Nicholas Petrone

Two-dimensional flexible nanoelectronics

2014/2015 represents the tenth anniversary of modern graphene research. Over this decade, graphene has proven to be attractive for thin-film transistors owing to its remarkable electronic, optical, mechanical and thermal properties. Even its major drawback--zero bandgap--has resulted in something positive: a resurgence of interest in two-dimensional semiconductors, such as dichalcogenides and buckled nanomaterials with sizeable bandgaps. With the discovery of hexagonal boron nitride as an ideal dielectric, the materials are now in place to advance integrated flexible nanoelectronics, which uniquely take advantage of the unmatched portfolio of properties of two-dimensional crystals, beyond the capability of conventional thin films for ubiquitous flexible systems.

High-Strength Chemical-Vapor–Deposited Graphene and Grain Boundaries

Graphene Staying Strong Although exfoliated graphene can be extremely strong, it is produced on too small a scale for materials application. Graphene can be produced on a more practical scale by chemical vapor deposition, but the presence of grain boundaries between crystallites apparently weakens the material. Lee et al. (p. 1073) show that postprocessing steps during the removal of the graphene sheets can oxidize the grain boundaries and weaken them. If these steps are avoided, the material is comparable in strength to exfoliated graphene. Unless subjected to chemical attack, the grain boundaries in chemical-vapor–deposited graphene do not weaken the material. Pristine graphene is the strongest material ever measured. However, large-area graphene films produced by means of chemical vapor deposition (CVD) are polycrystalline and thus contain grain boundaries that can potentially weaken the material. We combined structural characterization by means of transmission electron microscopy with nanoindentation in order to study the mechanical properties of CVD-graphene films with different grain sizes. We show that the elastic stiffness of CVD-graphene is identical to that of pristine graphene if postprocessing steps avoid damage or rippling. Its strength is only slightly reduced despite the existence of grain boundaries. Indentation tests directly on grain boundaries confirm that they are almost as strong as pristine. Graphene films consisting entirely of well-stitched grain boundaries can retain ultrahigh strength, which is critical for a large variety of applications, such as flexible electronics and strengthening components.

Chemical Vapor Deposition-Derived Graphene with Electrical Performance of Exfoliated Graphene

While chemical vapor deposition (CVD) promises a scalable method to produce large-area graphene, CVD-grown graphene has heretofore exhibited inferior electronic properties in comparison with exfoliated samples. Here we test the electrical transport properties of CVD-grown graphene in which two important sources of disorder, namely grain boundaries and processing-induced contamination, are substantially reduced. We grow CVD graphene with grain sizes up to 250 μm to abate grain boundaries, and we transfer graphene utilizing a novel, dry-transfer method to minimize chemical contamination. We fabricate devices on both silicon dioxide and hexagonal boron nitride (h-BN) dielectrics to probe the effects of substrate-induced disorder. On both substrate types, the large-grain CVD graphene samples are comparable in quality to the best reported exfoliated samples, as determined by low-temperature electrical transport and magnetotransport measurements. Small-grain samples exhibit much greater variation in quality and inferior performance by multiple measures, even in samples exhibiting high field-effect mobility. These results confirm the possibility of achieving high-performance graphene devices based on a scalable synthesis process.

Optical Third-Harmonic Generation in Graphene

We report strong third-harmonic generation in monolayer graphene grown by chemical vapor deposition and transferred to an amorphous silica (glass) substrate; the photon energy is in threephoton resonance with the exciton-shifted van Hove singularity at the M point of graphene. The polarization selection rules are derived and experimentally verified. In addition, our polarization- and azimuthal-rotation-dependent third-harmonic-generation measurements reveal in-plane isotropy as well as anisotropy between the in-plane and out-of-plane nonlinear optical responses of graphene. Since the third-harmonic signal exceeds that from bulk glass by more than 2 orders of magnitude, the signal contrast permits background-free scanning of graphene and provides insight into the structural properties of graphene.

Large Physisorption Strain in Chemical Vapor Deposition of Graphene on Copper Substrates

Graphene single layers grown by chemical vapor deposition on single crystal Cu substrates are subject to nonuniform physisorption strains that depend on the orientation of the Cu surface. The strains are revealed in Raman spectra and quantitatively interpreted by molecular dynamics (MD) simulations. An average compressive strain on the order of 0.5% is determined in graphene on Cu(111). In graphene on Cu (100), MD simulations interpret the observed highly nonuniform strains.

Graphene Field-Effect Transistors with Gigahertz-Frequency Power Gain on Flexible Substrates

The development of flexible electronics operating at radio-frequencies (RF) requires materials that combine excellent electronic performance and the ability to withstand high levels of strain. In this work, we fabricate graphene field-effect transistors (GFETs) on flexible substrates from graphene grown by chemical vapor deposition (CVD). Our devices demonstrate unity-current-gain frequencies, f(T), and unity-power-gain frequencies, f(max), up to 10.7 GHz and 3.7 GHz, respectively, with strain limits of 1.75%. These devices represent the only reported technology to achieve gigahertz-frequency power gain at strain levels above 0.5%. As such, they demonstrate the potential of CVD graphene to enable a broad range of flexible electronic technologies which require both high flexibility and RF operation.

Graphene Field-Effect Transistors Based on Boron–Nitride Dielectrics

Two-dimensional atomic sheets of graphene represent a new class of nanoscale materials with potential applications in electronics. However, exploiting the intrinsic characteristics of graphene devices has been problematic due to impurities and disorder in the surrounding dielectric and graphene/dielectric interfaces. Recent advancements in fabricating graphene heterostructures by alternately layering graphene with crystalline hexagonal boron nitride (hBN), its insulating isomorph, have led to an order of magnitude improvement in graphene device quality. Here, recent developments in graphene devices utilizing boron-nitride dielectrics are reviewed. Field-effect transistor (FET) characteristics of these systems at high bias are examined. Additionally, existing challenges in material synthesis and fabrication and the potential of graphene/BN heterostructures for novel electronic applications are discussed.

Low-Voltage Organic Electronics Based on a Gate-Tunable Injection Barrier in Vertical graphene-organic Semiconductor Heterostructures

The vertical integration of graphene with inorganic semiconductors, oxide semiconductors, and newly emerging layered materials has recently been demonstrated as a promising route toward novel electronic and optoelectronic devices. Here, we report organic thin film transistors based on vertical heterojunctions of graphene and organic semiconductors. In these thin heterostructure devices, current modulation is accomplished by tuning of the injection barriers at the semiconductor/graphene interface with the application of a gate voltage. N-channel devices fabricated with a thin layer of C60 show a room temperature on/off ratio >10(4) and current density of up to 44 mAcm(-2). Because of the ultrashort channel intrinsic to the vertical structure, the device is fully operational at a driving voltage of 200 mV. A complementary p-channel device is also investigated, and a logic inverter based on two complementary transistors is demonstrated. The vertical integration of graphene with organic semiconductors via simple, scalable, and low-temperature fabrication processes opens up new opportunities to realize flexible, transparent organic electronic, and optoelectronic devices.

Flexible Graphene Field-Effect Transistors Encapsulated in Hexagonal Boron Nitride

Flexible graphene field-effect transistors (GFETs) are fabricated with graphene channels fully encapsulated in hexagonal boron nitride (hBN) implementing a self-aligned fabrication scheme. Flexible GFETs fabricated with channel lengths of 2 μm demonstrate exceptional room-temperature carrier mobility (μFE = 10 000 cm(2) V(-1) s(-1)), strong current saturation characteristics (peak output resistance, r0 = 2000 Ω), and high mechanical flexibility (strain limits of 1%). These values of μFE and r0 are unprecedented in flexible GFETs. Flexible radio frequency FETs (RF-FETs) with channel lengths of 375 nm demonstrate μFE = 2200 cm(2) V(-1) s(-1) and r0 = 132.5 Ω. Unity-current gain frequencies, fT, and unity-power gain frequencies, fmax, reach 12.0 and 10.6 GHz, respectively. The corresponding ratio of cutoff frequencies approaches unity (fmax/fT = 0.9), a record value for flexible GFETs. Intrinsic fT and fmax are 29.7 and 15.7 GHz, respectively. The outstanding electronic characteristics are attributed to the improved dielectric environment provided by full hBN encapsulation of the graphene channel in conjunction with an optimized, self-aligned device structure. These results establish hBN as a mechanically robust dielectric that can yield enhanced electronic characteristics to a diverse array of graphene-based flexible electronics.

Photoelectrochemical Behavior of n‑Type Si(111) Electrodes Coated With a Single Layer of Graphene

The behavior of graphene-coated n-type Si(111) photoanodes was compared to the behavior of H-terminated n-type Si(111) photoanodes in contact with aqueous K3[Fe(CN)6]/K4[Fe(CN)6] as well as in contact with a series of outer-sphere, one-electron redox couples in nonaqueous electrolytes. The n-Si/Graphene electrodes exhibited stable short-circuit photocurrent densities of over 10 mA cm(-2) for >1000 s of continuous operation in aqueous electrolytes, whereas n-Si-H electrodes yielded a nearly complete decay of the current density within ~100 s. The values of the open-circuit photovoltages and the flat-band potentials of the Si were a function of both the Fermi level of the graphene and the electrochemical potential of the electrolyte solution, indicating that the n-Si/Graphene did not form a buried junction with respect to the solution contact.