以昇陳

A new dopant‐free hole transport material DTP‐C6Th is developed for efficient planar n‐i‐p perovskite solar cells. The champion power conversion efficiency (PCE) reaches 21.04% after careful device engineering with poly(methyl methacrylate) passivation and composition tuning of perovskite. The DTP‐C6Th‐based devices without encapsulation show no PCE drop in the glovebox and retain over 85% of the initial PCE in air after storage for 60 days.

Abstract

Dopant‐free hole transport materials (HTMs) are essential for commercialization of perovskite solar cells (PSCs). However, power conversion efficiencies (PCEs) of the state‐of‐the‐art PSCs with small molecule dopant‐free HTMs are below 20%. Herein, a simple dithieno[3,2‐b:2′,3′‐d]pyrrol‐cored small molecule, DTP‐C6Th, is reported as a promising dopant‐free HTM. Compared with commonly used spiro‐OMeTAD, DTP‐C6Th exhibits a similar energy level, a better hole mobility of 4.18 × 10⁻⁴ cm² V⁻¹ s⁻¹, and more efficient hole extraction, enabling efficient and stable PSCs with a dopant‐free HTM. With the addition of an ultrathin poly(methyl methacrylate) passivation layer and properly tuning the composition of the perovskite absorber layer, a champion PCE of 21.04% is achieved, which is the highest value for small molecule dopant‐free HTM based PSCs to date. Additionally, PSCs using the DTP‐C6Th HTM exhibit significantly improved long‐term stability compared with the conventional cells with the metal additive doped spiro‐OMeTAD HTM. Therefore, this work provides a new candidate and effective device engineering strategy for achieving high PCEs with dopant‐free HTMs.

Spiro‐OMeTAD(TFSI)₂ is successfully employed in the fabrication of highly efficient n–i–p perovskite solar cells as a p‐dopant in the absence of lithium bis(trifluoromethane)sulfonimide (LiTFSI) and air exposure. With this approach, the proportion of [spiro‐OMeTAD]⁺ is precisely controlled, and the spiro‐OMeTAD(TFSI)₂‐doped devices show a remarkably improved long‐term stability and well‐retained hole‐transporting material (HTM) morphology after aging for 300 h.

Abstract

To date, the most efficient perovskite solar cells (PSCs) employ an n–i–p device architecture that uses a 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenyl‐amine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) hole‐transporting material (HTM), which achieves optimum conductivity with the addition of lithium bis(trifluoromethane)sulfonimide (LiTFSI) and air exposure. However, this additive along with its oxidation process leads to poor reproducibility and is detrimental to stability. Herein, a dicationic salt spiro‐OMeTAD(TFSI)₂, is employed as an effective p‐dopant to achieve power conversion efficiencies of 19.3% and 18.3% (apertures of 0.16 and 1.00 cm²) with excellent reproducibility in the absence of LiTFSI and air exposure. As far as it is known, these are the highest‐performing n–i–p PSCs without LiTFSI or air exposure. Comprehensive analysis demonstrates that precise control of the proportion of [spiro‐OMeTAD]⁺ directly provides high conductivity in HTM films with low series resistance, fast hole extraction, and lower interfacial charge recombination. Moreover, the spiro‐OMeTAD(TFSI)₂‐doped devices show improved stability, benefitting from well‐retained HTM morphology without forming aggregates or voids when tested under an ambient atmosphere. A facile approach is presented to fabricate highly efficient PSCs by replacing LiTFSI with spiro‐OMeTAD(TFSI)₂. Furthermore, this study provides an insight into the relationship between device performance and the HTM doping level.

Nature Photonics, Published online: 15 July 2019; doi:10.1038/s41566-019-0476-5

A blue emitter based on thermally activated delayed fluorescence is narrowband and efficient.

Two novel donor–acceptor‐type hole‐transporting materials are developed and characterized. Due to the good energy level alignment, appropriate hole‐transporting ability, and most importantly, the excellent film morphology, the MPA‐BTTI‐based dopant‐free inverted perovskite solar cell exhibits a remarkable power conversion efficiency of 21.17% with negligible hysteresis and long‐time operational stability.

Abstract

Hole‐transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long‐term stability, high‐performance dopant‐free small‐molecule HTMs (SM‐HTMs) are greatly desired. However, such dopant‐free SM‐HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor–acceptor‐type SM‐HTMs (MPA‐BTI and MPA‐BTTI) are devised, which synergistically integrate several design principles for high‐performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant‐free MPA‐BTTI‐based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long‐term stability under illumination, which breaks the long‐time standing bottleneck in the development of dopant‐free SM‐HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well‐aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA‐BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high‐performance dopant‐free SM‐HTMs in PVSCs.

Ternary polymer solar cells are successfully developed by combining a fullerene derivative and a nonfullerene material as acceptors. The introduction of PC₆₁BM into the PBDB‐TF:Y6 blend effectively improves the charge transport properties and reduces the nonradiative energy loss. Ultimately, the main photovoltaic parameters are simultaneously enhanced in the ternary devices, leading to an outstanding efficiency of 16.5% (certificated as 16.2%).

Abstract

Recent advances in the material design and synthesis of nonfullerene acceptors (NFAs) have revealed a new landscape for polymer solar cells (PSCs) and have boosted the power conversion efficiencies (PCEs) to over 15%. Further improvements of the photovoltaic performance are a significant challenge in NFA‐PSCs based on binary donor:acceptor blends. In this study, ternary PSCs are fabricated by incorporating a fullerene derivative, PC₆₁BM, into a combination of a polymer donor (PBDB‐TF) and a fused‐ring NFA (Y6) and a very high PCE of 16.5% (certified as 16.2%) is recorded. Detailed studies suggest that the loading of PC₆₁BM into the PBDB‐TF:Y6 blend can not only enhance the electron mobility but also can increase the electroluminescence quantum efficiency, leading to balanced charge transport and reduced nonradiative energy losses simultaneously. This work suggests that utilizing the complementary advantages of fullerene and NFAs is a promising way to finely tune the detailed photovoltaic parameters and further improve the PCEs of PSCs.

The side chain length of polymer donors can lead to miscibility differences. Shortening the side chains of polymer donors improves the device performance of fullerene‐based solar cells, but deteriorates the performance of small molecular and polymeric nonfullerene solar cells. Morphology investigations unveil that the miscibility between donor and acceptor in blend films depends on the side chain length of polymer donors.

Abstract

The development of nonfullerene acceptors has brought polymer solar cells into a new era. Maximizing the performance of nonfullerene solar cells needs appropriate polymer donors that match with the acceptors in both electrical and morphological properties. So far, the design rationales for polymer donors are mainly borrowed from fullerene‐based solar cells, which are not necessarily applicable to nonfullerene solar cells. In this work, the influence of side chain length of polymer donors based on a set of random terpolymers PTAZ‐TPD10‐Cn on the device performance of polymer solar cells is investigated with three different acceptor materials, i.e., a fullerene acceptor [70]PCBM, a polymer acceptor N2200, and a fused‐ring molecular acceptor ITIC. Shortening the side chains of polymer donors improves the device performance of [70]PCBM‐based devices, but deteriorates the N2200‐ and ITIC‐based devices. Morphology studies unveil that the miscibility between donor and acceptor in blend films depends on the side chain length of polymer donors. Upon shortening the side chains of the polymer donors, the miscibility between the donor and acceptor increases for the [70]PCBM‐based blends, but decreases for the N2200‐ and ITIC‐based blends. These findings provide new guidelines for the development of polymer donors to match with emerging nonfullerene acceptors.

Nature Photonics, Published online: 08 July 2019; doi:10.1038/s41566-019-0488-1

Long-lived, efficient organic light-emitting diodes based on a simple design of a single layer of an active light-emitting medium sandwiched between two contacts and no additional charge injection and transport layers are reported.

Interfacial hot carrier extraction in MAPbI₃ perovskite films is explored by femtosecond transient absorption spectroscopy. Compared to hot electrons, the extraction of hot holes is more efficient at the interface of MAPbI₃.

Abstract

Charge‐carriers photoexcited above a semiconductor's bandgap rapidly thermalize to the band‐edge. The cooling of these difficult to collect “hot” carriers caps the available photon energy that solar cells–including efficient perovskite solar cells–may utilize. Here, the dynamics and efficiency of hot carrier extraction from MAPbI₃ (MA = methylammonium) perovskite by spiro‐OMeTAD (a hole‐transporting layer) and TiO₂ (an electron‐transporting layer) are investigated and explained using both ultrafast electronic spectroscopy and theoretical modeling. Time‐resolved spectroscopy reveals a quasi‐equilibrium distribution of hot carriers forming upon excess‐energy excitation of the perovskite–a distribution largely unaffected by the presence of TiO₂. In contrast, the quasi‐equilibrium distribution of hot carriers is virtually nonexistent when spiro‐OMeTAD is present, which is indicative of efficient hot hole extraction at the interface of MAPbI₃. Density functional theory calculations predict that deep energy‐levels of MAPbI₃ exhibit electronically delocalized character, with significant overlap with the localized valence band charge of the spiro‐OMeTAD molecules lying on the surface of MAPbI₃. Consequently, hot holes are easily extracted from the deep energy‐levels of MAPbI₃ by spiro‐OMeTAD. These findings uncover the origins of efficient hot hole extraction in perovskites and offer a practical blueprint for optimizing solar cell interlayers to enable hot carrier utilization.

A nonvolatile n‐type molecular dopant (12a,18a)‐5,6,12,12a,13, 18,18a,19‐octahydro‐5,6‐dimethyl‐13,18‐ [1′,2′]‐benzenobisbenzimidazo [1,2‐b:2′,1′‐d]benzo[i][2.5]benzodiazocine potassium triflate adduct is introduced and its ability to improve the operating characteristics of high electron mobility organic transistors based on a polymer and a small molecule is demonstrated. The doping process is shown to reduce the contact resistance and activation energy while simultaneously increasing the electron mobility in both transistors.

Abstract

Molecular doping is a powerful yet challenging technique for enhancing charge transport in organic semiconductors (OSCs). While there is a wealth of research on p‐type dopants, work on their n‐type counterparts is comparatively limited. Here, reported is the previously unexplored n‐dopant (12a,18a)‐5,6,12,12a,13,18,18a,19‐octahydro‐5,6‐dimethyl‐ 13,18[1′,2′]‐benzenobisbenzimidazo [1,2‐b:2′,1′‐d]benzo[i][2.5]benzodiazo‐cine potassium triflate adduct (DMBI‐BDZC) and its application in organic thin‐film transistors (OTFTs). Two different high electron mobility OSCs, namely, the polymer poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐ bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2′‐bithiophene)] and a small‐molecule naphthalene diimides fused with 2‐(1,3‐dithiol‐2‐ylidene)malononitrile groups (NDI‐DTYM2) are used to study the effectiveness of DMBI‐BDZC as a n‐dopant. N‐doping of both semiconductors results in OTFTs with improved electron mobility (up to 1.1 cm² V⁻¹ s⁻¹), reduced threshold voltage and lower contact resistance. The impact of DMBI‐BDZC incorporation is particularly evident in the temperature dependence of the electron transport, where a significant reduction in the activation energy due to trap deactivation is observed. Electron paramagnetic resonance measurements support the n‐doping activity of DMBI‐BDZC in both semiconductors. This finding is corroborated by density functional theory calculations, which highlights ground‐state electron transfer as the main doping mechanism. The work highlights DMBI‐BDZC as a promising n‐type molecular dopant for OSCs and its application in OTFTs, solar cells, photodetectors, and thermoelectrics.

High‐performance ternary‐blend solar cells are fabricated by incorporating two nonfullerene acceptors. The enhanced power conversion efficiency mainly benefits from the broadened light harvesting and the optimized morphology. This work demonstrates that elaborately selecting a suitable third component with complementary basic properties is critical for the development of high‐performance ternary solar cells.

Abstract

Ternary polymer solar cells (PSCs) are one of the most promising device architectures that maintains the simplicity of single‐junction devices and provides an important platform to better tailor the multiple performance parameters of PSCs. Herein, a ternary PSC system is reported employing a wide bandgap polymeric donor (PBTA‐PS) and two small molecular nonfullerene acceptors (labeled as LA1 and 6TIC). LA1 and 6TIC keep not only well‐matched absorption profiles but also the rational crystallization properties. As a result, the optimal ternary PSC delivers a state of the art power conversion efficiency (PCE) of 14.24%, over 40% higher than the two binary devices, resulting from the prominently increased short‐circuit current density (J _sc) of 22.33 mA cm⁻², moderate open‐circuit voltage (V _oc) of 0.84 V, and a superior fill factor approaching 76%. Notably, the outstanding PCE of the ternary PSC ranks one of the best among the reported ternary solar cells. The greatly improved performance of ternary PSCs mainly derives from combining the complementary properties such as absorption and crystallinity. This work highlights the great importance of the rational design of matched acceptors toward highly efficient ternary PSCs.

Diketopyrrolopyrrole (DPP)‐based polymers have gained significant research interest in the organic electronics community. In this work, a combination of a DPP polymer derivative, PBDTT‐DPP, is used, blending with IEICO‐4F, a state‐of‐the‐art small‐molecule acceptor, yielding a champion power conversion efficiency of 9.66%, among the best performance of DPP‐based solar cells.

Abstract

The high crystallinity and ability to harvest near‐infrared photons make diketopyrrolopyrrole (DPP)‐based polymers one of the most promising donors for high performing organic solar cells (OSCs). However, DPP‐based OSC devices still suffer from the trade‐off between energetic loss (E _loss) and maximum external quantum efficiency (EQE_max), which significantly hinders their potential. Thus far, the replacement of fullerenes with small molecule acceptors did not wisdom the performance development of DPP‐donor‐based solar cells due to severe charge recombination issues. In this work, efficient DPP‐based solar cells are reported using low bandgap fused ring electron acceptor, IEICO‐4F. PBDTT‐DPP:IEICO‐4F OSC devices deliver a champion power conversion efficiency of 9.66% with successful interface engineering along with low E _loss of 0.57 eV and a high EQE_max (>70%).

Dimeric single‐component charge‐transfer complexes (SCCTCs) by self‐complexation of a donor–π–acceptor molecule (PIPAQ) are revealed and fully investigated, wherein the strong intermolecular charge transfer leads to unprecedented deep‐red/near‐infrared emission. This SCCTCs can be formed in thin films and applied in electroluminescence devices to realize high efficiencies via a thermally activated delayed fluorescence channel.

Abstract

Formation of a single‐component charge‐transfer complex (SCCTC) is unveiled in solid state of an intermolecular charge‐transfer molecule 2‐(4‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)phenyl)anthracene‐9,10‐dione (PIPAQ). Intermolecular donor–acceptor interactions between two PIPAQ molecules is the primary driving force for self‐association and contributes to intermolecular charge transfer. The SCCTC character is fully verified by crystallographic, photophysical, electron spin resonance, and vibrational characterizations. The PIPAQ‐based SCCTC is first applied in light‐emitting devices as an emissive layer to realize efficient deep‐red/near‐infrared electroluminescence. This work provides new insights into SCCTC and represents an important step toward their applications in optoelectronic devices.

Electron and soft X‐ray spectroscopies are powerful techniques to study the chemical and electronic structure of surfaces and interfaces. The use of these techniques to study solar devices and to unravel some of the most pertinent aspects of recent cutting‐edge developments (and world‐record efficiency improvements) in chalcopyrite thin‐film solar cells is discussed.

Abstract

Thin‐film solar cells have great potential to overtake the currently dominant silicon‐based solar cell technologies in a strongly growing market. Such thin‐film devices consist of a multilayer structure, for which charge‐carrier transport across interfaces plays a crucial role in minimizing the associated recombination losses and achieving high solar conversion efficiencies. Further development can strongly profit from a high‐level characterization that gives a local, electronic, and chemical picture of the interface properties, which allows for an insight‐driven optimization. Herein, the authors' recent progress of applying a “toolbox” of high‐level laboratory‐ and synchrotron‐based electron and soft X‐ray spectroscopies to characterize the chemical and electronic properties of such applied interfaces is provided. With this toolbox in hand, the activities are paired with those of experts in thin‐film solar cell preparation at the cutting edge of current developments to obtain a deeper understanding of the recent improvements in the field, e.g., by studying the influence of so‐called “post‐deposition treatments”, as well as characterizing the properties of interfaces with alternative buffer layer materials that give superior efficiencies on large, module‐sized areas.

The incorporation of π‐extended phosphoniumfluorene electrolytes as hole‐blocking layers in planar perovskite solar cells results in a significant enhancement in both the fill factor and the open‐circuit voltage of the devices. The latter can be enhanced by up to 120 mV as compared to the commonly used bathocuproine hole blocking layer.

Abstract

Four π‐extended phosphoniumfluorene electrolytes (π‐PFEs) are introduced as hole‐blocking layers (HBL) in inverted architecture planar perovskite solar cells with the structure of ITO/PEDOT:PSS/MAPbI₃/PCBM/HBL/Ag. The deep‐lying highest occupied molecular orbital energy level of the π‐PFEs effectively blocks holes, decreasing contact recombination. It is demonstrated that the incorporation of π‐PFEs introduces a dipole moment at the PCBM/Ag interface, resulting in significant enhancement of the built‐in potential of the device. This enhancement results in an increase in the open‐circuit voltage of the device by up to 120 mV, when compared to the commonly used bathocuproine HBL. The results are confirmed both experimentally and by numerical simulation. This work demonstrates that interfacial engineering of the transport layer/contact interface by small molecule electrolytes is a promising route to suppress nonradiative recombination in perovskite devices and compensates for a nonideal energetic alignment at the hole‐transport layer/perovskite interface.