Conventional Organic Photovoltaic Research Articles

Boosting charge separation in organic photovoltaics: unveiling dipole moment variations in excited non-fullerene acceptor layers.

The power conversion efficiency (PCE) of organic photovoltaics (OPVs) has reached more than 19% due to the rapid development of non-fullerene acceptors (NFAs). To compete with the PCEs (26%) of commercialized silicon-based inorganic photovoltaics, the drawback of OPVs should be minimized. This drawback is the intrinsic large loss of open-circuit voltage; however, a general approach to this issue remains elusive. Here, we report a discovery regarding highly efficient NFAs, specifically ITIC. We found that charge-transfer (CT) and charge dissociation (CD) can occur even in a neat ITIC film without the donor layer. This is surprising, as these processes were previously believed to take place exclusively at donor/acceptor heterojunctions. Femtosecond time-resolved visible to mid-infrared measurements revealed that in the neat ITIC layers, the intermolecular CT immediately proceeds after photoirradiation (<0.1 ps) to form weakly-bound excitons with a binding energy of 0.3 eV, which are further dissociated into free electrons and holes with a time-constant of 56 ps. Theoretical calculations indicate that stacking faults in ITIC (i.e., V-type molecular stacking) induce instantaneous intermolecular CT and CD in the neat ITIC layer. In contrast, J-type stacking does not support such CT and CD. This previously unknown pathway is triggered by the larger dipole moment change on the excited state generated at the lower symmetric V-type molecular stacking of ITIC. This is in sharp contrast with the need of sufficient energy offset for CT and CD at the donor-acceptor heterojunction, leading to the significant voltage loss in conventional OPVs. These results demonstrate that the rational molecular design of NFAs can increase the local dipole moment change on the excited state within the NFA layer. This finding paves the way for a groundbreaking route toward the commercialization of OPVs.

A series of perylene diimide cathode interlayer materials for green solvent processing in conventional organic photovoltaics.

Herein, we report on the design, synthesis, physical and chemical properties, and organic photovoltaic (OPV) device performance of four new cathode interlayer (CIL) materials based on bay N-annulated perylene diimides. Starting from the previously reported N-annulated perylene diimide (PDIN-H), the N-position was functionalized with a benzyl and pentafluorobenzyl group to make PDIN-B and PDIN-FB, respectively. Similarly, starting from the previously reported cyanated N-annulated perylene diimide (CN-PDIN-H), the N-position was functionalized with a benzyl and pentafluorobenzyl group to make CN-PDIN-B and CN-PDIN-FB, respectively. The materials exhibit solubility in the green solvent, ethyl acetate, and thus were processed into thin films using ethyl acetate as the solvent. The optoelectronic properties were assessed for both solution and film, and the electrochemical properties were probed in solution. To validate the potential as electron transporting layers, each film was used in conventional OPVs as the CIL with processing from ethyl acetate, while using a bulk heterojunction (BHJ) comprised of PM6:Y6. High power conversion efficiencies (PCEs) of 13% were achieved compared to control devices using the standard PFN-Br CIL.

Flexible Solution-Processed Electron-Transport-Layer-Free Organic Photovoltaics for Indoor Application

Organic photovoltaics (OPVs) have unique advantages of low weight, mechanical flexibility, and solution processability, which make them exceptionally suitable for integrating low-power Internet of Things devices. However, achieving improved operational stability together with solution processes that are applicable to large-scale fabrication remains challenging. Their major limitation arises due to the instable factors that occur both inside the thick active film and from the ambient environment, which cannot be completely resolved via the current encapsulation techniques used for flexible OPVs. Additionally, thin active layers are highly vulnerable to point defects, which result in low yield rates and impede the laboratory-to-industry translation. In this study, flexible fully solution-processed OPVs with improved indoor efficiency and long-term operational stability than that of conventional OPVs with evaporated electrodes are achieved. Benefiting from the oxygen and water vapor permeation barrier of the spontaneously formed gallium oxide layers on the exposed eutectic gallium-indium surface, fast degradation of the OPVs with thick active layers is prevented, maintaining 93% of its initial Pmax after 5000 min of indoor operation under 1000 lx light-emitting diode (LED) illumination. Additionally, by using the thick active layer, spin-coated silver nanowires could be directly used as bottom electrodes without complicated flattening processes, thereby substantially simplifying the fabrication process and proposing a promising manufacturing technique for devices with high-throughput energy demands.

Large-Area Nonfullerene Organic Photovoltaic Modules with a High Certified Power Conversion Efficiency

Achieving large-area organic photovoltaic (OPV) modules with reasonable cost and performance is an important step toward commercialization. In this work, solution-processed conventional and inverted OPV modules with an area of 216 cm2 were fabricated by the blade coating method. Film uniformity was controlled by adjusting the fabrication parameters of the blade coating procedure. The influence of the concentration of the solutions of the interfacial materials on OPV module performance was investigated. For OPV modules based on the PM6:Y6 photoactive layer, a certificated power conversion efficiency (PCE) of 9.10% was achieved for the conventional OPV modules based on the TASiW-12 interfacial layer while a certificated PCE of 11.27% was achieved for the inverted OPV modules based on the polyethylenimine (PEI) interfacial layer. As for OPV modules based on a commercially available photoactive layer, PV-X Plus, a PCE of 8.52% was achieved in the inverted OPV modules. A halogen-free solvent, o-xylene, was used as the solvent for PV-X Plus, which makes the industrial production much more environmentally friendly.

Solution-Processed Electron-Transport Layer-free Organic Photovoltaics with Liquid Metal Cathodes

Flexible, lightweight, and large-area solar cells provide new power supply opportunities in the renewable energy field and facilitate the supply of power to internet-of-things devices and wearable devices. The choice of printing process technologies is a key parameter for such flexible power sources because of their energy-saving process technology and high throughput rate. In addition to selecting the appropriate printing method for the active and charge transport layers, the development of printed electrodes is critical. Numerous printable materials have been developed to replace conventional evaporated top electrodes. However, achieving fully solution-processed organic photovoltaics (OPVs) with power conversion efficiency (PCE) comparable to OPVs with vacuum-deposited transparent and top electrodes is challenging. This is because of the difficulty of forming a uniform interface between the top solution-processed electrode and the active layers while preventing deterioration. In this study, an electron transport layer-free, eutectic gallium-indium (EGaIn) top-cathode strategy was developed and a record PCE of 12.7% in fully solution-processed, flexible OPVs was achieved. Direct coating of EGaIn on the active layer, in a nitrogen atmosphere, is conducive for energy band matching and obtaining physically perfect interfaces without any penetrations or voids. An average PCE of 14.1% and enhanced operating stability, comparable to conventional OPVs, were achieved with indium tin oxide transparent electrodes by eliminating the electron-transport layer. The fully solution-processed flexible OPVs fabricated with the embedded silver nanowire strategy in ultrathin transparent polyimide, achieved an average PCE of 12.7%, representing a promising technique to meet green and high-throughput energy demands.

Carbon-Bridged 1,2-Bis(2-thienyl)ethylene: An Extremely Electron Rich Dithiophene Building Block Enabling Electron Acceptors with Absorption above 1000 nm for Highly Sensitive NIR Photodetectors.

The emerging donor-acceptor-donor (A-D-A)-type nonfullerene acceptors (NFAs) featuring near-infrared (NIR) photoresponsivity have greatly boosted the development of organic photovoltaics (OPVs) and display great potential for sensitive NIR organic photodetectors (OPDs). However, NIR NFAs with absorption above 1000 nm, which is of great importance for application in NIR OPDs for bioimaging, remote communication, night surveillance, etc., are still rare due to the scarcity of strong electron-rich cores. We report herein a new dithiophene building block, namely PDT, which exhibits the strongest electron-donating ability among the widely used dithiophene building blocks. By applying PDT and PDTT as the electron-donating cores and DFIC as the electron-accepting terminals, we developed two new NIR electron acceptors, PDTIC-4F and PDTTIC-4F, with optical absorptions up to 1030 nm, surpassing that of the well-known O6T-4F acceptor. In comparison with the carbon-oxygen-bridged core COi8 in O6T-4F, the synthetic complexity of PDT and PDTT is significantly reduced. Conventional OPV devices based on PM6:PDTTIC-4F display power conversion efficiencies (PCEs) of up to 10.70% with a broad external quantum efficiency (EQE) response from the ultraviolet-visible to the infrared, leading to a high short-circuit current density (Jsc) of 25.90 mA cm-2. Encouraged by these results, we investigated inverted PM6:PDTTIC-4F-based OPD devices by suppressing the dark current via modulation of the film thickness. The optimal OPD device exhibits compelling performance metrics that can compete with those of commercial silicon photodiodes: a record responsivity of 0.55 A W-1 (900 nm) among photodiode-type OPDs and excellent shot-noise-limited specific detectivity (Dsh*) of over 1013 jones.

Distributions of Potential and Contact-Induced Charges in Conventional Organic Photovoltaics.

The interfaces of dissimilar materials play central roles in photophysical events in organic photovoltaics (OPVs). Depth profiles of electrostatic potential and contact-induced charges determine the energy-level lineup of the frontier orbitals at electrode/organic and organic heterointerfaces. They are critical for the elementary processes in an OPV cell, such as generation and diffusion of free carriers. A simple electrostatic model describes the energetics in organic heterojunctions supported by an electrode, and experiments via photoelectron spectroscopy and the Kelvin probe method validate the potential distribution in the stacking direction of the device. A comparative study has clarified the significance of Fermi-level pinning and resulting electrostatic fields in determining the energy-level alignment. In this review, we discuss how parameters of device constituents affect the distributions of potential and the dark charges in conventional OPVs comprising metallophthalocyanine and C60 as donor and acceptor, respectively. The results of previous studies, together with additional numerical simulations, suggest that a number of the factors influence the depth profiles of the dark charge and potential, such as the work function of bottom materials, layer thickness, structural inhomogeneity at interfaces, top electrode, and stacking sequence.

Mechanism and Analysis of Thermal Burn-In Degradation of OPVs Induced by Evaporated HTL

In this study, we focus on the analysis of thermal burn-in degradation behavior of organic photovoltaics (OPVs) at 85 °C under nitrogen atmosphere. In this thermal aging as the accelerated test, the thermal burn-in loss (initially rapid drop) in the power conversion efficiency (PCE) of the inverted OPV devices based on ITO/ZnO/PTB7:PC <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">71</sub> BM/MoO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> /Ag was shown over 40% PCE reduction. We systematically investigate the effects of bulk heterojunction structure and Ag electrode on thermal degradation. Moreover, we adopt two device architectures to investigate the effect of contact between the charge carrier transport layer and active layer on thermal burn-in loss. The degradation mechanism and origin of thermal burn-in loss induced by the evaporated MoO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> molecules or charge traps are proposed for the first time. The impedance analysis was conducted to verify the mechanism. Insight into the burn-in mechanism will be helpful for developing OPV fabrication strategies and designs to effectively reduce the thermal burn-in loss. The conventional OPV with the structure of ITO/MoO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> /PTB7:PC <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">71</sub> BM/ZnO/Ag remains ~94% of its initial PCE after 500 h of thermal aging at 85 °C.

Incorporation of a Metal Oxide Interlayer using a Virus-Templated Assembly for Synthesis of Graphene-Electrode-Based Organic Photovoltaics.

PSS) interlayer. Notably, bilayer-structured OPVs with synergistically integrated WO3 /PEDOT:PSS achieved >60 % enhancement in device performance.

One-Step Synthesis of ZnO Nanocrystals in n-Butanol with Bandgap Control: Applications in Hybrid and Organic Photovoltaic Devices

Solution-grown ZnO nanocrystals (NCs) offer a viable path for large-area, low-temperature processing required for optoelectronics on flexible substrates. They can function as the acceptor in hybrid photovoltaic (HPV) devices or the electron transport layer (ETL) in organic photovoltaic (OPV) devices. We demonstrate a one-step synthesis, using diethanolamine (DEA) and water as additives, to produce ZnO NCs in n-butanol with controlled bandgap. We found that the addition of DEA enhances ZnO NC dispersion, which facilitates the formation of smooth films. For a given DEA concentration, varying the water volume fraction in precursor solution controls the ZnO NC grain size, hence its bandgap. We studied the impact of ZnO bandgap on HPV and OPV device performance. While ZnO NCs with higher bandgap increase the open circuit voltage of bilayer polymer/ZnO HPV devices, ETLs of ZnO NCs with different bandgaps result in identical inverted OPV device performance. The ZnO NC suspensions in n-butanol also allow the fabrication of conventional OPV devices, as they form uniform thin films on top of organics without additional processing. Compared to devices with Ca/Al contacts, these conventional devices exhibit equivalent performance but superior stability in air. These ZnO NC n-butanol suspensions could be readily applied to other optoelectronic and photovoltaic applications, for which type II heterojunction is desired and low-temperature solution processing is required.

Improved photovoltaic characteristics of organic cells with heterointerface layer as a hole-extraction layer inserted between ITO anode and donor layer

We have fabricated an improved organic photovoltaic (OPV) cell in which organic heterointerface layer is inserted between indium-tin-oxide (ITO) anode and copper-phthalocyanine (CuPc) donor layer in the conventional OPV cell of ITO/CuPc/fullerene (C60)/bathophenanthroline (Bphen)/Al to enhance the power conversion efficiency (PCE) and fill factor (FF). The inserted ITO-buffer layer consists of electron-transporting layer (ETL) and hole-transporting layer (HTL). We have changed the ETL and HTL materials variously and also changed their layer thickness variously. It is confirmed that ETL materials with higher LUMO level than the work function of ITO give low PCE and FF. All the double layer buffers give higher PCE than a single layer buffer of TAPC. The highest PCE of 1.67% and FF of 0.57% are obtained from an ITO buffer consisted of 3nm thick ETL of hexadecafkluoro-copper-phthalocyanine (F16CuPc) and 3nm thick HTL of 1,1-bis-(4-methyl-phenyl)-aminophenylcyclohexane (TAPC). This PCE is 1.64 times higher than PCE of the cell without ITO buffer and 2.98 times higher than PCE of the cell with single layer ITO buffer of TAPC. PCE is found to increase with increasing energy difference (ΔE) between the HOMO level of HTL and LUMO level of F16CuPc in a range of ΔE<0.6eV. From the ΔE dependence of PCE, it is suggested that electrons moved from ITO to the LUMO level of the electron-transporting F16CuPc are recombined, at the F16CuPc/HTL-interface, with holes transported from CuPc to the HOMO level of HTL in the double layer ITO buffer ETL, leading to efficient extraction of holes photo-generated in CuPc donor layer.

Layer-by-Layer All-Transfer-Based Organic Solar Cells

For the first time, we describe a novel cost- and time-effective vacuum-free process to fabricate bulk-heterojunction (BHJ) organic photovoltaics (OPVs) via layer-by-layer selective stamping transfer of all layers. By controlling the surface properties of polyurethane acrylate (PUA) stamping molds with ultraviolet (UV)-ozone (UVO) exposure, poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS), BHJ layer, and metal cathode were uniformly transferred layer by layer onto each of the bottom layers. Among several interfaces between each layer, we found that the interface between the active layer and metal cathode is a critical factor in obtaining conventional device-like efficiency. To enhance the interfacial connectivity between the BHJ layer and metal cathode and increase electron extraction from the BHJ layer, a titanium oxide (TiOx) interlayer was introduced. Cell performance was optimized by controlling the concentration of TiOx solution. The poly(3-hexylthiophene-2,5-diyl)/[6,6]-phenyl-C61-butyric acid methyl ester (P3HT/PC60BM) BHJ device fabricated by transferring PEDOT/PSS, TiOx/active layer, and Al cathode showed 2.01% power conversion efficiency. This efficiency is not comparable to those of conventional OPVs, but our approach shows the possibility of fabricating OPVs via the layer-by-layer transfer method for the first time.

Achieving Fill Factor Above 80% in Organic Solar Cells by Charged Interface

Poor carrier mobility in organic semiconductors and high free carrier recombination at the polymer interfaces hinder efficient collection of photogenerated carriers in organic photovoltaic (OPV) devices. This inefficiency in charge collection is reflected in the low fill factor (FF) of the OPV cells (FF <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">OPV</sup> ~ 65%) compared with its inorganic counterparts (FF ~ 85%). In this paper, we show that the FF of the OPV devices made of the conventional low-mobility materials can be radically improved (>;80%) by introducing a “fixed charge layer” at the donor-acceptor interfaces. We find that the fixed charges prevent free-carrier accumulation at the interface and, hence, minimize charge loss due to interfacial recombination. We use detailed device simulation to estimate the fixed charge density required for significant performance gain in typical P3HT:PCBM cells. We conclude by suggesting several strategies for introducing such charged interfaces within the conventional OPV device structure.

Surface Characterization of Polythiophene:Fullerene Blends on Different Electrodes Using Near Edge X-ray Absorption Fine Structure

We study the top surface composition of blends of the conjugated polymer regioregular poly-3-hexylthiophene (P3HT) with the fullerene (6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM), an important model system for organic photovoltaics (OPVs), using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). We compare the ratio of P3HT to PCBM near the air/film interface that results from preparing blend films on two sets of substrates: (1) poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) coated indium tin oxide (ITO) as is commonly used in conventional OPV structures and (2) ZnO substrates that are either unmodified or modified with a C(60)-like self-assembled monolayer, similar to those that have been recently reported in inverted OPV structures. We find that the top surface (the film/air interface) is enriched in P3HT compared to the bulk, regardless of substrate or annealing conditions, indicating that changes in device performance due to substrate modification treatments should be attributed to the buried substrate/film interface and the bulk of the film rather than the exposed film/air interface.