@misc{TallaridaAdelmannDelabieetal., author = {Tallarida, Massimo and Adelmann, Christoph and Delabie, Annelies and Elshocht, Sven van and Caymax, Matty and Schmeißer, Dieter}, title = {Surface chemistry and Fermi level movement during the self-cleaning of GaAs by trimethyl-aluminum}, series = {Applied physics letters}, volume = {99}, journal = {Applied physics letters}, number = {4}, issn = {1077-3118}, doi = {10.1063/1.3615784}, pages = {042906-1 -- 042906-3}, language = {en} } @misc{PopoviciDelabieAdelmannetal., author = {Popovici, Mihaela and Delabie, Annelies and Adelmann, Christoph and Meersschaut, Johan and Franquet, Alexis and Tallarida, Massimo and Berg, Jaap van den and Richard, Olivier and Swerts, Johan and Tomida, Kazuyuki and Kim, Min-Soo and Tielens, Hilde and Bender, Hugo and Conard, Thierry and Jurczak, Malgorzata and Elshocht, Sven van and Schmeißer, Dieter}, title = {Understanding the Interface Reactions of Rutile TiO2 Grown by Atomic Layer Deposition on Oxidized Ruthenium}, series = {ECS Journal of Solid State Science and Technology}, volume = {2}, journal = {ECS Journal of Solid State Science and Technology}, number = {1}, issn = {2162-8769}, doi = {10.1149/2.035301jss}, pages = {N23 -- N27}, abstract = {The atomic layer deposition of titanium oxide TiO2 on ruthenium and oxidized ruthenium with titanium methoxide as metal precursor and H2O and O3 as oxidant was investigated by Rutherford backscattering (RBS) and time of flight secondary ion mass spectrometry (TOFSIMS). An ultra-thin layer of TiO2 deposited a priori with H2O plays the role of protection of Ru(Ox) substrates against etching by O3. Information about thin films (∼3 nm) interfacial reactions, thickness and structure was brought by Medium Energy Ion Scattering Spectroscopy (MEIS) and X-ray absorption spectroscopy (XAS) measurements. The growth enhancements observed in the first stages of the deposition depends on the pre-treatment (pre-oxidation, H2O based interlayer thickness) of the Ru substrate. Thick films (∼14 nm) were analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The as deposited TiO2 films are crystalline with rutile structure, as resulted from structural analyzes. However, the presence of small amounts of anatase was detected by soft X-ray absorption spectroscopy (XAS) and is strongly influenced by the surface pre-treatment of the Ru substrate. The electrical properties (equivalent oxide thickness and leakage current density) correlate with a different rutile/anatase ratio present in the films.}, language = {en} } @misc{TallaridaAdelmannDelabieetal., author = {Tallarida, Massimo and Adelmann, Christoph and Delabie, Annelies and van Elshocht, Sven and Caymax, Matty and Schmeißer, Dieter}, title = {GaAs clean up studied with synchrotron radiation photoemission}, series = {IOP Conference Series : Materials Science and Engineering}, journal = {IOP Conference Series : Materials Science and Engineering}, number = {41}, issn = {1757-899X}, doi = {10.1088/1757-899X/41/1/012003}, pages = {012003}, abstract = {In this contribution we describe the chemical changes at the surface of GaAs upon adsorption of tri-methyl-aluminum (TMA). TMA is used to grow Al2O3 with atomic layer deposition (ALD) usually using H2O as oxygen source. Recently, it was pointed out that the adsorption of TMA on various III-V surfaces reduces the native oxide, allowing the growth of an abrupt III-V/High-K interface with reduced density of defects. Synchrotron radiation photoemission spectroscopy (SR-PES) is a powerful method to characterize surfaces and interfaces of many materials, as it is capable todetermine their chemical composition as well as the electronic properties. We performed in-situ SR-PES measurements after exposing a GaAs surface to TMA pulses at about 250°C. Upon using the possibility of tuning the incident photon energy we compared the Ga3d spectra at 41 eV, 71 eV, 91 eV and 121 eV, as well as the As3d at 71 eV and 91 eV. Finally, we show that using SR-PES allows a further understanding of the surface composition, which is usually not accessible with other techniques.}, language = {en} } @misc{TallaridaAdelmannDelabieetal., author = {Tallarida, Massimo and Adelmann, Christoph and Delabie, Annelies and Elshocht, Sven van and Caymax, Matty and Schmeißer, Dieter}, title = {III-V/Oxide Interfaces Investigated with Synchrotron Radiation Photoemission Spectroscopy}, series = {ECS Transactions}, volume = {50}, journal = {ECS Transactions}, number = {4}, issn = {1938-6737}, doi = {10.1149/05004.0123ecst}, pages = {123 -- 128}, abstract = {We used synchrotron radiation photoemission spectroscopy (SR-PES) to investigate the surface of GaAs and other III-V semiconductors after tri-methyl-aluminum (TMA) pulses performed at 250{degree sign}C. We observed the removal of native oxide and the growth of Al-oxide upon measuring the As3d, Ga3d, Al2p and VB spectra. After seven TMA pulses we performed one water pulse. As3d and Ga3d peaks showed almost no lineshape change, but a decrease of intensity due to the water adsorption. The valence band shows a change in the secondary electron cut-off and the decrease of work function. We conclude that water mostly adsorbs molecularly and induces the work function decrease. The molecular absorption of water indicates that the seven TMA pulses produce a passivated surface only partially terminated with OH groups.}, language = {en} } @misc{AdelmannCuypersTallaridaetal., author = {Adelmann, Christoph and Cuypers, Daniel and Tallarida, Massimo and Rodriguez, Leonard and De Clercq, Astrid and Friedrich, Daniel and Conard, Thierry and Delabie, Annelies and Seo, Jin Won and Locquet, Jean-Pierre and De Gendt, Stefan and Schmeißer, Dieter and Elshocht, Sven van and Caymax, Matty}, title = {Surface Chemistry and Interface Formation during the Atomic Layer Deposition of Alumina from Trimethylaluminum and Water on Indium Phosphide}, series = {Chemistry of Materials}, volume = {25}, journal = {Chemistry of Materials}, number = {7}, issn = {1520-5002}, doi = {10.1021/cm304070h}, pages = {1078 -- 1091}, abstract = {The surface chemistry and the interface formation during the initial stages of the atomic layer deposition (ALD) of Al2O3 from trimethylaluminum (TMA) and H2O on InP(100)were studied by synchrotron radiation photoemission spectroscopy and scanning tunneling microscopy. The effect of the ex situ surface cleaning by either H2SO4 or (NH4)2S was examined. It is shown that the native oxide on the InP surface consisted mainly of indium hydrogen phosphates with a P enrichment at the interface with InP. After a (NH4)2S treatment, S was present on the surface as a sulfide in both surface and subsurface sites. Exposure to TMA led to the formation of a thin AlPO4 layer, irrespective of the surface cleaning. The surface Fermi level of p-type InP was found to be pinned close to midgap after H2SO4 cleaning and moved only slightly further toward the conduction band edge upon TMA exposure, indicating that the AlPO4/InP interface was rather defective. (NH4)2S passivation led to a Fermi level position of p-type InP close to the conduction band edge. Hence, the InP surface was weakly inverted, which can be attributed to surface doping by S donors. TMA exposure was found to remove surface S, which was accompanied by a shift of the Fermi level to midgap, consistent with the removal of (part of) the S donors in combination with a defective AlPO4/InP interface. Further TMA/H2O ALD did not lead to any detectable changes of the AlPO4/InP interface and suggested simple overgrowth with Al2O3.}, language = {en} } @inproceedings{CuypersDorpTallaridaetal., author = {Cuypers, Daniel and Dorp, Dennis H. von and Tallarida, Massimo and Brizzi, Simone and Rodriguez, Leonard and Conard, Thierry and Arnauts, Sophia and Schmeißer, Dieter and Adelmann, Christoph and De Gendt, Stefan}, title = {Study of InP Surfaces After Wet Chemical Treatments}, series = {Meeting Abstracts-Electrochemical Society, San Francisco, 2013}, booktitle = {Meeting Abstracts-Electrochemical Society, San Francisco, 2013}, publisher = {The Electrochemical Society}, pages = {S. 2132}, language = {en} } @misc{CuypersDorpTallaridaetal., author = {Cuypers, Daniel and Dorp, Dennis H. von and Tallarida, Massimo and Brizzi, Simone and Rodriguez, Leonard and Conard, Thierry and Arnauts, Sophia and Schmeißer, Dieter and Adelmann, Christoph and De Gendt, Stefan}, title = {Study of InP Surfaces after Wet Chemical Treatments}, series = {ECS Transactions}, volume = {58}, journal = {ECS Transactions}, number = {6}, issn = {1938-6737}, doi = {10.1149/05806.0297ecst}, pages = {297 -- 303}, abstract = {In this work synchrotron radiation photoemission spectroscopy (SRPES) is used to study InP surfaces after different wet chemical treatments. All results are compared to a typical fingerprint of surface components present on an as received InP sample. It is shown that acidified (HCl and H₂SO₄) treatments efficiently remove the native phosphate, although components like Pᴼ, Inᴼ and P(2±∆)+ remain present. In alkaline solution (NH₄OH) oxide remains present at the surface. As an alternative treatment, the immersion into (NH₄)₂S was studied. This passivation treatment results in fewer surface components which suggests that a higher quality surface is obtained.}, language = {en} } @misc{CuypersDorpTallaridaetal., author = {Cuypers, Daniel and Dorp, Dennis H. von and Tallarida, Massimo and Brizzi, Simone and Conard, Thierry and Rodriguez, Leonard and Mees, M. and Arnauts, Sophia and Schmeißer, Dieter and Adelmann, Christoph and De Gendt, Stefan}, title = {Study of InP Surfaces after Wet Chemical Treatments}, series = {ECS Journal of Solid State Science and Technology}, volume = {3}, journal = {ECS Journal of Solid State Science and Technology}, number = {1}, issn = {2162-8777}, doi = {10.1149/2.005401jss}, pages = {N3016 -- N3022}, abstract = {The influence of different wet chemical treatments (HCl, H₂SO₄, NH₄OH) on the composition of InP surfaces is studied by using synchrotron radiation photoemission spectroscopy (SRPES). It is shown that a significant amount of oxide remains present after immersion in a NH₄OH solution which is ascribed to the insolubility of In³⁺ at higher pH values. Acidic treatments efficiently remove the native oxide, although components like Pᴼ, Inᴼ and P(2±Δ)+ suboxides are observed. Alternatively, the influence of a passivation step in (NH₄)₂S solution on the surface composition was investigated. The InP surface after immersion into (NH₄)₂S results in fewer surface components, without detection of Pᴼ and P(2±Δ)+ suboxides. Finally, slight etching of InP surfaces in HCl/H₂O₂ solution followed by a native oxide removal step, showed no significant effect on the surface composition.}, language = {en} } @misc{AdelmannSchramChewetal., author = {Adelmann, Christoph and Schram, Tom and Chew, Soon Aik and Woicik, J. C. and Brizzi, Simone and Tallarida, Massimo and Schmeißer, Dieter and Horiguchi, Naoto and Elshocht, Sven van and Ragnarsson, Lars-{\AA}ke}, title = {On the scalability of doped hafnia thin films}, series = {Applied Physics Letters}, journal = {Applied Physics Letters}, number = {104}, issn = {0003-6951}, doi = {10.1063/1.4870075}, pages = {122906-1 -- 122906-4}, abstract = {The scaling behavior of Gd- and Al-doped HfO2 films as gate dielectrics in metal-oxide-semiconductor (MOS) capacitors was studied. For equivalent oxide thicknesses (EOTs) in the range of 10 {\AA}, crystallized Gd:HfO2 showed higher leakage current densities than crystallized Al:HfO2, with undoped HfO2 in between. Ultimately, the scalability of Al:HfO2 was limited by the ability to crystallize the films at a given thermal budget. As a result, for post-deposition annealing at 800 °C, the EOT of Al:HfO2 based MOS capacitors was limited to ∼8 {\AA}. However, for such an EOT, leakage current densities were reduced by about 100× with respect to HfO2. This demonstrates the high potential of Al:HfO2 for low-standby-power MOS devices.}, language = {en} } @misc{NourbakhshAdelmannSongetal., author = {Nourbakhsh, Amirhasan and Adelmann, Christoph and Song, Yi and Lee, Chang Seung and Asselberghs, Inge and Huyghebaert, Cedric and Brizzi, Simone and Tallarida, Massimo and Schmeißer, Dieter and Elshocht, Sven van and Heyns, Marc and Kong, Jing and Palacios, Tom{\´a}s and De Gendt, Stefan}, title = {Graphene oxide monolayers as atomically thin seeding layers for atomic layer deposition of metal oxides}, series = {Nanoscale}, volume = {2015}, journal = {Nanoscale}, number = {7}, issn = {2040-3364}, doi = {10.1039/C5NR01128K}, pages = {10781 -- 10789}, abstract = {Graphene oxide (GO) was explored as an atomically-thin transferable seed layer for the atomic layer deposition (ALD) of dielectric materials on any substrate of choice. This approach does not require specific chemical groups on the target surface to initiate ALD. This establishes GO as a unique interface which enables the growth of dielectric materials on a wide range of substrate materials and opens up numerous prospects for applications. In this work, a mild oxygen plasma treatment was used to oxidize graphene monolayers with well-controlled and tunable density of epoxide functional groups. This was confirmed by synchrotron-radiation photoelectron spectroscopy. In addition, density functional theory calculations were carried out on representative epoxidized graphene monolayer models to correlate the capacitive properties of GO with its electronic structure. Capacitance-voltage measurements showed that the capacitive behavior of Al2O3/GO depends on the oxidation level of GO. Finally, GO was successfully used as an ALD seed layer for the deposition of Al2O3 on chemically inert single layer graphene, resulting in high performance top-gated field-effect transistors.}, language = {en} } @inproceedings{BrizziTallaridaAdelmannetal., author = {Brizzi, Simone and Tallarida, Massimo and Adelmann, Christoph and Ragnarsson, Lars-{\AA}ke and Elshocht, Sven van and Schmeißer, Dieter}, title = {Structural changes in HfO2 thin films: thickness and doping dependence}, series = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, booktitle = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {In this work we show results regarding MOCVD and ALD HfO2 as well as Al-doped HfO2. We use Synchrotron Radiation Photoemission Spectroscopy (SRPES) to determine Hf/O atomic ratios and X-ray Absorption Spectroscopy (XAS) to investigate the electronic properties related to their crystallization. MOCVD films are synthesized at temperatures ranging from ambient to 400∘C and show structures from completely amorphous to monoclinic. ALD films are amorphous as deposited, and can crystallize after post-deposition anneal depending on the percentage of Al-doping. We discuss PES results in order to determine how close to stoichiometry the Hf/O atomic ratios of the films are, as well as the doping level. From XAS data, instead, we can point out how orbital hybridizations are related to structural and physical properties.}, language = {en} } @misc{CuypersFleischmannDorpetal., author = {Cuypers, Daniel and Fleischmann, Claudia and Dorp, Dennis H. von and Brizzi, Simone and Tallarida, Massimo and M{\"u}ller, Matthias and H{\"o}nicke, Philipp and Billen, Arne and Chintala, Ravi and Conard, Thierry and Schmeißer, Dieter and Vandervorst, Wilfried and Elshocht, Sven van and Armini, Silvia and De Gendt, Stefan and Adelmann, Christoph}, title = {Sacrificial Self-Assembled Monolayers for the Passivation of GaAs(100) Surfaces and Interfaces}, series = {Chemistry of Materials}, volume = {28}, journal = {Chemistry of Materials}, number = {16}, issn = {0897-4756}, doi = {10.1021/acs.chemmater.6b01732}, pages = {5689 -- 5701}, abstract = {The use of sacrificial self-assembled monolayers (SAMs) to prepare clean n-type GaAs (100) surfaces without band bending in vacuo is demonstrated. GaAs surface passivation using octadecanethiol SAMs after HCl cleaning is shown to lead to an enhancement of the room-temperature photoluminescence intensity. Synchrotron-radiation photoelectron spectroscopy (SRPES) finds that the interfacial oxide between GaAs and the SAM remains below the detection limit. Evidence for both Ga-S and As-S bonds at the GaAs-thiolate interface is found. The limited thermal stability of the SAM allows the desorption of the alkyl chains by in situ thermal annealing at temperatures above 180 °C, leaving S bonded to Ga behind. The resulting surface contains only a very small amount of O (0.05 ML coverage) and C (about 3\% of the SAM remaining) and shows no band bending with the surface Fermi level close to the conduction band. Atomic layer deposition of Al₂O₃ on this surface occurs via the formation of Al-S bonds without introducing any additional band bending. This indicates that the surface preparation of n-type GaAs (100) using sacrificial octadecanethiol SAMs followed by in situ thermal removal provides a route toward GaAs/oxide interfaces without interfacial oxides and without band bending.}, language = {en} } @misc{DorpNynsCuypersetal., author = {Dorp, Dennis H. von and Nyns, Laura and Cuypers, Daniel and Ivanov, Tsvetan and Brizzi, Simone and Tallarida, Massimo and Fleischmann, Claudia and H{\"o}nicke, Philipp and M{\"u}ller, Matthias and Richard, Olivier and Schmeißer, Dieter and De Gendt, Stefan and Lin, Dennis H. C. and Adelmann, Christoph}, title = {Amorphous Gadolinium Aluminate as a Dielectric and Sulfur for Indium Phosphide Passivation}, series = {ACS Applied Electronic Materials}, volume = {1}, journal = {ACS Applied Electronic Materials}, number = {11}, issn = {2637-6113}, doi = {10.1021/acsaelm.9b00388}, pages = {2190 -- 2201}, abstract = {The passivation of n-type InP (100) using sulfur in combination with a gadolinium aluminate (GAO) dielectric layer has been studied. Photoluminescence, minority-carrier lifetime, and capacitance-voltage measurements indicate that a (NH4)2S vapor passivation step prior to atomic layer deposition of the oxide effectively lowers the interface state density. Surface and interface chemistry were studied by synchrotron radiation photoemission spectroscopy (SRPES). The effect of ex situ surface passivation after native oxide removal in HCl solution was examined. It was observed that surface reoxidation occurred during (NH4)2S vapor exposure, leading to the formation of Inx(HPO4)y. S was present on the surface as a sulfide in both surface and subsurface sites. After atomic layer deposition of GAO, sulfates were detected in addition to Inx(HPO4)y, which was confirmed by near-edge X-ray absorptionfine structure analysis. The S in the stack was quantified using reference-free grazing incidence X-rayfluorescence analysis. X-ray absorption spectroscopy showed that Gd was oxidized and present in the 3+ oxidation state, most likely as a phosphate close to the InP interface and possibly mixed with sulfates. Energy-dependent SRPES measurements of Al 2p and Gd 4d core levels, complemented by transmission electron microscopy, further suggest that the dielectric layer was segregated. Valence band measurements confirm the effective passivation of InP, indicating unpinning of the surface Fermi level.}, language = {en} }