Large area, patterned growth of 2D MoS2 and lateral MoS2-WS2 heterostructures for nano- and opto-electronic applications.

The patterned growth of transition metal dichalcogenides (TMDs) and their lateral heterostructures is paramount for the fabrication of application-oriented electronics and optoelectronics devices. However, the large scale patterned growth of TMDs remains challenging. Here, we demonstrate the synthesis of patterned polycrystalline 2D MoS2 thin films on device ready SiO2/Si substrates, eliminating any etching and transfer steps using a combination of plasma enhanced atomic layer deposition (PEALD) and thermal sulfurization. As an inherent advantage of ALD, precise thickness control ranging from a monolayer to few-layered MoS2 has been achieved. Furthermore, uniform films with exceptional conformality over 3D structures are obtained. Finally, the approach has been leveraged to obtain in-plane lateral heterostructures of 2D MoS2 and WS2 thin films over a large area which opens up an avenue for their direct integration in future nano- and opto-electronic device applications.

High-frequency, scaled graphene transistors on diamond-like carbon.

Owing to its high carrier mobility and saturation velocity, graphene has attracted enormous attention in recent years. In particular, high-performance graphene transistors for radio-frequency (r.f.) applications are of great interest. Synthesis of large-scale graphene sheets of high quality and at low cost has been demonstrated using chemical vapour deposition (CVD) methods. However, very few studies have been performed on the scaling behaviour of transistors made from CVD graphene for r.f. applications, which hold great potential for commercialization. Here we report the systematic study of top-gated CVD-graphene r.f. transistors with gate lengths scaled down to 40 nm, the shortest gate length demonstrated on graphene r.f. devices. The CVD graphene was grown on copper film and transferred to a wafer of diamond-like carbon. Cut-off frequencies as high as 155 GHz have been obtained for the 40-nm transistors, and the cut-off frequency was found to scale as 1/(gate length). Furthermore, we studied graphene r.f. transistors at cryogenic temperatures. Unlike conventional semiconductor devices where low-temperature performance is hampered by carrier freeze-out effects, the r.f. performance of our graphene devices exhibits little temperature dependence down to 4.3 K, providing a much larger operation window than is available for conventional devices.

Area-selective atomic layer deposition of platinum using photosensitive polyimide.

Area-selective atomic layer deposition (AS-ALD) of platinum (Pt) was studied using photosensitive polyimide as a masking layer. The polyimide films were prepared by spin-coating and patterned using photolithography. AS-ALD of Pt using poly(methyl-methacrylate) (PMMA) masking layers was used as a reference. The results show that polyimide has excellent selectivity towards the Pt deposition, after 1000 ALD cycles less than a monolayer of Pt is deposited on the polyimide surface. The polyimide film could easily be removed after ALD using a hydrogen plasma, due to a combination of weakening of the polyimide resist during Pt ALD and the catalytic activity of Pt traces on the polyimide surface. Compared to PMMA for AS-ALD of Pt, polyimide has better temperature stability. This resulted in an improved uniformity of the Pt deposits and superior definition of the Pt patterns. In addition, due to the absence of reflow contamination using polyimide the nucleation phase during Pt ALD is drastically shortened. Pt patterns down to 3.5 µm were created with polyimide, a factor of ten smaller than what is possible using PMMA, at the typical Pt ALD processing temperature of 300 °C. Initial experiments indicate that after further optimization of the polyimide process Pt features down to 100 nm should be possible, which makes AS-ALD of Pt using photosensitive polyimide a promising candidate for patterning at the nanoscale.

Atomic layer deposition of Pd and Pt nanoparticles for catalysis: on the mechanisms of nanoparticle formation.

The deposition of Pd and Pt nanoparticles by atomic layer deposition (ALD) has been studied extensively in recent years for the synthesis of nanoparticles for catalysis. For these applications, it is essential to synthesize nanoparticles with well-defined sizes and a high density on large-surface-area supports. Although the potential of ALD for synthesizing active nanocatalysts for various chemical reactions has been demonstrated, insight into how to control the nanoparticle properties (i.e. size, composition) by choosing suitable processing conditions is lacking. Furthermore, there is little understanding of the reaction mechanisms during the nucleation stage of metal ALD. In this work, nanoparticles synthesized with four different ALD processes (two for Pd and two for Pt) were extensively studied by transmission electron spectroscopy. Using these datasets as a starting point, the growth characteristics and reaction mechanisms of Pd and Pt ALD relevant for the synthesis of nanoparticles are discussed. The results reveal that ALD allows for the preparation of particles with control of the particle size, although it is also shown that the particle size distribution is strongly dependent on the processing conditions. Moreover, this paper discusses the opportunities and limitations of the use of ALD in the synthesis of nanocatalysts.

Structural Aspects of MoS x Prepared by Atomic Layer Deposition for Hydrogen Evolution Reaction.

Molybdenum sulfides (MoS x ) in both crystalline and amorphous forms are promising earth-abundant electrocatalysts for hydrogen evolution reaction (HER) in acid. Plasma-enhanced atomic layer deposition was used to prepare thin films of both amorphous MoS x with adjustable S/Mo ratio (2.8-4.7) and crystalline MoS2 with tailored crystallinity, morphology, and electrical properties. All the amorphous MoS x films transform into highly HER-active amorphous MoS2 (overpotential 210-250 mV at 10 mA/cm2 in 0.5 M H2SO4) after electrochemical activation at approximately -0.3 V vs reversible hydrogen electrode. However, the initial film stoichiometry affects the structure and consequently the HER activity and stability. The material changes occurring during activation are studied using ex situ and quasi in situ X-ray photoelectron spectroscopy. Possible structures of as-deposited and activated catalysts are proposed. In contrast to amorphous MoS x , no changes in the structure of crystalline MoS2 catalysts are observed. The overpotentials of the crystalline films range from 300 to 520 mV at 10 mA/cm2, being the lowest for the most defective catalysts. This work provides a practical method for deposition of tailored MoS x HER electrocatalysts as well as new insights into their activity and structure.

Influence of High-κ Dielectrics Integration on ALD-Based MoS2 Field-Effect Transistor Performance.

The integration of high-κ dielectrics on MoS2 field-effect transistors (FETs) is essential for the realization of MoS2 in ultrascaled nanoelectronic devices and circuits. Most studies covering this topic are based on exfoliated MoS2 flakes or chemical vapor deposition (CVD) grown MoS2 films, whereas other techniques, such as atomic layer deposition (ALD), are also gaining attention for the growth of MoS2 in recent years. In this work, we grow large-area MoS2 by means of plasma-enhanced (PE-)ALD and evaluate the influence of high-κ dielectrics on the properties of ALD-based MoS2 FETs through electrical characterization combined with surface-chemical and high-resolution scanning transmission electron microscopy (HR-STEM) analyses. We grow HfO x , AlO x , or both by means of PE-ALD or thermal ALD on our fabricated devices and show that, in addition to the dielectric constant, three other major parameters related to the processing of the dielectrics can simultaneously affect the MoS2 FET electrical characteristics and govern its doping. These parameters are the stoichiometry of the dielectric, its carbon impurity content, and the degree to which the MoS2 surface oxidizes upon the dielectric growth. When grown at 100 °C, our HfO x films are oxygen-vacant whereas our AlO x films are oxygen-rich. In addition, carbon impurities are incorporated into the dielectrics at low deposition temperatures, being one of the likely causes of the MoS2 FET overall n-type performance in all of the studied cases. Our investigations also reveal that PE-ALD of HfO x or AlO x oxidizes the MoS2 surface, whereas thermal ALD AlO x leaves MoS2 almost intact. In this respect, if thermal ALD AlO x of proper thickness is grown between MoS2 and HfO x , it can reduce the degree to which the MoS2 surface oxidizes by HfO x and meanwhile improve the total dielectric constant, altogether leading to the most optimal electrical performance in ALD-based MoS2 FETs.

Correction to Nb Doping and Alloying of 2D WS2 by Atomic Layer Deposition for 2D Transition Metal Dichalcogenide Transistors and HER Electrocatalysts.

[This corrects the article DOI: 10.1021/acsanm.4c00094.].

Nb Doping and Alloying of 2D WS2 by Atomic Layer Deposition for 2D Transition Metal Dichalcogenide Transistors and HER Electrocatalysts.

We utilize plasma-enhanced atomic layer deposition to synthesize two-dimensional Nb-doped WS2 and NbxW1-xSy alloys to expand the range of properties and improve the performance of 2D transition metal dichalcogenides for electronics and catalysis. Using a supercycle deposition process, films are prepared with compositions spanning the range from WS2 to NbS3. While the W-rich films form crystalline disulfides, the Nb-rich films form amorphous trisulfides. Through tuning the composition of the films, the electrical resistivity is reduced by 4 orders of magnitude compared to pure ALD-grown WS2. To produce Nb-doped WS2 films, we developed a separate ABC-type supercycle process in which a W precursor pulse precedes the Nb precursor pulse, thereby reducing the minimum Nb content of the film by a factor of 3 while maintaining a uniform distribution of the Nb dopant. Initial results are presented on the electrical and electrocatalytic performances of the films. Promisingly, the NbxW1-xSy films of 10 nm thickness and composition x ≈ 0.08 are p-type semiconductors and have a low contact resistivity of (8 ± 1) × 102 Ω cm to Pd/Au contacts, demonstrating their potential use in contact engineering of 2D TMD transistors.

Structure and electronic transport in graphene wrinkles.

Wrinkling is a ubiquitous phenomenon in two-dimensional membranes. In particular, in the large-scale growth of graphene on metallic substrates, high densities of wrinkles are commonly observed. Despite their prevalence and potential impact on large-scale graphene electronics, relatively little is known about their structural morphology and electronic properties. Surveying the graphene landscape using atomic force microscopy, we found that wrinkles reach a certain maximum height before folding over. Calculations of the energetics explain the morphological transition and indicate that the tall ripples are collapsed into narrow standing wrinkles by van der Waals forces, analogous to large-diameter nanotubes. Quantum transport calculations show that conductance through these "collapsed wrinkle" structures is limited mainly by a density-of-states bottleneck and by interlayer tunneling across the collapsed bilayer region. Also through systematic measurements across large numbers of devices with wide "folded wrinkles", we find a distinct anisotropy in their electrical resistivity, consistent with our transport simulations. These results highlight the coupling between morphology and electronic properties, which has important practical implications for large-scale high-speed graphene electronics.

State-of-the-art graphene high-frequency electronics.

High-performance graphene transistors for radio frequency applications have received much attention and significant progress has been achieved. However, devices based on large-area synthetic graphene, which have direct technological relevance, are still typically outperformed by those based on mechanically exfoliated graphene. Here, we report devices with intrinsic cutoff frequency above 300 GHz, based on both wafer-scale CVD grown graphene and epitaxial graphene on SiC, thus surpassing previous records on any graphene material. We also demonstrate devices with optimized architecture exhibiting voltage and power gains reaching 20 dB and a wafer-scale integrated graphene amplifier circuit with voltage amplification.

ALD-grown two-dimensional TiSx metal contacts for MoS2 field-effect transistors.

Metal contacts to MoS2 field-effect transistors (FETs) play a determinant role in the device electrical characteristics and need to be chosen carefully. Because of the Schottky barrier (SB) and the Fermi level pinning (FLP) effects that occur at the contact/MoS2 interface, MoS2 FETs often suffer from high contact resistance (Rc). One way to overcome this issue is to replace the conventional 3D bulk metal contacts with 2D counterparts. Herein, we investigate 2D metallic TiSx (x ∼ 1.8) as top contacts for MoS2 FETs. We employ atomic layer deposition (ALD) for the synthesis of both the MoS2 channels as well as the TiSx contacts and assess the electrical performance of the fabricated devices. Various thicknesses of TiSx are grown on MoS2, and the resultant devices are electrically compared to the ones with the conventional Ti metal contacts. Our findings show that the replacement of 5 nm Ti bulk contacts with only ∼1.2 nm of 2D TiSx is beneficial in improving the overall device metrics. With such ultrathin TiSx contacts, the ON-state current (ION) triples and increases to ∼35 µA µm-1. Rc also reduces by a factor of four and reaches ∼5 MΩ µm. Such performance enhancements were observed despite the SB formed at the TiSx/MoS2 interface is believed to be higher than the SB formed at the Ti/MoS2 interface. These device metric improvements could therefore be mainly associated with an increased level of electrostatic doping in MoS2, as a result of using 2D TiSx for contacting the 2D MoS2. Our findings are also well supported by TCAD device simulations.

Toolbox of Advanced Atomic Layer Deposition Processes for Tailoring Large-Area MoS2 Thin Films at 150 °C.

Two-dimensional MoS2 is a promising material for applications, including electronics and electrocatalysis. However, scalable methods capable of depositing MoS2 at low temperatures are scarce. Herein, we present a toolbox of advanced plasma-enhanced atomic layer deposition (ALD) processes, producing wafer-scale polycrystalline MoS2 films of accurately controlled thickness. Our ALD processes are based on two individually controlled plasma exposures, one optimized for deposition and the other for modification. In this way, film properties can be tailored toward different applications at a very low deposition temperature of 150 °C. For the modification step, either H2 or Ar plasma can be used to combat excess sulfur incorporation and crystallize the films. Using H2 plasma, a higher degree of crystallinity compared with other reported low-temperature processes is achieved. Applying H2 plasma steps periodically instead of every ALD cycle allows for control of the morphology and enables deposition of smooth, polycrystalline MoS2 films. Using an Ar plasma instead, more disordered MoS2 films are deposited, which show promise for the electrochemical hydrogen evolution reaction. For electronics, our processes enable control of the carrier density from 6 × 1016 to 2 × 1021 cm-3 with Hall mobilities up to 0.3 cm2 V-1 s-1. The process toolbox forms a basis for rational design of low-temperature transition metal dichalcogenide deposition processes compatible with a range of substrates and applications.

Large-scale graphene transistors with enhanced performance and reliability based on interface engineering by phenylsilane self-assembled monolayers.

In this letter, we report the dielectric/graphene interface physics and engineering of large-scale, chemical vapor deposited (CVD) graphene transistors by self-assembling a molecular-scale organosilane monolayer onto the dielectric surface. We show that phenyl-alkyl-terminated self-assembled monolayers (SAM) at the dielectric/graphene interface consistently improve the graphene device performance and reliability. The extrinsic field-effect mobility of large-scale CVD graphene transistors on the phenyl-SAM engineered dielectric is currently up to 2500 cm(2)/(V s) at room temperature, considerably higher than the counterparts without the SAM. In addition, significant reduction on the bias stress instability and hysteresis is achieved by the SAM-based interface engineering. Further analysis reveals that charge injection from graphene to the dielectric/graphene interface dominates the observed hysteresis behavior. For both graphene transistors with and without SAMs, the bias stress stability, that is, Dirac point shift under bias stress, is well described by the stretched exponential model with its fitting parameters clearly indicating different interface properties.

High-frequency graphene voltage amplifier.

While graphene transistors have proven capable of delivering gigahertz-range cutoff frequencies, applying the devices to RF circuits has been largely hindered by the lack of current saturation in the zero band gap graphene. Herein, the first high-frequency voltage amplifier is demonstrated using large-area chemical vapor deposition grown graphene. The graphene field-effect transistor (GFET) has a 6-finger gate design with gate length of 500 nm. The graphene common-source amplifier exhibits ∼5 dB low frequency gain with the 3 dB bandwidth greater than 6 GHz. This first AC voltage gain demonstration of a GFET is attributed to the clear current saturation in the device, which is enabled by an ultrathin gate dielectric (4 nm HfO(2)) of the embedded gate structures. The device also shows extrinsic transconductance of 1.2 mS/µm at 1 V drain bias, the highest for graphene FETs using large-scale graphene reported to date.

The graphene-gold interface and its implications for nanoelectronics.

We combine optical microspectroscopy and electronic measurements to study how gold deposition affects the physical properties of graphene. We find that the electronic structure, the electron-phonon coupling, and the doping level in gold-plated graphene are largely preserved. The transfer lengths for electrons and holes at the graphene-gold contact have values as high as 1.6 µm. However, the interfacial coupling of graphene and gold causes local temperature drops of up to 500 K in operating electronic devices.

Atomic Layer Deposition of Large-Area Polycrystalline Transition Metal Dichalcogenides from 100 °C through Control of Plasma Chemistry.

Two-dimensional transition metal dichalcogenides, such as MoS2, are intensely studied for applications in electronics. However, the difficulty of depositing large-area films of sufficient quality under application-relevant conditions remains a major challenge. Herein, we demonstrate deposition of polycrystalline, wafer-scale MoS2, TiS2, and WS2 films of controlled thickness at record-low temperatures down to 100 °C using plasma-enhanced atomic layer deposition. We show that preventing excess sulfur incorporation from H2S-based plasma is the key to deposition of crystalline films, which can be achieved by adding H2 to the plasma feed gas. Film composition, crystallinity, growth, morphology, and electrical properties of MoS x films prepared within a broad range of deposition conditions have been systematically characterized. Film characteristics are correlated with results of field-effect transistors based on MoS2 films deposited at 100 °C. The capability to deposit MoS2 on poly(ethylene terephthalate) substrates showcases the potential of our process for flexible devices. Furthermore, the composition control achieved by tailoring plasma chemistry is relevant for all low-temperature plasma-enhanced deposition processes of metal chalcogenides.

Effects of the Structure and Temperature on the Nature of Excitons in the Mo0.6W0.4S2 Alloy.

We studied the nature of excitons in the transition metal dichalcogenide alloy Mo0.6W0.4S2 compared to pure MoS2 and WS2 grown by atomic layer deposition (ALD). For this, optical absorption/transmission spectroscopy and time-dependent density functional theory (TDDFT) were used. The effects of temperature on A and B exciton peak energies and line widths in optical transmission spectra were compared between the alloy and pure MoS2 and WS2. On increasing the temperature from 25 to 293 K, the energy of the A and B exciton peaks decreases, while their line width increases due to exciton-phonon interactions. The exciton-phonon interactions in the alloy are closer to those for MoS2 than those for WS2. This suggests that exciton wave functions in the alloy have a larger amplitude on Mo atoms than that on W atoms. The experimental absorption spectra could be reproduced by TDDFT calculations. Interestingly, for the alloy, the Mo and W atoms had to be distributed over all layers. Conversely, we could not reproduce the experimental alloy spectrum by calculations on a structure with alternating layers, in which every other layer contains only Mo atoms and the layers in between also contain W atoms. For the latter atomic arrangement, the TDDFT calculations yielded an additional optical absorption peak that could be due to excitons with some charge transfer character. From these results, we conclude that ALD yields an alloy in which Mo and W atoms are distributed uniformly among all layers.

Conformal Growth of Nanometer-Thick Transition Metal Dichalcogenide TiS x -NbS x Heterostructures over 3D Substrates by Atomic Layer Deposition: Implications for Device Fabrication.

The scalable and conformal synthesis of two-dimensional (2D) transition metal dichalcogenide (TMDC) heterostructures is a persisting challenge for their implementation in next-generation devices. In this work, we report the synthesis of nanometer-thick 2D TMDC heterostructures consisting of TiS x -NbS x on both planar and 3D structures using atomic layer deposition (ALD) at low temperatures (200-300 °C). To this end, a process was developed for the growth of 2D NbS x by thermal ALD using (tert-butylimido)-tris-(diethylamino)-niobium (TBTDEN) and H2S gas. This process complemented the TiS x thermal ALD process for the growth of 2D TiS x -NbS x heterostructures. Precise thickness control of the individual TMDC material layers was demonstrated by fabricating multilayer (5-layer) TiS x -NbS x heterostructures with independently varied layer thicknesses. The heterostructures were successfully deposited on large-area planar substrates as well as over a 3D nanowire array for demonstrating the scalability and conformality of the heterostructure growth process. The current study demonstrates the advantages of ALD for the scalable synthesis of 2D heterostructures conformally over a 3D substrate with precise thickness control of the individual material layers at low temperatures. This makes the application of 2D TMDC heterostructures for nanoelectronics promising in both BEOL and FEOL containing high-aspect-ratio 3D structures.

On the Contact Optimization of ALD-Based MoS2 FETs: Correlation of Processing Conditions and Interface Chemistry with Device Electrical Performance.

Despite the extensive ongoing research on MoS2 field effect transistors (FETs), the key role of device processing conditions in the chemistry involved at the metal-to-MoS2 interface and their influence on the electrical performance are often overlooked. In addition, the majority of reports on MoS2 contacts are based on exfoliated MoS2, whereas synthetic films are even more susceptible to the changes made in device processing conditions. In this paper, working FETs with atomic layer deposition (ALD)-based MoS2 films and Ti/Au contacts are demonstrated, using current-voltage (I-V) characterization. In pursuit of optimizing the contacts, high-vacuum thermal annealing as well as O2/Ar plasma cleaning treatments are introduced, and their influence on the electrical performance is studied. The electrical findings are linked to the interface chemistry through X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM) analyses. XPS evaluation reveals that the concentration of organic residues on the MoS2 surface, as a result of resist usage during the device processing, is significant. Removal of these contaminations with O2/Ar plasma changes the MoS2 chemical state and enhances the MoS2 electrical properties. Based on the STEM analysis, the observed progress in the device electrical characteristics could also be associated with the formation of a continuous TiS x layer at the Ti-to-MoS2 interface. Scaling down the Ti interlayer thickness and replacing it with Cr is found to be beneficial as well, leading to further device performance advancements. Our findings are of value for attaining optimal contacts to synthetic MoS2 films.

Gate-variable light absorption and emission in a semiconducting carbon nanotube.

We investigate the gate field dependence of light absorption and emission of an individual, suspended semiconducting carbon nanotube using Raman and photoluminescence spectroscopies. We find a strong reduction in the absorption strength and a red shift of the E(33) state of the nanotube with increasing gate field. The photoluminescence from the E(11) state is quenched even stronger. We explain these observations in terms of field-doping and its effects on both the radiative and nonradiative decay rates of the excitons. Thus, gate field-induced doping constitutes an effective means of controlling the optical properties of carbon nanotube devices.