以昇陳

Nature Photonics, Published online: 03 August 2020; doi:10.1038/s41566-020-0667-0

An organic molecule, TpAT-tFFO, which is designed to support rapid reverse intersystem crossing allows the fabrication of efficient organic light-emitting diodes.

Three homologous small molecule donors with hydrogen, fluorine, and chlorine substitution afford organic solar cells with efficiencies over 10% in combination with a common acceptor. The chlorinated derivative exhibits a more crystalline nanomorphology with relatively pure domains and provides more than 12% efficiency.

Abstract

Compared to conjugated polymers, small‐molecule organic semiconductors present negligible batch‐to‐batch variations, but presently provide comparatively low power conversion efficiencies (PCEs) in small‐molecular organic solar cells (SM‐OSCs), mainly due to suboptimal nanomorphology. Achieving precise control of the nanomorphology remains challenging. Here, two new small‐molecular donors H13 and H14, created by fluorine and chlorine substitution of the original donor molecule H11, are presented that exhibit a similar or higher degree of crystallinity/aggregation and improved open‐circuit voltage with IDIC‐4F as acceptor. Due to kinetic and thermodynamic reasons, H13‐based blend films possess relatively unfavorable molecular packing and morphology. In contrast, annealed H14‐based blends exhibit favorable characteristics, i.e., the highest degree of aggregation with the smallest paracrystalline π–π distortions and a nanomorphology with relatively pure domains, all of which enable generating and collecting charges more efficiently. As a result, blends with H13 give a similar PCE (10.3%) as those made with H11 (10.4%), while annealed H14‐based SM‐OSCs have a significantly higher PCE (12.1%). Presently this represents the highest efficiency for SM‐OSCs using IDIC‐4F as acceptor. The results demonstrate that precise control of phase separation can be achieved by fine‐tuning the molecular structure and film formation conditions, improving PCE and providing guidance for morphology design.

Oxidation control of graphene quantum dots can tune the singlet–triplet energy splitting, which induces a dramatic afterglow transition from phosphorescence to thermally activated delayed fluorescence. Matrix‐assisted stabilization of triplet excited states provides ultralong lifetimes to such afterglow emissions. A new design approach for engineering singlet–triplet energy splitting through facile molecular manipulation will enable the realization of smart multimodal afterglow materials.

Abstract

Long‐lived afterglow emissions, such as room‐temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF), are beneficial in the fields of displays, bioimaging, and data security. However, it is challenging to realize a single material that simultaneously exhibits both RTP and TADF properties with their relative strengths varied in a controlled manner. Herein, a new design approach is reported to control singlet–triplet energy splitting (∆E _ST) in graphene quantum dots (GQD)/graphene oxide quantum dots (GOQDs) by varying the ratio of oxygenated carbon to sp² carbon (γ_OC). It is demonstrated that ∆E _ST decreases from 0.365 to 0.123 eV as γ_OC increases from 4.63% to 59.6%, which in turn induces a dramatic transition from RTP to TADF. Matrix‐assisted stabilization of triplet excited states provides ultralong lifetimes to both RTP and TADF. Embedded in boron oxynitride, the low oxidized (4.63%) GQD exhibits an RTP lifetime (τ^T _avg) of 783 ms, and the highly oxidized (59.6%) GOQD exhibits a TADF lifetime (τ^DF _avg) of 125 ms. Furthermore, the long‐lived RTP and TADF materials enable the first demonstration of anticounterfeiting and multilevel information security using GQD. These results will open up a new approach to the engineering of singlet–triplet splitting in GQD for controlled realization of smart multimodal afterglow materials.

The development of the bulk heterojunction, in terms of materials design, device engineering, and the underpinning physical understanding, has led to significant improvements in organic photovoltaics. Looking forward, the bulk heterojunction concept is likely to allow even greater solar cell efficiencies and interestingly, can be applied to other organic electronic applications, such as organic photodetectors and photocatalysts.

Abstract

Organic semiconductors require an energetic offset in order to photogenerate free charge carriers efficiently, owing to their inability to effectively screen charges. This is vitally important in order to achieve high power conversion efficiencies in organic solar cells. Early heterojunction‐based solar cells were limited to relatively modest efficiencies (<4%) owing to limitations such as poor exciton dissociation, limited photon harvesting, and high recombination losses. The development of the bulk heterojunction (BHJ) has significantly overcome these issues, resulting in dramatic improvements in organic photovoltaic performance, now exceeding 18% power conversion efficiencies. Here, the design and engineering strategies used to develop the optimal bulk heterojunction for solar‐cell, photodetector, and photocatalytic applications are discussed. Additionally, the thermodynamic driving forces in the creation and stability of the bulk heterojunction are presented, along with underlying photophysics in these blends. Finally, new opportunities to apply the knowledge accrued from BHJ solar cells to generate free charges for use in promising new applications are discussed.

Semiconductor nanocrystals doped with electronic impurities are proposed as triplet sensitizers in photon upconversion assisted by triplet–triplet annihilation (TTA). Upon photoexcitation, the nanocrystals’ photoholes are routed to a long‐living, impurity‐related state in resonance with the capping ligands’ triplet. This results in 100% efficiency in triplet sensitization and leads to the highest upconversion quantum yield ever achieved for nanocrystal‐based TTA upconverters.

Abstract

Low‐power photon upconversion (UC) based on sensitized triplet–triplet annihilation (sTTA) is considered as the most promising upward wavelength‐shifting technique to enhance the light‐harvesting capability of solar devices. Colloidal nanocrystals (NCs) with conjugated organic ligands have been recently proposed to extend the limited light‐harvesting capability of molecular absorbers. Key to their functioning is efficient energy transfer (ET) from the NC to the triplet state of the ligands that sensitize free annihilator moieties responsible for the upconverted luminescence. The ET efficiency is typically limited by parasitic processes, above all nonradiative hole‐transfer to the ligand highest occupied molecular orbital (HOMO). Here, a new exciton‐manipulation approach is demonstrated that enables loss‐free ET by electronically doping CdSe NCs with gold impurities that introduce a hole‐accepting intragap state above the HOMO energy of 9‐anthracene acid ligands. Upon photoexcitation, the NC photoholes are rapidly routed to the Au‐level, producing a long‐lived bound exciton in perfect resonance with the ligand triplet. This hinders hole‐transfer leading to ≈100% efficient ET that translates into an upconversion quantum yield as high as ≈12% (≈24% in the normalized definition), which is the highest performance for NC‐based upconverters based on sTTA to date and approaches the record efficiency of optimized organic systems.

Nature Photonics, Published online: 03 August 2020; doi:10.1038/s41566-020-0668-z

An organic molecule, 5Cz-TRZ, with multiple donor units supports fast reverse intersystem crossing, allowing fabrication of high-performance organic light-emitting diodes.

Nature Photonics, Published online: 10 August 2020; doi:10.1038/s41566-020-0673-2

Deactivation of deep-strong light–matter coupling is achieved by femtosecond switching of terahertz cavities. This disruption leads to pronounced high-frequency polarization oscillations evolving much faster than the oscillation cycle of light.

A high‐performance all‐polymer solar cell (PCE of 12.06%) is achieved based on a novel polymer acceptor with a voltage loss of 0.52 eV, which is one of the smallest values reported for all‐polymer solar cells to date.

Abstract

Although the field of all‐polymer solar cells (all‐PSCs) has seen rapid progress in device efficiencies during the past few years, there are limited choices of polymer acceptors that exhibit strong absorption in the near‐IR region and achieve high open‐circuit voltage (V _OC) at the same time. In this paper, an all‐PSC device is demonstrated with a 12.06% efficiency based on a new polymer acceptor (named PT‐IDTTIC) that exhibits strong absorption (maximum absorption coefficient: 2.41 × 10⁵ cm⁻¹) and a narrow optical bandgap (1.49 eV). Compared to previously reported polymer acceptors such as those based on the indacenodithiophene (IDT) core, the indacenodithienothiophene (IDTT) core has further extended fused ring, providing the polymer with extended absorption into the near‐IR region and also increases the electron mobility of the polymer. By blending PT‐IDTTIC with the donor polymer, PM6, a high‐efficiency all‐PSC is achieved with a small voltage loss of 0.52 V, without sacrificing J _SC and FF, which demonstrates the great potential of high‐performance all‐PSCs.

A high‐performance all‐polymer solar cell (PCE of 12.06%) is achieved based on a novel polymer acceptor with a voltage loss of 0.52 eV, which is one of the smallest values reported for all‐polymer solar cells to date.

Abstract

Although the field of all‐polymer solar cells (all‐PSCs) has seen rapid progress in device efficiencies during the past few years, there are limited choices of polymer acceptors that exhibit strong absorption in the near‐IR region and achieve high open‐circuit voltage (V _OC) at the same time. In this paper, an all‐PSC device is demonstrated with a 12.06% efficiency based on a new polymer acceptor (named PT‐IDTTIC) that exhibits strong absorption (maximum absorption coefficient: 2.41 × 10⁵ cm⁻¹) and a narrow optical bandgap (1.49 eV). Compared to previously reported polymer acceptors such as those based on the indacenodithiophene (IDT) core, the indacenodithienothiophene (IDTT) core has further extended fused ring, providing the polymer with extended absorption into the near‐IR region and also increases the electron mobility of the polymer. By blending PT‐IDTTIC with the donor polymer, PM6, a high‐efficiency all‐PSC is achieved with a small voltage loss of 0.52 V, without sacrificing J _SC and FF, which demonstrates the great potential of high‐performance all‐PSCs.

The extension of the conjugated antenna units relating transition from high order singlet excited states in heavy atom‐free chromophores greatly enhances the phosphorescence rate (k _p) without a large increase of vibration‐based radiationless transition rate (k _nr(RT)) with large triplet yield, which results in the room‐temperature phosphorescence (RTP) yield (Φ_p(RT)) of 50% as well as the RTP lifetime (τ_p(RT)) of 1.0 s.

Abstract

Persistent (lifetime > 100 ms) room‐temperature phosphorescence (p RTP) is important for state‐of‐the‐art security and bioimaging applications. An unclear relationship between chromophores and physical parameters relating to p RTP has prevented obtaining an RTP yield of over 50% and a lifetime over 1 s. Here highly efficient p RTP is reported under ambient conditions from heavy atom‐free chromophores. A heavy atom‐free aromatic core substituted with a long‐conjugated amino group considerably accelerates the phosphorescence rate independent of the intramolecular vibration‐based nonradiative rate from the lowest excited triplet state. One of the designed heavy atom‐free dopant chromophores presents an RTP yield of 50% with a lifetime of 1 s under ambient conditions. The afterglow brightness under strong excitation is at least 10⁴ times stronger than that of conventional long‐persistent luminescence emitters. Here it is shown that highly efficient p RTP materials allow for high‐resolution gated emission with a size of the diffraction limit using small‐scale and low‐cost photodetectors.

A series of copolymers via a random copolymerization approach are designed and synthesized. The well‐defined fibril interpenetrating morphology with appropriate phase separation in PT2‐based blends can efficiently suppress the unfavorable aggregation, resulting in excellent morphological stability and high efficiency. The work demonstrates the importance of optimization of fibril network morphology in realizing high‐efficiency and ambient‐stable polymer solar cells.

Abstract

Morphological stability is crucially important for the long‐term stability of polymer solar cells (PSCs). Many high‐efficiency PSCs suffer from metastable morphology, resulting in severe device degradation. Here, a series of copolymers is developed by manipulating the content of chlorinated benzodithiophene‐4,8‐dione (T1‐Cl) via a random copolymerization approach. It is found that all the copolymers can self‐assemble into a fibril nanostructure in films. By altering the T1‐Cl content, the polymer crystallinity and fibril width can be effectively controlled. When blended with several nonfullerene acceptors, such as TTPTT‐4F, O‐INIC3, EH‐INIC3, and Y6, the optimized fibril interpenetrating morphology can not only favor charge transport, but also inhibit the unfavorable molecular diffusion and aggregation in active layers, leading to excellent morphological stability. The work demonstrates the importance of optimization of fibril network morphology in realizing high‐efficiency and ambient‐stable PSCs, and also provides new insights into the effect of chemical structure on the fibril network morphology and photovoltaic performance of PSCs.

A highly efficient organic solar cell with a ternary architecture is successfully demonstrated by enhancing and balancing charge transport as well as matching integer charge transfer energy in a bulk heterojunction blend. As a result, a power conversion efficiency of 17.13% is obtained with the significantly improved fill factor of 0.813.

Abstract

Ternary architecture is one of the most effective strategies to boost the power conversion efficiency (PCE) of organic solar cells (OSCs). Here, an OSC with a ternary architecture featuring a highly crystalline molecular donor DRTB‐T‐C4 as a third component to the host binary system consisting of a polymer donor PM6 and a nonfullerene acceptor Y6 is reported. The third component is used to achieve enhanced and balanced charge transport, contributing to an improved fill factor (FF) of 0.813 and yielding an impressive PCE of 17.13%. The heterojunctions are designed using so‐called pinning energies to promote exciton separation and reduce recombination loss. In addition, the preferential location of DRTB‐T‐C4 at the interface between PM6 and Y6 plays an important role in optimizing the morphology of the active layer.

A stable croconium derivative, “CR‐TPE‐T”, is designed to exhibit the unique biradical property and strong π–π stacking in the solid state, which facilitate not only a broad absorption spectrum from 300 to 1600 nm for effective sunlight harvesting, but also highly efficient photothermal conversion by boosting nonradiative decay, enabling a high solar‐energy‐to‐vapor efficiency of 87.2% under one sun irradiation.

Abstract

With recent progress in photothermal materials, organic small molecules featured with flexibility, diverse structures, and tunable properties exhibit unique advantages but have been rarely applied in solar‐driven water evaporation owing to limited sunlight absorption resulting in low solar–thermal conversion. Herein, a stable croconium derivative, named CR‐TPE‐T, is designed to exhibit the unique biradical property and strong π–π stacking in the solid state, which facilitate not only a broad absorption spectrum from 300 to 1600 nm for effective sunlight harvesting, but also highly efficient photothermal conversion by boosting nonradiative decay. The photothermal efficiency is evaluated to be 72.7% under 808 nm laser irradiation. Based on this, an interfacial‐heating evaporation system based on CR‐TPE‐T is established successfully, using which a high solar‐energy‐to‐vapor efficiency of 87.2% and water evaporation rate of 1.272 kg m⁻² h⁻¹ under 1 sun irradiation are obtained, thus making an important step toward the application of organic‐small‐molecule photothermal materials in solar energy utilization.

An all‐round phototheranostic agent based on a single aggregation‐induced emission (AIE)‐active fluorophore allowing fluorescence imaging (FLI), photoacoustic imaging (PAI), photothermal imaging (PTI), photothermal therapy (PTT), and photodynamic therapy (PDT) is constructed by subtly regulating the balance between radiative and nonradiative excited‐state energy dissipations, which thus actualizes unprecedented performance on near‐infrared‐II (NIR‐II) FLI‐PAI‐PTI trimodal imaging‐guided PDT–PTT synergistic therapy.

Abstract

Aiming to achieve versatile phototheranostics with the integrated functionalities of multiple diagnostic imaging and synergistic therapy, the optimum use of dissipated energy through both radiative and nonradiative pathways is definitely appealing, yet a significantly challenging task. To the best of the knowledge, there have been no previous reports on a single molecular species effective at affording all phototheranostic modalities including fluorescence imaging (FLI), photoacoustic imaging (PAI), photothermal imaging (PTI), photodynamic therapy (PDT), and photothermal therapy (PTT). Herein, a simple and highly powerful one‐for‐all phototheranostics based on aggregation‐induced emission (AIE)‐active fluorophores is tactfully designed and constructed. Thanks to its strong electron donor–acceptor interaction and finely modulated intramolecular motion, the AIE fluorophore‐based nanoparticles simultaneously exhibit bright near‐infrared II (NIR‐II) fluorescence emission, efficient reactive oxygen species generation, and high photothermal conversion efficiency upon NIR irradiation, indicating the actualization of a balance between radiative and nonradiative energy dissipations. Furthermore, the unprecedented performance on NIR‐II FLI‐PAI‐PTI trimodal‐imaging‐guided PDT–PTT synergistic therapy is demonstrated by the precise tumor diagnosis and complete tumor elimination outcomes. This study thus brings a new insight into the development of superior versatile phototheranostics for practical cancer theranostics.

High‐performance photonic transistor memory devices are fabricated using conjugated rod–coil materials as a photoactive floating gate, in which the conjugated rods and side‐chain coils act as charge‐trapping and tunneling moieties, respectively. By inheriting their self‐assembled structure, both n‐type and p‐type memory devices exhibit a fast response, a current contrast over 10⁵, and an extremely low programing driving force of 0.1 V.

Abstract

A novel approach for using conjugated rod–coil materials as a floating gate in the fabrication of nonvolatile photonic transistor memory devices, consisting of n‐type Sol‐PDI and p‐type C10‐DNTT, is presented. Sol‐PDI and C10‐DNTT are used as dual functions of charge‐trapping (conjugated rod) and tunneling (insulating coil), while n‐type BPE‐PDI and p‐type DNTT are employed as the corresponding transporting layers. By using the same conjugated rod in the memory layer and transporting channel with a self‐assembled structure, both n‐type and p‐type memory devices exhibit a fast response, a high current contrast between “Photo‐On” and “Electrical‐Off” bistable states over 10⁵, and an extremely low programing driving force of 0.1 V. The fabricated photon‐driven memory devices exhibit a quick response to different wavelengths of light and a broadband light response that highlight their promising potential for light‐recorder and synaptic device applications.

Addressing the challenge of room‐temperature high‐sensitivity photodetection in the shortwave infrared (SWIR) region, a novel SWIR‐absorbing organic charge‐transfer complex on a graphene transistor device with the photogating effect at the tetrathiafulvalene–chloranil/graphene interface is reported. It exhibits a tunable, high‐speed, broadband vis–SWIR photoresponse and high specific detectivity (up to ≈10¹³ Jones) at a wavelength of 2 µm.

Abstract

Room‐temperature, high‐sensitivity, and broadband photodetection up to the shortwave infrared (SWIR) region is extremely significant for a wide variety of optoelectronic applications, including contamination identification, thermal imaging, night vision, agricultural inspection, and atmospheric remote sensing. Small‐bandgap semiconductor‐based SWIR photodetectors generally require deep cooling to suppress thermally generated charge carriers to achieve increased sensitivity. Meanwhile, the photogating effect can provide an alternative way to achieve superior photosensitivity without the need for cooling. The optical photogating effect originates from charge trapping of photoinduced carriers at defects or interfaces, resulting in an extremely high photogain (10⁶ or higher). Here, a highly sensitive SWIR hybrid photodetector, fabricated by integrating an organic charge transfer complex on a graphene transistor, is reported. The organic charge transfer complex (tetrathiafulvalene–chloranil) has an exceptional low‐energy intermolecular electronic transition down to 0.5 eV, with the aim of achieving efficient SWIR absorption for wavelengths greater than 2 µm. The photogating effect at the organic complex and graphene interface enables an extremely high photogain and a high detectivity of ≈10¹³ Jones, along with a response time of 8 ms, at room temperature for a wavelength of 2 µm.

Nonthermalized photocarrier energy is harnessed to achieve near‐infrared to visible light upconversion in a metal–insulator–semiconductor van der Waals heterostructure tunnel diode consisting of few‐layer graphene, hexagonal boron nitride, and monolayer tungsten disulfide. The photocarrier transport dynamics governed by Fowler–Nordheim tunneling are electrically tunable by two orders of magnitude using voltage bias applied to the device.

Abstract

Ultrafast interlayer charge transfer is one of the most distinct features of van der Waals (vdW) heterostructures. Its dynamics competes with carrier thermalization such that the energy of nonthermalized photocarriers may be harnessed by band engineering. In this study, nonthermalized photocarrier energy is harnessed to achieve near‐infrared (NIR) to visible light upconversion in a metal–insulator–semiconductor (MIS) vdW heterostructure tunnel diode consisting of few‐layer graphene (FLG), hexagonal boron nitride (hBN), and monolayer tungsten disulfide (WS₂). Photoexcitation of the electrically biased heterostructure with 1.58 eV NIR laser in the linear absorption regime generates emission from the ground exciton state of WS₂, which corresponds to upconversion by ≈370 meV. The upconversion is realized by electrically assisted interlayer transfer of nonthermalized photoexcited holes from FLG to WS₂, followed by formation and radiative recombination of excitons in WS₂. The photocarrier transfer rate can be described by Fowler–Nordheim tunneling mechanism and is electrically tunable by two orders of magnitude by tuning voltage bias applied to the device. This study highlights the prospects for realizing novel electro‐optic upconversion devices by exploiting electrically tunable nonthermalized photocarrier relaxation dynamics in vdW heterostructures.