Yuhan Zhang

Two-dimensional quasi-freestanding molecular crystals for high-performance organic field-effect transistors

Two-dimensional atomic crystals are extensively studied in recent years due to their exciting physics and device applications. However, a molecular counterpart, with scalable processability and competitive device performance, is still challenging. Here, we demonstrate that high-quality few-layer dioctylbenzothienobenzothiophene molecular crystals can be grown on graphene or boron nitride substrate via van der Waals epitaxy, with precisely controlled thickness down to monolayer, large-area single crystal, low process temperature and patterning capability. The crystalline layers are atomically smooth and effectively decoupled from the substrate due to weak van der Waals interactions, affording a pristine interface for high-performance organic transistors. As a result, monolayer dioctylbenzothienobenzothiophene molecular crystal field-effect transistors on boron nitride show record-high carrier mobility up to 10 cm(2) V(-1) s(-1) and aggressively scaled saturation voltage ~1 V. Our work unveils an exciting new class of two-dimensional molecular materials for electronic and optoelectronic applications.

Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit.

One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ∼3  nm. Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

A van der Waals pn heterojunction with organic/inorganic semiconductors

van der Waals (vdW) heterojunctions formed by two-dimensional (2D) materials have attracted tremendous attention due to their excellent electrical/optical properties and device applications. However, current 2D heterojunctions are largely limited to atomic crystals, and hybrid organic/inorganic structures are rarely explored. Here, we fabricate the hybrid 2D heterostructures with p-type dioctylbenzothienobenzothiophene (C8-BTBT) and n-type MoS2. We find that few-layer C8-BTBT molecular crystals can be grown on monolayer MoS2 by vdW epitaxy, with pristine interface and controllable thickness down to monolayer. The operation of the C8-BTBT/MoS2 vertical heterojunction devices is highly tunable by bias and gate voltages between three different regimes: interfacial recombination, tunneling, and blocking. The pn junction shows diode-like behavior with rectifying ratio up to 105 at the room temperature. Our devices also exhibit photovoltaic responses with a power conversion efficiency of 0.31% and a photoresponsivity of 22 mA/W. With wide material combinations, such hybrid 2D structures will offer possibilities for opto-electronic devices that are not possible from individual constituents.

Precise, Self-Limited Epitaxy of Ultrathin Organic Semiconductors and Heterojunctions Tailored by van der Waals Interactions

Precise assembly of semiconductor heterojunctions is the key to realize many optoelectronic devices. By exploiting the strong and tunable van der Waals (vdW) forces between graphene and organic small molecules, we demonstrate layer-by-layer epitaxy of ultrathin organic semiconductors and heterostructures with unprecedented precision with well-defined number of layers and self-limited characteristics. We further demonstrate organic p-n heterojunctions with molecularly flat interface, which exhibit excellent rectifying behavior and photovoltaic responses. The self-limited organic molecular beam epitaxy (SLOMBE) is generically applicable for many layered small-molecule semiconductors and may lead to advanced organic optoelectronic devices beyond bulk heterojunctions.

Reflectivity behavior of two-dimensional ordered array of metallodielectric composite particles at large incidence angles

Optical reflectance of a two-dimensional (2D) metallodielectric (MD) photonic crystal composed of hexagonal array of close-packed silver-shell polystyrene-core composite particles has been studied at off-normal incidence under both P and S polarizations. A dramatic change in reflectivity behavior of the 2D MD film from a 2D colloidal crystal template and a homogeneous silver film has been observed. The phenomenon of strong reflectance bands of the 2D MD film was explained as a selective coupling of the incident light with surface plasmon of the 2D textured structure via the 2D grating.

Two dimensional WS2 lateral heterojunctions by strain modulation

“Strain engineering” has been widely used to tailor the physical properties of layered materials, like graphene, black phosphorus, and transition-metal dichalcogenides. Here, we exploit thermal strain engineering to construct two dimensional (2D) WS2 in-plane heterojunctions. Kelvin probe force microscopy is used to investigate the surface potentials and work functions of few-layer WS2 flakes, which are grown on SiO2/Si substrates by chemical vapor deposition, followed by a fast cooling process. In the interior regions of strained WS2 flakes, work functions are found to be much larger than that of the unstrained regions. The difference in work functions, together with the variation of band gaps, endows the formation of heterojunctions in the boundaries between inner and outer domains of WS2 flakes. This result reveals that the existence of strain offers a unique opportunity to modulate the electronic properties of 2D materials and construct 2D lateral heterojunctions.

Realization of vertical and lateral van der Waals heterojunctions using two-dimensional layered organic semiconductors

Van der Waals (vdW) heterojunctions based on two-dimensional (2D) atomic crystals have been extensively studied in recent years. Herein, we show that both vertical and lateral vdW heterojunctions can be realized with layered molecular crystals using a two-step physical vapor transport (PVT) process. Both types of heterojunctions show clean and sharp interfaces without phase mixing under atomic force microscopy (AFM). They also exhibit a strong interfacial built-in electric field similar to that of their inorganic counterparts. These heterojunctions have greater potential for device applications than individual materials. The lateral heterojunction (LHJ) devices show rectifying characteristics due to the asymmetric energy barrier for holes at the interface, while the vertical heterojunction (VHJ) devices behave like metal–insulator–semiconductor tunnel junctions, with pronounced negative differential conductance (NDC). Our work extends the concept of vdW heterojunctions to molecular materials, which can be generalized to other layered organic semiconductors (OSCs) to obtain new device functionalities.

Unveiling the structural origin of the high carrier mobility of a molecular monolayer on boron nitride

Very recently, it was demonstrated that the carrier mobility of a molecular monolayer dioctylbenzothienobenzothiophene (C8-BTBT) on boron nitride can reach 10 cm2/Vs, the highest among the previously reported monolayer molecular field-effect transistors. Here we show that the high-quality single crystal of the C8-BTBT monolayer may be the key origin of the record-high carrier mobility. We discover that the C8-BTBT molecules prefer layer-by-layer growth on both hexagonal boron nitride and graphene. The flatness of these substrates substantially decreases the C8-BTBT nucleation density and enables repeatable growth of large-area single crystal of the C8-BTBT monolayer. Our experimental result indicates that only out-of-plane roughness greater than 0.6 nm of the substrates could induce disturbance in the crystal growth and consequently affect the charge transport. This information would be important in guiding the growth of high-quality epitaxy molecular film.

Low-voltage, High-performance Organic Field-Effect Transistors Based on 2D Crystalline Molecular Semiconductors

Two dimensional (2D) molecular crystals have attracted considerable attention because of their promising potential in electrical device applications, such as high-performance field-effect transistors (FETs). However, such devices demand high voltages, thereby considerably increasing power consumption. This study demonstrates the fabrication of organic FETs based on 2D crystalline films as semiconducting channels. The application of high-κ oxide dielectrics allows the transistors run under a low operating voltage (−4 V). The devices exhibited a high electrical performance with a carrier mobility up to 9.8 cm2 V−1 s−1. Further results show that the AlOx layer is beneficial to the charge transport at the conducting channels of FETs. Thus, the device strategy presented in this work is favorable for 2D molecular crystal-based transistors that can operate under low voltages.

Synthesis of three-dimensional AlN–Si3N4 branched heterostructures and their photoluminescence properties

The synthesis of heterostructures with branched morphology is of great importance for exploiting novel physical and chemical properties in nanoscience and nanotechnology fields. In this study, by combining the extended vapor–liquid–solid (EVLS) and vapor–solid (VS) growth methods, we successfully fabricate three-dimensional (3D) AlN–Si3N4 branched heterostructures with the core of Si3N4 nanostructures and branched AlN nanocones with adjustable diameter and length. The photoluminescence (PL) spectra of the AlN–Si3N4 branched heterostructures display new emission bands besides those of the as-synthesized Si3N4 nanostructures, which may be ascribed to the emission bands of AlN in the deep- or trap-level state. From these results we propose a general strategy for designing and preparing 3D branched heterostructures for novel optoelectronic devices.