Low-Temperature Cross-Linked Hole Transport Layer for High-Performance Blue Quantum-Dot Light-Emitting Diodes.

Quantum-dot light-emitting diodes (QLEDs), a kind of promising optoelectronic device, demonstrate potential superiority in next-generation display technology. Thermal cross-linked hole transport materials (HTMs) have been employed in solution-processed QLEDs due to their excellent thermal stability and solvent resistance, whereas the unbalanced charge injection and high cross-linking temperature of cross-linked HTMs can inhibit the efficiency of QLEDs and limit their application. Herein, a low-temperature cross-linked HTM of 4,4'-bis(3-(((4-vinylbenzyl)oxy)methyl)-9H-carbazol-9-yl)-1,1'-biphenyl (DV-CBP) with a flexible styrene side chain is introduced, which reduces the cross-linking temperature to 150 °C and enhances the hole mobility up to 1.01 × 10-3 cm2 V-1 s-1. More importantly, the maximum external quantum efficiency of 21.35% is successfully obtained on the basis of the DV-CBP as a cross-linked hole transport layer (HTL) for blue QLEDs. The low-temperature cross-linked high-mobility HTL using flexible side chains could be an excellent alternative for future HTL development.

Charge Carrier Regulation for Efficient Blue Quantum-Dot Light-Emitting Diodes Via a High-Mobility Coplanar Cyclopentane[b]thiopyran Derivative.

The performance of blue quantum dot light-emitting diodes (QLEDs) is limited by unbalanced charge injection, resulting from insufficient holes caused by low mobility or significant energy barriers. Here, we introduce an angular-shaped heteroarene based on cyclopentane[b]thiopyran (C8-SS) to modify the hole transport layer poly-N-vinylcarbazole (PVK), in blue QLEDs. C8-SS exhibits high hole mobility and conductivity due to the π···π and S···π interactions. Introducing C8-SS to PVK significantly enhanced hole mobility, increasing it by 2 orders of magnitude from 2.44 × 10-6 to 1.73 × 10-4 cm2 V-1 s-1. Benefiting from high mobility and conductivity, PVK:C8-SS-based QLEDs exhibit a low turn-on voltage (Von) of 3.2 V. More importantly, the optimized QLEDs achieve a high peak power efficiency (PE) of 7.13 lm/W, which is 2.65 times that of the control QLEDs. The as-proposed interface engineering provides a novel and effective strategy for achieving high-performance blue QLEDs in low-energy consumption lighting applications.

Progress of Hole-Transport Layers in Mixed Sn-Pb Perovskite Solar Cells.

Hybrid organic-inorganic lead halide perovskite solar cells (PSCs) have rapidly emerged as a promising photovoltaic technology, with record efficiencies surpassing 26%, approaching the theoretical Shockley-Queisser limit. The advent of all-perovskite tandem solar cells (APTSCs), integrating Pb-based wide-bandgap (WBG) with mixed Sn-Pb narrow-bandgap (NBG) perovskites, presents a compelling pathway to surpass this limit. Despite recent innovations in hole transport layers (HTLs) that have significantly improved the efficiency and stability of lead-based PSCs, an effective HTL tailored for Sn-Pb NBG PSCs remains an unmet need. This review highlights the essential role of HTLs in enhancing the performance of Sn-Pb PSCs, focusing on their ability to mitigate non-radiative recombination and optimize the buried interface, thereby improving film quality. The distinct attributes of Sn-Pb perovskites, such as their lower energy levels and accelerated crystallization rates, necessitate HTLs with specialized properties. In this study, the latest advancements in HTLs are systematically examined for Sn-Pb PSCs, encompassing organic, self-assembled monolayer (SAM), inorganic materials, and HTL-free designs. The review critically assesses the inherent limitations of each HTL category, and finally proposes strategies to surmount these obstacles to reach higher device performance.

High Electrical Conductivity and Hole Transport in an Insightfully Engineered Columnar Liquid Crystal for Solution-Processable Nanoelectronics.

Discotic liquid crystals (DLCs) are widely acknowledged as a class of organic semiconductors that can harmonize charge carrier mobility and device processability through supramolecular self-assembly. In spite of circumventing such a major challenge in fabricating low-cost charge transport layers, DLC-based hole transport layers (HTLs) have remained elusive in modern organo-electronics. In this work, a minimalistic design strategy is envisioned to effectuate a cyanovinylene-integrated pyrene-based discotic liquid crystal (PY-DLC) with a room-temperature columnar hexagonal mesophase and narrow bandgap for efficient semiconducting behavior. Adequately combined photophysical, electrochemical, and theoretical studies investigate the structure-property relations, logically correlating them with efficient hole transport. With a low reorganization energy of 0.2 eV, PY-DLC exhibits superior charge extraction ability from the contact electrodes at low values of applied voltage, achieving an electrical conductivity of 3.22 × 10-4 S m-1, the highest reported value for any pristine DLC film in a vertical charge transport device. The columnar self-assembly, in conjunction with solution-processable self-healed films, results in commendably elevated values of hole mobility (≈10-3 cm2 V-1s-1). This study provides an unprecedented constructive outlook toward the development of DLC semiconductors as practical HTLs in organic electronics.

Reducing Depletion Region Width at Electrode Interface via a Hole-transport Layer for Over 18% Efficiency in Organic Solar Cells.

The large depletion region width at the electrode interface may cause serious energy loss in charge collection of organic solar cells (OSCs), depressing the open-circuit voltage and power conversion efficiency (PCE). Herein, a pH neutral solution-processed conjugated polyelectrolyte PIDT-F:IMC as hole transport layer (HTL) to reduce the depletion region width in efficient OSCs is developed. By utilizing "mutual doping" strategy, the doping density of PIDT-F:IMC is increased by more than two orders of magnitude, which significantly reduces the depletion region width at the anode interface from 55 to 7.4 nm, playing an effective role in decreasing the energy loss in hole collection. It is also revealed that the optimal thickness of HTL should be consistent with the depletion region width for achieving the minimum energy loss. The OSC modified by PIDT-F:IMC shows a high PCE of 18.2%, along with an amazing fill factor of 0.79. Moreover, a PCE of 16.5% is achieved in the 1 cm2 OSC by using a blade-coated PIDT-F:IMC HTL, indicating the good compatibility of PIDT-F:IMC with large-area processing technology. The PIDT-F:IMC-modified OCS exhibits a lifetime of 400 h under operational conditions, which is ten times longer than that of the PEDOT:PSS device.

Perovskite Solar Cells Based on Polymerized Chlorophyll Films as Environmentally Friendly Hole-Transporting Layers.

Hole-transporting layers (HTLs) play a crucial role in the performance of inverted, p-i-n perovskite solar cells (PSCs). Chlorophylls (Chls) are naturally abundant organic photoconductors on earth, with good charge carrier mobility and appropriate Fermi energy levels that make them promising candidates for use in photovoltaic devices. However, Chls films prepared using the solution method exhibit lower carrier mobility compared to other organic polymer films, which limits their application in PSCs. To address this issue, Chls molecules are chemically linked to reduce the charge transfer barrier, thus the transfer of charges between molecules is transformed to intramolecular charge transfer. This study synthesizes and characterizes two polymerized Chl films, PolyCuChl and PolyNiChl, as HTLs of CH3 NH3 PbI3 -based PSCs. PSCs based on the electrochemical polymerization of PolyChl HTLs demonstrate an enhanced power conversion efficiency (PCE) of up to 19.0%, which is the highest efficiency among devices based on Chl materials. Furthermore, these devices demonstrated exceptional long-term stability. These results highlight the potential of polymerized Chl films as a viable alternative to conventional HTLs in PSCs. The approach utilizes abundant, environmentally friendly, and versatile Chl derivatives, and can be extended to develop next-generation HTL materials for improved PSC performance.

Work Function Tuning of Carbon Electrode to Boost the Charge Extraction in Hole Transport Layer-Free Perovskite Solar Cells.

Perovskite solar cell (PSC) is a promising photovoltaic technology that achieves over 26% power conversion efficiency (PCE). However, the high materials costs, complicated fabrication process, as well as poor long-term stability, are stumbling blocks for the commercialization of the PSCs in normal structures. The hole transport layer (HTL)-free carbon-based PSCs (C-PSCs) are expected to overcome these challenges. However, C-PSCs have suffered from relatively low PCE due to severe energy loss at the perovskite/carbon interface. Herein, the study proposes to boost the hole extraction capability of carbon electrode by incorporating functional manganese (II III) oxide (Mn3O4). It is found that the work function (WF) of the carbon electrode can be finely tuned with different amounts of Mn3O4 addition, thus the interfacial charge transfer efficiency can be maximized. Besides, the mechanical properties of carbon electrode can also be strengthened. Finally, a PCE of 19.03% is achieved. Moreover, the device retains 90% of its initial PCE after 2000 h of storage. This study offers a feasible strategy for fabricating efficient paintable HTL-free C-PSCs.

Dual Hole Transport Layers Heterojunction and Band Alignment Engineered Mo:BiVO4 Photoanodes for Efficient Water Splitting.

BiVO4-based photoanode is one of the most promising photoanodes for photoelectrocatalytic water splitting. However, the serious problem of interface charge recombination limits its further development. Here, a Mo:BiVO4/NiOx/CPF-TCzB/NiCoBi photoanode is constructed with double hole transport layer and an energy level gradient to achieve an effective photo-generated holes extraction and accumulation at the surface electrocatalyst. The conjugated polycarbazole framework CPF-TCzB is used as hole transport layer to eliminate the charge recombination center between Mo:BiVO4 and NiCoBi electrocatalyst and realize the extraction and storage of photo-generated hole; NiOx nanoparticles are further inserted between Mo:BiVO4 and CPF-TCzB to form a gradient energy level, eliminating the energy level barrier and optimizing band alignment. As a result, Mo:BiVO4/NiOx/CPF-TCzB/NiCoBi achieves a much higher photocurrent densities of 3.14 mA cm-2 than that of Mo:BiVO4 (0.42 mA cm-2) at 0.6 V versus RHE. This work provides an specific way to adjust the band structure of BiVO4-based photoanodes and realize efficient hole extraction and storage for PEC water splitting.

Bidirectional Inhibiting Interfacial Ion Migration in the Inorganic Hole Transport Layer for Perovskite Light-Emitting Diodes.

Cu2ZnSnS4 (CZTS) is strong candidate for hole transport in perovskite light emitting diodes (PeLEDs) due to their cost-effectiveness, deep highest occupied molecular orbital (HOMO), and high hole mobility. However, its inherent polymetallic ions usually deteriorate the quality of the perovskite emission layer (EML) affecting device performance. In this study, a bidirectional anchoring strategy is proposed by adding 15-crown-5 ether (15C5) into CZTS hole transport layer (HTL) to suppress the reaction between HTL and EML. The 15C5 molecule interacts with Cu+, Zn2+ and Sn2+ cations forming host-guest complexes to impede their migration, which is elucidated by density functional theory calculations. Additionally, 15C5 can neutralize lead (Pb) defects by the abundant oxygen (O) and high electronegative cavities to reduce the nonradiative recombination of FAPbBr3 film. This bidirectional anchoring strategy effectively improves hole charge transport efficiency and suppresses nonradiative recombination at the HTL/EML interface. As a result, the optimized PeLEDs present a 3.5 times peak external quantum efficiency (EQE) from 3.12% to 11.08% and the maximum luminance (Lmax) increased from 24495 to 50584 cd m-2. These findings offer innovative insights into addressing the metal ion migration issue commonly observed in inorganic HTLs.

One-Stone-for-Multiple-Birds Additive Strategy for Highly Efficient and Stable Carbon-Based Hole-Transport-Layer-Free CsPbI2Br Solar Cells.

During fabrication and operation of perovskite solar cells (PSCs), defects commonly arise within the crystals as well as at grain boundaries. However, conventional additive strategies typically only serve to mitigate the occurrence of a single defect and fail to significantly enhance device performance. Herein, carbon-based hole-transport-layer-free CsPbI2Br devices are focused on, one kind of important PSCs with more stable structure and an appropriate bandgap for a semitransparent solar cell or a top cell in a tandem configuration, and present a highly efficient one-stone-for-multiple-birds additive strategy based on lanthanide trifluoromethanesulfonates (Ln(OTF)3, Ln: neodymium (Nd), europium (Eu), dysprosium (Dy), thulium (Tm)). Density functional theory calculations reveal that the Ln3+ ions with a smaller radius can elevate defect formation energy for Pb and I vacancies within the crystals, while the presence of OTF- can effectively passivating uncoordinated Pb2+ at grain boundaries. In addition, Ln(OTF)3 addition increases the grain size and meanwhile reduces the surface roughness of the CsPbI2Br layers. All these positive contributions lead to a significant enhancement in power conversion efficiency (PCE) to 15.13% which is among the top PCEs reported for the corresponding solar cells, from 11.80% of the pristine device without Tm(OTF)3 addition, while notably boosting long-term stability and reducing current-voltage hysteresis.

A Fluorination Strategy and Low-Acidity Anchoring Group in Self-Assembled Molecules for Efficient and Stable Inverted Perovskite Solar Cells.

Herein, we synthesized two donor-acceptor (D-A) type small organic molecules with self-assembly properties, namely MPA-BT-BA and MPA-2FBT-BA, both containing a low acidity anchoring group, benzoic acid. After systematically investigation, it is found that, with the fluorination, the MPA-2FBT-BA demonstrates a lower highest occupied molecular orbital (HOMO) energy level, higher hole mobility, higher hydrophobicity and stronger interaction with the perovskite layer than that of MPA-BT-BA. As a result, the device based-on MPA-2FBT-BA displays a better crystallization and morphology of perovskite layer with larger grain size and less non-radiative recombination. Consequently, the device using MPA-2FBT-BA as hole transport material achieved the power conversion efficiency (PCE) of 20.32 % and remarkable stability. After being kept in an N2 glove box for 116 days, the unsealed PSCs' device retained 93 % of its initial PCE. Even exposed to air with a relative humidity range of 30±5 % for 43 days, its PCE remained above 91 % of its initial condition. This study highlights the vital importance of the fluorination strategy combined with a low acidity anchoring group in SAMs, offering a pathway to achieve efficient and stable PSCs.

Rational Design of New Small Derivatives of 2,2'-Bithiophene as Hole Transport Material for Perovskite Solar Cells.

Using Density Functional Theory (DFT) and Time Dependent DFT (TD-DFT) methods, this inquiry theoretically examines seven novel hole-transport materials (HTMs) namely DFBT1, DFBT2, DFBT3, DFBT4, DFBT5, DFBT6, and DFBT7 based on the 2,2'bithiophene core for future use as HTMs for perovskite solar cells (PSCs). The model molecule has been modified through substituting the end groups situated on the diphenylamine moieties with a tow acceptor bridged by thiophene, this modification was performed to test the impact of the π-bridge and acceptor on the electronic, photophysical, and photovoltaic properties of the newly created molecules. DFBT1 - DFBT7 displayed a lower band gap (1.49 eV to 2.69 eV) than the model molecule (3.63 eV). Additionally, the newly engineered molecules presented a greater λmax ranging from 393.07 nm to 541.02 nm in dimethylformamide solvent, as compared to the model molecule (380.61 nm). The PCEs of all newly designed molecules (22.42% to 29.21%) were high compared with the reference molecule (19.62%). Thus, this study showed that all seven newly small molecules were excellent candidates for a novel PSC.

Suppressing Nonradiative Recombination by Electron-Donating Substituents in 2D Conjugated Triphenylamine Polymers toward Efficient Perovskite Optoelectronics.

Highly efficient perovskite optoelectronics (POEs) have been limited by nonradiative recombination. We report a strategy to inhibit the nonradiative recombination of 2D triphenylamine polymers in the hole transport layer (HTL) via introducing electron-donating groups to enhance the conjugation effect and electron cloud density. The conjugated systems with electron-donating groups present smaller energy level oscillation compared to the ones with electron-absorbing groups, as confirmed by nonadiabatic molecular dynamics (NAMD) calculation. Further study reveals that the introduction of low-frequency phonons in the electron-donating group systems shortens the nonadiabatic coupling and inhibits the nonradiative recombination. Such electron-donating groups can decrease the valence band maximum of 2D polymers and promote hole transport. Our report provides a new design strategy to suppress nonradiative recombination in HTL for application in efficient POEs.

Engineering of Hole Transporting Interface by Incorporating the Atomic-Precision Ag6 Nanoclusters for High-Efficiency Blue Perovskite Light-Emitting Diodes.

Properties of the underlying hole transport layer (HTL) play a crucial role in determining the optoelectronic performance of perovskite light-emitting devices (PeLEDs). However, endowing the current HTL system with a deep highest occupied molecular orbital (HOMO) level concurrent with high hole mobility is still a big challenge, in particular being an open constraint toward high-efficiency blue PeLEDs. In this regard, employing the poly(9-vinylcarbazole) as a model, we perform efficient incorporation of the atomic-precision metal nanoclusters (NCs), [Ag6PL6, PL = (S)-4-phenylthiazolidine-2-thione], to achieve significant tailoring in both HOMO energy level and hole mobility. As a result, the as-modified PeLEDs exhibit an external quantum efficiency (EQE) of 14.29% at 488 nm. The presented study exemplifies the success of metal NC involved HTL engineering and offers a simple yet effective additive strategy to settle the blue PeLED HTL dilemma, which paves the way for the fabrication of highly efficient blue PeLEDs.

Copper(I) Iodide Thin Films: Deposition Methods and Hole-Transporting Performance.

The pursuit of p-type semiconductors has garnered considerable attention in academia and industry. Among the potential candidates, copper iodide (CuI) stands out as a highly promising p-type material due to its conductivity, cost-effectiveness, and low environmental impact. CuI can be employed to create thin films with >80% transparency within the visible range (400-750 nm) and utilizing various low-temperature, scalable deposition techniques. This review summarizes the deposition techniques for CuI as a hole-transport material and their performance in perovskite solar cells, thin-film transistors, and light-emitting diodes using diverse processing methods. The preparation methods of making thin films are divided into two categories: wet and neat methods. The advancements in CuI as a hole-transporting material and interface engineering techniques hold promising implications for the continued development of such devices.

Effects of Antisolvent Treatment on Copper(I) Thiocyanate Hole Transport Layer in n-i-p Perovskite Solar Cells.

Copper(I) thiocyanate (CuSCN) is considered an efficient HTL of low cost and with high stability in perovskite solar cells (PSCs). However, the diethyl sulfide solvent used for CuSCN preparation is known to cause damage to the underlying perovskite layer in n-i-p PSCs. Antisolvent treatment of CuSCN during spin-coating can effectively minimize interfacial interactions. However, the effects of antisolvent treatment are not sufficiently understood. In this study, the effects of five different antisolvents were investigated. Scanning electron microscopy and X-ray diffraction analyses showed that the antisolvent treatment improved the crystallinity of the CuSCN layer on the perovskite layer and reduced damage to the perovskite layer. However, X-ray and ultraviolet photoelectron spectroscopy analyses showed that antisolvent treatment did not affect the chemical bonds or electronic structures of CuSCN. As a result, the power conversion efficiency of the PSCs was increased from 14.72% for untreated CuSCN to 15.86% for ethyl-acetate-treated CuSCN.

Improvement in Dibenzofuran-Based Hole Transport Materials for Flexible Perovskite Solar Cells.

The π-conjugated system and the steric configuration of hole transport materials (HTMs) could greatly affect their various properties and the corresponding perovskite solar cells' efficiencies. Here, a molecular engineering strategy of incorporating different amounts of p-methoxyaniline-substituted dibenzofurans as π bridge into HTMs was proposed to develop oligomer HTMs, named mDBF, bDBF, and tDBF. Upon extending the π-conjugation of HTMs, their HOMO energy levels were slightly deepened, significantly increasing the thermal stability and hole mobility. The incorporation of p-methoxyaniline bridges built one or two additional triphenylamine propeller structures, resulting in a denser film. Here, the tDBF-based n-i-p flexible perovskite solar cells createdchampion efficiency, giving a power conversion efficiency of 19.46%. And the simple synthesis and purification process of tDBF contributed to its low manufacturing cost in the laboratory. This work provided a reference for the development of low-cost and efficient HTMs.

A Homopolymer of Xanthenoxanthene-Based Polycyclic Heteroaromatic for Efficient and Stable Perovskite Solar Cells.

Highly efficient perovskite solar cells typically rely on spiro-OMeTAD as a hole transporter, achieving a 25.7 % efficiency record. However, these cells are susceptible to harsh 85 °C conditions. Here, we present a peri-xanthenoxanthene-based semiconducting homopolymer (p-TNI2) with matched energy levels and a high molecular weight, synthesized nearly quantitatively through facile oxidative polymerization. Compared to established materials, p-TNI2 excels in hole mobility, morphology, modulus, and waterproofing. Implementing p-TNI2 as the hole transport layer results in n-i-p perovskite solar cells with an initial average efficiency of 24.6 %, rivaling 24.4 % for the spiro-OMeTAD control cells under identical conditions. Furthermore, the p-TNI2-based cells exhibit enhanced thermostability at 85 °C and operational robustness.

Triisocyanate Derived Interlayer and High-Melting-Point Doping Promoter Boost Operational Stability of Perovskite Solar Cells.

Formamidinium lead triiodide serves as the optimal light-absorbing layer in single-junction perovskite solar cells. However, achieving operational stability of high-efficiency n-i-p type devices at elevated temperatures remains challenging. In this work, we implemented effective surface modifications on microcrystalline perovskite films. This involved the nucleophilic addition of formamidinium cations and coordination of residual PbI2 with triphenylmethane triisocyanate as well as subsequent polymerization. The in situ growth of a cross-linking network chemically anchored on the perovskite film in this approach effectively reduced trap densities, favorably altered surface work function, suppressing interface charge recombination and thus enhancing cell efficiency. Coupled with a high-melting-point air-doping promoter, we fabricated n-i-p type perovskite solar cells surpassing 25 % efficiency, demonstrating excellent operational stability at 65 °C.

Cascade Reaction in Organic Hole Transport Layer Enables Efficient Perovskite Solar Cells.

The doped organic hole transport layer (HTL) is crucial for achieving high-efficiency perovskite solar cells (PSCs). However, the traditional doping strategy undergoes a time-consuming and environment-dependent oxidation process, which hinders the technology upgrades and commercialization of PSCs. Here, we reported a new strategy by introducing a cascade reaction in traditional doped Spiro-OMeTAD, which can simultaneously achieve rapid oxidation and overcome the erosion of perovskite by 4-tert-butylpyridine (tBP) in organic HTL. The ideal dopant iodobenzene diacetate was utilized as the initiator that can react with Spiro to generate Spiro⋅+ radicals quickly and efficiently without the participation of ambient air, with the byproduct of iodobenzene (DB). Then, the DB can coordinate with tBP through a halogen bond to form a tBP-DB complex, minimizing the sustained erosion from tBP to perovskite. Based on the above cascade reaction, the resulting Spiro-based PSCs have a champion PCE of 25.76 % (certificated of 25.38 %). This new oxidation process of HTL is less environment-dependent and produces PSCs with higher reproducibility. Moreover, the PTAA-based PSCs obtain a PCE of 23.76 %, demonstrating the excellent applicability of this doping strategy on organic HTL.