Solution-processed Semiconductors Research Articles

Performance enhancement of solution-processed organic thin-film transistors incorporating an improved Corbino structure

The solution-processed organic thin-film transistors (OTFTs) with a minimal device footprint and improved performance are desirable for flexible electronics and other circuit applications. It is demonstrated that the enhanced performance can be achieved for solution-processed OTFTs by adopting an improved Corbino structure. The bottom-gate bottom-contact OTFTs of W/L ratio of 500 are fabricated using the standard poly-3-hexylthiophene (P3HT) as a semiconductor with an improved interdigitated pseudo-Corbino (IPC) structure. The exhibited IPC structure is a combination of interdigitated structure in the enclosed-Corbino design to achieve infinite output resistance, suppressed parasitic leakage current, and high ON current by accommodating a high W/L ratio in a minimal device footprint. For the fabricated solution-processed OTFTs, infinite output resistance with an OFF-current of the order of 10−12 A and an ON/OFF ratio of drain current of the order of 107 is achieved. Incorporating an enhanced hexamethyldisilazane treatment of the SiO2 gate dielectric improves the ON/OFF ratio to a record value of 108 and the mobility of the order of 10−2 cm2/Vs for P3HT. Implementation of IPC-TFT structure for intentionally chosen moderate-mobility, solution-processed P3HT semiconductor results in a consistent low OFF-current, high ON/OFF ratio, and infinite output resistance with excellent device-to-device uniformity.

Solution-processable ordered defect compound semiconductors for high-performance electronics.

Solution-processable semiconductors hold promise in enabling applications requiring cost-effective electronics at scale but suffer from low performance limited by defects. We show that ordered defect compound semiconductor CuIn5Se8, which forms regular defect complexes with defect-pair compensation, can simultaneously achieve high performance and solution processability. CuIn5Se8 transistors exhibit defect-tolerant, band-like transport supplying an output current above 35 microamperes per micrometer, with a large on/off ratio greater than 106, a small subthreshold swing of 189 ± 21 millivolts per decade, and a high field-effect mobility of 58 ± 10 square centimeters per volt per second, with excellent uniformity and stability, superior to devices built on its less defective parent compound CuInSe2, analogous binary compound In2Se3, and other solution-deposited semiconductors. They can be monolithically integrated with carbon nanotube transistors to form high-speed and low-voltage three-dimensional complementary logic circuits and with micro-light-emitting diodes to realize high-resolution displays.

Silver Telluride Colloidal Quantum Dot Solid for Fast Extended Shortwave Infrared Photodetector.

Extended shortwave infrared (eSWIR) photodetectors that employ solution-processable semiconductors have attracted attention for use in applications such as ranging, night vision, and gas detection. Colloidal quantum dots (CQDs) are promising materials with facile bandgap tunability across the visible-to-mid-infrared wavelengths. However, toxic elements, such as Hg and Pb, and the slow response time of CQD-based IR photodetectors, limit their commercial viability. This article presents a novel eSWIR photodetector that is fabricated using silver telluride (Ag2Te) CQDs. Effective thiolate ligand exchange enables a lower trap density and improved carrier mobility in CQD solids. Furthermore, a vertical p-n photodiode architecture with a favorable energy-level landscape is utilized to facilitate charge extraction, resulting in a fast, room-temperature-operable, and toxic-element-free CQD photodetector. The best eSWIR Ag2Te CQD photodetector exhibits a fall time of 72ns, representing the fastest response time among all prior CQD-based eSWIR photodetectors, including those containing toxic elements, such as Pb and Hg.

Inkjet-printed p-type tellurene and n-type MoS2 transistors for CMOS electronics

Abstract Two-dimensional semiconductor materials combine exceptional electronic transport properties with mechanical flexibility and hence can be an ideal choice for large-area flexible and wearable electronics. While inkjet printing may be a suitable approach to fabricate high throughput electronic components on polymer substrates, solution-processed 2D semiconductor network transistors suffer from two major hindrances: extremely high inter-flake resistance and the lack of high-performance p-type semiconductors. This study shows that inkjet-printed tellurium nanowires or tellurene nanoflakes can offer high-performance p-type TFTs with current density up to 100 μA/μm and an On-Off ratio >105. In order to circumvent the high inter-flake junction resistance, a narrow-channel, near-vertical device architecture has been used that ensures predominantly intra-flake/ intra-nanowire transport, which resulted in three orders of magnitude increase in the current density compared to conventional devices without compromising on the On-Off ratio. Moreover, we show the whole device operation within ± 2 V, with a threshold voltage close to 0 V. The complete device fabrication is carried out at room temperature, thereby making it compatible with inexpensive polymer substrates. Next, outstanding device performance has also been realized with electrochemically-exfoliated and inkjet-printed n-type MoS2 TFTs, demonstrating a current density of 60 μA/μm and an On-Off ratio of 106. Furthermore, we show tellurene-based p-type depletion-load unipolar inverters and CMOS inverters alongside n-type MoS2 TFTs, demonstrating a signal gain of 12 and 11, respectively. The CMOS inverters are found to operate at a frequency of 1 kHz.

Enhanced electrical performance and stability of solution-processed oxide semiconductor thin-film transistors via an incorporation of deionized water oxidizer

Solution-processed amorphous oxide semiconductor thin films contain poor metal-oxygen-metal (M-O-M) networks and numerous impurities, making it difficult to manufacture high-performance semiconductor devices with excellent stability. In this study, we enhance the electrical performance and device stability of solution-processed oxide thin-film transistors (TFTs) by incorporating water molecular oxidants. In solution, a water molecule can be easily incorporated by adding deionized water (DW) to the precursor solution. The DW-incorporated precursor solutions induced the production of oxide semiconductor thin films with improved M-O-M networks and fewer defect states. Therefore, compared to conventional case, the DW-incorporated indium zinc oxide (InZnO) TFT showed improved device performances and significantly reduced changes of threshold voltage under positive gate bias stress and negative gate bias/illumination stress conditions. This approach of incorporating DW into the precursor solutions provides a promising route for fabricating high-quality amorphous semiconductor films and transistor devices.

A library of 2D electronic material inks synthesized by liquid-metal-assisted intercalation of crystal powders

Solution-processable 2D semiconductor inks based on electrochemical molecular intercalation and exfoliation of bulk layered crystals using organic cations has offered an alternative pathway to low-cost fabrication of large-area flexible and wearable electronic devices. However, the growth of large-piece bulk crystals as starting material relies on costly and prolonged high-temperature process, representing a critical roadblock towards practical and large-scale applications. Here we report a general liquid-metal-assisted approach that enables the electrochemical molecular intercalation of low-cost and readily available crystal powders. The resulted solution-processable MoS2 nanosheets are of comparable quality to those exfoliated from bulk crystals. Furthermore, this method can create a rich library of functional 2D electronic inks ( >50 types), including 2D wide-bandgap semiconductors of low electrical conductivity. Lastly, we demonstrated the all-solution-processable integration of 2D semiconductors with 2D conductors and 2D dielectrics for the fabrication of large-area thin-film transistors and memristors at a greatly reduced cost.

Spin coating on a budget: A 3D-Printed all-mechanical alternative for cost-effective thin-film deposition

Spin coating stands out as the most employed thin-film deposition technique across a variety of scientific fields. Particularly in the past two decades, spin coaters have become increasingly popular due to the emergence of solution-processed semiconductors such as quantum dots and perovskites. However, acquiring commercial spin coaters from reputable suppliers remains a significant financial burden for many laboratories, particularly for smaller research or educational facilities. Prompted by the simple mechanical principles of the device, in this work, we present a 3D-printed analogue that can be printed and assembled in under 10 h and costs less than 5 euros per device. The operating principle is fully mechanical since the rotating motion is induced by gas flow. It does not require any additional components such as DC motors, motor drivers, circuitry or software and thus it can be fully operational off the grid. Additionally, the gas flow generates a purging effect that was found to be rather advantageous for film formation. To prove the effectiveness of this device, we have employed it to fabricate planar thin-film antimony sulfide (Sb2S3) solar cells. The optoelectronic characteristics of solar cells revealed noteworthy improvements, particularly in terms of repeatability, when compared to those fabricated with a commercial spin coater.

Modulating the Structure and Optoelectronic Properties of Solution-Processed Bismuth-Based Nanocrystals.

Bismuth-based chalcogenides have emerged as promising candidates for next-generation, solution-processable semiconductors, mainly benefiting from their facile fabrication, low cost, excellent stability, and tunable optoelectronic properties. Particularly, the recently developed AgBiS2 solar cells have shown striking power conversion efficiencies. High performance bismuth-based photodetectors have also been extensively studied in the past few years. However, the fundamental properties of these Bi-based semiconductors have not been sufficiently investigated, which is crucial for further improving the device performance. Here, we introduce multiple time-resolved and steady-state techniques to fully characterize the charge carrier dynamics and charge transport of solution-processed Bi-based nanocrystals. It was found that the Ag-Bi ratio plays a critical role in charge transport. For Ag-deficient samples, silver bismuth sulfide thin films behave as localized state induced hopping charge transport, and the Ag-excess samples present band-like charge transport. This finding is crucial for developing more efficient Bi-based semiconductors and optoelectronic devices.

Perovskite/organic tandem device to realize light detection and emission dual function

Developing highly integrated smart optoelectronic systems is vital to modern technology, yet critically challenging. This study introduces a tandem device that incorporates an organic photodiode (OPD) and a perovskite light emitting diode (PeLED), enabling simultaneous light detection and emission in one compact device, prepared by all-solution fabrication process. It shows that precise control of interfacial properties plays a critical role in establishing the all-solution processed OPD/PeLED multi-layered dual-function device which is critical for charge transport, recombination, and generation. The integrated structure allows for light detection and emission function selectively by controlling the polarity of the external bias. The optoelectronic performance of the dual-function tandem device is comparable to that of the discrete control OPD and PeLED, i.e., the tandem device achieves a responsivity of 94 mA/W at 850 nm under −1 V and a luminance result of 1319 cd/m2 at 516 nm under 7 V, which is comparable to 101 mA/W and 1983 cd/m2 for the control OPD and PeLED operated under the same conditions. This work demonstrates the promising properties of the monolithically integrated dual-functional device and its potential for application in health monitoring and wearable electronic devices.

Understanding Antiferromagnetic Coupling in Lead-Free Halide Double Perovskite Semiconductors.

Solution-processable semiconductors with antiferromagnetic (AFM) order are attractive for future spintronics and information storage technology. Halide perovskites containing magnetic ions have emerged as multifunctional materials, demonstrating a cross-link between structural, optical, electrical, and magnetic properties. However, stable optoelectronic halide perovskites that are antiferromagnetic remain sparse, and the critical design rules to optimize magnetic coupling still must be developed. Here, we combine the complementary magnetometry and electron-spin-resonance experiments, together with first-principles calculations to study the antiferromagnetic coupling in stable Cs2(Ag:Na)FeCl6 bulk semiconductor alloys grown by the hydrothermal method. We show the importance of nonmagnetic monovalence ions at the BI site (Na/Ag) in facilitating the superexchange interaction via orbital hybridization, offering the tunability of the Curie-Weiss parameters between -27 and -210 K, with a potential to promote magnetic frustration via alloying the nonmagnetic BI site (Ag:Na ratio). Combining our experimental evidence with first-principles calculations, we draw a cohesive picture of the material design for B-site-ordered antiferromagnetic halide double perovskites.

Observation of Ferromagnetism in Dilute Magnetic Halide Perovskite Semiconductors.

Dilute magnetic semiconductors (DMSs) have attracted much attention because of their potential use in spintronic devices. Here, we demonstrate the observation of robust ferromagnetism in a solution-processable halide perovskite semiconductor with dilute magnetic ions. By codoping of magnetic (Fe2+) and aliovalent (Bi3+) metal ions into CH3NH3PbCl3 (MAPbCl3) perovskite, ferromagnetism with well-saturated magnetic hysteresis loops and a maximum coercivity field of 1280 Oe was observed below 12 K. The ferromagnetic resonance measurements revealed that the incorporation of aliovalent ions modulates the carrier concentration and plays an essential role in realizing the ferromagnetism in dilute magnetic halide perovskites. Magnetic ions are proposed to interact through itinerant charge carriers to achieve ferromagnetic coupling. Our work provides a new avenue for the development of solution-processable magnetic semiconductors.

Colloidal InAs Quantum Dot-Based Infrared Optoelectronics Enabled by Universal Dual-Ligand Passivation.

Solution-processed low-bandgap semiconductors are crucial to next-generation infrared (IR) detection for various applications, such as autonomous driving, virtual reality, recognitions, and quantum communications. In particular, III-V group colloidal quantum dots (CQDs) are interesting as nontoxic bandgap-tunable materials and suitable for IR absorbers; however, the device performance is still lower than that of Pb-based devices. Herein, a universal surface-passivation method of InAs CQDs enabled by intermediate phase transfer (IPT), a preliminary process that exchanges native ligands with aromatic ligands on the CQD surface is presented. IPT yields highly stable CQD ink. In particular, desirable surface ligands with various reactivities can be obtained by dispersing them in green solvents. Furthermore, CQD near-infrared (NIR) photodetectors are demonstrated using solution processes. Careful surface ligand control via IPT is revealed that enables the modulation of surface-mediated photomultiplication, resulting in a notable gain control up to ≈10 with a fast rise/fall response time (≈12/36ns). Considering the figure of merit (FOM), EQE versus response time (or -3dB bandwidth), the optimal CQD photodiode yields one of the highest FOMs among all previously reported solution-processed nontoxic semiconductors comprising organics, perovskites, and CQDs in the NIR wavelength range.

Supramolecular assembly of blue and green halide perovskites with near-unity photoluminescence.

The metal-halide ionic octahedron is the optoelectronic unit for halide perovskites, and a crown ether-assisted supramolecular assembly approach can pack various ionic octahedra into tunable symmetries. In this work, we demonstrate near-unity photoluminescence quantum yield (PLQY) blue and green emission with the supramolecular assembly of hafnium (Hf) and zirconium (Zr) halide octahedral clusters. (18C6@K)2HfBr6 powders showed blue emission with a near-unity PLQY (96.2%), and green emission was also achieved with (18C6@K)2ZrCl4Br2 powders at a PLQY of 82.7%. These highly emissive powders feature facile low-temperature solution-based synthesis conditions and maintain high PLQY in solution-processable semiconductor inks under ambient conditions, and they were used in thin-film displays and emissive three-dimensional-printed architectures that exhibited high spatial resolution.

Rational ligand design for enhanced carrier mobility in self-powered SWIR photodiodes based on colloidal InSb quantum dots.

Solution-processed colloidal III-V semiconductor quantum dot photodiodes (QPDs) have potential applications in short-wavelength infrared (SWIR) imaging due to their tunable spectral response range, possible multiple-exciton generation, operation at 0-V bias voltage and low-cost fabrication and are also expected to replace lead- and mercury-based counterparts that are hampered by reliance on restricted elements (RoHS). However, the use of III-V CQDs as photoactive layers in SWIR optoelectronic applications is still a challenge because of underdeveloped ligand engineering for improving the in-plane conductivity of the QD assembled films. Here, we report on ligand engineering of InSb CQDs to enhance the optical response performance of self-powered SWIR QPDs. Specifically, by replacing the conventional ligand (i.e., oleylamine) with sulfide, the interparticle distance between the CQDs was shortened from 5.0 ± 0.5 nm to 1.5 ± 0.5 nm, leading to improved carrier mobility for high photoresponse speed to SWIR light. Furthermore, the use of sulfide ligands resulted in a low dark current density (∼nA cm-2) with an improved EQE of 18.5%, suggesting their potential use in toxic-based infrared image sensors.

Heterointerface engineering of layered double hydroxide/MAPbBr3 heterostructures enabling tunable synapse behaviors in a two-terminal optoelectronic device.

Solution-processable semiconductor heterostructures enable scalable fabrication of high performance electronic and optoelectronic devices with tunable functions via heterointerface control. In particular, artificial optical synapses require interface manipulation for nonlinear signal processing. However, the limited combinations of materials for heterostructure construction have restricted the tunability of synaptic behaviors with simple device configurations. Herein, MAPbBr3 nanocrystals were hybridized with MgAl layered double hydroxide (LDH) nanoplates through a room temperature self-assembly process. The formation of such heterostructures, which exhibited an epitaxial relationship, enabled effective hole transfer from MAPbBr3 to LDH, and greatly reduced the defect states in MAPbBr3. Importantly, the ion-conductive nature of LDH and its ability to form a charged surface layer even under low humidity conditions allowed it to attract and trap holes from MAPbBr3. This imparted tunable synaptic behaviors and short-term plasticity (STP) to long-term plasticity (LTP) transition to a two-terminal device based on the LDH-MAPbBr3 heterostructures. The further neuromorphic computing simulation under varying humidity conditions showcased their potential in learning and recognition tasks under ambient conditions. Our work presents a new type of epitaxial heterostructure comprising metal halide perovskites and layered ion-conductive materials, and provides a new way of realizing charge-trapping induced synaptic behaviors.

Solution ALD Processing of Halide Perovskite Thin Films Yields Superior Functional Quality and Stability Than Classical Processing

The range of materials accessible by classical ALD is limited by the volatility requirement applied to the precursors. However, solution ALD (sALD) transfers the self-limiting surface reaction principle of ALD into the solution processing realm and allows for the same level of control in the deposition of ionic or molecular solids, such as polymers, metal-organic frameworks, and halide perovskites, which cannot be delivered from the gas phase.We have developed an sALD procedure for the direct deposition of the prototypical halide perovskite compound, methylammonium triiodoplumbate(IV), (H3CNH3)(PbI3), also referred to as methylammonium lead iodide or MAPI. The process saturates upon dosage variation to a self-limiting growth rate. The material is obtained in crystalline and highly pure, stoichiometric form at room temperature. All analytical techniques confer to indicate the absence of any lead iodide trace. The MAPI layers generated by sALD can be integrated into planar heterojunction stacks and yield functional solar cells.The direct comparison of films of several thickness values prepared in pairs by sALD and by a state-of-the-art spin-coating method shows that the sALD films always overperform their spin-coated counterparts both in terms of charge carrier lifetimes and in terms of stability towards decomposition under thermal, radiative or vacuum stress.Thus, experimental atomic-level control of solution-processed semiconductors is accessible for the first time. It can now be applied to the accurate investigation of halide perovskite photophysics and photochemistry fundamentals as they pertain to transport and interface phenomena.

Defect-Engineered Semiconducting van der Waals Thin Film at Metal-Semiconductor Interface of Field-Effect Transistors.

The significance of metal-semiconductor interfaces and their impact on electronic device performance have gained increasing attention, with a particular focus on investigating the contact metal. However, another avenue of exploration involves substituting the contact metal at the metal-semiconductor interface of field-effect transistors with semiconducting layers to introduce additional functionalities to the devices. Here, a scalable approach for fabricating metal-oxide-semiconductor (channel)-semiconductor (interfacial layer) field-effect transistors is proposed by utilizing solution-processed semiconductors, specifically semiconducting single-walled carbon nanotubes and molybdenum disulfide, as the channel and interfacial semiconducting layers, respectively. The work function of the interfacial MoS2 is modulated by controlling the sulfur vacancy concentration through chemical treatment, which results in distinctive energy band alignments within a single device configuration. The resulting band alignments lead to multiple functionalities, including multivalued transistor characteristics and multibit nonvolatile memory (NVM) behavior. Moreover, leveraging the stable NVM properties, we demonstrate artificial synaptic devices with 88.9% accuracy of MNIST image recognition.

Indoor Self-Powered Perovskite Optoelectronics with Ultraflexible Monochromatic Light Source.

Self-powered skin optoelectronics fabricated on ultrathin polymer films is emerging as one of the most promising components for the next-generation Internet of Things (IoT) technology. However, a longstanding challenge is the device underperformance owing to the low process temperature of polymer substrates. In addition, broadband electroluminescence (EL) based on organic or polymer semiconductors inevitably suffers from periodic spectral distortion due to Fabry-Pérot (FP) interference upon substrate bending, preventing advanced applications. Here, ultraflexible skin optoelectronics integrating high-performance solar cells and monochromatic light-emitting diodes using solution-processed perovskite semiconductors is presented. n-i-p perovskite solar cells and perovskite nanocrystal light-emitting diodes (PNC-LEDs), with power-conversion and current efficiencies of 18.2% and 15.2cd A-1 , respectively, are demonstrated on ultrathin polymer substrates with high thermal stability, which is a record-high efficiency for ultraflexible perovskite solar cell. The narrowband EL with a full width at half-maximum of 23nm successfully eliminates FP interference, yielding bending-insensitive spectra even under 50% of mechanical compression. Photo-plethysmography using the skin optoelectronic device demonstrates a signal selectivity of 98.2% at 87bpm pulse. The results presented here pave the way to inexpensive and high-performance ultrathin optoelectronics for self-powered applications such as wearable displays and indoor IoT sensors.

Bilayer channel structure to improve the stability of solution-processed metal oxide transistors under AC stress

In this work, we report solution-processed bilayer channel thin film transistors (TFTs) based on solution-processed amorphous oxide semiconductors (AOSs) that fulfill both superb electrical performance and device stability against applied alternating current (AC) drain bias stress. Acceptor-like states generation via hot carrier effect (HCE) is a representative device degradation mechanism suggested for AOS-based TFTs when subjected to AC bias stress, featuring threshold voltage (Vth) shift and on-current (Ion) lowering. As excess electric field and accumulated carriers in the AOS channel cause HCE, alleviating carrier accumulation is a key solution for mitigating HCE. Bilayer channel TFTs comprising two different AOSs could work as a countermeasure to overcome HCE since proper energy band alignment of two channels creates a conduction band difference that act as the energy barrier for carriers. In this regard, we employed amorphous indium-gallium-zinc oxide (IGZO) and zinc-tin oxide (ZTO) as bottom and top layer, respectively, for bilayer channel TFT. Designed bilayer channel showed a conduction band difference of 0.18 eV, and fabricated TFT based on this architecture exhibited high mobility over to 5.9 cm2/Vs with slight Vth shift of 0.1 V and Ion lowering of 1.7% for 1000 s against applied AC stress, demonstrating device stability under AC drain bias stress.

Solution-Processed Semiconductor Materials as Cathode Interlayers for Organic Solar Cells.

Cathode interlayers (CILs) play a crucial role in improving the photovoltaic efficiency and stability of OSCs. CILs generally consists of two kinds of materials, interfacial dipole-based CILs and SPS-based CILs. With good charge transporting ability, excellent compatibility with large-area processing methods, and highly tunable optoelectronic properties, the SPS-based CILs exhibit remarkable superiorities to their interfacial dipole-based counterparts in practical use, making them promising candidate in developing efficient CILs for OSCs. This mini-review highlights the great potential of SPS-based CILs in OSC applications and elucidates the working mechanism and material design strategy of SPS materials. Afterward, the SPS-based CIL materials are summarized and discussed in four sections, including organic small molecules, conjugated polymers, nonconjugated polymers, and TMOs. The structure-property-performance relationship of SPS-based CIL materials is revealed, which may provide readers new insight into the molecular design of SPS-based CILs. The mechanisms to endow SPS-based CILs with thickness insensitivity, resistance to environmental erosion, and photo-electric conversion ability are also elucidated. Finally, after a brief summary, the remaining issues and the prospects of SPS-based CILs are suggested.