Ambient-Stable 2D Dion-Jacobson Phase Tin Halide Perovskite Field-Effect Transistors with Mobility over 1.6 Cm2 V-1 s-1.

Solution-processed metal halide perovskites hold immense potential for the advancement of next-generation field-effect transistors (FETs). However, the instability of perovskite-based transistors has impeded their progress and practical applications. Here, ambient-stable high-performance FETs based on 2D Dion-Jacobson phase tin halide perovskite BDASnI4 , which has high film quality and excellent electrical properties, are reported. The perovskite channels are established by engineering the film crystallization process via the employment of ammonium salt interlayers and the incorporation of NH4 SCN additives within the precursor solution. The refined FETs demonstrate field-effect hole mobilities up to 1.61 cm2 V-1 s-1 and an on/off ratio surpassing 106 . Moreover, the devices show impressive operational and environmental stability and retain their functional performance even after being exposed to ambient conditions with a temperature of 45 °C and humidity of 45% for over 150 h.

Protocol for fabrication and characterization of two-dimensional lead halide perovskite thin-film transistors.

Two-dimensional (2D) lead halide perovskites (LHPs) are highly attractive for fabricating thin-film transistors (TFTs), but it remains a challenge for 2D LHP TFTs to work at room temperature (RT). Here, we present a protocol for fabricating 2D LHP TFTs that operate well at RT and exhibit high bias-stress stability and storage stability. We describe steps for preparing materials and equipment followed by fabrication of devices. We then detail measurement of device output characteristics and extraction of performance parameters. For complete details on the use and execution of this protocol, please refer to Qiu et al. (2023).1.

Novel Organic Superbase Dopants for Ultraefficient N-Doping of Organic Semiconductors.

Doping is a powerful technique for engineering the electrical properties of organic semiconductors (OSCs), yet efficient n-doping of OSCs remains a central challenge. Herein, the discovery of two organic superbase dopants, namely P2-t-Bu and P4-t-Bu as ultra-efficient n-dopants for OSCs is reported. Typical n-type semiconductors such as N2200 and PC61 BM are shown to experience a significant increase of conductivity upon doping by the two dopants. In particular, the optimized electrical conductivity of P2-t-Bu-doped PC61 BM reaches a record-high value of 2.64 S cm-1 . The polaron generation efficiency of P2-t-Bu-doped in PC61 BM is found to be over 35%, which is 2-3 times higher than that of benchmark n-dopant N-DMBI. In addition, a deprotonation-initiated, nucleophilic-attack-based n-doping mechanism is proposed for the organic superbases, which involves the deprotonation of OSC molecules, the nucleophilic attack of the resulting carbanions on the OSC's π-bonds, and the subsequent n-doping through single electron transfer process between the anionized and neutral OSCs. This work highlights organic superbases as promising n-dopants for OSCs and opens up opportunities to explore and develop highly efficient n-dopants.

A Methodology of Fabricating Novel Electrodes for Semiconductor Devices: Doping and Van der Waals Integrating Organic Semiconductor Films.

Electrodes are indispensable components in semiconductor devices, and now are mainly made from metals, which are convenient for use but not ideal for emerging technologies such as bioelectronics, flexible electronics, or transparent electronics. Here the methodology of fabricating novel electrodes for semiconductor devices using organic semiconductors (OSCs) is proposed and demonstrated. It is shown that polymer semiconductors can be heavily p- or n-doped to achieve sufficiently high conductivity for electrodes. In contrast with metals, the doped OSC films (DOSCFs) are solution-processable, mechanically flexible, and have interesting optoelectronic properties. By integrating the DOSCFs with semiconductors through van der Waals contacts different kinds of semiconductor devices can be constructed. Importantly, these devices exhibit higher performance than their counterparts with metal electrodes, and/or excellent mechanical or optical properties that are unavailable in metal-electrode devices, suggesting the superiority of DOSCF electrodes. Given the existing large amount of OSCs, the established methodology can provide abundant electrode choices to meet the demand of various emerging devices.

Ferroelectric Wide-Bandgap Metal Halide Perovskite Field-Effect Transistors: Toward Transparent Electronics.

Transparent field-effect transistors (FETs) are attacking intensive interest for constructing fancy "invisible" electronic products. Presently, the main technology for realizing transparent FETs is based on metal oxide semiconductors, which have wide-bandgap but generally demand sputtering technique or high-temperature (>350 °C) solution process for fabrication. Herein, a general device fabrication strategy for metal halide perovskite (MHP) FETs is shown, by which transparent perovskite FETs are successfully obtained using low-temperature (<150 °C) solution process. This strategy involves the employment of ferroelectric copolymer poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) as the dielectric, which conquers the challenging issue of gate-electric-field screening effect in MHP FETs. Additionally, an ultra-thin SnO2 is inserted between the source/drain electrodes and MHPs to facilitate electron injection. Consequently, n-type semi-transparent MAPbBr3 FETs and fully transparent MAPbCl3 FETs which can operate well at room temperature with mobility over 10-3  cm2  V-1  s-1 and on/off ratio >103 are achieved for the first time. The low-temperature solution processability of these FETs makes them particularly attractive for applications in low-cost, large-area transparent electronics.

Revealing the Electrophilic-Attack Doping Mechanism for Efficient and Universal p-Doping of Organic Semiconductors.

Doping is of great importance to tailor the electrical properties of semiconductors. However, the present doping methodologies for organic semiconductors (OSCs) are either inefficient or can only apply to some OSCs conditionally, seriously limiting their general applications. Herein, a novel p-doping mechanism is revealed by investigating the interactions between the dopant trityl tetrakis(pentafluorophenyl) borate (TrTPFB) and poly(3-hexylthiophene) (P3HT). It is found that electrophilic attack of the trityl cations on thiophenes results in the formation of tritylated thiophenium ions, which subsequently induce electron transfer from neighboring P3HT chains to realize p-doping. This unique p-doping mechanism enables TrTPFB to p-dope various OSCs including those with high ionization energy (IE ≈ 5.8 eV). Moreover, this doping mechanism endows TrTPFB with strong doping capability, leading to doping efficiency of over 80% in P3HT. The discovery and elucidation of this novel doping mechanism not only points out that strong electrophiles are a class of efficient p-dopants for OSCs, but also provides new opportunities toward highly efficient doping of various OSCs.

Doping of Sn-based two-dimensional perovskite semiconductor for high-performance field-effect transistors and thermoelectric devices.

Doping is an important technique for semiconductor materials and devices, yet effective and controllable doping of organic-inorganic halide perovskites is still a challenge. Here, we demonstrate a facile way to dope two-dimensional Sn-based perovskite (PEA)2SnI4 by incorporating SnI4 in the precursor solutions. It is observed that Sn4+ produces p-doping effect on the perovskite, which increases the electrical conductivity by 105 times. The dopant SnI4 is also found to improve the film morphology of (PEA)2SnI4, leading to reduced trap states. This doping technique allows us to improve the room temperature mobility of (PEA)2SnI4 field-effect transistors from 0.25 to 0.68 cm2 V-1 s-1 thanks to reduced trapping effects in the doped devices. Moreover, the doping technique enables the characterization and improvement of the thermoelectric performance of (PEA)2SnI4 films, which show a high power factor of 3.92 µW m-1 K-2 at doping ratio of 5 mol %.

Solution-Processed CsPbBr3 Quantum Dots/Organic Semiconductor Planar Heterojunctions for High-Performance Photodetectors.

Planar heterojunctions (PHJs) are fundamental building blocks for construction of semiconductor devices. However, fabricating PHJs with solution-processable semiconductors such as organic semiconductors (OSCs) is a challenge. Herein, utilizing the orthogonal solubility and good wettability between CsPbBr3 perovskite quantum dots (PQDs) and OSCs, fabrication of solution-processed PQD/OSC PHJs are reported. The phototransistors based on bilayer PQD/PDVT-10 PHJs show responsivity up to 1.64 × 104 A W-1 , specific detectivity of 3.17 × 1012 Jones, and photosensitivity of 5.33 × 106 when illuminated by 450 nm light. Such high photodetection performance is attributed to efficient charge dissociation and transport, as well as the photogating effect in the PHJs. Furthermore, the tri-layer PDVT-10/PQD/Y6 PHJs are used to construct photodiodes working in self-powered mode, which exhibit broad range photoresponse from ultraviolet to near-infrared, with responsivity approaching 10-1 A W-1 and detectivity over 106 Jones. These results present a convenient and scalable production processes for solution-processed PHJs and show their great potential for optoelectronic applications.

Band-like transport in non-fullerene acceptor semiconductor Y6.

The recently reported non-fullerene acceptor (NFA) Y6 has been extensively investigated for high-performance organic solar cells. However, its charge transport property and physics have not been fully studied. In this work, we acquired a deeper understanding of the charge transport in Y6 by fabricating and characterizing thin-film transistors (TFTs), and found that the electron mobility of Y6 is over 0.3-0.4 cm2/(V⋅s) in top-gate bottom-contact devices, which is at least one order of magnitude higher than that of another well-known NFA ITIC. More importantly, we observed band-like transport in Y6 spin-coated films through temperature-dependent measurements on TFTs. This is particularly amazing since such transport behavior is rarely seen in polycrystalline organic semiconductor films. Further morphology characterization and discussions indicate that the band-like transport originates from the unique molecule packing motif of Y6 and the special phase of the film. As such, this work not only demonstrates the superior charge transport property of Y6, but also suggests the great potential of developing high-mobility n-type organic semiconductors, on the basis of Y6.

Protocol for doping of an Sn-based two-dimensional perovskite semiconductor by incorporating SnI4 for field-effect transistors and thermoelectric devices.

Doping is an important technique for semiconductor materials, yet effective and controllable doping of organic-inorganic halide perovskites is still a challenge. Here, we present a protocol to dope 2D perovskite (PEA)2SnI4 by incorporating SnI4 in the precursor solutions. We detail steps for preparation of field-effect transistors (FETs) and thermoelectric devices (TEs) based on SnI4-doped (PEA)2SnI4 films. We further describe characterization via conductivity measurement using the four-point probe method, FETs performance, and TEs performance measurements. For complete details on the use and execution of this protocol, please refer to Liu et al. (2022).1.

Doped Vertical Organic Field-Effect Transistors Demonstrating Superior Bias-Stress Stability.

Bias-stress stability is essential to the practical applications of organic field-effect transistors (OFETs), yet it remains a challenge issue in conventional planar OFETs. Here, the feasibility of achieving high bias-stress stability in vertical structured OFETs (VOFETs) in combination with doping techniques is demonstrated. VOFETs with silver nanowires as source electrodes are fabricated and the device performance is optimized by understanding the influence of device parameters on performance. Then, the bias-stress stability of the optimized PDVT-10 VOFETs is investigated and found to be superior to the corresponding planar OFETs, which is attributed to reduced trapping effects of gate dielectrics in the VOFETs. Moreover, the bias-stress stability can be further improved by doping PDVT-10 to passivate bulk traps. Consequently, the characteristic time of doped PDVT-10 VOFETs extracted from stretched exponential equation is found to be over four times larger than that of the planar PDVT-10 OFETs under the same bias-stress conditions. These results present the promising applications of VOFETs as well as an effective strategy to achieve highly bias-stress stable OFETs.

Traps in metal halide perovskites: characterization and passivation.

Metal halide perovskites (MHPs) have become a research focus in the field of optoelectronics due to their excellent optoelectronic properties and simple and cost-effective thin film manufacturing processes. In particular, the power conversion efficiency (PCE) of solar cells (SCs) and external quantum efficiency (EQE) of light-emitting diodes (LEDs) based on perovskite materials have reached 25.2% and 21.6%, respectively, in a short period, making perovskites especially promising for fabricating next-generation optoelectronic devices. Despite these inspiring results, obtaining high-performance, high-stability MHP-based devices still faces many challenges, among which the defects and the consequent traps in MHPs are key factors. Defect-induced traps can trap charge carriers or even act as non-radiative recombination centers, seriously degrading the device performance, causing hysteresis and deteriorating the stability of MHP-based devices. Thus, understanding the chemical/physical nature of traps and adopting appropriate strategies to passivate traps are important to enhance the device performance and stability. Herein we present a review in which the knowledge and understanding of traps in MHPs are considered and discussed. Moreover, the latest efforts on passivating traps in MHPs for improving device performance are summarized, with the hope of providing guidance to future development of high-performance and high-stability MHP-based devices.