| 1. |
- Boix, Virgínia, et al.
(författare)
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Area-selective Electron-beam induced deposition of Amorphous-BNx on graphene
- 2021
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Ingår i: Applied Surface Science. - : Elsevier BV. - 0169-4332. ; 557, s. 149806-149806
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Tidskriftsartikel (refereegranskat)abstract
- Thin, stable and inert dielectric spacers are essential for manufacturing electronic devices based on 2D materials. However, direct synthesis on top of 2D materials is difficult due to their inert nature. In this work, we studied how an electron beam induces fragmentation of borazine and enables spatially confined synthesis of amorphous-BNx on graphene at room temperature. Using a combination of X-ray Photoelectron Spectroscopy, Low Energy Electron Microscopy, and Scanning Tunneling Microscopy we studied the morphology of the heterostructure, its chemical composition, and finally its temperature evolution. We find that electron-beam induced deposition starts by the binding of heavily fragmentized borazine, including atomic boron, followed by the growth of a multilayer with a 1:0.7 B:N ratio. The final structure exhibits a thermal stability up to 1400 K and ~ 50 nm spatial control provided by the electron beam. Our studies provide surface science insight into the use of electron beams for synthesis and lateral control of stable and inert layers in 2D heterostructures.
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| 2. |
- Boix, Virginia, et al.
(författare)
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Following the Kinetics of Undercover Catalysis with APXPS and the Role of Hydrogen as an Intercalation Promoter
- 2022
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 12:16, s. 9897-9907
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Tidskriftsartikel (refereegranskat)abstract
- While improved catalytic properties of many surfaces covered by two-dimensional materials have been demonstrated, a detailed in situ picture of gas delivery, undercover reaction, and product removal from the confined space is lacking. Here, we demonstrate how a combination of gas pulses with varying compositions and time-resolved ambient pressure photoelectron spectroscopy can be used to obtain such knowledge. This approach allows us to sequentially form and remove undercover reaction products, in contrast to previous work, where co-dosing of reactant gases was used. In more detail, we study CO and H2 oxidation below oxygen-intercalated graphene flakes partially covering an Ir(111) surface. We show that hydrogen rapidly mixes into a p(2 × 1)-O structure below the graphene flakes and converts it into a dense OH-H2O phase. In contrast, CO exposure only leads to oxygen removal from the confined space and little CO intercalation. Finally, our study shows that H2 mixed into CO pulses can be used as a promoter to change the undercover chemistry. Their combined exposure leads to the formation of OH-H2O below the flakes, which, in turn, unbinds the flakes for enough time for CO to intercalate, resulting in a CO structure stable only in coexistence with the OH-H2O phase. Altogether, our study proves that promoter chemistry in the form of adding trace gases to the gas feed is essential to consider for undercover reactions.
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| 3. |
- Boix, Virginia, et al.
(författare)
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Graphene as an Adsorption Template for Studying Double Bond Activation in Catalysis
- 2022
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 126:33, s. 14116-14124
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Tidskriftsartikel (refereegranskat)abstract
- Hydrogenated graphene (H-Gr) is an extensively studied system not only because of its capabilities as a simplified model system for hydrocarbon chemistry but also because hydrogenation is a compelling method for Gr functionalization. However, knowledge of how H-Gr interacts with molecules at higher pressures and ambient conditions is lacking. Here we present experimental and theoretical evidence that room temperature O2exposure at millibar pressures leads to preferential removal of H dimers on H-functionalized graphene, leaving H clusters on the surface. Our density functional theory (DFT) analysis shows that the removal of H dimers is the result of water or hydrogen peroxide formation. For water formation, we show that the two H atoms in the dimer motif attack one end of the physisorbed O2molecule. Moreover, by comparing the reaction pathways in a vacuum with the ones on free-standing graphene and on the graphene/Ir(111) system, we find that the main role of graphene is to arrange the H atoms in geometrical positions, which facilitates the activation of the O═O double bond.
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| 4. |
- D'Acunto, Giulio, et al.
(författare)
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Atomic Layer Deposition of Hafnium Oxide on InAs : Insight from Time-Resolved in Situ Studies
- 2020
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Ingår i: ACS Applied Electronic Materials. - : American Chemical Society (ACS). - 2637-6113. ; 2:12, s. 3915-3922
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Tidskriftsartikel (refereegranskat)abstract
- III-V semiconductors, such as InAs, with an ultrathin high-κ oxide layer have attracted a lot of interests in recent years as potential next-generation metal-oxide-semiconductor field-effect transistors, with increased speed and reduced power consumption. The deposition of the high-κ oxides is nowadays based on atomic layer deposition (ALD), which guarantees atomic precision and control over the dimensions. However, the chemistry and the reaction mechanism involved are still partially unknown. This study reports a detailed time-resolved analysis of the ALD of high-κ hafnium oxide (HfOx) on InAs(100). We use ambient pressure X-ray photoemission spectroscopy and monitor the surface chemistry during the first ALD half-cycle, i.e., during the deposition of the metalorganic precursor. The removal of In and As native oxides, the adsorption of the Hf-containing precursor molecule, and the formation of HfOx are investigated simultaneously and quantitatively. In particular, we find that the generally used ligand exchange model has to be extended to a two-step model to properly describe the first half-cycle in ALD, which is crucial for the whole process. The observed reactions lead to a complete removal of the native oxide and the formation of a full monolayer of HfOx already during the first ALD half-cycle, with an interface consisting of In-O bonds. We demonstrate that a sufficiently long duration of the first half-cycle is essential for obtaining a high-quality InAs/HfO2 interface.
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| 5. |
- D'acunto, Giulio, et al.
(författare)
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Bimolecular Reaction Mechanism in the Amido Complex-Based Atomic Layer Deposition of HfO2
- 2023
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 35:2, s. 529-538
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Tidskriftsartikel (refereegranskat)abstract
- The surface chemistry of the initial growth during the first or first few precursor cycles in atomic layer deposition is decisive for how the growth proceeds later on and thus for the quality of the thin films grown. Yet, although general schemes of the surface chemistry of atomic layer deposition have been developed for many processes and precursors, in many cases, knowledge of this surface chemistry remains far from complete. For the particular case of HfO2 atomic layer deposition on a SiO2 surface from an alkylamido-hafnium precursor and water, we address this lack by carrying out an operando atomic layer deposition experiment during the first cycle of atomic layer deposition. Ambient-pressure X-ray photoelectron spectroscopy and density functional theory together show that the decomposition of the metal precursor on the stoichiometric SiO2 surface in the first half-cycle of atomic layer deposition proceeds via a bimolecular reaction mechanism. The reaction leads to the formation of Hf-bonded methyl methylene imine and free dimethylamine. In addition, ligand exchange takes place involving the surface hydroxyls adsorbed at defect sites of the SiO2 surface.
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| 6. |
- D’Acunto, Giulio, et al.
(författare)
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Oxygen relocation during HfO2 ALD on InAs
- 2022
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Ingår i: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 236, s. 71-85
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Tidskriftsartikel (refereegranskat)abstract
- Atomic layer deposition (ALD) is one of the backbones for today’s electronic device fabrication. A critical property of ALD is the layer-by-layer growth, which gives rise to the atomic-scale accuracy. However, the growth rate - or growth per cycle - can differ significantly depending on the type of system, molecules used, and several other experimental parameters. Typically, ALD growth rates are constant in subsequent ALD cycles, making ALD an outstanding deposition technique. However, contrary to this steady-state - when the ALD process can be entirely decoupled from the substrate on which the material is grown - the deposition’s early stage does not appear to follow the same kinetics, chemistry, and growth rate. Instead, it is to a large extent determined by the surface composition of the substrate. Here, we present evidence of oxygen relocation from the substrate-based oxide, either the thermal or native oxide of InAs, to the overlayer of HfO2 in the initial ALD phase. This phenomenon enables control of the thickness of the initial ALD layer by controlling the surface conditions of the substrate prior to ALD. On the other hand, we observe a complete removal of the native oxide from InAs already during the first ALD half-cycle, even if the thickness of the oxide layer exceeds one monolayer, together with a self-limiting thickness of the ALD layer of a maximum of one monolayer of HfO2. These observations not only highlight several limitations of the widely used ligand exchange model, but they also give promise for a better control of the industrially important self-cleaning effect of III-V semiconductors, which is crucial for future generation high-speed MOS.
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| 7. |
- D'Acunto, Giulio, et al.
(författare)
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Role of Temperature, Pressure, and Surface Oxygen Migration in the Initial Atomic Layer Deposition of HfO2on Anatase TiO2(101)
- 2022
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 126:29, s. 12210-12221
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Tidskriftsartikel (refereegranskat)abstract
- The atomic layer deposition of HfO2on a TiO2(101) surface from tetrakis(dimethylamido)hafnium and water is investigated using a combination of in situ vacuum X-ray photoelectron spectroscopy (XPS) and time-resolved ambient pressure XPS. Precursor pressures and surface temperature are tuned as to map the space state of the deposition. In the initial stages of ALD, a reaction mechanism based on dissociative adsorption dominates over a classic ligand exchange mechanism, typically evoked when metal-amido complexes and water are used as the precursors for metal oxide ALD. Surface species, including a dimethyl ammonium ion and an imine, are identified. It is found that they can be formed only if the active role of the TiO2(101) surface is taken into consideration. The temperature of the surface enhances the formation of these species based on an insertion reaction of a hydrogen atom, which then assists the formation of more than the expected monolayer of HfO2. A HfO2overlayer is produced already during the first half-cycle, enabled by a reduction of the TiO2support. Dosing water at high pressure allows hydroxyl formation, which marks the transition toward a well-described ligand exchange reaction type. From the experiments performed, we find that the ALD of HfO2at room temperature, performed at high pressure, is mainly based on dissociation and that no side reaction occurs. These insights into the ALD reaction mechanism highlight how in situ studies can help understand how deposition parameters affect the growth of HfO2and how the ALD model for transition metal oxide formation from amido complexes and water can be extended.
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| 8. |
- D'Acunto, Giulio, et al.
(författare)
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Time evolution of surface species during the ALD of high-k oxide on InAs
- 2023
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Ingår i: Surfaces and Interfaces. - 2468-0230. ; 39:102927
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the reaction mechanisms involved during the early stage of atomic layer deposition (ALD) of HfO2 on InAs is a key requirement for improving interfaces in III-V semiconductor-based devices. InAs is an excellent candidate to outperform silicon regarding speed and power consumption, and combined with HfO2, it gives promise for a new generation of ultra-fast MOSFETs. However, an improved interface quality and in-depth understanding of the involved surface species are needed. Here, we use in situ and operando ambient pressure XPS to follow in real-time the reaction mechanisms which control the ALD chemistry. Besides the removal of all unwanted oxide from the III-V, the same oxygen atoms are found to form HfOx already from the first half-cycle. In contrast to the standard ALD model, no hydroxyl groups are needed on the InAs surface. Furthermore, we observe an insertion reaction forming unexpected surface species. The second ALD half-cycle allows the immediate removal of all organic species leaving behind a uniform HfO2 layer partially terminated by hydroxyl groups. We find that prolonged exposure times upon both half-cycles guarantee a sharp InAs/HfO2 interface. Such an improved interface is an important step towards fast and sustainable III-V semiconductor-based electronics.
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| 9. |
- Guo, Meiyuan, et al.
(författare)
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Using Iron L-Edge and Nitrogen K-Edge X-ray Absorption Spectroscopy to Improve the Understanding of the Electronic Structure of Iron Carbene Complexes
- 2024
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Ingår i: Inorganic Chemistry. - 0020-1669. ; 63:27, s. 12457-12468
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Tidskriftsartikel (refereegranskat)abstract
- Iron-centered N-heterocyclic carbene compounds have attracted much attention in recent years due to their long-lived excited states with charge transfer (CT) character. Understanding the orbital interactions between the metal and ligand orbitals is of great importance for the rational tuning of the transition metal compound properties, e.g., for future photovoltaic and photocatalytic applications. Here, we investigate a series of iron-centered N-heterocyclic carbene complexes with +2, + 3, and +4 oxidation states of the central iron ion using iron L-edge and nitrogen K-edge X-ray absorption spectroscopy (XAS). The experimental Fe L-edge XAS data were simulated and interpreted through restricted-active space (RAS) and multiplet calculations. The experimental N K-edge XAS is simulated and compared with time-dependent density functional theory (TDDFT) calculations. Through the combination of the complementary Fe L-edge and N K-edge XAS, direct probing of the complex interplay of the metal and ligand character orbitals was possible. The σ-donating and π-accepting capabilities of different ligands are compared, evaluated, and discussed. The results show how X-ray spectroscopy, together with advanced modeling, can be a powerful tool for understanding the complex interplay of metal and ligand.
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| 10. |
- Irish, Austin, et al.
(författare)
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Nitrogen plasma passivation of GaAs nanowires resolved by temperature dependent photoluminescence
- 2022
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Ingår i: NANO EXPRESS. - : Institute of Physics (IOP). - 2632-959X. ; 3:4
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrate a significant improvement in the optical performance of GaAs nanowires achieved using a mixed nitrogen-hydrogen plasma which passivates surface states and reduces the rate of nonradiative recombination. This has been confirmed by time-resolved photoluminescence measurements. At room temperature, the intensity and lifetime of radiative recombination in the plasma-treated nanowires was several times greater than that of the as-grown GaAs nanowires. Low-temperature measurements corroborated these findings, revealing a dramatic increase in photoluminescence by two orders of magnitude. Photoelectron spectroscopy of plasma passivated nanowires demonstrated a yearlong stability achieved through the replacement of surface oxygen with nitrogen. Furthermore, the process removed the As-0 defects observed on non-passivated nanowires which are known to impair devices. The results validate plasma as a nitridation technique suitable for nanoscale GaAs crystals. As a simple ex situ procedure with modest temperature and vacuum requirements, it represents an easy method for incorporating GaAs nanostructures into optoelectronic devices.
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