The low limit of the deposition temperature for atomic layer deposition (ALD) of noble metals has been studied. Two approaches were taken; using pure oxygen instead of air and using a noble metal starting surface instead of Al2O3. Platinum thin films were obtained by ALD from MeCpPtMe3 and pure oxygen at deposition temperature as low as 200 °C, which is significantly lower than the low-temperature limit of300 °C previously reported for the platinum ALD process in which air was used as the oxygen source. The platinum films grown in this study had smooth surfaces, adhered well to the substrate, and had low impurity contents. ALD of ruthenium, on the other hand, took place at lower deposition temperatures on an iridium seed layer than on an Al2O3 layer. On iridium surface, ruthenium films were obtained from RuCp2 and oxygen at 225 °C and from Ru(thd)3 and oxygen at 250 °C, whereas no films were obtained on Al2O3 at temperatures lower than 275 and 325 °C, respectively. The crystal orientation of the ruthenium films was found to depend on the precursor. ALD of palladium from a palladium β-ketoiminate precursor and oxygen at 250 and 275 °C was also studied. However, the film-growth rate did not saturate to a constant level when the precursor pulse times were increased.
ZnO is a wide band gap metal oxide with a very interesting combination of semiconducting, transparent optical and catalytic properties. Recently, an amplified interest in ZnO has appeared due to the impressive progress made in nanofabrication of tailored ZnO nanostructures and functional surfaces. However, the fundamental principles governing the structure of even the clean low-index ZnO surfaces have not been adequately explained. From an interplay of high-resolution scanning probe microscopy (SPM), X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments, and density functional theory (DFT) calculations, we identify here a group of hitherto unresolved surface structures which stabilize the clean polar O-terminated ZnO(0001) surface. The found honeycomb structures are truly remarkable since their existence deviates from expectations using a conventional electrostatic model which applies to the opposite Zn-terminated (0001) surface. As a common principle, the differences for the clean polar ZnO surfaces are explained by a higher bonding flexibility of the exposed 3-fold coordinated surface Zn atoms as compared to O atoms.
Compared to the most well-known 2D material, graphene, which is a semi-metal, the semiconducting 2H phase of MoS 2 is advantageous in having a band gap suitable for electronic applications. In bulk form, MoS 2 has an indirect band gap of 1.3 eV, which increases as a function of decreasing film thickness. In monolayer MoS 2 (thickness ≈0.6 nm), the band gap becomes direct with a width of 1.8 eV. [1] Importantly, to meet the requirements of different applications, properties of MoS 2 and other TMDCs can be tuned by controlling the thickness, [1] doping and alloying, [5][6][7][8] surface modification and functionalization, [9][10][11] strain, [12,13] and by creating heterostructures with other 2D materials. [6,[14][15][16] The appealing properties of TMDCs have led to a wide range of proposed applications. MoS 2 has been extensively studied as a channel material in conventional field-effect transistors, [17][18][19][20][21] as well as phototransistors and other optoelectronic devices. [16,21,22] The 2D structure of TMDCs plays a crucial role in possible applications relying on more exotic quantum phenomena, such as valleytronics. [23,24] MoS 2 has also shown promise in, for example, catalysis, [25] batteries, [26] photovoltaics, [27] sensors, [28] and medicine. [29] The production of high-quality, large-area MoS 2 films with a thickness controllable down to a monolayer, as required in many of the aforementioned applications, still remains a major challenge. Additionally, in many cases, the processing temperature should be kept as low as possible in order to avoid damaging sensitive substrates, such as polymers or nanostructures. Initially, flakes of monolayer MoS 2 were produced from natural MoS 2 crystals using micromechanical exfoliation, a topdown method capable of producing high-quality monolayers, albeit with poor throughput as well as limited control over flake thickness and dimensions. [4,30,31] Liquid-phase exfoliation of bulk crystals, on the other hand, offers good scalability, but often suffers from limited flake size, poor crystallinity, or contamination. [4,31,32] Bottom-up methods offer a more controllable way to produce MoS 2 films. High-quality MoS 2 thin films are most commonly deposited by chemical vapor deposition (CVD) or sulfurization of metal or metal oxide thin films. The most common Molybdenum disulfide (MoS 2 ) is a semiconducting 2D material, which has evoked wide interest due to its unique properties. However, the lack of controlled and scalable methods for the production of MoS 2 films at low temperatures remains a major hindrance on its way to applications. In this work, atomic layer deposition (ALD) is used to deposit crystalline MoS 2 thin films at a relatively low temperature of 300 °C. A new molybdenum precursor, Mo(thd) 3 (thd = 2,2,6,6-tetramethylheptane-3,5-dionato), is synthesized, characterized, and used for film deposition with H 2 S as the sulfur precursor. Self-limiting growth with a low growth rate of ≈0.025 Å cycle −1 , straightforward thickness control, and large-area uni...
Low-energy deposition of individual metal clusters ͑6-2000 atoms͒ on a ͑100͒ surface is studied for copper, nickel, platinum, silver, and gold by means of molecular-dynamics simulations. For different temperatures ranging from 0 to 750 K we determine the maximum size of clusters that will achieve complete contact epitaxy upon deposition. The results show that two mechanisms contribute to epitaxial alignment. For the smallest cluster sizes, the heat of adsorption released at the interface will immediately ͑ps time scales͒ allow the cluster to melt and become epitaxial by resolidification. This effect gives roughly the same limit for all elements studied. On longer ͑ns͒ time scales, the clusters can align epitaxially by thermally actived motion of twinning dislocations. This mechanism leads to much higher limits of epitaxy than the resolidification process. Moreover, the resulting limits differ significantly between the elements.
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