Sunil Bhardwaj

In Situ Observations of the Atomistic Mechanisms of Ni Catalyzed Low Temperature Graphene Growth

The key atomistic mechanisms of graphene formation on Ni for technologically relevant hydrocarbon exposures below 600 °C are directly revealed via complementary in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. For clean Ni(111) below 500 °C, two different surface carbide (Ni2C) conversion mechanisms are dominant which both yield epitaxial graphene, whereas above 500 °C, graphene predominantly grows directly on Ni(111) via replacement mechanisms leading to embedded epitaxial and/or rotated graphene domains. Upon cooling, additional carbon structures form exclusively underneath rotated graphene domains. The dominant graphene growth mechanism also critically depends on the near-surface carbon concentration and hence is intimately linked to the full history of the catalyst and all possible sources of contamination. The detailed XPS fingerprinting of these processes allows a direct link to high pressure XPS measurements of a wide range of growth conditions, including polycrystalline Ni catalysts and recipes commonly used in industrial reactors for graphene and carbon nanotube CVD. This enables an unambiguous and consistent interpretation of prior literature and an assessment of how the quality/structure of as-grown carbon nanostructures relates to the growth modes.

Low temperature growth of ultra-high mass density carbon nanotube forests on conductive supports

We grow ultra-high mass density carbon nanotube forests at 450 °C on Ti-coated Cu supports using Co-Mo co-catalyst. X-ray photoelectron spectroscopy shows Mo strongly interacts with Ti and Co, suppressing both aggregation and lifting off of Co particles and, thus, promoting the root growth mechanism. The forests average a height of 0.38 μm and a mass density of 1.6 g cm−3. This mass density is the highest reported so far, even at higher temperatures or on insulators. The forests and Cu supports show ohmic conductivity (lowest resistance ∼22 kΩ), suggesting Co-Mo is useful for applications requiring forest growth on conductors.

Use of plasma treatment to grow carbon nanotube forests on TiN substrate

Hydrogen plasma pretreatment is used to enforce the growth of vertically-aligned carbon nanotube forests on TiN substrates. The evolution of the substrate, catalyst, and nanotubes are studied by in situ and ex-situ photoemission and X-ray diffraction in order to understand the growth mechanism. We find that TiN retains its crystallographic structure and its conductivity during plasma pretreatment and nanotube growth, which is confirmed by electrical measurements. Plasma pretreatment is found to favor the growth of nanotube forests by root growth, as it binds the catalyst nanoparticles more strongly to the substrate than thermal pretreatment. We find that plasma pretreatment time should be limited, otherwise poor or no growth is found.

Stability of graphene doping with MoO3 and I2

We dope graphene by evaporation of MoO3 or by solution-deposition of I2 and assess the doping stability for its use as transparent electrodes. Electrical measurements show that both dopants increase the graphene sheet conductivity and find that MoO3-doped graphene is significantly more stable during thermal cycling. Raman spectroscopy finds that neither dopant creates defects in the graphene lattice. In-situ photoemission determines the minimum necessary thickness of MoO3 for full graphene doping.

Heterogeneous and homogeneous routes in water oxidation catalysis starting from Cu(II) complexes with tetraaza macrocyclic ligands

Since the first report in 2012, molecular copper complexes have been proposed as efficient electrocatalysts for water oxidation reactions, carried out in alkaline/neutral aqueous media. However, in some cases the copper species have been recognized as precursors of an active copper oxide layer, electrodeposited onto the working electrode. Therefore, the question whether copper catalysis is molecular or not is particularly relevant in the field of water oxidation. In this study, we investigate the electrochemical activity of copper(II) complexes with two tetraaza macrocyclic ligands, distinguishing heterogeneous or homogeneous processes depending on the reaction media. In an alkaline aqueous solution, and upon application of an anodic bias to working electrodes, an active copper oxide layer is observed to electrodeposit at the electrode surface. Conversely, water oxidation in neutral aqueous buffers is not associated to formation of the copper oxide layer, and could be exploited to evaluate and optimize a molecular, homogeneous catalysis.

Plasma stabilisation of metallic nanoparticles on silicon for the growth of carbon nanotubes

Ammonia (NH3) plasma pretreatment is used to form and temporarily reduce the mobility of Ni, Co, or Fe nanoparticles on boron-doped mono- and poly-crystalline silicon. X-ray photoemission spectroscopy proves that NH3 plasma nitrides the Si supports during nanoparticle formation which prevents excessive nanoparticle sintering/diffusion into the bulk of Si during carbon nanotube growth by chemical vapour deposition. The nitridation of Si thus leads to nanotube vertical alignment and the growth of nanotube forests by root growth mechanism.

Low Temperature Growth of Carbon Nanotube Forests Consisting of Tubes with Narrow Inner Spacing Using Co/Al/Mo Catalyst on Conductive Supports

We grow dense carbon nanotube forests at 450 °C on Cu support using Co/Al/Mo multilayer catalyst. As a partial barrier layer for the diffusion of Co into Mo, we apply very thin Al layer with the nominal thickness of 0.50 nm between Co and Mo. This Al layer plays an important role in the growth of dense CNT forests, partially preventing the Co-Mo interaction. The forests have an average height of ∼300 nm and a mass density of 1.2 g cm(-3) with tubes exhibiting extremely narrow inner spacing. An ohmic behavior is confirmed between the forest and Cu support with the lowest resistance of ∼8 kΩ. The forest shows a high thermal effusivity of 1840 J s(-0.5) m(-2) K(-1), and a thermal conductivity of 4.0 J s(-1) m(-1) K(-1), suggesting that these forests are useful for heat dissipation devices.

1.5 MeV proton irradiation effects on electrical and structural properties of TiO2/n-Si interface

In this paper, we report the effect of 1.5 MeV proton beam irradiation dose on the structural and electrical properties of TiO2 thin films deposited on n–Si substrates. The formation and transformation of different TiO2 phases in the irradiated thin films were characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS). X-ray diffraction measurements revealed that the as grown film was rich in Ti5O9 phase and then converted to mixed phases of TiO2 (rutile and anatase) after exposure with radiation doses up to 5 × 1014 cm−2. The XPS results revealed the formation of oxygen vacancy (negative) traps in the exposed TiO2 films, which showed strong dependence on the dose. The C-V measurements showed that proton radiations also damaged the Si substrate and created deep level defects in the substrate, which caused a shift of 0.26 ± 0.01 V in the flat band voltage (VFB). I–V measurements showed that the ideality factor increased and the rectification ratio dropped with the increase in the radiati...

The synergistic effect in the Fe-Co bimetallic catalyst system for the growth of carbon nanotube forests

We report the growth of multi-walled carbon nanotube forests employing an active-active bimetallic Fe-Co catalyst. Using this catalyst system, we observe a synergistic effect by which—in comparison to pure Fe or Co—the height of the forests increases significantly. The homogeneity in the as-grown nanotubes is also improved. By both energy dispersive spectroscopy and in-situ x-ray photoelectron spectroscopy, we show that the catalyst particles consist of Fe and Co, and this dramatically increases the growth rate of the tubes. Bimetallic catalysts are thus potentially useful for synthesising nanotube forests more efficiently.

Carbon nanotube forests as top electrode in electroacoustic resonators

We grow carbon nanotube forests on piezoelectric AlN films and fabricate and characterize nanotube-based solidly mounted bulk acoustic wave resonators employing the forests as the top electrode material. The devices show values for quality factor at anti-resonance of ∼430, and at resonance of ∼100. The effective coupling coefficient is of ∼6%, and the resonant frequencies are up to ∼800 MHz above those observed with metallic top electrodes. AlN promotes a strong catalyst-support interaction, which reduces Fe catalyst mobility, and thus enforces the growth of forests by the base growth mechanism.