The State-of-the-Art Solution-Processed Single Component Organic Photodetectors Achieved by Strong Quenching of Intermolecular Emissive State and High Quadrupole Moment in Non-Fullerene Acceptors.

A bulk-heterojunction (BHJ) blend is commonly used as the photoactive layer in organic photodetectors (OPDs) to utilize the donor (D)/acceptor (A) interfacial energetic offset for exciton dissociation. However, this strategy often complicates optimization procedures, raising serious concerns over device processability, reproducibility, and stability. Herein, highly efficient OPDs fabricated with single-component organic semiconductors are demonstrated via solution-processing. The non-fullerene acceptors (NFAs) with strong intrinsic D/A character are used as the photoactive layer, where the emissive intermolecular charge transfer excitonic (CTE) states are formed within <1 ps, and efficient photocurrent generation is achieved via strong quenching of these CTE states by reverse bias. Y6 and IT-4F-based OPDs show excellent OPD performances, low dark current density (≈10-9 A cm-2 ), high responsivity (≥0.15 A W-1 ), high specific detectivity (>1012 Jones), and fast photo-response time (<10 µs), comparable to the state-of-the-art BHJ OPDs. Together with strong CTE state quenching by electric field, these excellent OPD performances are also attributed to the high quadrupole moments of NFA molecules, which can lead to large interfacial energetic offset for efficient CTE dissociation. This work opens a new way to realize efficient OPDs using single-component systems via solution-processing and provides important molecular design rules.

Molecular orientation-dependent energetic shifts in solution-processed non-fullerene acceptors and their impact on organic photovoltaic performance.

The non-fullerene acceptors (NFAs) employed in state-of-art organic photovoltaics (OPVs) often exhibit strong quadrupole moments which can strongly impact on material energetics. Herein, we show that changing the orientation of Y6, a prototypical NFA, from face-on to more edge-on by using different processing solvents causes a significant energetic shift of up to 210 meV. The impact of this energetic shift on OPV performance is investigated in both bilayer and bulk-heterojunction (BHJ) devices with PM6 polymer donor. The device electronic bandgap and the rate of non-geminate recombination are found to depend on the Y6 orientation in both bilayer and BHJ devices, attributed to the quadrupole moment-induced band bending. Analogous energetic shifts are also observed in other common polymer/NFA blends, which correlates well with NFA quadrupole moments. This work demonstrates the key impact of NFA quadruple moments and molecular orientation on material energetics and thereby on the efficiency of high-performance OPVs.

A Universal Perovskite Nanocrystal Ink for High-Performance Optoelectronic Devices.

Semiconducting lead halide perovskite nanocrystals (PNCs) are regarded as promising candidates for next-generation optoelectronic devices due to their solution processability and outstanding optoelectronic properties. While the field of light-emitting diodes (LEDs) and photovoltaics (PVs), two prime examples of optoelectronic devices, has recently seen a multitude of efforts toward high-performance PNC-based devices, realizing both devices with high efficiencies and stabilities through a single PNC processing strategy has remained a challenge.  In this work, diphenylpropylammonium (DPAI) surface ligands, found through a judicious ab-initio-based ligand search, are shown to provide a solution to this problem. The universal PNC ink with DPAI ligands presented here, prepared through a solution-phase ligand-exchange process, simultaneously allows single-step processed LED and PV devices with peak electroluminescence external quantum efficiency of 17.00% and power conversion efficiency of 14.92% (stabilized output 14.00%), respectively. It is revealed that a careful design of the aromatic rings such as in DPAI is the decisive factor in bestowing such high performances, ease of solution processing, and improved phase stability up to 120 days. This work illustrates the power of ligand design in producing PNC ink formulations for high-throughput production of optoelectronic devices; it also paves a path for "dual-mode" devices with both PV and LED functionalities.

Effects on Photovoltaic Characteristics by Organic Bilayer- and Bulk-Heterojunctions: Energy Losses, Carrier Recombination and Generation.

We investigate the photovoltaic characteristics of organic solar cells (OSCs) for two distinctly different nanostructures, by comparing the charge carrier dynamics for bilayer- and bulk-heterojunction OSCs. Most interestingly, both architectures exhibit fairly similar power conversion efficiencies (PCEs), reflecting a comparable critical domain size for charge generation and charge recombination. Although this is, at first hand, surprising, a detailed analysis points out the similarity between these two concepts. A bulk-heterojunction architecture arranges the charge generating domains in a 3D ensemble across the whole bulk, while bilayer architectures arrange the specific domains on top of each other, rather than sharp bilayers. Specifically, for the polymer PBDB-T-2F, we find that the enhanced charge generation in a bulk composite is partially compensated by reduced recombination in the bilayer architecture, when nonfullerene acceptors (NFAs) are used instead of a fullerene acceptor. Overall, we demonstrate that bilayer-heterojunction OSCs with NFAs can reach competitive PCEs compared to the corresponding bulk-heterojunction OSCs because of reduced nonradiative open-circuit voltage losses, and suppressed trap-assisted recombination, as a result of a vertically separated donor-to-acceptor nanostructure. In contrast, the bilayer-heterojunction OSCs with the fullerene acceptor exhibited poor photovoltaic characteristics compared to the corresponding bulk devices because of highly aggregated acceptor molecules on top of the polymer donor. Although free carrier generation is reduced in a in a bilayer-heterojunction, because of reduced donor/acceptor interfaces and a limited exciton diffusion length, more favorable transport pathways for unipolar charge collection can partially compensate the aforementioned disadvantages. We propose that the unique properties of NFAs may open a technical venue for the bilayer-heterojunction as a great and easy alternative to the bulk heterojunction.

Recent progress in indoor organic photovoltaics.

Among various potential applications of organic photovoltaics (OPVs), indoor power generation has great potential because of several advantages over outdoor light harvesting under 1 sun conditions. Commonly used indoor light sources have narrower emission spectra with lower intensity (by 3 orders of magnitude) as compared to the solar spectrum. Highly tunable optical absorption, large absorption coefficients, and small leakage currents under dim lighting conditions make OPVs promising candidates for indoor applications. For optimizing indoor photovoltaic materials and devices, several key issues (different from those under 1 sun conditions), such as developing new indoor photovoltaic materials and devices with suitable absorption spectra, large open-circuit voltages with low energy loss, minimized trap-mediated charge recombination and leakage currents, and device stability under indoor conditions, should be considered carefully. In this review, the recent progress in optimization of indoor photovoltaic materials and devices, and the key strategies to optimize the indoor photovoltaic characteristics will be summarized and discussed.

Morphology-Dependent Hole Transfer under Negligible HOMO Difference in Non-Fullerene Acceptor-Based Ternary Polymer Solar Cells.

In the field of organic solar cells, it has been generally accepted until recently that a difference in band energies of at least 0.3 eV between the highest occupied molecular orbital (HOMO) level of the donor and the HOMO of the acceptor is required to provide adequate driving force for efficient photoinduced hole transfer due to the large binding energy of excitons in organic materials. In this work, we investigate polymeric donor:non-fullerene acceptor junctions in binary and ternary blend polymer solar cells, which exhibit efficient photoinduced hole transfer despite negligible HOMO offset and demonstrate that hole transfer in this system is dependent on morphology. The morphology of the organic blend was gradually tuned by controlling the amount of ITIC and PC70BM. High external quantum efficiency was achieved at long wavelengths, despite ITIC-to-PC70BM ratio of 1:9, which indicates efficient photoinduced hole transfer from ITIC to the donor despite an undesirable HOMO energy offset. Transient absorption spectra further confirm that hole transfer from ITIC to the donor becomes more efficient upon optimizing the morphology of the ternary blend compared to that of donor:ITIC binary blend.

Alkoxybenzothiadiazole-Based Fullerene and Nonfullerene Polymer Solar Cells with High Shunt Resistance for Indoor Photovoltaic Applications.

We synthesized three semicrystalline polymers (PTTBTBO, PDTBTBO, and P2FDTBTBO) by modulating the intra- and intermolecular noncovalent Coulombic interactions and investigated their photovoltaic characteristics under various light intensities. Low series (Rs) and high shunt (Rsh) resistances are essential prerequisites for good device properties under standard illumination (100 mW cm-2). Considering these factors, among three polymers, PDTBTBO polymer solar cells (PSCs) exhibited the most desirable characteristics, with peak power conversion efficiencies (PCE) of 7.52 and 9.60% by being blended with PC71BM under standard and dim light (2.5 mW cm-2), respectively. P2FDTBTBO PSCs exhibited a low PCE of 3.69% under standard light due to significant charge recombination with high Rs (9.42 Ω cm2). However, the PCE was remarkably improved by 2.3 times (8.33% PCE) under dim light, showing negligible decrease in open-circuit voltage and remarkable increase in fill factor, which is due to an exceptionally high Rsh of over 1000 kΩ cm2. Rs is less significant under dim light because the generated current is too small to cause noticeable Rs-induced voltage losses. Instead, high Rsh becomes more important to avoid leakage currents. This work provides important tips to further optimize PSCs for indoor applications with low-power electronic devices such as Internet of things sensors.

Non-halogenated diphenyl-chalcogenide solvent processing additives for high-performance polymer bulk-heterojunction solar cells.

The ability to control the morphologies of active layers is a critical factor in the successful development of polymer solar cells (PSCs), and solvent processing additives offer a simple and effective way to accomplish this. In particular, diphenyl ether (DPE) is one of the most effective solvent additives but analogous additives based on this structure have not yet been extensively investigated. In this work, we have fabricated PSCs and investigated photovoltaic device characteristics using the series of non-halogenated, diphenyl-chalcogen solvent additives; DPE, diphenyl sulfide (DPS) and diphenyl selenide (DPSe). DPS devices showed optimal power conversion efficiencies (PCEs) of up to 9.08%, and DPE devices also showed similarly high PCEs of up to 8.85%. In contrast, DPSe devices showed relatively low PCEs (5.45% at best) which we attribute to significant surface recombination and high series resistance, which led to limited open-circuit voltage (V OC). In the case of DPS, fast, field-independent photocurrent saturation with negligible bimolecular recombination led to efficient charge separation and collection, which resulted in the highest PCEs. Additionally, using 1,2,4-trimethylbenzene and DPS as an entirely non-halogenated solvent/additive system, we successfully demonstrated device fabrication with comparably high PCEs of up to 8.4%. This work elucidates the effects of diphenyl-based solvent additives in PSCs and suggests a great potential of DPS as an effective non-halogenated solvent additive.

ZnO decorated germanium nanoparticles as anode materials in Li-ion batteries.

Germanium exhibits high charge capacity and high lithium diffusivity, both are the key requirements for electrode materials in high performance lithium ion batteries (LIBs). However, high volume expansion and segregation from the electrode during charge-discharge cycling have limited use of germanium in LIBs. Here, we demonstrate that ZnO decorated Ge nanoparticles (Ge@ZnO NPs) can overcome these limitations of Ge as an LIB anode material. We produced Ge NPs at high rates by laser pyrolysis of GeH4, then coated them with solution phase synthesized ZnO NPs. Half-cell tests revealed dramatically enhanced cycling stability and higher rate capability of Ge@ZnO NPs compared to Ge NPs. Enhancements arise from the core-shell structure of Ge@ZnO NPs as well as production of metallic Zn from the ZnO layer. These findings not only demonstrate a new surface treatment for Ge NPs, but also provide a new opportunity for development of high-rate LIBs.

Alkyl Side-Chain Engineering in Wide-Bandgap Copolymers Leading to Power Conversion Efficiencies over 10.

A series of wide-bandgap (WBG) copolymers with different alkyl side chains are synthesized. Among them, copolymer PBT1-EH with moderatly bulky side chains on the acceptor unit shows the best photovoltaic performance with power conversion efficiency over 10%. The results suggest that the alkyl side-chain engineering is an effective strategy to further tuning the optoelectronic properties of WBG copolymers.