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Institute
Band structure and electrical properties of MBE grown HfO2 - based alkaline earth perovskites
(2010)
Ultra thin dielectric films (<20 nm) deposited on TiN electrodes are interesting for MIM capacitor application. High capacitance density and dielectric permittivity must be accompanied by extremely low leakage currents (10−8 A/cm2) at bias 0.5 V. To achieve such low leakage currents, high band gap and proper band alignment is required. Occupied electronic states can be probed with standard laboratory photoemission methods. Probing of unoccupied states is more challenging. Synchrotron based PES in combination with XAS forms a powerful method to study the band alignment. ASAM end station located at the U 49/2 PGM 2 beamline of BESSY II (Berlin) offers excellent conditions for performing such measurements. We investigated HfO2 - based alkaline earth perovskite - BaHfO3 with subsequent admixture of TiO2, resulting in formation of BaHf0.5Ti0.5O3 compound. The analysis of data indicates that band gap for HfO2 is similar to BaHfO3 and amounts 5.8 eV; for BaHf0.5Ti0.5O3 it decreases to 3.8 eV. We conclude that the addition of TiO2 to BaHfO3 increases significantly the dielectric permittivity but also impacts the band gap alignment. The conduction band offset shrinks, influencing the leakage current behavior.
Thin dielectric buffers of cubic PrO2(111) on Si(111) are ideally suited to integrate Ge onto Si by moderating the lattice mismatch between the materials. The leakage current across this dielectric buffer is strongly influenced by the electronic band diagram and defects inside the band gap. Therefore, we measured the band offsets, band gaps and defect positions by means of synchrotron radiation based photoemission spectroscopy techniques (XPS and XAS) with special emphasis on the Pr-silicate interface. In a next step we compare the spectroscopic data with information from dielectric studies, based on temperature dependent leakage current studies. We observe a close relation between dielectric properties and the electronic structure.
Band gap and electronic structure determination with XAS and UPS of thin Pr-oxide films on Si(111)
(2008)
Pr2O3 is currently under consideration as a potential alternative gate dielectric candidate for sub-0.1 µm Complementary Metal Oxide Semiconductor (CMOS) technology. For all thin gate dielectrics, the interface with silicon plays a key role, and in most cases is a dominant factor in determining overall electrical properties. We studied the Pr2O3/Si(001) interface by a non-destructive depth profiling using synchrotron radiation photo-electron spectroscopy and ab initio calculations. Our results provide evidence that a chemical reactive interface exists consisting of a mixed Si-Pr oxide such as (Pr2O3)x(SiO2)1−x, typically in non-stoichiometric composition. There is no formation of neither an interfacial SiO2 nor interfacial silicide: all Si-Pr bonds are oxidized and all SiO4 units dissolve in the Pr oxide. Interfacial silicates like (Pr2O3)x(SiO2)1−x are promising high-k dielectric materials because they represent incremental modification of SiO2 films by Pr ions so that the interface characteristics can be similar to Si-SiO2 interface properties. Under ultrahigh vacuum conditions, silicide formation is observed when the silicate film is heated above 800∘C. The praseodymium silicate system observed at the interface between Si(001) and Pr2O3 offers greater flexibility towards integration of Pr2O3 into future CMOS technologies.
For the integration of 100 % Ge onto the Si platform, a buffer oxide approach has been developed recently, using rare earth oxides to tune the lattice constant between the Si and the Ge. Among these buffer oxides, PrO2 is a prospective candidate with high quality crystalline growth on Si, moderated by an interfacial Pr-silicate between. In order to specify electronic properties of thin PrO2 and its interface on Si(111), especially the width of the band gap, we performed synchrotron radiation based XPS, UPS and XAS measurements at the U49/2 PGM 2 beamline at BESSY II and correlate the results with our structural characterisation performed by TEM and XRD. In order to evaluate the dielectric properties of thin PrO2 layers on Si(111), we performed temperature-, time-, voltage-, and layer thickness-dependent leakage current measurements (J-V). Here, we identified relaxation behaviour in the leakage current, successfully addressed to defect like states inside the Pr-silicate interface layer, corroborated by frequency dependent capacitance versus voltage (C-V) measurements.
Hetero- oxides are the candidates to replace SiO2 as the gate dielectric material for sub-0.1µm CMOS technology. In particular, the basic interaction mechanisms at the interface are a key issue and a solid knowledge of these mechanisms is required to address reliability issues. The challenge in material science is to understand the chemical bonding of the hetero oxides and Si on a microscopic scale. This report focuses on the interaction of the high dielectric constant (DK) material Pr2O3 with SiO2 and the bare Si(001) surface. Photoelectron spectroscopy (PES) using tunable Synchrotron radiation (undulator U49/2 at BESSY II) is shown to provide spectroscopic information which is used for characterization of the electronic structure elements at the interface as well as for a non-destructive depth profiling. The chemical state of the Si atoms at the interface is identified and the chemical stability of the various oxide phases is discussed. We determine the variation of the elemental composition across the interface and follow the stability of the silicate phase.
Near-term downscaling of the metal-oxide-semiconductor field-effect transistors (MOSFETs) requires the replacement of the SiO2 gate oxide with a material having a higher dielectric constant. Recent studies indicate that silicate materials are the most promising candidates; among them are Pr silicates. Applying a combination of x-ray photoelectron spectroscopy (XPS), electrical measurements (C-V), and ab initio calculations, we investigated the effect of thin Ti doping on the structural and electrical properties of the gate stacks composed of a Pr silicate film and a SiO2-based interfacial buffer layer. Metallic Ti was deposited at room temperature after the formation of the Pr silicate dielectric. The resulting layered structures were annealed under ultra-high vacuum (UHV) at various temperatures between 70∘C and 880∘C. XPS indicates that the evaporated layer preserves its metallic character over the whole range of UHV annealing temperatures. Synchrotron radiation XPS at BESSY II shows that large amounts of Ti atoms incorporated into the Pr silicate remain metallic even after air exposure at room temperature. Annealing in nitrogen ambient at 300∘C leads to the oxidation of these atoms so that a mixed Pr:Ti silicate is formed. We show that the so formed dielectrics exhibit an improved equivalent oxide thickness and a reduced density of interface states.