Whats special about Y6; the working mechanism of neat Y6 organic solar cell

Non-fullerene acceptors (NFA) have delivered advance in bulk heterojunction organic solar cell efficiencies, with the significant milestone of 20% now in sight. However, these materials challenge the accepted wisdom of how organic solar cells work. In this work we present neat Y6 device with efficiency above 4.5%. We thoroughly investigate mechanisms of charge generation and recombination as well as transport in order to understand what is special about Y6. Our data suggest Y6 generates bulk free charges, with ambipolar mobility, which can be extracted in the presence of transport layersComment: 11 pages, 5 figure

Photophysics of fused ring electron acceptors for photovoltaic applications

Organic photovoltaic cells (OPVs) have received significant interest over the last decade as they offer the potential of cheap renewable energy via direct photon to electron conversion of abundantly available Sun light. Compared to the inorganic equivalents, they offer lightweight, low-cost, and flexibility advantages. Conventional OPVs are typically based on blends of electron-donor materials and fullerene-based electron-acceptor materials that form bulk-heterojunctions (BHJs). But the attention has recently shifted to organic non-fullerene acceptors especially fused ring electron acceptors (FREAs) owing to their attractive properties including flexible energy levels, tunable band gap, crystallinity, and planarity. Thus the power conversion efficiency (PCE) of OPVs has recently attained a record of 16% by synthesizing FREAs with modified chemical structures. Owing to the high crystallinity and packing orientation of acceptors, FREA based OPV systems are characterized by large and pure phases sized 20-50 nm. This is consistent with the observation that charge generation dynamics in these systems lacked the ultrafast component that characterizes most fullerene blends. To test the hypothesis that the optimal phase size can be large due to facile exciton diffusion in FREAs, a planar indacenodithiophene (IDT) based FREA, IDIC is selected as a model system to study the exciton dynamics. Chapter 3 includes the exciton diffusion measurements in IDIC films using transient absorption spectroscopy which resolves a substantially high, quasi-activationless diffusion coefficient that exceeds that of typical organic semiconductors. The study also includes a deep insight of the key factors behind the enhanced exciton diffusion in IDIC and is shown to arise from different molecular and packing factors which enhance the long-range resonant energy transfer. Rapid exciton diffusion in IDIC films introduced the possibility of solution-processed bilayer devices. Chapter 4 comprises both device and photophysics of planar bilayer devices with a PCE of 11.1% which is readily accounted for the material and device design. By pairing a mid-band gap polymer donor with a range of FREAs, it is shown that the combination of high molecular packing densities and absorption coefficients, long exciton diffusion lengths, and efficient, resonant, long-range energy transfer between donor and acceptor layers enable efficient bilayer devices. By designing new materials with these characteristics, along with orthogonal solubility for layer-by-layer deposition of clean bilayers, it is suggested that the clear connection between material design and function in the bilayer structure will accelerate the development of more efficient organic photovoltaic devices. The molecular packing of active layer components has a crucial role in the device performance of OPV devices. Especially for FREA based OPV systems, the longrange structural order induced by end group - stacking is considered as the critical factor for achieving high PCEs. Chapter 5 includes a deep spectroscopic insight into the exciton and charge transport processes in a series of FREA based OPV systems having different molecular packing and ordering. Here the molecular stacking manipulation in FREAs is achieved by changing the length of alkyl side-chains so that the FREA backbone is changed from a - stacking mode to a non-stacking mode. Transient absorption spectroscopic analysis of neat FREAs and blends reveals that exciton diffusion and intermolecular charge transfer processes do not necessarily rely on the molecular - stacking, while close atom contact can also enable these processes. This work provides new insights into the design of advanced materials for next generation organic photovoltaics considering diverse transport channels formed by close atom interactions. Chapter 6 discusses the advantages of ternary OPV strategy in BHJ world with a 13% efficient ternary device based on a highly efficient FREA, FOIC. The introduction of a mid-band gap small molecule donor TR into the binary blend PTB7- Th:FOIC improves the open circuit voltage (Voc), short circuit current (Jsc), fill factor (FF), and thereby the overall device performance. Transient absorption spectroscopy reveals ultrafast resonant energy transfer from TR to PTB7-Th domains which is consistent with their intermixed morphology. Additionally, the study also includes the rapid long-range energy transfer from PTB7-Th to FOIC phases tha

Photophysics of fused ring electron acceptors for photovoltaic applications

Organic photovoltaic cells (OPVs) have received significant interest over the last decade as they offer the potential of cheap renewable energy via direct photon to electron conversion of abundantly available Sun light. Compared to the inorganic equivalents, they offer lightweight, low-cost, and flexibility advantages. Conventional OPVs are typically based on blends of electron-donor materials and fullerene-based electron-acceptor materials that form bulk-heterojunctions (BHJs). But the attention has recently shifted to organic non-fullerene acceptors especially fused ring electron acceptors (FREAs) owing to their attractive properties including flexible energy levels, tunable band gap, crystallinity, and planarity. Thus the power conversion efficiency (PCE) of OPVs has recently attained a record of 16% by synthesizing FREAs with modified chemical structures.  Owing to the high crystallinity and packing orientation of acceptors, FREA based OPV systems are characterized by large and pure phases sized 20-50 nm. This is consistent with the observation that charge generation dynamics in these systems lacked the ultrafast component that characterizes most fullerene blends. To test the hypothesis that the optimal phase size can be large due to facile exciton diffusion in FREAs, a planar indacenodithiophene (IDT) based FREA, IDIC is selected as a model system to study the exciton dynamics. Chapter 3 includes the exciton diffusion measurements in IDIC films using transient absorption spectroscopy which resolves a substantially high, quasi-activationless diffusion coefficient that exceeds that of typical organic semiconductors. The study also includes a deep insight of the key factors behind the enhanced exciton diffusion in IDIC and is shown to arise from different molecular and packing factors which enhance the long-range resonant energy transfer.  Rapid exciton diffusion in IDIC films introduced the possibility of solution-processed bilayer devices. Chapter 4 comprises both device and photophysics of planar bilayer devices with a PCE of 11.1% which is readily accounted for the material and device design. By pairing a mid-band gap polymer donor with a range of FREAs, it is shown that the combination of high molecular packing densities and absorption coefficients, long exciton diffusion lengths, and efficient, resonant, long-range energy transfer between donor and acceptor layers enable efficient bilayer devices. By designing new materials with these characteristics, along with orthogonal solubility for layer-by-layer deposition of clean bilayers, it is suggested that the clear connection between material design and function in the bilayer structure will accelerate the development of more efficient organic photovoltaic devices.  The molecular packing of active layer components has a crucial role in the device performance of OPV devices. Especially for FREA based OPV systems, the longrange structural order induced by end group - stacking is considered as the critical factor for achieving high PCEs. Chapter 5 includes a deep spectroscopic insight into the exciton and charge transport processes in a series of FREA based OPV systems having different molecular packing and ordering. Here the molecular stacking manipulation in FREAs is achieved by changing the length of alkyl side-chains so that the FREA backbone is changed from a - stacking mode to a non-stacking mode. Transient absorption spectroscopic analysis of neat FREAs and blends reveals that exciton diffusion and intermolecular charge transfer processes do not necessarily rely on the molecular - stacking, while close atom contact can also enable these processes. This work provides new insights into the design of advanced materials for next generation organic photovoltaics considering diverse transport channels formed by close atom interactions.  Chapter 6 discusses the advantages of ternary OPV strategy in BHJ world with a 13% efficient ternary device based on a highly efficient FREA, FOIC. The introduction of a mid-band gap small molecule donor TR into the binary blend PTB7- Th:FOIC improves the open circuit voltage (Voc), short circuit current (Jsc), fill factor (FF), and thereby the overall device performance. Transient absorption spectroscopy reveals ultrafast resonant energy transfer from TR to PTB7-Th domains which is consistent with their intermixed morphology. Additionally, the study also includes the rapid long-range energy transfer from PTB7-Th to FOIC phases that</p

Fast photoresponse from hybrid monolayer MoS₂/organic photodetector

International audienceAs a direct‐bandgap transition semiconductor with high carrier mobility, monolayer (ML) transition metal dichalcogenides (TMDCs) have attracted significant attention as a promising class of material for photodetection. It is reported that these layers exhibit a persistent photoconductance (PPC) effect, which is assigned to long‐lasting hole capture by deep traps. Therefore, TMDCs‐based photodetectors show a high photoresponse but also a slow response. Herein, intensity‐modulated photocurrent spectroscopy (IMPS) with steady‐state background illumination is performed to investigate the photoresponse dynamics in a hybrid photodetector based on ML MoS 2 covered with an ultrathin layer of phthalocyanine (H 2 Pc) molecules. The results demonstrate that adding the H 2 Pc layer speeds up the photoresponse of the neat ML‐MoS 2 photodetector by almost two orders of magnitude without deteriorating its responsivity. The origin of these improvements is revealed by applying the Hornbeck–Haynes model to the photocarrier dynamics in the IMPS experiment. It is shown that the improved response speed of the hybrid device arises mostly from a faster detrapping of holes in the presence of the H 2 Pc layer, while the trap densities remain rather unchanged. Meanwhile, the additional absorption of photons in the H 2 Pc layer contributes to photocarrier generation, resulting in an enlarged responsivity of the hybrid device

Influence of the energy level alignment on charge transfer and recombination at the monolayer-MoS₂/organic hybrid interface

International audienceMonolayer (ML) transition-metal dichalcogenides (TMDCs) exhibit numerous unique optoelectronic features. This motivates recent efforts to combine TMDCs with organic semiconductors to form heterostructures with tailorable properties that feature the advantages of both materials. Here, we study the photoinduced charge transfer across hybrid interfaces of ML-MoS2 and a series of organic semiconductors─often used as hole transport materials─where we systematically tune the offsets of the frontier energy levels. Steady-state photoluminescence and ultrafast transient absorption spectroscopy reveal that a larger energy level offset causes a lower efficiency of photoinduced charge transfer but also a longer lifetime of the charge separated state. Both observations are explained in the framework of Marcus’ theory of electron transfer. In fact, our observations question direct electron–hole recombination across the hybrid interface as the main decay pathway for photogenerated carriers in the considered systems. Instead, back transfer of holes to ML-MoS2 is suggested as the key decay channel. Adding a 1 nm LiF interlayer causes a significant slowdown of interfacial carrier recombination while not suppressing free carrier formation. This strategy serves as a guideline for optimizing further hybrid systems toward high-performance ML-TMDC/organic-based optoelectronic devices

What is special about Y6; the working mechanism of neat Y6 organic solar cells

International audienceNon-fullerene acceptors (NFAs) have delivered advancement in bulk heterojunction organic solar cell efficiencies, with a significant milestone of 20% now in sight. However, these materials challenge the accepted wisdom of how organic solar cells work. In this work we present a neat Y6 device with an efficiency above 4.5%. We thoroughly investigate mechanisms of charge generation and recombination as well as transport in order to understand what is special about Y6. Our data suggest that Y6 generates bulk free charges, with ambipolar mobility, which can be extracted in the presence of transport layers

Unraveling the influence of non-fullerene acceptor molecular packing on photovoltaic performance of organic solar cells

In non-fullerene organic solar cells, the long-range structure ordering induced by end-group π–π stacking of fused-ring non-fullerene acceptors is considered as the critical factor in realizing efficient charge transport and high power conversion efficiency. Here, we demonstrate that side-chain engineering of non-fullerene acceptors could drive the fused-ring backbone assembly from a π–π stacking mode to an intermixed packing mode, and to a non-stacking mode to refine its solid-state properties. Different from the above-mentioned understanding, we find that close atom contacts in a non-stacking mode can form efficient charge transport pathway through close side atom interactions. The intermixed solid-state packing motif in active layers could enable organic solar cells with superior efficiency and reduced non-radiative recombination loss compared with devices based on molecules with the classic end-group π–π stacking mode. Our observations open a new avenue in material design that endows better photovoltaic performance

Photophysical pathways in efficient bilayer organic solar cells: The importance of interlayer energy transfer

The development of organic photovoltaic (OPV) cells has long been guided by the idea that excitons - bound electron-hole pairs created by light absorption - diffuse only 5-10 nm. True for many materials, this constraint led to an inherently complex device architecture - the bulk heterojunction - that has obscured our understanding of device physics, and handicapped rational material design. Here, we investigate the photophysics of a series of planar bilayer heterojunction devices incorporating fused-ring electron acceptors with power conversion efficiencies up to 11%. Using ultrafast optical spectroscopy, we demonstrate the importance of long-range layer-tolayer energy transfer in planar structures, isolating this effect by including an insulating layer between the donor and acceptor layers to eliminate charge transfer effects. We show that the slab geometry facilitates substantially longer-range energy transfer than between isolated molecules or small domains. Along with high molecular packing densities, high absorption coefficients, and long exciton diffusion lengths, we show that these effects amount to exciton harvesting length scales that match the light absorption lengths and thereby enable efficient bilayer devices. Our quantitative analysis of bilayer structures also accounts for large domain sizes in bulkheterojunction devices including fused-ring electron acceptors, and it quantifies the importance of strong resonant spectral overlap is for material selection and design for highly efficient OPVs