TY - GEN A1 - Das, Chittaranjan A1 - Henkel, Karsten A1 - Tallarida, Massimo A1 - Schmeißer, Dieter A1 - Gargouri, Hassan A1 - Kärkkänen, Irina A1 - Schneidewind, Jessica A1 - Gruska, Bernd A1 - Arens, Michael T1 - Thermal and plasma enhanced atomic layer deposition of TiO2: Comparison of spectroscopic and electric properties T2 - Journal of Vacuum Science and Technology A N2 - Titanium oxide (TiO2) deposited by atomic layer deposition (ALD) is used as a protective layer in photocatalytic water splitting system as well as a dielectric in resistive memory switching. The way ALD is performed (thermally or plasma-assisted) may change the growth rate as well as the electronic properties of the deposited films. In the present work, the authors verify the influence of the ALD mode on functional parameters, by comparing the growth rate and electronic properties of TiO2 films deposited by thermal (T-) and plasma-enhanced (PE-) ALD. The authors complete the study with the electrical characterization of selected samples by means of capacitance–voltage and current–voltage measurements. In all samples, the authors found a significant presence of Ti3+ states, with the lowest content in the PE-ALD grown TiO2 films. The observation of Ti3+ states was accompanied by the presence of in-gap states above the valence band maximum. For films thinner than 10 nm, the authors found also a strong leakage current. Also in this case, the PE-ALD films showed the weakest leakage currents, showing a correlation between the presence of Ti3+ states and leakage current density. KW - titanium oxide (TiO2) KW - atomic layer deposition KW - plasma enhanced atomic layer deposition KW - synchrotron radiation photoelectron spectroscopy (SR-PES) KW - x-ray absorption spectroscopy KW - capacitance-voltage (CV) KW - current-voltage (IV) KW - ellipsometry KW - in-gap states Y1 - 2015 U6 - https://doi.org/10.1116/1.4903938 SN - 1520-8559 SN - 0734-2101 VL - 2015 IS - 33 SP - 01A144-1 EP - 01A144-8 ER - TY - CHAP A1 - Tallarida, Massimo A1 - Sohal, Rakesh A1 - Schmeißer, Dieter T1 - Electronic properties of the 2x1 3C-SiC surface reconstruction studied with resonant photoemission T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft, Reihe 6, Bd. 41 N2 - We have studied the 2x1 reconstructed surface of the 3C-SiC polytype by means of photoemission spectroscopy. The reconstruction was characterized through Si2p and C1s core level and angle-integrated valence band spectroscopy, and confirmed by the observation of a two-domain 2x1 LEED pattern. The electronic properties of this surface were investigated by collecting valence band spectra at photon energies near the Si2p and C1s absorption edges. The results show a strong dependence of the photoemission intensity on the excitation energy with characteristic resonances for certain valence band features. With a detailed study of the resonances we are able to assign the electronic origin of the resonating states and the nature of the electronic transition near the absorption edges. Y1 - 2006 UR - http://www.dpg-verhandlungen.de/year/2006/conference/dresden/part/hl/session/5/contribution/2 SN - 0420-0195 SP - S. 239 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Kolanek, Krzysztof A1 - Karavaev, Konstantin A1 - Tallarida, Massimo A1 - Schmeißer, Dieter T1 - Atomic layer deposition of HfO2 onto SiO2 substrates investigated in-situ by non-contact UHV/AFM T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft, Reihe 6, Bd. 45 N2 - We investigated in-situ the atomic layer deposition (ALD) of HfO2 onto SiO2 substrates with ultra high vacuum (UHV) non-contact atomic force microscope (NC-AFM). The ALD process was started after detailed analysis of the initial Si(001)/SiO2 substrate. The ALD cycles, made by using tetrakis-di-methyl-amido-Hf (TDMAHf) and water as precursors, were performed on the SiO2 substrate maintained at 230 ∘C. We studied the relation between the film growth and the root mean square surface roughness, surface skewness, kurtosis, fractal dimension and correlation length. In the initial stages of the ALD process with our analysis of the surface height histograms we were capable of determination: HfO2 layer thickness, surface coverage and surface roughness of a substrate and deposited material. Observation of the surface height histograms evolution during deposition allowed us to verify conformal and effective ALD growth on SiO2 substrate. With this detailed analysis of the surface topography we confirmed the completion of the first HfO2 layer after four ALD cycles. Y1 - 2010 SN - 0420-0195 SP - S. 248 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Michling, Marcel A1 - Tallarida, Massimo A1 - Kolanek, Krzysztof A1 - Schmeißer, Dieter T1 - In-situ EELS and UPS measurements on HfO2 ALD layers T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft, Reihe 6, Bd. 45 N2 - In this contribution we report on our in-situ cycle-by-cycle (up to 10 cycles) investigations of the HfO2 ALD process using the methods of EELS and UPS. We used TDMA-Hf as a precursor and p-type Si wafer with natural oxide as the substrate. The EELS measurements were done with a primary energy of 52,5 eV and the UPS measurements with He I (21,218 eV). The change in the onset of the loss function is readily observed. Already after two cycles the value approach to the bulk value of HfO2. Upon ALD growth there is a remarkable decrease in the intensity of states within the gap. They are rather smooth and saturate after 10 cycles. With UPS we follow the variation of the VB onset and changes in the secondary electron onset. We summarize our data in a band diagram not based on bulk values but on cycle dependent quantities. With these cycle-by-cycle experiments we study the initial growth of HfO2 especially in the very first cycles. Y1 - 2010 UR - http://www.dpg-verhandlungen.de/year/2010/conference/regensburg/part/ds/session/24/contribution/5 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Starzyk, Łukasz A1 - Tallarida, Massimo A1 - Schmeißer, Dieter T1 - Electrically optimized high-κ metal gate MOSFET by specific modification of the band alignment T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft, Reihe 6, Bd. 45 N2 - The electrical optimization of metal/oxide/semiconductor gate stacks by specific modification of the band alignment for advanced MOS technology incorporating high dielectric constant (κ) materials is explored. Because of requirements concerning continued scaling of MOSFET transistors, gate oxides and cobalt electrode have been grown successively on Si substrate respectively by means of atomic layer deposition (ALD) and evaporation. The thicknesses of high-κ films were around 2 nm. In case of work function engineering, interfaces’ chemistry plays a fundamental role. We applied synchrotron radiation based x-ray photoelectron spectroscopy (SR XPS) to characterize our samples, which allows step by step in situ investigations. Co 2p, Al 2p, Hf 4f, Si 2p and O 1s core levels spectra were measured and analyzed. From valence band (VB) spectra we determined Schottky barrier height and electronic bands offsets. Y1 - 2010 UR - http://www.dpg-verhandlungen.de/year/2010/conference/regensburg/part/ds/session/23/contribution/3 SN - 0420-0195 SP - S. 231 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Wyrodek, Jakub A1 - Tallarida, Massimo A1 - Schmeißer, Dieter A1 - Weisheit, Martin T1 - Determination of interfacial layers in high - k ALD nanolaminate materials by ARXPS and SRXPS measurements T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft, Reihe 6, Bd. 45 N2 - The interfacial layers of high dielectric constant (high - k) nanolaminate films are here explored. Problems concerning ALD nanolaminate layers deals mainly with lack of accurate methods to determine in depth profile of few nm thick stacks. Modified angle resolved XPS(ARXPS) and synchrotron radiation XPS(SRXPS) are proposed as methods suitable in layer profiling. Studied stacks containing ZrO/HfO or AlO/ZrO, were prepared on Si substrates by atomic layer deposition (ALD). Two sets of experiments were covered. First dealt with initial growth (up to 20 cycles, with thickness d < 2nm) of AlO/ZrO and included layer by layer insitu investigation by SRXPS. Second experiment refer to industrial grown ZrO/HfO films ( d ∼ 3nm ) processed with various parameters resulting in both, layer by layer and homogenous depositions. For those samples exsitu XPS, with angle dependent variation of probing depth, measurements were covered. By comparing obtained intensity ratios for different angles with computational developed stack model it was found that no simple layer by layer but some intermixing growth occurred including interaction with silicon substrate. Y1 - 2010 UR - http://www.dpg-verhandlungen.de/year/2010/conference/regensburg/part/ds/session/24/contribution/6 SN - 0420-0195 SP - S. 232 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Karavaev, Konstantin A1 - Tallarida, Massimo A1 - Schmeißer, Dieter A1 - Zschech, Ehrenfried T1 - In-situ ALD growth of Hafnium oxide films T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft ; Reihe 6, Bd. 43 N2 - We report on a novel system for in-situ atomic layer growth (ALD) of high-k dielectric films. First results were obtained for Hf-oxide samples by using Hf-tetrachloride as precursor and water as oxidizer. We compare the photoelectron spectra of Si2p, O1s and Hf4f of our in-situ prepared films with samples (ex-situ) prepared by industrial ALD reactors and discuss similarities and differences observed in the core level spectra of the various samples by considering the different growth conditions. Y1 - 2008 UR - http://www.dpg-verhandlungen.de/year/2008/conference/berlin/part/ds/session/23/contribution/12 SN - 0420-0195 SP - S. 244 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Tallarida, Massimo A1 - Karavaev, Konstantin A1 - Schmeißer, Dieter A1 - Zschech, Ehrenfried T1 - Photoemission and absorption spectroscopy for in situ investigations of the ALD growth T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft, Reihe 6, Bd. 43 N2 - We have investigated the growth of Hf-oxide on Si by means of photoemission and X-ray absorption spectroscopy using synchrotron radiation at Bessy, Berlin. The Hf-oxide layers were grown via atomic layer deposition (ALD) using an in-situ ALD reactor attached to the investigation chamber. The XPS and XAS spectra were measured after every deposition cycle by transferring the sample into the investigation chamber without breaking the vacuum. From the experimental data we have obtained information about the early stages of the Hf-oxide growth, concerning in particular the reactivity of the interface with Si. Due to the possibility to study the layers after every cycle and with different oxidation parameters without exposing them to contaminants, the in situ investigation revealed to be a very important method to understand the growth properties of Hf-oxide. Y1 - 2008 UR - http://www.dpg-verhandlungen.de/year/2008/conference/berlin/part/ds/session/22/contribution/5 SN - 0420-0195 SP - S. 242 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Karavaev, Konstantin A1 - Tallarida, Massimo A1 - Schmeißer, Dieter T1 - Evolution of the interfacial layer during the atomic layer deposition of HfO2 on Si/SiO2 substrates T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft, Reihe 6, Bd. 44 N2 - We studied the formation of the interfacial layer in the Si/SiO2/HfO2 system using the in-situ Atomic Layer Deposition (ALD) reactor developed in our group [1,2]. We measured the X-ray photoelectron and X-ray absorption spectra with synchrotron radiation at the beamline U49-2/PGM2-BESSY II. The ALD growth was obtained using different Hf-precursors (HfCl4,TEMAHf and TDMAHf) on various prepared substrates at different temperatures. The investigation was carried out in-situ giving the possibility to determine the properties of the grown film after every ALD cycle without breaking the vacuum. We observed the evolution of the Si/SiO2/HfO2 system during the formation of first three Hf-oxide layers, detecting the interfacial growth of SiO2 during the initial ALD cycles from the XPS spectra of Si2p. We discuss how the interfacial layer growth depends on the various ALD parameters. [1] M. Tallarida, K. Karavaev, and D. Schmeisser, J. Appl. Phys. 104, 064116 (2008); [2] M. Tallarida, K. Karavaev, and D. Schmeisser, J. Vac. Sci. Technol. B, accepted for publication. Y1 - 2009 SN - 0420-0195 SP - S. 160 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Kolanek, Krzysztof A1 - Karavaev, Konstantin A1 - Tallarida, Massimo A1 - Schmeißer, Dieter T1 - In-situ investigations of the atomic layer deposition of HfO2 with UHV/AFM T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft, Reihe 6, Bd. 44 N2 - We studied in-situ the atomic layer deposition (ALD) of HfO2 with ultra high vacuum (UHV) atomic force microscope (AFM), using the ALD reactor developed by our group [1, 2]. The reactor was attached to the Omicron Large Sample-UHV/AFM system in the AFM-Lab of the Angewandte Physik-Sensorik chair at the BTU-Cottbus. We investigated different Si(001)/SiO2 substrates and surface preparation techniques performed before the ALD process. After each ALD cycle (using TDMAHf and H2O as precursors), we studied the influence of the HfO2 growth on the root mean square (RMS) roughness; the surface fractal dimension and the height histogram: the surface skewness and kurtosis. We focused on the influence of the substrate temperature on the surface topography during the ALD. The in-situ studies of the ALD process with the UHV/AFM system correlated with the experiments performed with photoelectron spectroscopy can be used for understanding the fundamental properties of the ALD of HfO2 on Si(001). [1] M. Tallarida, K. Karavaev, and D. Schmeisser, J. Appl. Phys. 104, 064116 (2008); [2] M. Tallarida, K. Karavaev, and D. Schmeisser, J. Vac. Sci. Technol. B, accepted for publication. Y1 - 2009 UR - http://www.dpg-verhandlungen.de/year/2009/conference/dresden/part/ds/session/11/contribution/6 SN - 0420-0195 SP - S. 160 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Tallarida, Massimo A1 - Karavaev, Konstantin A1 - Kolanek, Krzysztof A1 - Schmeißer, Dieter T1 - Basics of the atomic layer deposition of HfO2 onto Si/SiO2 substrates: in-situ investigations with XPS, XAS and UHV-AFM T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft ; Reihe 6, Bd. 44 N2 - We developed a reactor for investigating in-situ the atomic layer deposition (ALD) of HfO2. X-ray photoelectron and X-ray absorption spectra were collected after each ALD cycle using synchrotron radiation at the beamline U49-2/PGM2 - BESSY II, Berlin. The morphology of the substrate and thin film surfaces was investigated after each ALD cycle with an UHV-AFM microscopy attached to the ALD reactor. We studied the ALD on differently prepared substrates, at different substrate temperatures, and using different Hf-precursors (HfCl4, TEMAHf, TDMAHf). We observed the evolution of the Si/SiO2/HfO2 system during the formation of the first three Hf-oxide layers [1]; we detected the incorporation of Cl into the Hf-oxide films and proposed a mechanism responsible for the Cl contamination [2]; we found evidence of the interfacial-SiO2 growth during the initial ALD cycles and of dipole formation at the HfO2/SiO2 interface. In this contribution we illustrate the basics of the technique used, and discuss the physical-chemical properties of ALD on the basis of the experimental results. [1] M. Tallarida, K. Karavaev, and D. Schmeisser, J. Appl. Phys. 104, 064116 (2008); [2] M. Tallarida, K. Karavaev, and D. Schmeisser, J. Vac. Sci. Technol. B, accepted for publication. Y1 - 2009 UR - http://www.dpg-verhandlungen.de/year/2009/conference/dresden/part/ds/session/11/contribution/4 SN - 0420-0195 SP - S. 159 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Tallarida, Massimo A1 - Karavaev, Konstantin A1 - Kolanek, Krzysztof A1 - Schmeißer, Dieter T1 - In-situ experimental approach to the study of atomic layer deposition with atomic force microscope, X-ray photoelectron and X-ray absorption spectroscopy T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft ; Reihe 6, Bd. 44 N2 - We describe our experimental approach to the investigation of atomic layer deposition (ALD). ALD is a powerful deposition technique for growing conformal thin films of composite materials with atomically accurate thickness on large area [1]. Despite the enormous industrial interest growing around ALD, its fundamental properties were not yet properly studied. We developed an ALD reactor for the in-situ investigations using XPS, XAS and AFM as experimental techniques. We studied the chemical-physical properties of the growing thin films after each deposition cycle. Here, we illustrate the recent results concerning the ALD of HfO2 obtained using different Hf-precursors on various substrates [2]. We show how the in-situ investigations could deliver an important insight into the fundamental characteristics of ALD and how these information could be used to modify and optimize the deposition parameters. [1] M. Leskelä, M. Ritala, Thin Solid Films, 409, 138, 2002; [2] M. Tallarida, K. Karavaev, and D. Schmeisser, J. Appl. Phys. 104, 064116 (2008). Y1 - 2009 UR - http://www.dpg-verhandlungen.de/year/2009/conference/dresden/part/ds/session/26/contribution/15 SN - 0420-0195 SP - S.176 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER -