Mechanisms of Ultrafast Charge Separation in a PTB7/Monolayer MoS₂ van der Waals Heterojunction

Mixed-dimensional van der Waals heterojunctions comprising polymer and two-dimensional (2D) semiconductors have many characteristics of an ideal charge separation interface for optoelectronic and photonic applications. However, the photoelectron dynamics at polymer–2D semiconductor heterojunction interfaces are currently not sufficiently understood to guide the optimization of devices for these applications. This Letter reports a systematic exploration of the time-dependent photophysical processes that occur upon photoexcitation of a type-II heterojunction between the polymer PTB7 and monolayer MoS₂. In particular, photoinduced electron transfer from PTB7 to electronically hot states of MoS₂ occurs in less than 250 fs. This process is followed by a 1–5 ps exciton diffusion-limited electron transfer from PTB7 to MoS₂ and a sub-3 ps photoinduced hole transfer from MoS₂ to PTB7. The equilibrium between excitons and polaron pairs in PTB7 determines the charge separation yield, whereas the 3–4 ns lifetime of photogenerated carriers is probably limited by MoS₂ defects

Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene–MoS₂ van der Waals Heterojunction

van der Waals heterojunctions between two-dimensional (2D) layered materials and nanomaterials of different dimensions present unique opportunities for gate-tunable optoelectronic devices. Mixed-dimensional p–n heterojunction diodes, such as p-type pentacene (0D) and n-type monolayer MoS₂ (2D), are especially interesting for photovoltaic applications where the absorption cross-section and charge transfer processes can be tailored by rational selection from the vast library of organic molecules and 2D materials. Here, we study the kinetics of excited carriers in pentacene–MoS₂ p–n type-II heterojunctions by transient absorption spectroscopy. These measurements show that the dissociation of MoS₂ excitons occurs by hole transfer to pentacene on the time scale of 6.7 ps. In addition, the charge-separated state lives for 5.1 ns, up to an order of magnitude longer than the recombination lifetimes from previously reported 2D material heterojunctions. By studying the fractional amplitudes of the MoS₂ decay processes, the hole transfer yield from MoS₂ to pentacene is found to be ∼50%, with the remaining holes undergoing trapping due to surface defects. Overall, the ultrafast charge transfer and long-lived charge-separated state in pentacene–MoS₂ p–n heterojunctions suggest significant promise for mixed-dimensional van der Waals heterostructures in photovoltaics, photodetectors, and related optoelectronic technologies

Elucidating the Photoresponse of Ultrathin MoS₂ Field-Effect Transistors by Scanning Photocurrent Microscopy

The mechanisms underlying the intrinsic photoresponse of few-layer (FL) molybdenum disulfide (MoS₂) field-effect transistors are investigated via scanning photocurrent microscopy. We attribute the locally enhanced photocurrent to band-bending-assisted separation of photoexcited carriers at the MoS₂/Au interface. The wavelength-dependent photocurrents of FL MoS₂ transistors qualitatively follow the optical absorption spectra of MoS₂, providing direct evidence of interband photoexcitation. Time and spectrally resolved photocurrent measurements at varying external electric fields and carrier concentrations establish that drift-diffusion currents dominate photothermoelectric currents in devices under bias

Charge Separation at Mixed-Dimensional Single and Multilayer MoS₂/Silicon Nanowire Heterojunctions

Layered two-dimensional (2-D) semiconductors can be combined with other low-dimensional semiconductors to form nonplanar mixed-dimensional van der Waals (vdW) heterojunctions whose charge transport behavior is influenced by the heterojunction geometry, providing a new degree of freedom to engineer device functions. Toward that end, we investigated the photoresponse of Si nanowire/MoS₂ heterojunction diodes with scanning photocurrent microscopy and time-resolved photocurrent measurements. Comparison of n-Si/MoS₂ isotype heterojunctions with p-Si/MoS₂ heterojunction diodes under varying biases shows that the depletion region in the p–n heterojunction promotes exciton dissociation and carrier collection. We measure an instrument-limited response time of 1 μs, which is 10 times faster than the previously reported response times for planar Si/MoS₂ devices, highlighting the advantages of the 1-D/2-D heterojunction. Finite element simulations of device models provide a detailed understanding of how the electrostatics affect charge transport in nanowire/vdW heterojunctions and inform the design of future vdW heterojunction photodetectors and transistors

Solution-Processed Self-Assembled Nanodielectrics on Template-Stripped Metal Substrates

The coupling of hybrid organic–inorganic gate dielectrics with emergent unconventional semiconductors has yielded transistor devices exhibiting record-setting transport properties. However, extensive electronic transport measurements on these high-capacitance systems are often convoluted with the electronic response of the semiconducting silicon substrate. In this report, we demonstrate the growth of solution-processed zirconia self-assembled nanodielectrics (Zr-SAND) on template-stripped aluminum substrates. The resulting Zr-SAND on Al structures leverage the ultrasmooth (r.m.s. roughness <0.4 nm), chemically uniform nature of template-stripped metal substrates to demonstrate the same exceptional electronic uniformity (capacitance ∼700 nF cm^–2, leakage current <1 μA cm^–2 at −2 MV cm^–1) and multilayer growth of Zr-SAND on Si, while exhibiting superior temperature and voltage capacitance responses. These results are important to conduct detailed transport measurements in emergent transistor technologies featuring SAND as well as for future applications in integrated circuits or flexible electronics

Fundamental Performance Limits of Carbon Nanotube Thin-Film Transistors Achieved Using Hybrid Molecular Dielectrics

In the past decade, semiconducting carbon nanotube thin films have been recognized as contending materials for wide-ranging applications in electronics, energy, and sensing. In particular, improvements in large-area flexible electronics have been achieved through independent advances in postgrowth processing to resolve metallic <i>versus</i> semiconducting carbon nanotube heterogeneity, in improved gate dielectrics, and in self-assembly processes. Moreover, controlled tuning of specific device components has afforded fundamental probes of the trade-offs between materials properties and device performance metrics. Nevertheless, carbon nanotube transistor performance suitable for real-world applications awaits understanding-based progress in the integration of independently pioneered device components. We achieve this here by integrating high-purity semiconducting carbon nanotube films with a custom-designed hybrid inorganic–organic gate dielectric. This synergistic combination of materials circumvents conventional design trade-offs, resulting in concurrent advances in several transistor performance metrics such as transconductance (6.5 μS/μm), intrinsic field-effect mobility (147 cm²/(V s)), subthreshold swing (150 mV/decade), and on/off ratio (5 × 10⁵), while also achieving hysteresis-free operation in ambient conditions

Large-Area, Low-Voltage, Antiambipolar Heterojunctions from Solution-Processed Semiconductors

The emergence of semiconducting materials with inert or dangling bond-free surfaces has created opportunities to form van der Waals heterostructures without the constraints of traditional epitaxial growth. For example, layered two-dimensional (2D) semiconductors have been incorporated into heterostructure devices with gate-tunable electronic and optical functionalities. However, 2D materials present processing challenges that have prevented these heterostructures from being produced with sufficient scalability and/or homogeneity to enable their incorporation into large-area integrated circuits. Here, we extend the concept of van der Waals heterojunctions to semiconducting p-type single-walled carbon nanotube (s-SWCNT) and n-type amorphous indium gallium zinc oxide (a-IGZO) thin films that can be solution-processed or sputtered with high spatial uniformity at the wafer scale. The resulting large-area, low-voltage p–n heterojunctions exhibit antiambipolar transfer characteristics with high on/off ratios that are well-suited for electronic, optoelectronic, and telecommunication technologies

Hybrid, Gate-Tunable, van der Waals p–n Heterojunctions from Pentacene and MoS₂

The recent emergence of a wide variety of two-dimensional (2D) materials has created new opportunities for device concepts and applications. In particular, the availability of semiconducting transition metal dichalcogenides, in addition to semimetallic graphene and insulating boron nitride, has enabled the fabrication of “all 2D” van der Waals heterostructure devices. Furthermore, the concept of van der Waals heterostructures has the potential to be significantly broadened beyond layered solids. For example, molecular and polymeric organic solids, whose surface atoms possess saturated bonds, are also known to interact via van der Waals forces and thus offer an alternative for scalable integration with 2D materials. Here, we demonstrate the integration of an organic small molecule p-type semiconductor, pentacene, with a 2D n-type semiconductor, MoS₂. The resulting p–n heterojunction is gate-tunable and shows asymmetric control over the antiambipolar transfer characteristic. In addition, the pentacene/MoS₂ heterojunction exhibits a photovoltaic effect attributable to type II band alignment, which suggests that MoS₂ can function as an acceptor in hybrid solar cells

High-Field Transport and Thermal Reliability of Sorted Carbon Nanotube Network Devices

We examine the high-field operation, power dissipation, and thermal reliability of sorted carbon nanotube network (CNN) devices, with <1% to >99% semiconducting nanotubes. We combine systematic electrical measurements with infrared (IR) thermal imaging and detailed Monte Carlo simulations to study high-field transport up to CNN failure by unzipping-like breakdown. We find that metallic CNNs carry peak current densities up to an order of magnitude greater than semiconducting CNNs at comparable nanotube densities. Metallic CNNs also appear to have a factor of 2 lower intrinsic thermal resistance, suggesting a lower thermal resistance at metallic nanotube junctions. The performance limits and reliability of CNNs depend on their makeup, and could be improved by carefully engineered heat dissipation through the substrate, contacts, and nanotube junctions. These results are essential for optimization of CNN devices on transparent or flexible substrates which typically have very low thermal conductivity

High-Field Transport and Thermal Reliability of Sorted Carbon Nanotube Network Devices

We examine the high-field operation, power dissipation, and thermal reliability of sorted carbon nanotube network (CNN) devices, with <1% to >99% semiconducting nanotubes. We combine systematic electrical measurements with infrared (IR) thermal imaging and detailed Monte Carlo simulations to study high-field transport up to CNN failure by unzipping-like breakdown. We find that metallic CNNs carry peak current densities up to an order of magnitude greater than semiconducting CNNs at comparable nanotube densities. Metallic CNNs also appear to have a factor of 2 lower intrinsic thermal resistance, suggesting a lower thermal resistance at metallic nanotube junctions. The performance limits and reliability of CNNs depend on their makeup, and could be improved by carefully engineered heat dissipation through the substrate, contacts, and nanotube junctions. These results are essential for optimization of CNN devices on transparent or flexible substrates which typically have very low thermal conductivity