Free‐Standing 2D Hexagonal Aluminum Nitride Dielectric Crystals for High‐Performance Organic Field‐Effect Transistors

The existence of defects and traps in a transistor plays an adverse role on efficient charge transport. In response to this challenge, extensive research has been conducted on semiconductor crystalline materials in the past decades. However, the development of dielectric crystals for transistors is still in its infancy due to the lack of appropriate dielectric crystalline materials and, most importantly, the crystal morphology required by the gate dielectric layer, which is also crucial for the construction of high‐performance transistor as it can greatly improve the interfacial quality of carrier transport path. Here, a new type of dielectric crystal of hexagonal aluminum nitride (AlN) with the desired 2D morphology of combing thin thickness with large lateral dimension is synthesized. Such a suitable morphology in combination with the outstanding dielectric properties of AlN makes it promising as a gate dielectric for transistors. Furthermore, ultrathin 2,6‐diphenylanthracene molecular crystals with only a few molecular layers can be prepared on AlN crystal via van der Waals epitaxy. As a result, this all‐crystalline system incorporating dielectric and semiconductor crystals greatly enhances the overall performance of a transistor, indicating the importance of minimizing defects and preparing high‐quality semiconductor/dielectric interface in a transistor configuration.     

Substrate Selection for Full Exploitation of Organic Semiconductor Films: Epitaxial Rubrene on β‐Alanine Single Crystals

Rubrene (RUB) is one of the most studied organic semiconductors because, in the orthorhombic single‐crystal phase, it exhibits a record exciton diffusion length and one of the highest charge carrier mobilities ever reported. Here, thin films of oriented crystalline RUB are successfully grown in vacuum on millimeter‐sized (010)‐β‐alanine (β‐ala) single crystals with a step‐growth protocol, exploiting organic epitaxy. The experimental characterization demonstrates that these RUB films grow in the orthorhombic polymorph with the (100)_RUB plane in contact with the (010)_β‐ala surface and with precise azimuthal orientations. A complementary study of the RUB(100)/β‐ala(010) interface, performed by computational simulations, confirms the epitaxial relations expected by considering the molecular scale corrugations of the surfaces. Moreover, thanks to the wide transparency region of β‐ala, the RUB absorption bands in the UV range are directly detected for the first time. Finally, removal of the water‐soluble substrate enables the integration of the films in field effect transistors as high quality active organic layers. The characteristics of such RUB‐based devices confirm the quality and versatility of epitaxial thin films for use in organic electronics.     

Hall Effect in Bulk‐Doped Organic Single Crystals

The standard technique to separately and simultaneously determine the carrier concentration per unit volume (N , cm^?3) and the mobility (μ) of doped inorganic single crystals is to measure the Hall effect. However, this technique has not been reported for bulk‐doped organic single crystals. Here, the Hall effect in bulk‐doped single‐crystal organic semiconductors is measured. A key feature of this work is the ultraslow co‐deposition technique, which reaches as low as 10^?9 nm s^?1 and enables us to dope homoepitaxial organic single crystals with acceptors at extremely low concentrations of 1 ppm. Both the hole concentration per unit volume (N , cm^?3) and the Hall mobility (μ_H) of bulk‐doped rubrene single crystals, which have a band‐like nature, are systematically observed. It is found that these rubrene single crystals have (i) a high ionization rate and (ii) scattering effects because of lattice disturbances, which are peculiar to this organic single crystal.     

Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation

Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure–property correlations for materials ordered at this length scale (10–100 nm). A solvent‐evaporation‐induced crystallization method providing access to large (millimeter to centimeter) single‐crystal mesostructures, specifically bicontinuous gyroids, in thick films (>100 µm) derived from block copolymers is reported. After in‐depth crystallographic characterization of single‐crystal block copolymer–preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single‐crystal‐like cleavage along mesoscale facets. The method can prepare macroscopic bulk single crystals with other block copolymer systems, suggesting that the method is broadly applicable to block copolymer materials assembled by solvent evaporation. It is expected that such bulk single crystals will enable fundamental understanding and control of emergent mesostructure‐based properties in block‐copolymer‐directed metal, semiconductor, and superconductor materials.     

Carbon Nanolights in Piezopolymers are Self‐Organizing Toward Color Tunable Luminous Hybrids for Kinetic Energy Harvesting

Herein, an all‐solid‐state sequential self‐organization and self‐assembly process is reported for the in situ construction of a color tunable luminous inorganic/polymer hybrid with high direct piezoresponse. The primary inorganic self‐organization in solid polymer and the subsequent polymer self‐assembly are achieved at high pressure with the first utilization of piezo‐copolymer (PVDF‐TrFE) as the host matrix of guest carbon quantum dots (CQDs). This process induces the spontaneous formation of a highly ordered, microscale, polygonal, and hierarchically structured CQDs/PVDF‐TrFE hybrid with multicolor photoluminescence, consisting of very thermodynamic stable polar crystalline nanowire arrays. The electrical polarization‐free CQDs/PVDF‐TrFE hybrids can efficiently harvest the environmental available kinetic mechanical energy with a new large‐scale group‐cooperation mechanism. The open‐circuit voltage and short‐circuit current outputs reach up to 29.6 V cm^?2 and 550 nA cm^?2, respectively. The CQDs/PVDF‐TrFE–based hybrid nanogenerator demonstrates drastically improved durable and reliable features during the real‐time demonstration of powering commercial light emitting diodes. No attenuation/fluctuation of the electrical signals is observed for ≈10 000 continuous working cycles. This study may offer a new design concept for progressively but spontaneously constructing novel multiple self‐adaptive complex inorganic/polymer hybrids that promise applications in the next generation of self‐powered autonomous optoelectronic devices.     

Band‐Gap Engineering at a Semiconductor–Crystalline Oxide Interface

The epitaxial growth of crystalline oxides on semiconductors provides a pathway to introduce new functionalities to semiconductor devices. Key to electrically coupling crystalline oxides with semiconductors to realize functional behavior is to control the manner in which their bands align at interfaces. Here, principles of band‐gap engineering traditionally used at heterojunctions between conventional semiconductors are applied to control the band offset between a single crystalline oxide and a semiconductor. Reactive molecular beam epitaxy is used to realize atomically abrupt and structurally coherent interfaces between SrZr_xTi_1−xO₃ and Ge, in which the band‐gap of the former is enhanced with Zr content x. Structural and electrical characterization of SrZr_xTi_1−xO₃‐Ge heterojunctions for x = 0.2 to 0.75 are presented and it is demonstrated that the band offset can be tuned from type‐II to type‐I, with the latter being verified using photoemission measurements. The type‐I band offset provides a platform to integrate the dielectric, ferroelectric, and ferromagnetic functionalities of oxides with semiconducting devices.     

Position- and Orientation-Controlled Growth of Wulff-Shaped Colloidal Crystals Engineered with DNA

Colloidal crystals have emerged as promising candidates for building optical microdevices. Techniques now exist for synthesizing them with control over their nanoscale features (e.g., particle compositions, sizes, shapes, and lattice parameters and symmetry); however, the ability to tune macroscale structural features, such as the relative positions of crystals to one another and lattice orientations, has yet to be realized. Here, inspiration is drawn from epitaxial growth strategies in atomic crystallization, and patterned substrates are prepared that, when used in conjunction with DNA-mediated nanoparticle crystallization, allow for control over individual Wulff-shaped crystal growth, location, and orientation. In addition, the approach allows exquisite control over the patterned substrate/crystal lattice mismatch, something not yet realized for any epitaxy process. This level of structural control is a significant step toward realizing complex, integrated devices with colloidal crystal components, and this approach provides a model system for further exploration in epitaxy systems.     

High‐Temperature Ionic Epitaxy of Halide Perovskite Thin Film and the Hidden Carrier Dynamics

High‐temperature vapor phase epitaxy (VPE) has been proved ubiquitously powerful in enabling high‐performance electro‐optic devices in III–V semiconductor field. A typical example is the successful growth of p‐type GaN by VPE for blue light‐emitting diodes. VPE excels as it controls film defects such as point/interface defects and grain boundary, thanks to its high‐temperature processing condition and controllable deposition rate. For the first time, single‐crystalline high‐temperature VPE halide perovskite thin film has been demonstrated—a unique platform on unveiling previously uncovered carrier dynamics in inorganic halide perovskites. Toward wafer‐scale epitaxial and grain boundary‐free film is grown with alkali halides as substrates. It is shown the metal alkali halides could be used as universal substrates for VPE growth of perovskite due to their similar material chemistry and lattice constant. With VPE, hot photoluminescence and nanosecond photo‐Dember effect are revealed in inorganic halide perovskite. These two phenomena suggest that inorganic halide perovskite could be as compelling as its organic–inorganic counterpart regarding optoelectronic properties and help explain the long carrier lifetime in halide perovskite. The findings suggest a new avenue on developing high‐quality large‐scale single‐crystalline halide perovskite films requiring precise control of defects and morphology.     

Dielectric response of polymer relaxors

Dielectric response of vinylidene fluoride type ferroelectric polymers is dominated by that of segmental motions in the amorphous phase in temperature range 200–300 K and contributions related to the local mode and ferroelectric–paraelectric transition in the crystalline phase of the polymer at higher temperatures. Diffuse and frequency-dependent dielectric anomaly observed in fast electron irradiated polyvinylidene fluoride-trifluoroethylene P(VDF/TrFE) has been related to relaxor-like behavior induced in the semicrystalline ferroelectric copolymers. As random field and the response of polar nanosize clusters determine the relaxor behavior the effects of disorder and fast electron irradiation (below and above T _C) on the three contributions to the dielectric response of PVDF, P(VDF/TrFE)(75/25) and P(VDF/TrFE)(50/50) are shown. The processes involved in radiation-induced functionalization of PVDF-type polymers are discussed on the basis of results of ESR, IR and Raman spectroscopy studies.     

Epitaxial growth of solution grown polyvinylchloride (PVC) films

Thin films of polyvinylchloride (PVC) have been grown epitaxially from three different solvents onto the (001) plane of rocksalt crystals by the isothermal immersion technique. The ranges of values of the growth parameters (temperature and concentration of the solution and immersion time) over which epitaxial growth is obtained have been established in each case. Films grown from a benzene and acetone mixture show epitaxy only at temperatures of 58°C or more and with concentrations below 0.1 g/100 ml. The epitaxial relation is (010) [110]_PVC∥(001) [110]_NaCl. The crystallites in the epitaxial films are of pyramidal shape and the molecular chains are folded in a direction perpendicular to the substrate. Films grown from ethyl methyl ketone solution show epitaxy only at temperatures of 65°C or more for concentrations greater than or equal to 0.15 g/100 ml. Films grown from cyclohexanone solution show epitaxy over a wide range of temperatures and concentrations. The epitaxial relation is (001) [110]_PVC∥(001) [110]_NaCl and the crystallites are rod- or fibre-like. The molecular chains in these crystallites are folded in a direction parallel to the substrate. Our studies show that epitaxial growth occurs in the earliest stage of growth of the films and further growth results in a mixture of amorphous and polycrystalline regions. The mechanism of epitaxial growth is explained in terms of our model for the growth of polymer chains. Two possible configurations of the molecular chains in the unit cell of PVC on a (001) rocksalt surface are proposed to explain the two epitaxial orientation relations observed.     

MoS2/Rubrene van der Waals Heterostructure: Toward Ambipolar Field‐Effect Transistors and Inverter Circuits

2D transition metal dichalcogenides are promising channel materials for the next‐generation electronic device. Here, vertically 2D heterostructures, so called van der Waals solids, are constructed using inorganic molybdenum sulfide (MoS₂) few layers and organic crystal – 5,6,11,12‐tetraphenylnaphthacene (rubrene). In this work, ambipolar field‐effect transistors are successfully achieved based on MoS₂ and rubrene crystals with the well balanced electron and hole mobilities of 1.27 and 0.36 cm² V^?1 s^?1, respectively. The ambipolar behavior is explained based on the band alignment of MoS₂ and rubrene. Furthermore, being a building block, the MoS₂/rubrene ambipolar transistors are used to fabricate CMOS (complementary metal oxide semiconductor) inverters that show good performance with a gain of 2.3 at a switching threshold voltage of ?26 V. This work paves a way to the novel organic/inorganic ultrathin heterostructure based flexible electronics and optoelectronic devices.     

Ultrahigh‐Detectivity Photodetectors with Van der Waals Epitaxial CdTe Single‐Crystalline Films

Van der Waals epitaxy (vdWE) is crucial for heteroepitaxy of covalence‐bonded semiconductors on 2D layered materials because it is not subject to strict substrate requirements and the epitaxial materials can be transferred onto various substrates. However, planar film growth in covalence‐bonded semiconductors remains a critical challenge of vdWE because of the extremely low surface energy of 2D materials. In this study, direct growth of wafer‐scale single‐crystalline cadmium telluride (CdTe) films is achieved on 2D layered transparent mica through molecular beam epitaxy. The vdWE CdTe films exhibit a flat surface resulting from the 2D growth regime, and high crystal quality as evidenced by a low full width at half maximum of 0.05° for 120 nm thick films. A perfect lattice fringe appears at the interfaces, implying a fully relaxed state of the epitaxial CdTe films correlated closely to the unique nature of vdWE. Moreover, the vdWE CdTe photodetectors demonstrate not only ultrasensitive optoelectronic response with optimal responsivity of 834 A W^?1 and ultrahigh detectivity of 2.4 × 10¹⁴ Jones but also excellent mechanical flexibility and durability, indicating great potential in flexible and wearable devices.     

Suppression of Persistent Photoconductivity of Rubrene Crystals using Gate‐Tunable Rubrene/Bi2Se3 Diodes with Photoinduced Negative Differential Resistance

Organic single‐crystalline semiconductors show great potential in high‐performance photodetectors. However, they suffer from persistent photoconductivity (PPC) due to the charge trapping, which has severely hindered high‐speed imaging applications. Here, a universal strategy of solving the PPC by integrating with topological insulator Bi₂Se₃ is provided. The rubrene/Bi₂Se₃ heterojunctions are selected as an example for general demonstration due to the reproducibly high mobility and broad optoelectronic applications of rubrene crystals. By virtue of high carrier concentration on Bi₂Se₃ surface and the strong built‐in electrical field, the photoresponse of the heterotransistor is significantly reduced for more than two orders (from over 10 s to 54 ms), meanwhile the photoresponsivity can reach 124 A W^?1. To the best of knowledge, this operating speed is among the fastest responses in organic–inorganic heterojunctions. The heterotransistor also shows unique negative differential resistance under positive gate bias, which can be explained by photoinduced de‐trapping of electron trap states in the bulk rubrene crystals. Besides, the rubrene/Bi₂Se₃ heterojunction behaves as a gate‐tunable backward‐like diode due to the inhomogenous carrier distribution in the thick rubrene crystal and inversion of relative Fermi level positions. The findings demonstrate versatile functionalities of the rubrene/Bi₂Se₃ heterojunctions for various emerging optoelectronic applications.     

Cover Picture: High‐Performance Organic Single‐Crystal Transistors on Flexible Substrates (Adv. Mater. 17/2006)

The cover shows a comparison of thin and thick rubrene single crystals where the flexibility of the thin rubrene crystals is clearly illustrated. On p. 2320, Yang, Bao, and co‐workers report that high performance flexible transistors on plastic substrates fabricated by using these rubrene “thin‐film” single‐crystals demonstrate mobility as high as 4.6 cm² Vs^–1 and ON/OFF ratios of approximately 10⁶.     

Photonic Microcapsules Containing Single‐Crystal Colloidal Arrays with Optical Anisotropy

Colloidal particles with a repulsive interparticle potential spontaneously form crystalline lattices, which are used as a motif for photonic materials. It is difficult to predict the crystal arrangement in spherical volume as lattices are incompatible with a spherical surface. Here, the optimum arrangement of charged colloids is experimentally investigated by encapsulating them in double‐emulsion drops. Under conditions of strong interparticle repulsion, the colloidal crystal rapidly grows from the surface toward the center of the microcapsule, forming an onion‐like arrangement. By contrast, for weak repulsion, crystallites slowly grow and fuse through rearrangement to form a single‐crystal phase. Single‐crystal structure is energetically favorable even for strong repulsion. Nevertheless, a high energy barrier to colloidal rearrangement kinetically arrests the onion‐like structure formed by heterogeneous nucleation. Unlike the isotropic onion‐shaped product, the anisotropic single‐crystal‐containing microcapsules selectively display—at certain orientations but not others—one of the distinct colors from the various crystal planes.     

Patterned Growth of Graphene over Epitaxial Catalyst

Rectangle‐ and triangle‐shaped microscale graphene films are grown on epitaxial Co films deposited on single‐crystal MgO substrates with (001) and (111) planes, respectively. A thin film of Co or Ni metal is epitaxially deposited on a MgO substrate by sputtering while heating the substrate. Thermal decomposition of polystyrene over this epitaxial metal film in vacuum gives rectangular or triangular pit structures whose orientation and shape are strongly dependent on the crystallographic orientation of the MgO substrate. Raman mapping measurements indicate preferential formation of few‐layer graphene films inside these pits. The rectangular graphene films are transferred onto a SiO₂/Si substrate while maintaining the original shape and field‐effect transistors are fabricated using the transferred films. These findings on the formation of rectangular/triangular graphene give new insights on the formation mechanism of graphene and can be applied for more advanced/controlled graphene growth.     

Large‐Area Atomic Layers of the Charge‐Density‐Wave Conductor TiSe2

Layered transition metal (Ti, Ta, Nb, etc.) dichalcogenides are important prototypes for the study of the collective charge density wave (CDW). Reducing the system dimensionality is expected to lead to novel properties, as exemplified by the discovery of enhanced CDW order in ultrathin TiSe₂. However, the syntheses of monolayer and large‐area 2D CDW conductors can currently only be achieved by molecular beam epitaxy under ultrahigh vacuum. This study reports the growth of monolayer crystals and up to 5 × 10⁵ µm² large films of the typical 2D CDW conductor—TiSe₂—by ambient‐pressure chemical vapor deposition. Atomic resolution scanning transmission electron microscopy indicates the as‐grown samples are highly crystalline 1T‐phase TiSe₂. Variable‐temperature Raman spectroscopy shows a CDW phase transition temperature of 212.5 K in few layer TiSe₂, indicative of high crystal quality. This work not only allows the exploration of many‐body state of TiSe₂ in 2D limit but also offers the possibility of utilizing large‐area TiSe₂ in ultrathin electronic devices.     

Semiconductor Nanowire Light‐Emitting Diodes Grown on Metal: A Direction Toward Large‐Scale Fabrication of Nanowire Devices

Bottom‐up nanowires are attractive for realizing semiconductor devices with extreme heterostructures because strain relaxation through the nanowire sidewalls allows the combination of highly lattice mismatched materials without creating dislocations. The resulting nanowires are used to fabricate light‐emitting diodes (LEDs), lasers, solar cells, and sensors. However, expensive single crystalline substrates are commonly used as substrates for nanowire heterostructures as well as for epitaxial devices, which limits the manufacturability of nanowire devices. Here, nanowire LEDs directly grown and electrically integrated on metal are demonstrated. Optical and structural measurements reveal high‐quality, vertically aligned GaN nanowires on molybdenum and titanium films. Transmission electron microscopy confirms the composition variation in the polarization‐graded AlGaN nanowire LEDs. Blue to green electroluminescence is observed from InGaN quantum well active regions, while GaN active regions exhibit ultraviolet emission. These results demonstrate a pathway for large‐scale fabrication of solid state lighting and optoelectronics on metal foils or sheets.