Direct Electrical Evidence of Plasmonic Near-Field Enhancement in Small Molecule Organic Solar Cells

We present a simple and versatile technique to introduce plasmonic silver nanoparticles into organic thin film devices by in situ vacuum deposition. Silver particles with 80 nm diameter at the back of small molecule organic solar cells increase the power conversion efficiency (PCE). Doped organic transport layers allow one to separate electrical and optical effects. By a systematic variation of the position of the silver particles within the solar cell stack, we can thus clearly distinguish a near-field photocurrent gain in the IR that decays to one-half on length scales of around 4 nm, and a less distance-dependent selective mirror effect for short wavelength, which allows one to optimize devices for different wavelengths simultaneously. Device optimization reveals that plasmonic increased absorption can be used to significantly reduce the thickness of the absorber layers and gain efficiency through improved transport properties. A plasmonic zinc phthalocyanine fullerene-C60 solar cell that yields improved photocurrent, fill factor, and PCE of 2.6% includes one-half of the absorber material of an optimized reference device with PCE of 2.4%. The design priciples for plasmonic solar cells are general and were confirmed in thin devices containing zinc 1,8,15,22-tetrafluoro-phthalocyanine, improving the PCE from 2.7% to 3.4%

Measurements of Efficiency Losses in Blend and Bilayer-Type Zinc Phthalocyanine/C₆₀ High-Vacuum-Processed Organic Solar Cells

Losses of charge carriers, due to the interfacial charge recombination processes, in small molecule organic solar cells (SMOSCs) have been investigated under operating conditions. The devices consist of zinc phthalocyanine (ZnPc) as electron donor material and C60 as electron acceptor. The results obtained by using time-resolved techniques such as charge extraction (CE) and photoinduced transient photovoltage (TPV) have been compared to the measurements carried out with impedance spectroscopy (IS) and show good agreement. Significantly, much difference is observed in either the charge density distribution versus the device voltage or the charge carriers lifetime when comparing bulk heterojunction versus bilayer-type ZnPc:C₆₀ devices. The implications of the faster charge carrier recombination with the device fill factor (FF) and the open circuit voltage (<i>V</i>_OC) are discussed

Femtosecond Dynamics of Photoexcited C₆₀ Films

The well known organic semiconductor C₆₀ is attracting renewed attention due to its centimeter-long electron diffusion length and high performance of solar cells containing 95% fullerene, yet its photophysical properties remain poorly understood. We elucidate the dynamics of Frenkel and intermolecular (inter-C₆₀) charge-transfer (CT) excitons in neat and diluted C₆₀ films from high-quality femtosecond transient absorption (TA) measurements performed at low fluences and free from oxygen or pump-induced photodimerization. We find from preferential excitation of either species that the CT excitons give rise to a strong electro-absorption (EA) signal but are extremely short-lived. The Frenkel exciton relaxation and triplet yield strongly depend on the C₆₀ aggregation. Finally, TA measurements on full devices with applied electric field allow us to optically monitor the dissociation of CT excitons into free charges for the first time and to demonstrate the influence of cluster size on the spectral signature of the C₆₀ anion

Evaluation and Control of the Orientation of Small Molecules for Strongly Absorbing Organic Thin Films

In the photoactive film of organic solar cells, the orientation of the absorber molecules is one of the key parameters to achieve high absorption and high photocurrents as well as efficient exciton and charge transport. However, most organic absorber small molecules, such as zinc-phthalocyanine (ZnPc) or diindenoperylene (DIP) grow more or less upright standing in crystalline thin films. Considering absorption, this molecular alignment is unfavorable. In this work we control the orientation of ZnPc and DIP in crystalline absorber films by varying the substrate or organic underlayer appropriately. For this purpose, a precise evaluation of the molecular orientation and packing is important. We find that a combination of the methods variable angle spectroscopic ellipsometry (VASE) and grazing incidence X-ray diffraction (GIXRD) can fulfill this requirement. The combination of these complementary methods shows that the growth of DIP and ZnPc is nearly upright standing on weakly interacting substrates, like glass or amorphous charge transport films. In contrast, on strongly interacting metal sublayers and PTCDA templating layers, both molecules arrange in a strongly tilted orientation (mean tilt angle 54°-71° with respect to the substrate normal), inducing a significant enhancement of absorption (maximum extinction coefficient from 0.72 to 1.3 for ZnPc and 0.14 to 0.4 for DIP). However, even when deposited on metal or PTCDA sublayers, not all ZnPc and DIP molecules in the film are oriented in the desired flat-lying fashion. This highlights that classifying organic films into either solely flat lying structures or solely upright standing structures, as often made in literature, is a too simplified picture

2-(2-Methoxyphenyl)-1,3-dimethyl-1<i>H</i>-benzoimidazol-3-ium Iodide as a New Air-Stable n-Type Dopant for Vacuum-Processed Organic Semiconductor Thin Films

2-(2-Methoxyphenyl)-1,3-dimethyl-1<i>H</i>-benzoimidazol-3-ium iodide (<i>o</i>-MeO-DMBI-I) was synthesized and employed as a strong n-type dopant for fullerene C₆₀, a well-known n-channel semiconductor. The coevaporated thin films showed a maximum conductivity of 5.5 S/cm at a doping concentration of 8.0 wt% (14 mol%), which is the highest value reported to date for molecular n-type conductors. <i>o</i>-MeO-DMBI-I can be stored and handled in air for extended periods without degradation and is thus promising for various organic electronic devices

Vacuum-Deposited Donors for Low-Voltage-Loss Nonfullerene Organic Solar Cells

The advent of nonfullerene acceptors (NFAs) enabled records of organic photovoltaics (OPVs) exceeding 19% power conversion efficiency in the laboratory. However, high-efficiency NFAs have so far only been realized in solution-processed blends. Due to its proven track record in upscaled industrial production, vacuum thermal evaporation (VTE) is of prime interest for real-world OPV commercialization. Here, we combine the benchmark solution-processed NFA Y6 with three different evaporated donors in a bilayer (planar heterojunction) architecture. We find that voltage losses decrease by hundreds of millivolts when VTE donors are paired with the NFA instead of the fullerene C60, the current standard acceptor in VTE OPVs. By showing that evaporated small-molecule donors behave much like solution-processed donor polymers in terms of voltage loss when combined with NFAs, we highlight the immense potential for evaporable NFAs and the urgent need to direct synthesis efforts toward making smaller, evaporable compounds

Comparative Study of Microscopic Charge Dynamics in Crystalline Acceptor-Substituted Oligothiophenes

By performing microscopic charge transport simulations for a set of crystalline dicyanovinyl-substituted oligothiophenes, we find that the internal acceptor–donor–acceptor molecular architecture combined with thermal fluctuations of dihedral angles results in large variations of local electric fields, substantial energetic disorder, and pronounced Poole–Frenkel behavior, which is unexpected for crystalline compounds. We show that the presence of static molecular dipoles causes large energetic disorder, which is mostly reduced not by compensation of dipole moments in a unit cell but by molecular polarizabilities. In addition, the presence of a well-defined π-stacking direction with strong electronic couplings and short intermolecular distances turns out to be disadvantageous for efficient charge transport since it inhibits other transport directions and is prone to charge trapping

Measurement of Small Molecular Dopant F4TCNQ and C₆₀F₃₆ Diffusion in Organic Bilayer Architectures

The diffusion of molecules through and between organic layers is a serious stability concern in organic electronic devices. In this work, the temperature-dependent diffusion of molecular dopants through small molecule hole transport layers is observed. Specifically we investigate bilayer stacks of small molecules used for hole transport (MeO-TPD) and p-type dopants (F4TCNQ and C₆₀F₃₆) used in hole injection layers for organic light emitting diodes and hole collection electrodes for organic photovoltaics. With the use of absorbance spectroscopy, photoluminescence spectroscopy, neutron reflectometry, and near-edge X-ray absorption fine structure spectroscopy, we are able to obtain a comprehensive picture of the diffusion of fluorinated small molecules through MeO-TPD layers. F4TCNQ spontaneously diffuses into the MeO-TPD material even at room temperature, while C₆₀F₃₆, a much bulkier molecule, is shown to have a substantially higher morphological stability. This study highlights that the differences in size/geometry and thermal properties of small molecular dopants can have a significant impact on their diffusion in organic device architectures

Surface Engineering Using Kumada Catalyst-Transfer Polycondensation (KCTP): Preparation and Structuring of Poly(3-hexylthiophene)-Based Graft Copolymer Brushes

Poly(4-vinylpyridine)-block-poly(4-iodo-styrene), P4VP-b-PS(I), block copolymers obtained by iodination of readily available P4VP-b-PS block copolymers strongly adhere to variety of polar substrates including Si wafers, glasses, or metal oxide surfaces by a polar P4VP block, forming polymer brushes of moderately stretched PS(I) chains. Kumada catalyst-transfer polycondensation (KCTP) from the P4VP-b-PS(I) brushes results into planar brushes of the graft copolymer in which relatively short (∼10 nm) poly(3-hexylthiophene), P3HT, grafts emanate from the surface-tethered PS(I) chains. Grafting of the P3HT leads to significant stretching of the PS(I) backbone as a result of increased excluded volume interactions. Specific adsorption of the P4VP block to polar surfaces was utilized in this work to pattern the P4VP25-b-PS(I)350 brush. The microscopically structured P4VP25-b-PS(I)350 brush was converted into the respectively patterned P4VP-PS(I)-g-P3HT one using KCTP. We also demonstrated that KCTP from functional block copolymers is an attractive option for nanostructuring with polymer brushes. P4VP75-b-PS(I)313 micelles obtained in selective solvent for the PS(I) block form a quasi-ordered hexagonal array on Si wafer. The P4VP75-b-PS(I)313 monolayer preserves the characteristic quasi-regular arrangement of the micelles even after extensive rinsing with various solvents. Although the grafting of P3HT from the nanopatterned P4VP75-b-PS(I)313 brush destroys the initial order, the particulate morphology in the resulting film is preserved. We believe that the developed method to structured brushes of conductive polymers can be further exploited in novel stimuli-responsive materials, optoectronic devices, and sensors

Temperature Activation of the Photoinduced Charge Carrier Generation Efficiency in Quaterthiophene:C₆₀ Mixed Films

We measure photoinduced excitations in a dicyanovinyl end-capped methylated quaterthiophene derivative in blends with the electron acceptor C₆₀, as already employed in organic photovoltaics. By using DFT calculations and analyzing the recombination characteristics of the excited states revealed by photoinduced absorption (PIA) spectroscopy, the absorption peaks are assigned to triplet exciton, cation, and anion transitions. We determine the temperature dependent generation and recombination behavior of triplet excitons and cations in the mixed layer. At 10 K, we observe an enhanced triplet exciton generation rate compared to the pristine donor layer due to back recombination from a charge-transfer (CT) state at the donor–acceptor interface. With increasing temperature, the triplet generation rate first increases which is ascribed to an enhanced singlet exciton migration to this interface. Above 150 K, the triplet generation rate declines due to the beginning CT exciton separation, leading to the generation of free charge carriers. This temperature activated behavior is ascribed to a temperature activated increase of charge carrier mobility, facilitating CT exciton splitting