P. Lysaght

The effect of interfacial layer properties on the performance of Hf-based gate stack devices

The influence of Hf-based dielectrics on the underlying SiO2 interfacial layer (IL) in high-k gate stacks is investigated. An increase in the IL dielectric constant, which correlates to an increase of the positive fixed charge density in the IL, is found to depend on the starting, pre-high-k deposition thickness of the IL. Electron energy-loss spectroscopy and electron spin resonance spectra exhibit signatures of the high-k-induced oxygen deficiency in the IL consistent with the electrical data. It is concluded that high temperature processing generates oxygen vacancies in the IL responsible for the observed trend in transistor performance.

Dipole model explaining high-k/metal gate field effect transistor threshold voltage tuning

An interface dipole model explaining threshold voltage (Vt) tuning in HfSiON gated n-channel field effect transistors (nFETs) is proposed. Vt tuning depends on rare earth (RE) type and diffusion in Si∕SiOx∕HfSiON∕REOx/metal gated nFETs as follows: Sr<Er<Sc+Er<La<Sc<none. This Vt ordering is very similar to the trends in dopant electronegativity (EN) (dipole charge transfer) and ionic radius (r) (dipole separation) expected for a interfacial dipole mechanism. The resulting Vt dependence on RE dopant allows distinction between a dipole model (dependent on EN and r) and an oxygen vacancy model (dependent on valence).

Grazing-incidence small angle x-ray scattering studies of phase separation in hafnium silicate films

Grazing-incidence small-angle x-ray scattering (GISAXS) and high-resolution transmission electron microscopy (HRTEM) were used to investigate phase separation in hafnium silicate films after rapid thermal annealing between 700 and 1000 °C. 4-nm-thick Hf–silicate films with 80 and 40 mol % HfO2, respectively, were prepared by metalorganic vapor deposition. Films of the two compositions showed distinctly different phase-separated microstructures, consistent with two limiting cases of microstructural evolution: nucleation/growth and spinodal decomposition. Films with 40 mol % HfO2 phase separated in the amorphous by spinodal decomposition and exhibited a characteristic wavelength in the plane of the film. Decomposition with a wavelength of ∼3 nm could be detected at 800 °C. At 1000 °C the films rapidly demixed with a wavelength of 5 nm. In contrast, films with 80 mol % HfO2 phase separated by nucleation and growth of crystallites, and showed a more random microstructure. The factors determining specific film...

Imaging local electronic corrugations and doped regions in graphene

Electronic structure heterogeneities are ubiquitous in two-dimensional graphene and profoundly impact the transport properties of this material. Here we show the mapping of discrete electronic domains within a single graphene sheet using scanning transmission X-ray microscopy in conjunction with ab initio density functional theory calculations. Scanning transmission X-ray microscopy imaging provides a wealth of detail regarding the extent to which the unoccupied levels of graphene are modified by corrugation, doping and adventitious impurities, as a result of synthesis and processing. Local electronic corrugations, visualized as distortions of the π*cloud, have been imaged alongside inhomogeneously doped regions characterized by distinctive spectral signatures of altered unoccupied density of states. The combination of density functional theory calculations, scanning transmission X-ray microscopy imaging, and in situ near-edge X-ray absorption fine structure spectroscopy experiments also provide resolution of a longstanding debate in the literature regarding the spectral assignments of pre-edge and interlayer states.

Interfacial Layer-Induced Mobility Degradation in High-

Analysis of electrical and scanning transmission electron microscopy (STEM) and electron energy loss spectra (EELS) data suggests that Hf-based high-k dielectrics deposited on a SiO2 layer modifies the oxygen content of the latter resulting in reduction of the oxide energy band gap and correspondingly increasing its k value. High-k deposition on thinner SiO2 films, below 1.1 nm, may lead to the formation of a highly oxygen deficient amorphous interfacial layer adjacent to the Si substrate. This layer was identified as an important factor contributing to mobility degradation in high-k transistors.

k

Using the concept of metastable phase diagrams, we discuss the microstructure evolution during annealing of amorphous ZrO2–SiO2 and HfO2–SiO2 thin films for gate dielectric applications. These systems are characterized by a low solid solubility, a liquid miscibility gap and a kinetic barrier to the formation of the complex, crystalline silicate. We show that phase partitioning is expected for most compositions. Compositions within the metastable extensions of the spinodal are unstable and will spontaneously unmix in the amorphous phase upon heating. Hafnia- or zirconia-rich phases will subsequently crystallize to form HfO2 or ZrO2. Most compositions outside the metastable extensions of the liquid phase miscibility gap must phase separate above the crystallization temperature by nucleation of crystalline HfO2 or ZrO2 out of an amorphous silica-rich matrix. We present calculations of the metastable extensions of the miscibility gap and spinodal. The calculations predict that SiO2-rich compositions, investigated for gate dielectric applications, will show spinodal decomposition if they contain less than ~90 mol% SiO2 at the typical device processing temperature of 1000°C. Experimental studies of Hf-silicate films with three different compositions, between ~40 and 80 mol% HfO2 that lie inside and outside the miscibility gap, respectively, are presented. All three compositions show phase separation. Despite the different pathways of microstructure evolution, the final phase separated microstructures are similar. Experimental verification of the pathways that lead to these microstructures requires further studies.

Transistors

Nitrogen incorporation in HfO2∕SiO2 films utilized as high-k gate dielectric layers in advanced metal-oxide-semiconductor field effect transistors has been investigated. Thin HfO2 blanket films deposited by atomic layer deposition on either SiO2 or NH3 treated Si (100) substrates have been subjected to NH3 and N2 anneal processing. Several high resolution techniques including electron microscopy with electron energy loss spectra, grazing incidence x-ray diffraction, and synchrotron x-ray photoelectron spectroscopy have been utilized to elucidate chemical composition and crystalline structure differences between samples annealed in NH3 and N2 ambients as a function of temperature. Depth profiling of core level binding energy spectra has been obtained by using variable kinetic energy x-ray photoelectron spectroscopy with tunable photon energy. An “interface effect” characterized by a shift of the Si4+ feature to lower binding energy at the HfO2∕SiO2 interface has been detected in the Si 1s spectra; however,...

Application of Metastable Phase Diagrams to Silicate Thin Films for Alternative Gate Dielectrics

High-k dielectric materials including zirconium oxide and hafnium oxide produced by atomic layer deposition have been evaluated for thermal stability. As-deposited samples have been compared with rapid thermal annealed samples over a range of source/drain dopant activation temperatures consistent with conventional complimentary metal oxide semiconductor polysilicon gate processes. Results of this initial investigation are presented utilizing analyses derived from X-ray diffraction (XRD), X-ray reflectometry (XRR), medium energy ion spectroscopy, high resolution transmission electron microscopy (HRTEM), tunneling atomic force microscopy, scanning electron microscopy, Auger electron spectroscopy and secondary ion mass spectroscopy. Changes in interface and surface roughness, percent crystallinity and phase identification for each material as a function of anneal temperature have been determined by XRD, XRR and HRTEM. Finally, high-k wet etch issues are presented relative to subsequent titanium silicide blanket film resistivity values.

Chemical analysis of HfO2∕Si (100) film systems exposed to NH3 thermal processing

The gate stack should be regarded as a multi-element interfacial layered structure wherein the high-k gate dielectric and gate electrodes (and their corresponding interfaces) must be successfully comprehended. The surface clean and subsequent surface conditioning prior to high-k deposition as well as post-deposition annealing parameters significantly impact the equivalent oxide thickness and leakage current as well as the traditional parameters such as threshold voltage, saturation current, transconductance, and sub-threshold swing. The control of both the fixed electrical charges and charge traps incorporated at the various interfaces and within the high-k bulk film is of paramount importance to achieve the requisite transistor characteristics and, in particular, the effective carrier mobility. Interactive effects within the gate stack process modules and the subsequent integrated circuit fabrication process require the utmost attention to achieve the desired IC performance characteristics and help facilitate the continuance of Moores Law towards the 10-nm physical gate length regime.

Experimental observations of the thermal stability of high-k gate dielectric materials on silicon

Fast transient charging effects (FTCE) are found to be the source of various undesirable characteristics of high-k devices, such as V/sub th/ instability, low DC mobility and poor reliability. The intrinsic characteristics of high-k transistors free from FTCE are demonstrated using ultra-short pulsed I-V measurements, and it is found that the intrinsic mobility of high-k devices can be much higher than what has been observed in DC based measurements. The FTCE model suggests that many of DC characterization methods developed for SiO/sub 2/ devices are not sufficiently adequate for high-k devices that exhibit significant transient charging. The existence of very strong concurrent transient charging during various reliability tests also degrades the validity of test results. Finally, the implication of FTCE on the high-k implementation strategy is discussed.