M. Toledano-Luque

Optical properties and structure of HfO2 thin films grown by high pressure reactive sputtering

Thin films of hafnium oxide (HfO2) have been grown by high pressure reactive sputtering on transparent quartz substrates (UV-grade silica) and silicon wafers. Deposition conditions were adjusted to obtain polycrystalline as well as amorphous films. Optical properties of the films deposited on the silica substrates were investigated by transmittance and reflectance spectroscopy in the ultraviolet, visible and near infrared range. A numerical analysis method that takes into account the different surface roughness of the polycrystalline and amorphous films was applied to calculate the optical constants (refractive index and absorption coefficient). Amorphous films were found to have a higher refractive index and a lower transparency than polycrystalline films. This is attributed to a higher density of the amorphous samples, which was confirmed by atomic density measurements performed by heavy-ion elastic recoil detection analysis. The absorption coefficient gave an excellent fit to the Tauc law (indirect gap), which allowed a band gap value of 5.54 eV to be obtained. The structure of the films (amorphous or polycrystalline) was found to have no significant influence on the nature of the band gap. The Tauc plots also give information about the structure of the films, because the slope of the plot (the Tauc parameter) is related to the degree of order in the bond network. The amorphous samples had a larger value of the Tauc parameter, i.e. more order than the polycrystalline samples. This is indicative of a uniform bond network with percolation of the bond chains, in contrast to the randomly oriented polycrystalline grains separated by grain boundaries.

Response of a single trap to AC negative Bias Temperature stress

We study the properties of a single gate oxide trap subjected to AC Bias Temperature Instability (BTI) stress conditions by means of Time Dependent Defect Spectroscopy. A theory for predicting the occupancy of a single trap after AC stress is developed based on first order kinetics and verified on experimental data. The developed theory can be used to develop circuit simulators and predict time dependent variability.

Titanium doped silicon layers with very high concentration

Ion implantation of Ti into Si at high doses has been performed. After laser annealing the maximum average of substitutional Ti atoms is about 1018u2002cm−3. Hall effect measurements show n-type samples with mobility values of about 400u2002cm2/Vu2009s at room temperature. These results clearly indicate that Ti solid solubility limit in Si has been exceeded by far without the formation of a titanium silicide layer. This is a promising result toward obtaining of an intermediate band into Si that allows the design of a new generation of high efficiency solar cell using Ti implanted Si wafers.

A comparative study of the electrical properties of TiO2 films grown by high-pressure reactive sputtering and atomic layer deposition

Oxide–semiconductor interface quality of high-pressure reactive sputtered (HPRS) TiO2 films annealed in O2 at temperatures ranging from 600 to 900 °C, and atomic layer deposited (ALD) TiO2 films grown at 225 or 275 °C from TiCl4 or Ti(OC2H5)4, and annealed at 750 °C in O2, has been studied on silicon substrates. Our attention has been focused on the interfacial state and disordered-induced gap state densities. From our results, HPRS films annealed at 900 °C in oxygen atmosphere exhibit the best characteristics, with Dit density being the lowest value measured in this work (5–6 × 1011 cm−2 eV−1), and undetectable conductance transients within our experimental limits. This result can be due to two contributions: the increase of the SiO2 film thickness and the crystallinity, since in the films annealed at 900 °C rutile is the dominant crystalline phase, as revealed by transmission electron microscopy and infrared spectroscopy. In the case of annealing in the range of 600–800 °C, anatase and rutile phases coexist. Disorder-induced gap state (DIGS) density is greater for 700 °C annealed HPRS films than for 750 °C annealed ALD TiO2 films, whereas 800 °C annealing offers DIGS density values similar to ALD cases. For ALD films, the studies clearly reveal the dependence of trap densities on the chemical route used.

High quality Ti-implanted Si layers above the Mott limit

In this paper, we present a detailed characterization of high quality layers of Si implanted with Ti at high doses. These layers are intended to the formation of an intermediate band (IB) solar cell. The main requirement to obtain an IB material is to reach an impurity concentration beyond the Mott limit, which is, in this case, much higher than the solid solubility limit. To overcome this limit we used the combination of ion implantation and pulsed-laser melting as nonequilibrium techniques. Time-of-flight secondary ion mass spectrometry measurements confirm that Ti concentration exceeds the theoretical Mott limit in the implanted layer, and glancing incidence x-ray diffraction and transmission electron microscopy measurements prove that good crystallinity can be achieved. Sheet resistance and Hall effect mobility show uncommon characteristics that can only been explained assuming the IB existence.

Physical properties of high pressure reactively sputtered TiO2

We present a study of the physical properties of TiO2 thin films deposited at 200°C on Si by high pressure reactive sputtering, a nonconventional deposition method. Just after deposition, the TiO2 films were in situ annealed in the deposition chamber at temperatures between 600 and 900°C in O2 atmosphere. Morphological, compositional, structural and electrical characterization of the samples was performed by means of several techniques, including transmission electron microscopy, heavy-ion elastic recoil detection analysis, infrared spectroscopy, x-ray and electron diffraction and capacitance-voltage measurements. Microscopy images show that the TiO2 films are polycrystalline, and that a SiO2 film spontaneously grows at the TiO2∕Si interface. The unannealed TiO2 films are oxygen rich, as shown by compositional measurements. By annealing this oxygen excess is released. For temperatures above 600°C the TiO2 films are stoichiometric. Infrared spectroscopy and diffraction measurements show that as-deposited f...

High-pressure reactively sputtered HfO2: Composition, morphology, and optical properties

Hafnium oxide films were deposited by high pressure reactive sputtering using different deposition pressures and times. The composition, morphology, and optical properties of the films, together with the sputtering process growth kinetics were investigated using heavy ion elastic recoil detection analysis, Fourier transform infrared spectroscopy, ultraviolet-visible-near infrared spectroscopy, x-ray diffraction, and transmission electron microscopy. The films showed a monoclinic polycrystalline structure, with a grain size depending on the deposition pressure. All films were slightly oxygen rich with respect to stoichiometric HfO2 and presented a significant amount of hydrogen up to 6 at. %, which is attributed to the high affinity for moisture of the HfO2 films. The absorption coefficient was fitted to the Tauc law, obtaining a band gap value of 5.54 eV. It was found that the growth rate of the HfO2 films depends on the deposition pressure P as P x7f1.75 . This dependence is explained by a diffusion model of the thermalized atoms in high-pressure sputtering. Additionally, the formation of an interfacial silicon oxide layer when the films were grown on silicon was observed, with a minimum thickness for deposition pressures around 1.2 mbars. This interfacial layer was formed mainly during the initial stages of the deposition process, with only a slight increase in thickness afterwards. These results are explained by the oxidizing action of the oxygen plasma and the diffusion of oxygen radicals and hydroxyl groups through the polycrystalline HfO2 film. Finally, the dielectric properties of the HfO2/SiO2 stacks were studied by means of conductance and capacitance measurements on Al/HfO2/SiO2/Si devices as a function of gate voltage and ac frequency signal.

Influence of interlayer trapping and detrapping mechanisms on the electrical characterization of hafnium oxide/silicon nitride stacks on silicon

Al/HfO2/SiNx:H/n-Si metal-insulator-semiconductor capacitors have been studied by electrical characterization. Films of silicon nitride were directly grown on n-type silicon substrates by electron cyclotron resonance assisted chemical vapor deposition. Silicon nitride thickness was varied from 3 to 6.6 nm. Afterwards, 12 nm thick hafnium oxide films were deposited by the high-pressure sputtering approach. Interface quality was determined by using current-voltage, capacitance-voltage, deep-level transient spectroscopy (DLTS), conductance transients, and flatband voltage transient techniques. Leakage currents followed the Poole–Frenkel emission model in all cases. According to the simultaneous measurement of the high and low frequency capacitance voltage curves, the interface trap density obtained for all the samples is in the 1011u2002cm−2u2009eV−1 range. However, a significant increase in this density of about two orders of magnitude was obtained by DLTS for the thinnest silicon nitride interfacial layers. In thi...

Depth localization of positive charge trapped in silicon oxynitride field effect transistors after positive and negative gate bias temperature stress

Positive charge trapped in the SiO(N) gate dielectric of deeply-scaled p-channel metal-oxide-semiconductor field-effect transistors is observed after both negative and positive gate bias temperature stress. Emission of elementary trapped charges is demonstrated and analyzed through the quantized threshold voltage transients observed after stress. The magnitude distribution of the threshold voltage steps is used to estimate the depth of the traps in the gate dielectric to be about 0.5 nm from the injecting silicon-dielectric interface in both cases.

Effect of interlayer trapping and detrapping on the determination of interface state densities on high-k dielectric stacks

The influence of the silicon nitride blocking layer thickness on the interface state densities (Dit) of HfO2/SiNx:H gate-stacks on n-type silicon have been analyzed. The blocking layer consisted of 3 to 7 nm thick silicon nitride films directly grown on the silicon substrates by electron-cyclotron-resonance assisted chemical-vapor-deposition. Afterwards, 12 nm thick hafnium oxide films were deposited by high-pressure reactive sputtering. Interface state densities were determined by deep-level transient spectroscopy (DLTS) and by the high and low frequency capacitance-voltage (HLCV) method. The HLCV measurements provide interface trap densities in the range of 1011u2002cm−2u2009eV−1 for all the samples. However, a significant increase in about two orders of magnitude was obtained by DLTS for the thinnest silicon nitride barrier layers. In this work we probe that this increase is an artifact due to the effect of traps located at the internal interface existing between the HfO2 and SiNx:H films. Because charge trapp...