Thin-film Organic Photovoltaics Research Articles

Deuteration-enhanced neutron contrasts to probe amorphous domain sizes in organic photovoltaic bulk heterojunction films

An organic photovoltaic bulk heterojunction comprises of a mixture of donor and acceptor materials, forming a semi-crystalline thin film with both crystalline and amorphous domains. Domain sizes critically impact the device performance; however, conventional X-ray scattering techniques cannot detect the contrast between donor and acceptor materials within the amorphous intermixing regions. In this study, we employ neutron scattering and targeted deuteration of acceptor materials to enhance the scattering contrast by nearly one order of magnitude. Remarkably, the PM6:deuterated Y6 system reveals a new length scale, indicating short-range aggregation of Y6 molecules in the amorphous intermixing regions. All-atom molecular dynamics simulations confirm that this short-range aggregation is an inherent morphological advantage of Y6 which effectively assists charge extraction and suppresses charge recombination as shown by capacitance spectroscopy. Our findings uncover the amorphous nanomorphology of organic photovoltaic thin films, providing crucial insights into the morphology-driven device performance.

Intrinsically Stretchable Organic Photovoltaic Thin Films Enabled by Optimized Donor–Acceptor Pairing

Intrinsically Stretchable Organic Photovoltaic Thin Films Enabled by Optimized Donor–Acceptor Pairing

All-polymer organic solar cells with nano-to-micron hierarchical morphology and large light receiving angle

Distributed photovoltaics in living environment harvest the sunlight in different incident angles throughout the day. The development of planer solar cells with large light-receiving angle can reduce the requirements in installation form factor and is therefore urgently required. Here, thin film organic photovoltaics with nano-sized phase separation integrated in micro-sized surface topology is demonstrated as an ideal solution to proposed applications. All-polymer solar cells, by means of a newly developed sequential processing, show large magnitude hierarchical morphology with facilitated exciton-to-carrier conversion. The nano fibrilar donor-acceptor network and micron-scale optical field trapping structure in combination contributes to an efficiency of 19.06% (certified 18.59%), which is the highest value to date for all-polymer solar cells. Furthermore, the micron-sized surface topology also contributes to a large light-receiving angle. A 30% improvement of power gain is achieved for the hierarchical morphology comparing to the flat-morphology devices. These inspiring results show that all-polymer solar cell with hierarchical features are particularly suitable for the commercial applications of distributed photovoltaics due to its low installation requirement.

Plasmonic enhancement in PTB7-Th:PC71BM organic photovoltaics

Organic photovoltaics struggles with limited exciton diffusion rate and low light absorption rates. The trade-off between these deficiencies limits the thickness of the active layer around 100–200 nm range. Plasmonic light management was introduced as one of the solutions to these problems in the last decade. The plasmonic metal nanostructures can manipulate light in subwavelength regime such as thin-film organic photovoltaics. In this work, we introduced a controllable and reproducible method to incorporate quasi-hexagonal arrays of Au nanostructure on the electron transport layer (ETL), which can directly facilitate light management in the active layer. The inverted PTB7-Th:PC71BM OPVs were selected as the model system, and Au nanostructure arrays were introduced in selected interfaces. In order to match the work function of Au nanostructures and the LUMO level of the PC71BM fullerene component of the bulk heterojunction, PEI was utilized to modify the work function of such surfaces. The plasmon-enhanced inverted OPV devices showed up to 22% higher power conversion efficiencies than reference devices. In order to elucidate the underlying reason for such high improvement, finite-difference time-domain simulations of whole OPV devices under AM1.5G solar illumination were performed. The results revealed up to 25 times higher local exciton generation rate in close proximity to the Au nanostructures and ETLs.

Ultrafast Fluctuations in PM6 Domains of Binary and Ternary Organic Photovoltaic Thin Films Probed with Two-Dimensional White-Light Spectroscopy.

We present two-dimensional white-light spectroscopy (2DWL) measurements of binary and ternary bulk heterojunctions of the polymer donor PM6 mixed with state-of-the-art nonfullerene acceptors Y6 or IT4F. The ternary film has a shorter lifetime and faster spectral diffusion than either of the binary films. 2D line shape analysis of the PM6 ground state bleach with a Kubo model determines that all three films have similar amplitudes of fluctuations (Δ = 0.29 fs-1) in their transition frequencies, but different relaxation times (ranging from 102 to 24 fs). The ternary film exhibits faster dynamics than either of the binary films. The short lifetime of the ternary blend is consistent with increased photoexcitation transfer and the fast frequency fluctuations are consistent with structural dynamics of aliphatic side chains. These results suggest that the femtosecond fluctuations of PM6 are impacted by the choice of the acceptor molecules. We hypothesize that those dynamics are either indicative, or perhaps the initial source, of structural dynamics that ultimately contribute to solar cell operation.

Effect of Micro/Nanostructured P3HT:PCBM Surfaces on the Performance of Organic Photovoltaic Devices

In this study, the effect of periodic patterned micro/nanostructures on the active layers of thin-film organic photovoltaics (OPVs) was investigated to improve the device performance. The patterned active layer structures were fabricated by a nanoimprinting technique using different templates, including compact disc recordable (CD-R), Blu-ray disc recordable (BD-R), nanowell arrays, nanodot arrays, and honeycomb structures. The OPVs consisted of Al/nanostructured P3HT:PCBM/PEDOT:PSS/ITO. Compared with a flat reference OPV, all the micro/nanostructured OPVs exhibited higher performances, originating from enhanced light absorption due to light scattering and surface plasmon excitation at the patterned Al/P3HT:PCBM interfaces.

Time-resolved electrostatic force microscopy using tip-synchronized charge generation with pulsed laser excitation

Nanoscale observation of charge distribution and electric polarization is crucial for understanding and controlling functional materials and devices. In particular, the importance of charge dynamics is well recognized, and direct methods to observe charge generation, transfer, and recombination processes are required. Here, we describe tip-synchronized time-resolved electrostatic force microscopy. Numerical modeling clarifies that the tip-synchronized method provides temporal resolution with the timescale of the cantilever oscillation cycle. This method enables us to resolve sub-microsecond charge migration on the surface. The recombination of photo-excited carriers in a bilayer organic photovoltaic thin film is observed as a movie with a 0.3 µs frame step time resolution. Analysis of the images shows that the carrier lifetime is 2.3 µs near the donor/acceptor interface. The tip-synchronized method increases the range of time-resolved electrostatic force microscopy, paving the way for studies of nanoscale charge dynamics.

Fine structures of organic photovoltaic thin films probed by frequency-shift electrostatic force microscopy

The localized charge and electrostatic properties of organic photovoltaic thin films are predominating factors for controlling energy conversion efficiency. The surface potential and electrostatic structures of organic photovoltaic thin films were investigated by frequency shift mode Kelvin force microscopy (KFM) and electrostatic force microscopy (EFM). The KFM images of a poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene]/phenyl-C61-butyric-acid-methyl ester (PCBM) blend thin film reveals that the PCBM domains precipitate as the topmost layer on the thin films. We find fine structures that were not observed in the topography and KFM images. The bias dependence of the EFM images suggests that the EFM contrast reflects the field-induced polarization, indicating the presence of charge trapping sites.

Wide range local resistance imaging on fragile materials by conducting probe atomic force microscopy in intermittent contact mode

An imaging technique associating a slowly intermittent contact mode of atomic force microscopy (AFM) with a home-made multi-purpose resistance sensing device is presented. It aims at extending the widespread resistance measurements classically operated in contact mode AFM to broaden their application fields to soft materials (molecular electronics, biology) and fragile or weakly anchored nano-objects, for which nanoscale electrical characterization is highly demanded and often proves to be a challenging task in contact mode. Compared with the state of the art concerning less aggressive solutions for AFM electrical imaging, our technique brings a significantly wider range of resistance measurement (over 10 decades) without any manual switching, which is a major advantage for the characterization of materials with large on-sample resistance variations. After describing the basics of the set-up, we report on preliminary investigations focused on academic samples of self-assembled monolayers with various thicknesses as a demonstrator of the imaging capabilities of our instrument, from qualitative and semi-quantitative viewpoints. Then two application examples are presented, regarding an organic photovoltaic thin film and an array of individual vertical carbon nanotubes. Both attest the relevance of the technique for the control and optimization of technological processes.

High-performance ternary blend all-polymer solar cells with complementary absorption bands from visible to near-infrared wavelengths

Ternary blend all-polymer solar cells open a new avenue for accelerating improvement in the efficiency of non-fullerene thin-film organic photovoltaics.

Decoupling optical and electronic optimization of organic solar cells using high-performance temperature-stable TiO2/Ag/TiO2 electrodes

An electrode structured with a TiO2/Ag/TiO2 (TAT) multilayer as indium tin oxide (ITO) replacement with a superior thermal stability has been successfully fabricated. This electrode allows to directly tune the optical cavity mode towards maximized photocurrent generation by varying the thickness of the layers in the sandwich structure. This enables tailored optimization of the transparent electrode for different organic thin film photovoltaics without alteration of their electro-optical properties. Organic photovoltaic featuring our TAT multilayer shows an improvement of ∼12% over the ITO reference and allows power conversion efficiencies (PCEs) up to 8.7% in PTB7:PC71BM devices.

An electron-accepting molecular unit exhibiting an orientational preference favorable for organic photovoltaic applications

Control of molecular orientation of organic semiconductor is essential for efficient light absorption and charge-carrier transport in organic optoelectronic devices. We synthesized compound 1 as a fundamental electron-accepting building block for the design of n-type semiconductors and conducting polymers. We found that this molecule, upon evaporation onto a substrate such as SiO2 and electron-donor films, spontaneously assembles with a face-on orientation relative to the substrate surface. This orientation is favorable for thin-film organic photovoltaics. Despite relatively small π-conjugation, 1 showed strong absorption in visible-light region and an appropriate lowest unoccupied molecular orbital energy for electron transfer with electron donors including copper phthalocyanine and poly(3-hexylthiophene). Accordingly, thin-film devices, fabricated using 1 and electron donors, exhibited a clear photovoltaic response. This suggests that compound 1 provides a promising building block for the development of active materials in organic photovoltaics.

Efficient zinc sulfide cathode layers for organic photovoltaic applications via n-type doping

We demonstrate efficient zinc sulfide cathode window layers in thin-film organic photovoltaics enabled by n-type doping zinc sulfide (ZnS) with aluminum sulfide (Al2S3) directly through co-deposition. By optimizing the Al2S3 concentration, the power conversion efficiency is improved from 0.6% ± 0.2% in undoped ZnS window layer devices to 1.8% ± 0.1%, identical to control devices. The mechanism for this performance enhancement is shown to stem from the enhanced conductivity and interface energetics of ZnS upon n-type doping. This work expands the catalog of efficient, inorganic, non-toxic, cathode side window layers that could be effective in a range of thin-film photovoltaic technologies.

Highly Transparent and Conductive ZnO: Al Thin Films from a Low Temperature Aqueous Solution Approach

A solution deposition approach for high-performance aluminum-doped zinc oxide (AZO) thin films (visible transparency > 90% and sheet resistance down to 25 Ω/sq) with process temperatures not exceeding 85 °C is presented. This allows the non-vacuum deposition of AZO on temperature sensitive substrates such as polymer films for flexible and transparent electronics, or inorganic and organic thin film photovoltaics.

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

There is an increasing demand for organic semiconducting materials with the emergence of organic electronic devices. In particular, large-area devices such as organic thin-film photovoltaics will require significant quantities of materials for device optimization, lifetime testing and commercialization. Sourcing large quantities of materials required for the optimization of large area devices is costly and often impossible to achieve. Continuous-flow synthesis enables straight-forward scale-up of materials compared to conventional batch reactions. In this study, poly(3-hexylthiophene), P3HT, was synthesized in a bench-top continuous-flow reactor. Precise control of the molecular weight was demonstrated for the first time in flow for conjugated polymers by accurate addition of catalyst to the monomer solution. The P3HT samples synthesized in flow showed comparable performance to commercial P3HT samples in bulk heterojunction solar cell devices.

Optimization of periodic nanostructures for enhanced light-trapping in ultra-thin photovoltaics

Nanophotonic light trapping offers a promising approach to increased efficiency in thin-film organic photovoltaics. In this paper, an extension of the direct-binary-search algorithm was adopted to optimize dielectric nanophotonic structures for increasing power output of ultra-thin organic solar cells. The optimized devices were comprised of an absorber layer sandwiched between two patterned, transparent, conducting cladding layers. Light trapping in such devices with an absorber thickness of only 10nm increases power output by a factor of 16 when compared to a flat reference device. We further show that even under oblique illumination with angles ranging from 0 to 60 degrees, such a device could produce over 7 times more power compared to a flat reference device. Finally, we also performed a spectral and parametric analysis of the optimized design, and show that the increase is primarily due to guided-mode resonances. Our simulations indicate that this new design approach has the potential to significantly increase the performance of ultra-thin solar cells in realistic scenarios.

Fabrication of multiscale electrodes on organic photovoltaic thin films and in situ electrical characterization by nanostencil combined with Qplus AFM

The authors demonstrate the fabrication of multiscale electrodes (with lateral dimensions ranging from 10 μm to a few hundred of nanometers) on organic donor–acceptor photovoltaic thin films by mean of nanostencil lithography. The experimental setup allows the realization and in situ investigation of structures by combining nanostencil and atomic force microscopy (AFM) capabilities based on the use of tuning forks. Qplus AFM sensors with tungsten etched tips were used for near field imaging, and as microprobes to contact the deposited electrodes. The photovoltaic behavior was characterized by mean of current–voltage measurements in dark and under selective illumination. The influence of the electrode geometry on the electrical parameters is analyzed and the effect of in situ annealing is discussed in view of frequency modulation AFM images of the active layer surface morphology. This illustrates the powerfulness of nanostencil combined with Qplus AFM for local investigations of organic photovoltaic materials and in situ fabrication of devices.

A neutron spin echo resolved grazing incidence scattering study of crystallites in organic photovoltaic thin films

Neutron spin echo resolved grazing incidence scattering (SERGIS) was used to probe crystallites of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) produced by extensive thermal annealing of a poly(3-hexylthiophene-2,5-diyl)(P3HT):PCBM organic photovoltaic layer. After annealing a thin film of P3HT:PCBM, PCBM crystallites appear on the sample surface, and a strong SERGIS signal is observed superimposed on the specular reflection. Features in the data can be readily correlated with length scales of the crystallites determined using atomic force microscopy and indicate that in such cases the SERGIS signal may be interpreted as a form of small angle neutron scattering.

Synchrotron radiation X-ray spectroscopic studies of interface electronic structure in molecular organic photovoltaic thin films

This paper reviews the application of synchrotron radiation-excited soft X-ray spectroscopies in the study of the interface electronic structure of small molecule organic photovoltaic materials. Recent results of photoemission, X-ray emission, and X-ray absorption experiments on a variety of bilayer systems grown in situ using organic molecular beam deposition will be discussed.

High-efficiency simple planar heterojunction organic thin-film photovoltaics with horizontally oriented amorphous donors

For high performance of organic thin-film photovoltaics (OPVs), high absorption and efficient charge transport of active materials are critical to compensate the short exciton diffusion length and low carrier mobility in organic semiconductors. It is desirable to control over molecular orientation in active layers to enhance both optical and electrical properties. In this letter, we show that amorphous donors having a planar molecular shape can be horizontally oriented, enabling active layers in OPVs to be thin while keeping high absorption in the devices. Based on anisotropic properties in optical design, a power conversion efficiency of more than 4% was achieved from a simple planar heterojunction. This result shows that using horizontally oriented amorphous materials is an effective approach to enhance OPV efficiency.