Showing papers on "Organic semiconductor published in 2021"
TL;DR: In this paper, a pyrene-based conjugated polymer is synthesized via the typical Suzuki-Miyaura reactions, and then employed as a substrate to anchor CdS nanocrystals.
Abstract: Inspired by natural photosynthesis, constructing inorganic/organic heterojunctions is regarded as an effective strategy to design high-efficiency photocatalysts. Herein, a step (S)-scheme heterojunction photocatalyst is prepared by in situ growth of an inorganic semiconductor firmly on an organic semiconductor. A new pyrene-based conjugated polymer, pyrene-alt-triphenylamine (PT), is synthesized via the typical Suzuki-Miyaura reactions, and then employed as a substrate to anchor CdS nanocrystals. The optimized CdS/PT composite, coupling 2 wt% PT with CdS, exhibits a robust H2 evolution rate of 9.28 mmol h-1 g-1 with continuous release of H2 bubbles, as well as a high apparent quantum efficiency of 24.3%, which is ≈8 times that of pure CdS. The S-scheme charge transfer mechanism between PT and CdS, is systematically demonstrated by photoirradiated Kelvin probe measurement and in situ irradiated X-ray photoelectron spectroscopy analyses. This work provides a protocol for preparing specific S-scheme heterojunction photocatalysts on the basis of inorganic/organic coupling.
369 citations
TL;DR: Acarbazole isomer, typically present as an impurity in commercially produced carbazole batches, is shown to be responsible for the ultralong phosphorescence observed in these compounds and their derivatives.
Abstract: Commercial carbazole has been widely used to synthesize organic functional materials that have led to recent breakthroughs in ultralong organic phosphorescence1, thermally activated delayed fluorescence2,3, organic luminescent radicals4 and organic semiconductor lasers5. However, the impact of low-concentration isomeric impurities present within commercial batches on the properties of the synthesized molecules requires further analysis. Here, we have synthesized highly pure carbazole and observed that its fluorescence is blueshifted by 54 nm with respect to commercial samples and its room-temperature ultralong phosphorescence almost disappears6. We discover that such differences are due to the presence of a carbazole isomeric impurity in commercial carbazole sources, with concentrations <0.5 mol%. Ten representative carbazole derivatives synthesized from the highly pure carbazole failed to show the ultralong phosphorescence reported in the literature1,7–15. However, the phosphorescence was recovered by adding 0.1 mol% isomers, which act as charge traps. Investigating the role of the isomers may therefore provide alternative insights into the mechanisms behind ultralong organic phosphorescence1,6–18. A carbazole isomer, typically present as an impurity in commercially produced carbazole batches, is shown to be responsible for the ultralong phosphorescence observed in these compounds and their derivatives.
298 citations
TL;DR: In this paper, a review of the recent achievements of fabricating ultrafine fibers using an electrospinning process is summarized, along with the characterization of their physical properties, such as electrical conductivity, wettability, and mechanical and thermal properties, which are further improved by modification.
192 citations
TL;DR: In this paper, a new approach to tune the morphology of photoactive layer is developed by utilizing the synergistic effect of dithieno[3,2-b:2',3'-d]thiophene (DTT) and 1-chloronaphthalene (CN).
Abstract: Controlling the self-assembling of organic semiconductors to form well-developed nanoscale phase separation in the bulk-heterojunction active layer is critical yet challenging for building high-performance organic solar cells (OSCs). Particularly, the similar anisotropic conjugated structures between nonfullerene acceptors and p-type organic semiconductor donors raise more complexity on manipulating their aggregation toward appropriate phase separation. Herein, a new approach to tune the morphology of photoactive layer is developed by utilizing the synergistic effect of dithieno[3,2-b:2',3'-d]thiophene (DTT) and 1-chloronaphthalene (CN). The volatilizable solid additive DTT with high crystallinity can restrict the over self-assembling of nonfullerene acceptors during the film casting process, and then allowing the refining of phase separation and molecular packing with the simultaneous volatilization of DTT under thermal annealing. Consequently, the PTQ10:m-BTP-PhC6:PC71 BM-based ternary OSCs processed by the dual additives of CN and DTT record a notable power-conversion efficiency of 18.89%, with a remarkable FF of 80.6%.
165 citations
TL;DR: This Account elucidate how a combination of steric constraints and hydrogen bonding receptor sites can guide the self-assembly of PBI dyes into slip-stacked packing motifs with J-type exciton coupling and discusses the supramolecular polymerization of multiple hydrogen-bonding PBI strands in organic and aqueous media.
Abstract: The discovery of the self-assembly of cyanine dyes into J-aggregates had a major impact on the development of dye chemistry due to the emergence of new useful properties in the aggregated state. The unique optical features of these J-aggregates are narrowed, bathochromically shifted absorption bands with almost resonant fluorescence with an increased radiative rate that results from the coherently coupled molecular transition dipoles arranged in a slip-stacked fashion. Because of their desirable properties, J-aggregates gained popularity in the field of functional materials and enabled the efficient photosensitization of silver halide grains in color photography. However, despite a good theoretical understanding of structure-property relationships by the molecular exciton model, further examples of J-aggregates remained scarce for a long time as supramolecular designs to guide the formation of dye aggregates into the required slip-stacked arrangement were lacking.Drawing inspiration from the bacteriochlorophyll c self-organization found in the chlorosomal light-harvesting antennas of green sulfur bacteria, we envisioned the use of nature's supramolecular blueprint to develop J-aggregates of perylene bisimides (PBIs). This class of materials is applied in high-performance color pigments and as n-type organic semiconductors in transistors and solar cells. Combining outstanding photochemical and thermal stability, high tinctorial strength and excellent fluorescence, PBIs are therefore an ideal model system for the preparation of J-aggregates with a wide range of potential applications.In this Account, we elucidate how a combination of steric constraints and hydrogen bonding receptor sites can guide the self-assembly of PBI dyes into slip-stacked packing motifs with J-type exciton coupling. We will discuss the supramolecular polymerization of multiple hydrogen-bonded PBI strands in organic and aqueous media and how minor structural modifications in monomeric PBI molecules can be used to obtain near-infrared absorbing J-aggregates, organogels, or thermoresponsive hydrogels. Pushing the boundaries of self-assembly into the bulk, engineering of the substituents' steric requirements by a dendron-wedge approach afforded adjustable numbers of helical strands of PBI J-aggregates in the columnar liquid-crystalline state and the preparation of lamellar phases. To fully explore their potential, we have studied PBI J-aggregates in collaborative work with spectroscopists, physicists, and theoreticians. In this way, exciton migration over distances of up to 180 nm was shown, and insights into the influence of static disorder on the transport of excitation energy in PBI J-aggregates were derived. Furthermore, the application of PBI J-aggregates as functional materials was demonstrated in photonic microcavities, thin-film transistors, and organic solar cells.
107 citations
TL;DR: In this article, a general concept of catalysed n-doping of organic semiconductors using air-stable precursor-type molecular dopants is presented, where the incorporation of a transition metal (for example, Pt, Au, Pd) as vapour-deposited nanoparticles or solution-processable organometallic complexes, as assessed by experimental and theoretical evidence, enables greatly increased η in a much shorter doping time and high electrical conductivities.
Abstract: Chemical doping is a key process for investigating charge transport in organic semiconductors and improving certain (opto)electronic devices1–9. N(electron)-doping is fundamentally more challenging than p(hole)-doping and typically achieves a very low doping efficiency (η) of less than 10%1,10. An efficient molecular n-dopant should simultaneously exhibit a high reducing power and air stability for broad applicability1,5,6,9,11, which is very challenging. Here we show a general concept of catalysed n-doping of organic semiconductors using air-stable precursor-type molecular dopants. Incorporation of a transition metal (for example, Pt, Au, Pd) as vapour-deposited nanoparticles or solution-processable organometallic complexes (for example, Pd2(dba)3) catalyses the reaction, as assessed by experimental and theoretical evidence, enabling greatly increased η in a much shorter doping time and high electrical conductivities (above 100 S cm−1; ref. 12). This methodology has technological implications for realizing improved semiconductor devices and offers a broad exploration space of ternary systems comprising catalysts, molecular dopants and semiconductors, thus opening new opportunities in n-doping research and applications12, 13. Electron doping of organic semiconductors is typically inefficient, but here a precursor molecular dopant is used to deliver higher n-doping efficiency in a much shorter doping time.
101 citations
TL;DR: In this paper, a skeleton merging approach through distortion of a perylene diimide core with four fused heteroaromatics was introduced to form an ortho-π-extended double helicene.
Abstract: Despite great challenges, the development of new molecular structures with multiple and even conflicting characteristics are eagerly pursued for exploring advanced applications. To develop high-performance chiral organic semiconducting molecules, a distorted π-system is required for strong coupling with circularly polarized light (CPL), whereas planar π-stacking systems are necessary for high charge-carrier mobility. To address this dilemma, in this work, we introduce a skeleton merging approach through distortion of a perylene diimide (PDI) core with four fused heteroaromatics to form an ortho-π-extended PDI double-[7]heterohelicene. PDI double helicene inherits a high dissymmetry factor from the helicene skeleton, and the extended π-planar system concurrently maintains a high level of charge transport properties. In addition, ortho-π-extension of the PDI skeleton brings about near-infrared (NIR) light absorption and ambipolar charge transport abilities, endowing the corresponding organic phototransistors with high photoresponsivity of 450 and 120 mA W−1 in p- and n-type modes respectively, along with a high external quantum efficiency (89%) under NIR light irradiations. Remarkably, these multiple characteristics enable high-performance broadband CPL detections up to NIR spectral region with chiral organic semiconductors. In organic semiconducting molecules materials, distorted π-systems enable strong coupling with circular polarized light while planar π-stacking systems are necessary for high charge-carrier mobility. Here, the authors address this dilemma by introducing a skeleton merging approach through distortion of a perylene diimide core with four fused heteroaromatics to form a π-extended double helicene.
99 citations
TL;DR: In this paper, a fast and reproducible doping method that involves bubbling a spiro-OMeTAD:LiTFSI solution with CO2 under ultraviolet light is presented.
Abstract: In perovskite solar cells, doped organic semiconductors are often used as charge-extraction interlayers situated between the photoactive layer and the electrodes. The π-conjugated small molecule 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9-spirobifluorene (spiro-OMeTAD) is the most frequently used semiconductor in the hole-conducting layer1-6, and its electrical properties considerably affect the charge collection efficiencies of the solar cell7. To enhance the electrical conductivity of spiro-OMeTAD, lithium bis(trifluoromethane)sulfonimide (LiTFSI) is typically used in a doping process, which is conventionally initiated by exposing spiro-OMeTAD:LiTFSI blend films to air and light for several hours. This process, in which oxygen acts as the p-type dopant8-11, is time-intensive and largely depends on ambient conditions, and thus hinders the commercialization of perovskite solar cells. Here we report a fast and reproducible doping method that involves bubbling a spiro-OMeTAD:LiTFSI solution with CO2 under ultraviolet light. CO2 obtains electrons from photoexcited spiro-OMeTAD, rapidly promoting its p-type doping and resulting in the precipitation of carbonates. The CO2-treated interlayer exhibits approximately 100 times higher conductivity than a pristine film while realizing stable, high-efficiency perovskite solar cells without any post-treatments. We also show that this method can be used to dope π-conjugated polymers.
81 citations
76 citations
TL;DR: In this article, a new building block BNT and a relevant polymer PBNT-BDD featuring B-N covalent bond for application in organic solar cells (OSCs) were reported.
Abstract: High-efficiency organic solar cells (OSCs) largely rely on polymer donors. Herein, we report a new building block BNT and a relevant polymer PBNT-BDD featuring B-N covalent bond for application in OSCs. The BNT unit is synthesized in only 3 steps, leading to the facile synthesis of PBNT-BDD. When blended with a nonfullerene acceptor Y6-BO, PBNT-BDD afforded a power conversion efficiency (PCE) of 16.1 % in an OSC, comparable to the benzo[1,2-b:4,5-b']dithiophene (BDT)-based counterpart. The nonradiative recombination energy loss of 0.19 eV was afforded by PBNT-BDD. PBNT-BDD also exhibited weak crystallinity and appropriate miscibility with Y6-BO, benefitting of morphological stability. The singlet-triplet gap (ΔEST ) of PBNT-BDD is as low as 0.15 eV, which is much lower than those of common organic semiconductors (≥0.6 eV). As a result, the triplet state of PBNT-BDD is higher than the charge transfer (CT) state, which would suppress the recombination via triplet state effectively.
73 citations
TL;DR: In this paper, the authors present a thorough discussion of the limitations of n-type materials, particularly their ambient operational instability, and suggest synthetic methods to overcome these, including electron-withdrawing groups or heteroatoms, rigidification and planarisation of the polymer backbone and increasing the conjugation length.
Abstract: This review outlines the design strategies which aim to develop high performing n-type materials in the fields of organic thin film transistors (OTFT), organic electrochemical transistors (OECT) and organic thermoelectrics (OTE). Figures of merit for each application and the limitations in obtaining these are set out, and the challenges with achieving consistent and comparable measurements are addressed. We present a thorough discussion of the limitations of n-type materials, particularly their ambient operational instability, and suggest synthetic methods to overcome these. This instability originates from the oxidation of the negative polaron of the organic semiconductor (OSC) by water and oxygen, the potentials of which commonly fall within the electrochemical window of n-type OSCs, and consequently require a LUMO level deeper than ∼-4 eV for a material with ambient stability. Recent high performing n-type materials are detailed for each application and their design principles are discussed to explain how synthetic modifications can enhance performance. This can be achieved through a number of strategies, including utilising an electron deficient acceptor-acceptor backbone repeat unit motif, introducing electron-withdrawing groups or heteroatoms, rigidification and planarisation of the polymer backbone and through increasing the conjugation length. By studying the fundamental synthetic design principles which have been employed to date, this review highlights a path to the development of promising polymers for n-type OSC applications in the future.
TL;DR: In this paper, a new strategy to design and synthesize an electron acceptor analogue, BTPR, is developed, which is introduced into OSCs as a third component to enhance the molecular packing order of electron acceptors with and without blending a polymer donor.
Abstract: Typical organic semiconductor materials exhibit a high trap density of states, ranging from 1016 to 1018 cm-3 , which is one of the important factors in limiting the improvement of power conversion efficiencies (PCEs) of organic solar cells (OSCs). In order to reduce the trap density within OSCs, a new strategy to design and synthesize an electron acceptor analogue, BTPR, is developed, which is introduced into OSCs as a third component to enhance the molecular packing order of electron acceptor with and without blending a polymer donor. Finally, the as-cast ternary OSC devices employing BTPR show a notable PCE of 17.8%, with a low trap density (1015 cm-3 ) and a low energy loss (0.217 eV) caused by non-radiative recombination. This PCE is among the highest values for single-junction OSCs. The trap density of OSCs with the BTPR additives, as low as 1015 cm-3 , is comparable to and even lower than those of several typical high-performance inorganic/hybrid counterparts, like 1016 cm-3 for amorphous silicon, 1016 cm-3 for metal oxides, and 1014 to 1015 cm-3 for halide perovskite thin film, and makes it promising for OSCs to obtain a PCE of up to 20%.
TL;DR: In this article, a charge transfer complex (CTC) strategy was proposed to reduce the energy disorder in the OS-CTLs by doping an organic semiconductor, 4,4'-(4,8-bis(5-(trimethylsilyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(N,N-bis (4-methoxyphenyl)aniline) (BDT-Si), in
Abstract: Solution-processed organic semiconductor charge-transport layers (OS-CTLs) with high mobility, low trap density, and energy level alignment have dominated the important progress in p-i-n planar perovskite solar cells (pero-SCs). Unfortunately, their inevitable long chains result in weak molecular stacking, which is likely to generate high energy disorder and deteriorate the charge-transport ability of OS-CTLs. Here, a charge-transfer complex (CTC) strategy to reduce the energy disorder in the OS-CTLs by doping an organic semiconductor, 4,4'-(4,8-bis(5-(trimethylsilyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) (BDT-Si), in a commercial hole-transport layer (HTL), poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine (PTAA), is proposed. The formation of the CTC makes the PTAA conjugated backbone electron-deficient, resulting in a quinoidal and stiffer character, which is likely to planarize the PTAA backbone and enhance the ordering of the film in nanoscale. The resultant HTL exhibits a reduced energy disorder, which simultaneously promotes hole transport in the HTL, hole extraction at the interface, energy level alignment, and quasi-Fermi level splitting in the device. As a result, the p-i-n planar pero-SCs with optimized HTL exhibit the best power conversion efficiency of 21.87% with good operating stability. This finding demonstrates that the CTC strategy is an effective way to reduce the energy disorder in HTLs and to improve the performance of planar pero-SCs.
TL;DR: In this article, an overview of surface and interface engineering strategies for perovskite surfaces is provided to minimize deep-level defect states. But, the authors do not provide a detailed review of these strategies.
Abstract: Surfaces and heterojunction interfaces, where defects and energy levels dictate charge-carrier dynamics in optoelectronic devices, are critical for unlocking the full potential of perovskite semiconductors. In this progress report, chemical structures of perovskite surfaces are discussed and basic physical rules for the band alignment are summarized at various perovskite interfaces. Common perovskite surfaces are typically decorated by various compositional and structural defects such as residual surface reactants, discrete nanoclusters, reactions by products, vacancies, interstitials, antisites, etc. Some of these surface species induce deep-level defect states in the forbidden band forming very harmful charge-carrier traps and affect negatively the interface band alignments for achieving optimal device performance. Herein, an overview of research progresses on surface and interface engineering is provided to minimize deep-level defect states. The reviewed subjects include selection of interface and substrate buffer layers for growing better crystals, materials and processing methods for surface passivation, the surface catalyst for microstructure transformations, organic semiconductors for charge extraction or injection, heterojunctions with wide bandgap perovskites or nanocrystals for mitigating defects, and electrode interlayer for preventing interdiffusion and reactions. These surface and interface engineering strategies are shown to be critical in boosting device performance for both solar cells and light-emitting diodes.
TL;DR: In this paper, a hierarchical self-assembly approach of horizontal epitaxial growth is demonstrated for the fine synthesis of organic core/mono-shell microwires with multicolor emission (red-green, red-blue, and green-blue), whose components are dibenzo[g,p]chrysene (DgpC)-based charge transfer (CT) complexes.
Abstract: White-light-emissive organic micro/nanostructures hold exotic potential applications in full-color displays, on-chip wavelength-division multiplexing, and backlights of portable display devices, but are rarely realized in organic core/shell heterostructures. Herein, through regulating the noncovalent interactions between organic semiconductor molecules, a hierarchical self-assembly approach of horizontal epitaxial-growth is demonstrated for the fine synthesis of organic core/mono-shell microwires with multicolor emission (red-green, red-blue, and green-blue) and especially organic core/double-shell microwires with radial red-green-blue (RGB) emission, whose components are dibenzo[g,p]chrysene (DgpC)-based charge-transfer (CT) complexes. In fact, the desired lattice mismatching (≈2%) and the excellent structure compatibility of these CT complexes facilitate the epitaxial-growth process for the facile synthesis of organic core/shell microwires. With the RGB-emissive substructures, these core/double-shell organic microwires are microscale white-light sources (CIE [0.34, 0.36]). Besides, the white-emissive core/double-shell microwires demonstrate the fascinating full-spectrum light transportation from 400 to 700 nm. This work indeed opens up a novel avenue for the accurate construction of organic core/shell heterostructures, which provides an attractive platform for the organic integrated optoelectronics.
TL;DR: In this paper, a technical roadmap and progress update for backplane thin film transistors (TFTs) used in organic light emitting diodes flat panel displays and next-generation flexible displays is provided.
Abstract: This review aims to provide a technical roadmap and progress update for backplane thin film transistors (TFTs) used in organic light emitting diodes flat panel displays and next-generation flexible...
TL;DR: In this paper, a review of various organic π-stacked structures has been presented, and the opportunities and challenges for utilizing and improving particular materials are discussed, as well as new insights into the theory, materials, and devices in the field of organic semiconductors.
Abstract: Organic semiconductors can be designed and constructed in π-stacked structures instead of the conventional π-conjugated structures. Through-space interaction (TSI) occurs in π-stacked optoelectronic materials. Thus, unlike electronic coupling along the conjugated chain, the functional groups can stack closely to facilitate spatial electron communication. Using π-stacked motifs, chemists and materials scientists can find new ways for constructing materials with aggregation-induced emission (AIE), thermally activated delayed fluorescence (TADF), circularly polarized luminescence (CPL), and room-temperature phosphorescence (RTP), as well as enhanced molecular conductance. Organic optoelectronic devices based on π-stacked molecules have exhibited very promising performance, with some of them exceeding π-conjugated analogues. Recently, reports on various organic π-stacked structures have grown rapidly, prompting this review. Representative molecular scaffolds and newly developed π-stacked systems could stimulate more attention on through-space charge transfer the well-known through-bond charge transfer. Finally, the opportunities and challenges for utilizing and improving particular materials are discussed. The previous achievements and upcoming prospects may provide new insights into the theory, materials, and devices in the field of organic semiconductors.
TL;DR: This brief review will demonstrate that the INCI strategy is very efficient in the design of high performance photovoltaic materials.
08 Jan 2021
TL;DR: In this article, a detailed investigation of the molecular properties of organic semiconductors is presented, based on the controlable assembly of the organic semiconductor components, which has opened an avenue for an in-depth perception of their structure-property relationships.
Abstract: Controllable assembly of organic semiconductors has opened an avenue for an in-depth perception of their structure–property relationships; however, a detailed investigation of their molecular contr...
TL;DR: In this article, the synthesis of two organic semiconductors which are anthraquinone and benzothia/selenadiazole-based π -conjugated D-A1-D-A2 (D-donor, A-acceptor) type co-polymers was reported.
TL;DR: In this article, the relationship between aggregate structure and functional properties of representative classes of dye aggregates is analyzed for the most advanced OSCs and wavelength-selective OPDs, providing important insights into the rational design of thin-film optoelectronic materials.
Abstract: Dye-dye interactions affect the optical and electronic properties in organic semiconductor films of light harvesting and detecting optoelectronic applications. This review elaborates how to tailor these properties of organic semiconductors for organic solar cells (OSCs) and organic photodiodes (OPDs). While these devices rely on similar materials, the demands for their optical properties are rather different, the former requiring a broad absorption spectrum spanning from the UV over visible up to the near-infrared region and the latter an ultra-narrow absorption spectrum at a specific, targeted wavelength. In order to design organic semiconductors satisfying these demands, fundamental insights on the relationship of optical properties are provided depending on molecular packing arrangement and the resultant electronic coupling thereof. Based on recent advancements in the theoretical understanding of intermolecular interactions between slip-stacked dyes, distinguishing classical J-aggregates with predominant long-range Coulomb coupling from charge transfer (CT)-mediated or -coupled J-aggregates, whose red-shifts are primarily governed by short-range orbital interactions, is suggested. Within this framework, the relationship between aggregate structure and functional properties of representative classes of dye aggregates is analyzed for the most advanced OSCs and wavelength-selective OPDs, providing important insights into the rational design of thin-film optoelectronic materials.
TL;DR: A novel methodology, water-surface drag coating, is demonstrated to fabricate high-quality OSC thin films with greatly enhanced charge transport properties, opening up opportunities for high-performance organic flexible electronics.
Abstract: Electronic properties of organic semiconductor (OSC) thin films are largely determined by their morphologies and crystallinities. However, solution-processed conjugated small-molecule OSC thin films usually exhibit abundant grain boundaries and impure grain orientations because of complex fluid dynamics during solution coating. Here, a novel methodology, water-surface drag coating, is demonstrated to fabricate high-quality OSC thin films with greatly enhanced charge transport properties. This method utilizes the water surface to alter the evaporation dynamics of solution to enlarge the grain size, and a unique drag-coating process to achieve the unidirectional growth of organic crystals. Using 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (Dif-TES-ADT) as an example, thin films with millimeter-sized single-crystal domains and pure crystallographic orientations are achieved, revealing a significant enhancement (4.7 times) of carrier mobility. More importantly, the resulting film can be directly transferred onto any desired flexible substrates, and flexible transistors based on the Dif-TES-ADT thin films show a mobility as high as 16.1 cm2 V-1 s-1 , which represents the highest mobility value for the flexible transistors reported thus far. The method is general for the growth of various high-quality OSC thin films, thus opening up opportunities for high-performance organic flexible electronics.
TL;DR: Triplet-triplet annihilation (TTA) upconversion is a unique process of converting two non-emissive triplet excitons to one singlet exciton with higher energy as mentioned in this paper.
Abstract: Organic semiconductor materials have been widely used in various optoelectronic devices due to their rich optical and/or electrical properties, which are highly related to their excited states. Therefore, how to manage and utilize the excited states in organic semiconductors is essential for the realization of high-performance optoelectronic devices. Triplet-triplet annihilation (TTA) upconversion is a unique process of converting two non-emissive triplet excitons to one singlet exciton with higher energy. Efficient optical-to-electrical devices can be realized by harvesting sub-bandgap photons through TTA-based upconversion. In electrical-to-optical devices, triplets generated after the combination of electrons and holes also can be efficiently utilized via TTA, which resulted in a high internal conversion efficiency of 62.5%. Currently, many interesting explorations and significant advances have been demonstrated in these fields. In this review, a comprehensive summary of these intriguing advances on developing efficient TTA upconversion materials and their application in optoelectronic devices is systematically given along with some discussions. Finally, the key challenges and perspectives of TTA upconversion systems for further improvement for optoelectronic devices and other related research directions are provided. This review hopes to provide valuable guidelines for future related research and advancement in organic optoelectronics.
TL;DR: In this article, the authors used ultrafast optical microscopy and nonadiabatic molecular dynamics simulations to study well-ordered poly(3-hexylthiophene) nanofiber films prepared using living crystallization-driven selfassembly, and reveal a highly efficient energy transport regime: transient exciton delocalization, where energy exchange with vibrational modes allows excitons to temporarily re-access spatially extended states under equilibrium conditions.
Abstract: Efficient energy transport is desirable in organic semiconductor (OSC) devices. However, photogenerated excitons in OSC films mostly occupy highly localized states, limiting exciton diffusion coefficients to below ~10-2 cm2/s and diffusion lengths below ~50 nm. We use ultrafast optical microscopy and nonadiabatic molecular dynamics simulations to study well-ordered poly(3-hexylthiophene) nanofiber films prepared using living crystallization-driven self-assembly, and reveal a highly efficient energy transport regime: transient exciton delocalization, where energy exchange with vibrational modes allows excitons to temporarily re-access spatially extended states under equilibrium conditions. We show that this enables exciton diffusion constants up to 1.1 ± 0.1 cm2/s and diffusion lengths of 300 ± 50 nm. Our results reveal the dynamic interplay between localized and delocalized exciton configurations at equilibrium conditions, calling for a re-evaluation of exciton dynamics and suggesting design rules to engineer efficient energy transport in OSC device architectures not based on restrictive bulk heterojunctions.
TL;DR: In this paper, a small-molecule electron donor (H31) based on a thiophene-substituted benzodithiophene core unit with trialkylsilyl side chains is designed and synthesized.
Abstract: Electron transport layers (ETLs) placed between the electrodes and a photoactive layer can enhance the performance of organic solar cells but also impose limitations. Most ETLs are ultrathin films, and their deposition can disturb the morphology of the photoactive layers, complicate device fabrication, raise cost, and also affect device stability. To fully overcome such drawbacks, efficient organic solar cells that operate without an ETL are preferred. In this study, a new small-molecule electron donor (H31) based on a thiophene-substituted benzodithiophene core unit with trialkylsilyl side chains is designed and synthesized. Blending H31 with the electron acceptor Y6 gives solar cells with power conversion efficiencies exceeding 13% with and without 2,9-bis[3-(dimethyloxidoamino)propyl]anthra[2,1,9-def:6,5,10-d′e′f ′]diisoquinoline-1,3,8,10(2H,9H)-tetrone (PDINO) as the ETL. The ETL-free cells deliver a superior shelf life compared to devices with an ETL. Small-molecule donor–acceptor blends thus provide interesting perspectives for achieving efficient, reproducible, and stable device architectures without electrode interlayers.
TL;DR: In this paper, the authors investigated the sub-gap spectral line-shapes of organic semiconductors and their blends by temperature-dependent quantum efficiency measurements and found that absorption due to singlet excitons is universally dominated by thermal broadening at low photon energies and the associated Urbach energy equals the thermal energy.
Abstract: In crystalline semiconductors, absorption onset sharpness is characterized by temperature dependent Urbach energies. These energies quantify the static, structural disorder causing localized exponential-tail states, and dynamic disorder from electron-phonon scattering. Applicability of this exponential-tail model to disordered solids has been long debated. Nonetheless, exponential fittings are routinely applied to sub-gap absorption analysis of organic semiconductors. Herein, we elucidate the sub-gap spectral line-shapes of organic semiconductors and their blends by temperature-dependent quantum efficiency measurements. We find that sub-gap absorption due to singlet excitons is universally dominated by thermal broadening at low photon energies and the associated Urbach energy equals the thermal energy, regardless of static disorder. This is consistent with absorptions obtained from a convolution of Gaussian density of excitonic states weighted by Boltzmann-like thermally activated optical transitions. A simple model is presented that explains absorption line-shapes of disordered systems, and we also provide a strategy to determine the excitonic disorder energy. Our findings elaborate the meaning of the Urbach energy in molecular solids and relate the photo-physics to static disorder, crucial for optimizing organic solar cells for which we present a new radiative open-circuit voltage limit.
01 Jun 2021
TL;DR: In this paper, the photo-and spin-physics of unpaired electron systems present new avenues for research in light-emitting applications, outlining how the photo and spin physics of radical doublet emitters can be used in optoelectronic applications.
Abstract: Organic light-emitting diodes (OLEDs) with doublet-spin radical emitters have emerged as a new route to efficient display technologies. In contrast to standard organic semiconductors, radical materials have unpaired electrons. This feature results in the most well-known examples of organic radicals being where they are reactive species in chemical reactions. Stabilized radicals can be used in optoelectronic applications, which exploit their optical and spin properties, allowing up to 100% internal quantum efficiency (IQE) for electroluminescence. Highly efficient OLEDs have been demonstrated, which operate in the doublet-spin electronic state manifold with doublet emission. The radical-based devices present a departure from the singlet- and triplet-level considerations that impose efficiency limits in OLEDs for typical organic semiconductors (25% IQE). This Perspective focuses on radical doublet emitters for optoelectronics, outlining how the photo- and spin-physics of unpaired electron systems present new avenues for research in light-emitting applications.