenomenally enhanced molar extinction coefficient which translates into far greater light harvesting and current collection in solid-state dye-sensitized solar cells. We also infer from transient photovoltage measurements that positioning the pendent extended π system away from the TiO2 surface has induced a favorable dipole shift, generating enhanced open-circuit voltage. The resulting power conversion efficiency for the solar cell has been increased from 2.4% to 3.2% when comparing the new sensitizer to an analogy with no pendent group.

Back Cover: A schematic illustration of the hybrid block copolymer [G2]-b-PPerAcr is shown. Also indicated is the energy transfer between the triphenylamine moieties and the perylene bisimide upon irradiation. Further details can be found in the article by A. S. Lang, F. R. Kogler, M. Sommer, U. Wiesner, and M. Thelakkat* on page 1243.

Most photorefractive (PR) materials require plasticizers in order to decrease the glass transition temperature, allowing for orientational enhancement by the chromophores. Introduction of the plasticizer, however, alters not only the viscosity but also the photoconductive properties of the material. This can be shown by comparing two different plasticizers which were introduced into a bifunctional low-molecular-weight PR glass and into a polyfluorene guest-host polymer. The latter reaches response times down to 600 microsecond(s) at a writing intensity of 1 W/cm<SUP>2</SUP>. We have recently improved the concept of low-molecular-weight PR glasses. A suitable, photoconducting unit allows the synthesis of a bifunctional system with a glass transition of 22.6 degree(s)C. Therefore, no plasticizer is needed. The material is based on a triphenyldiamine (TPD) moiety to which a nonlinear-optical chromophore is directly attached. The system is the first representative of a whole class of TPD molecules and polymers for photorefractive applications.

The influence of different electron extracting interlayers such as calcium (Ca), zirconium acetylacetonate (ZrAcac), and a polyfluorene derivative (PFN) in combination with an aluminum (Al) cathode is investigated on the performance of bulk‐heterojuntion solar cells. Two different photoactive systems, P3HT:PC 61 BM and PDPP:PC 71 BM, are selected for this study. The electroabsorption measurements have been carried out for obtaining the built‐in voltage ( V bi ) and transfer matrix simulations for the determination of parasitic absorption. The solar cell performance is influenced by different parameters such as diode turn‐on voltage, leakage currents, built‐in voltages, and parasitic absorption. The small diode turn‐on voltage and high parasitic absorption in Ca contact devices limit the open circuit voltage and short circuit current, respectively. Likewise, high leakage currents using ZrAcac contact limit the fill factor in P3HT:PC 61 BM solar cell devices. However, the PFN‐based devices with small parasitic absorption, smaller leakage currents, and a relatively high V bi show maximum performance with both material systems. This work highlights the importance of choosing the suitable interlayers in device optimization and clearly demonstrates that not only the low work function of an electron extracting interlayer but also its optical properties and charge selectivity significantly influence the final solar cell performance.

The backbone conformation of conjugated polymers affects, to a large extent, their optical and electronic properties. The usually flexible substituents provide solubility and influence the packing behavior of conjugated polymers in films or in bad solvents. However, the role of the side chains in determining and potentially controlling the backbone conformation, and thus the optical and electronic properties on the single polymer level, is currently under debate. Here, we investigate directly the impact of the side chains by studying the bulky-substituted poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT) and the common poly(3-hexylthiophene) (P3HT), both with a defined molecular weight and high regioregularity, using low-temperature single-chain photoluminescence (PL) spectroscopy and quantum-classical simulations. Surprisingly, the optical transition energy of PDOPT is significantly (∼2,000 cm^-1 or 0.25 eV) red-shifted relative to P3HT despite a higher static and dynamic disorder in the former. We ascribe this red shift to a side-chain induced backbone planarization in PDOPT, supported by temperature-dependent ensemble PL spectroscopy. Our atomistic simulations reveal that the bulkier 2,5-dioctylphenyl side chains of PDOPT adopt a clear secondary helical structural motif and thus protect conjugation, i.e., enforce backbone planarity, whereas, for P3HT, this is not the case. These different degrees of planarity in both thiophenes do not result in different conjugation lengths, which we found to be similar. It is rather the stronger electronic coupling between the repeating units in the more planar PDOPT which gives rise to the observed spectral red shift as well as to a reduced calculated electron-hole polarization.

Novel semiconductor block copolymers were synthesized using nitroxide-mediated radical polymerization (NMRP). They are comprised of a hole conductor block carrying tetraphenylbenzidine pendant units (PVDMTPD) and a second poly(4-vinylpyridine) (P4VP) block suitable for the preferential incorporation of n-type semiconductor nanocrystals. The conditions of NMRP for both monomers were optimized in order to get macroinitiators with well-defined molecular weights and very low polydispersity (<1.2). The resulting block polymers exhibit a lamellar morphology due to microphase separation. Furthermore, semiconductor nanocomposites were prepared using these diblock copolymers and light harvesting CdSe:Te nanocrystals, and their bulk morphologies were characterized by TEM. This new hybrid nanocomposite material maintains the original lamellar structure in which the hole conductor domains are separated from electron conducting/light harvesting nanocrystals that are confined in the P4VP domains. Thus, the challenging task of applying the block copolymer strategy to obtain fully functionalized semiconductor hybrid nanocomposites with morphological control and stability has been realized.