Chemical compositions and optical properties of HfOxNy thin films at different substrate temperatures

High-k HfO_xN_y thin films have been grown by radio frequency (rf) reactive sputtering of metal Hf target in N₂/Ar/O₂ ambient at different substrate temperatures. The chemical compositions of the films have been investigated as a function of substrate temperature by X-ray photoelectron spectroscopy (XPS). XPS measurements showed that nitrogen concentration increases with an increase in substrate temperature. Room-temperature spectroscopic ellipsometry (SE) with photon energy 0.75–6.5 eV was used to investigate the optical properties of the films. SE results demonstrated that refractive index n increases with an increase in substrate temperature. Based on TL parameters which were obtained from the best fit results used in a simulation of the measured spectra, meanwhile, we conclude that the energy band gap (E_g) decreases with an increase in substrate temperature.     

Formation of thin-film HfO<Subscript>2</Subscript>/Si(100) structures by high-frequency magnetron sputtering

The results of X-ray structural investigations and current-voltage measurements of the HfO₂/Si(100) structures are presented. The HfO₂ films of 50 nm thickness were deposited in a Si substrate by high-frequency magnetron sputtering in argon plasma and subjected to rapid thermal annealing at 500, 700, and/or 800°C in the Ar or O₂ ambient. It is shown that the HfO₂ films become polycrystalline after annealing. The presence of various crystalline phases in them and the form of the I–V characteristics of the Al/HfO₂/Si(100) test structures strongly depend on the growth conditions and the gas ambient during the rapid thermal annealing. It is established that the HfO₂ films deposited at a high-frequency bias at a substrate of −7 V during the growth and then passed through rapid thermal treatment in the O₂ ambient at 700°C have the highest breakdown voltages.     

Local crystal structural modifications in pulsed laser deposited high-k dielectric thin films on silicon and germanium

The thin film growth conditions are correlated with the local structures formed in Hf_xZr_1−xO₂ (x=0.0–1.0) high-k dielectric thin films on Si and Ge substrates during deposition. Pulsed laser deposition (PLD) technique has been used in the synthesis of the thin films with systematic variations of substrate temperature, Zr content of the targets and substrate selection. The local structural information acquired from extended X-ray absorption spectroscopy (EXAFS) is correlated with the thin film growth conditions. The response of the local structure around Hf and Zr atoms to growth parameters was investigated by EXAFS experiments performed at the National Synchrotron Light Source of Brookhaven National Laboratory. The competing crystal phases of oxides of Hf were identified and the intricate relation between the stabilized phase and the parameters as: the substrate temperature; Hf to Zr ratio; have been revealed. Specifically, HfO₂ thin films on Si(1 0 0) exhibit a tetragonal to monoclinic phase transformation upon increase in the substrate temperature during deposition whereas, HfO₂ PLD films on Ge(1 0 0) substrates remain in tetragonal symmetry regardless of the substrate temperature.     

Atomic-layer-deposited Al2O3 and HfO2 on GaN: A comparative study on interfaces and electrical characteristics

Al₂O₃, HfO₂, and composite HfO₂/Al₂O₃ films were deposited on n-type GaN using atomic layer deposition (ALD). The interfacial layer of GaON and HfON was observed between HfO₂ and GaN, whereas the absence of an interfacial layer at Al₂O₃/GaN was confirmed using X-ray photoelectron spectroscopy and transmission electron microscopy. The dielectric constants of Al₂O₃, HfO₂, and composite HfO₂/Al₂O₃ calculated from the C-V measurement are 9, 16.5, and 13.8, respectively. The Al₂O₃ employed as a template in the composite structure has suppressed the interfacial layer formation during the subsequent ALD-HfO₂ and effectively reduced the gate leakage current. While the dielectric constant of the composite HfO₂/Al₂O₃ film is lower than that of HfO₂, the composite structure provides sharp oxide/GaN interface without interfacial layer, leading to better electrical properties.     

High-k HfO2-Ta2O5 mixed layers: Electrical characteristics and mechanisms of conductivity

Electrical properties of mixed HfO₂-Ta₂O₅ films (10;15 nm) deposited by rf sputtering on Si have been studied from the view point of their applications as high-k layers, by standard capacitance-voltage and temperature dependent current-voltage characteristics. The effect of HfO₂ addition to the Ta₂O₅ is thickness dependent and the thicker layers exhibit advantages over the pure Ta₂O₅ (higher dielectric constant, enhanced charge storage density and improved interface quality). The process of HfO₂ and Ta₂O₅ mixing introduces negative oxide charge, tends to creates shallow bulk traps and modifies the dominant conduction mechanisms in the stack capacitors as compared to the Ta₂O₅-based one (a contribution of tunneling processes through traps located below the conduction band of mixed layers to the leakage current in the HfO₂-Ta₂O₅ stacks is observed). The traps involved in both Poole-Frenkel and tunneling processes are identified.     

The properties of high-k gate dielectric films deposited on HRSOI

In this paper, HfO₂ dielectric films with blocking layers (BL) of Al₂O₃ were deposited on high resistivity silicon-on-insulator (HRSOI), and the interfacial and electrical properties are reported. High-resolution transmission electron microscopy (HRTEM) indicated that BL could thin the interfacial layer, keep the interface smooth, and retain HfO₂ amorphous after annealing. Energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) confirmed that BL weaken Si diffusion and suppressed the further growth of HfSiO. Electrical measurements indicated that there was no hysteresis was observed in capacitance–voltage curves, and Flatband shift and interface state density is 0.05 V and −1.3 × 10¹² cm⁻², respectively.     

MIS characterization and modeling of the electrical properties of the epitaxial Caf2/Si(111) interface

CaF₂ layers have grown by molecular beam epitaxy on bothn-type andp- type Si(111). Capacitance-voltage (C-V) and current-voltage (I-V) measurements have been made on metal-insulator-semiconductor (MIS) capacitors to characterize these structures. For devices onp-type Si, C-V characteristics show only the insulator value of the capacitance over a wide range of applied voltages, indicating an accumulated surface. At room temperature, C-V characteristics ofn-type devices show the minimum value of the capacitance (corresponding to inversion) for small voltages, but modulation of the capacitance at larger voltages. At 200 K, this modulation is no longer present in the C-V curves. I-V curves show a rapid increase in the leakage current at relatively low fields at room temperature, and this leakage decreases dramatically with temperature. These results are largely independent of cleaning procedure, growth temperature, and the degree of misalignment of the substrate. The characteristics are modeled by assuming the Fermi level to be pinned at the valence-band edge, and the modulation in the C-V characteristics ofn-type samples to be driven by leakage currents. Work done at GE while a graduate student in the School of Electrical Engineering, Cornell University. Present address: Jet Propulsion Laboratory, 4800 Oak Grove Dr., Pasadena, CA 91109.     

Electrical characterization of high-k gate dielectrics fabricated using plasma oxidation and post-deposition annealing of a Hf/SiO2/Si structure

High permittivity (high-k) gate dielectrics were fabricated using the plasma oxidation of Hf metal/SiO₂/Si followed by the post-deposition annealing (PDA), which induced a solid-phase reaction between HfO_x and SiO₂. The oxidation time and PDA temperature affected the equivalent oxide thickness (EOT) and the leakage current density of the high-k dielectric films. The interfacial structure of the high-k dielectric film/Si was transformed from HfO_x/SiO₂/Si to HfSi_xO_y/Si after the PDA, which led to a reduction in EOT to 1.15 nm due to a decrease in the thickness of SiO₂. These high-k dielectric film structures were investigated by X-ray photoelectron spectroscopy. The leakage current density of high-k dielectric film was approximately four orders of magnitude lower than that of SiO₂.     

Annealing effect on physical and electrical characteristics of thin HfO2, HfSixOy and HfOyNz films on Si

We report the effect of annealing on electrical and physical characteristics of HfO₂, HfSi_xO_y and HfO_yN_z gate oxide films on Si. Having the largest thickness change of 0.3 nm after post deposition annealing (PDA), HfO_yN_z shows the lowest leakage current. It was found for both as-grown and annealed structures that Poole-Frenkel conduction is dominant at low field while Fowler-Nordheim tunneling in high field. Spectroscopic ellipsometry measurement revealed that the PDA process decreases the bandgap of the dielectric layers. We found that a decreasing of peak intensity in the middle HfO_yN_z layer as measured by Tof-SIMS may suggest the movement of N toward the interface region between the HfO_yN_z layer and the Si substrate during the annealing process.     

Integration of HfxTayN metal gate with SiO2 and HfOxNy gate dielectrics for MOS device applications

Interaction of Hf_xTa_yN metal gate with SiO₂ and HfO_xN_y gate dielectrics has been extensively studied. Metal-oxide-semiconductor (MOS) device formed with SiO₂ gate dielectric and Hf_xTa_yN metal gate shows satisfactory thermal stability. Time-of-flight secondary ion mass spectroscopy (TOF-SIMS) analysis results show that the diffusion depths of Hf and Ta are less significant in SiO₂ gate dielectric than that in HfO_xN_y. Compared to HfO_xN_y gate dielectric, SiO₂ shows better electrical properties, such as leakage current, hysteresis, interface trap density and stress-induced flat-band voltage shift. With an increase in post metallization annealing (PMA) temperature, the electrical characteristics of the MOS device with SiO₂ gate dielectric remain almost unchanged, indicating its superior thermal and electrical stability.     

Physical properties and electrical characteristics of H2O-based and O3-based HfO2 films deposited by ALD

Ozone (O₃) and H₂O are used as the oxidant to deposit hafnium oxide (HfO₂) thin films on p-type Si (1 0 0) wafers by atomic layer deposition (ALD). The physical properties and electrical characteristics of HfO₂ films change greatly for different oxidants and deposition temperature. Compared with O₃ as the oxidant, HfO₂ films grown with H₂O as the oxidant are more consistent in composition and growth rate. The O₃-based HfO₂ films have lower C impurity and higher concentration N impurity than the H₂O-based HfO₂ films. The impact of the annealing process on the electrical properties and stability of HfO₂ films are also investigated. A width step is observed in the O₃-based HfO₂ C–V curves, which disappears after annealing process. It is because the unstable Hf–O–N and Hf–N bonds in O₃-based HfO₂ films are re-bonded with the non-HfO₂ oxygen after annealing process, and the binding energy of N_1s shifts.     

Hafnium oxide thin films deposited by high pressure reactive sputtering in atmosphere formed with different Ar/O2 ratios

The physical and electrical properties of hafnium oxide (HfO₂) thin films deposited by high pressure reactive sputtering (HPRS) have been studied as a function of the Ar/O₂ ratio in the sputtering gas mixture. Transmission electron microscopy shows that the HfO₂ films are polycrystalline, except the films deposited in pure Ar, which are amorphous. According to heavy ion elastic recoil detection analysis, the films deposited without using O₂ are stoichiometric, which means that the composition of the HfO₂ target is conserved in the deposition films. The use of O₂ for reactive sputtering results in slightly oxygen-rich films. Metal-Oxide-Semiconductor (MOS) devices were fabricated to determine the deposited HfO₂ dielectric constant and the trap density at the HfO₂/Si interface (D_it) using the high–low frequency capacitance method. Poor capacitance–voltage (CV) characteristics and high values of D_it are observed in the polycrystalline HfO₂ films. However, a great improvement of the electrical properties was observed in the amorphous HfO₂ films, showing dielectric constant values close to 17 and a minimum D_it of 2×10¹¹ eV⁻¹ cm⁻².     

Photoconductivity of Hf-based binary metal oxides

In order to explore the possibility of bandgap engineering in binary oxide insulators we studied photoconductivity of nanometer-thin Hf oxide layers containing different fractions of cations of another sort (Si, Al, Sr, or Ce) deposited on (1 0 0)Si. The smallest bandgaps of the Hf:Al and Hf:Ce oxides are close to the values found in elemental Al₂O₃ (6-6.2 eV) and HfO₂ (5.6 eV), respectively, and show little sensitivity to the concentration of Al or Ce. This result suggests that the oxide sub-network with the largest bandgap preserves its gap energy, while development of a narrower gap is prevented, likely, by dilution of the second cation sub-network. In Hf:Si oxide samples photoconductivity thresholds of 5.6-5.9 eV, corresponding to the bandgap of HfO₂, were observed for all studied Si concentrations, suggesting phaseseparation to occur during deposition. Photoconductivity of SrHfO₃ exhibits two thresholds, at 4.4 and 5.7 eV, which are close to the bandgaps of elemental SrO₂ and HfO₂, respectively. These gap values indicate the phase separation also to occur in this binary oxide. Through this work photoconductivity is demonstrated to be a feasible method to trace phase separation in binary oxides, even in nanometer-thin layers.     

Experimental evidence of suppression on oxygen vacancy formation in Hf based high-κ gate dielectrics with La incorporation

Experimental evidence of suppression on oxygen vacancy formation in Hf based high-κ gate dielectrics with La incorporation is provided by using modified charge-pumping (CP) techniques. The original distribution of interface traps and bulk traps of pure HfO₂ and HfO₂/LaOx dielectric stack are extracted and compared by CP techniques. It is found that devices with HfO₂/LaOx dielectric stack have higher interface trap but lower bulk trap density than those with pure HfO₂. Especially, device with HfO₂/LaOx dielectric stack is highly resistant to constant voltage stress, which can be attributed to the suppression on oxygen vacancy formation in Hf based high-κ gate dielectrics with La incorporation.     

Physical and electrical characterization of polysilicon vs. TiN gate electrodes for HfO2 transistors

The effects of pre-deposition substrate treatments and gate electrode materials on the properties and performance of high-k gate dielectric transistors were investigated. The performance of O₃ vs. HF-last/NH₃ pre-deposition treatments followed by either polysilicon (poly-Si) or TiN gate electrodes was systematically studied in devices consisting of HfO₂ gate dielectric produced by atomic layer deposition (ALD). High-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) using X-ray spectra and Electron Energy Loss Spectra (EELS) were used to produce elemental profiles of nitrogen, oxygen, silicon, titanium, and hafnium to provide interfacial chemical information and to convey their changes in concentration across these high-k transistor gate-stacks of 1.0–1.8 nm equivalent oxide thickness (EOT). For the TiN electrode case, EELS spectra illustrate interfacial elemental overlap on a scale comparable to the HfO₂ microroughness. For the poly-Si electrode, an amorphous reaction region exists at the HfO₂/poly-Si interface. Using fast transient single pulse (SP) electrical measurements, electron trapping was found to be greater with poly-Si electrode devices, as compared to TiN. This may be rationalized as a result of a higher density of trap centers induced by the high-k/poly-Si material interactions and may be related to increased physical thickness of the dielectric film, as illustrated by HAADF-STEM images, and may also derive from the approximately 0.5 nm larger EOT associated with polysilicon electrodes on otherwise identical gate stacks.     

Intrinsic Defect Limit to the Growth of Orthorhombic HfO2 and (Hf,Zr)O2 with Strong Ferroelectricity: First-Principles Insights

It is believed that promoting the fraction of ferroelectric orthorhombic phase (o-phase) through O-poor growth conditions can increase the spontaneous polarization of HfO₂ and (Hf,Zr)O₂ thin films. However, the first-principles calculations show that the growth may be limited by the easy formation of point defects in the orthorhombic and tetragonal phases of HfO₂, ZrO₂, and (Hf,Zr)O₂. Their dominant defects, O interstitial (O_i) under O-rich conditions and O vacancy (V_O) under O-poor condition, have low formation energies and quite high density (10¹⁶–10¹⁹ cm⁻³ for 800–1400 K growth temperature). Especially, O_i has negative formation energy in tetragonal HfO₂ under O-rich condition, causing non-stoichiometry and limiting the crystalline-seed formation during o-phase growth. High-density defects can cause disordering of dipole moments and increase leakage current, both diminishing the polarization. These results explain the experimental puzzle that the measured polarization is much lower than the ideal value even in O-poor thin films and highlight that controlling defects is as important as promoting the o-phase fraction for enhancing ferroelectricity. The O-intermediate condition (average of O-rich and O-poor conditions) and low growth temperature are proposed for fabricating HfO₂ and (Hf,Zr)O₂ with fewer defects, lower leakage current, and stronger ferroelectricity, which challenges the belief that O-poor condition is optimal.     

Intrinsic bonding defects in transition metal elemental oxides

Gate dielectrics comprised of nanocrystalline HfO₂ in gate stacks with thin SiO₂/SiON interfacial transition regions display significant asymmetries with respect to trapping of Si substrate injected holes and electrons. Based on spectroscopic studies, and guided by ab initio theory, electron and hole traps in HfO₂ and other transition metal elemental oxides are assigned to O-atom divacancies, clustered at internal grain boundaries. Three engineering solutions for defect reduction are identified: i) deposition of ultra-thin, <2 nm, HfO₂ dielectric layers, in which grain boundary formation is suppressed by effectively eliminating inter-primitive unit cell π-bonding interactions, ii) chemically phase separated high HfO₂ silicates in which inter-primitive unit cell p-bonding interactions are suppressed by the two nanocrystalline grain size limitations resulting from SiO₂ inclusions, and iii) non-crystalline Zr/Hf Si oxynitrides without grain boundary defects.     

Control of Interface Traps in HfO2 Gate Dielectric on Silicon

The effects of postdeposition annealing (PDA) on the interface between HfO₂ high-k dielectric and bulk silicon were studied in detail. The key challenges of successfully adopting the high-k dielectric/Si gate stack into advanced complementary metal–oxide–semiconductor (CMOS) technology are mostly due to interfacial properties. We have proposed a PDA treatment at 600°C for several different durations (5 min to 25 min) in nitrogen or oxygen (95% N₂ + 5% O₂) ambient with a 5-nm-thick HfO₂ film on a silicon substrate. We found that oxidation of the HfO₂/Si interface, removal of the deep trap centers, and crystallization of the film take place during the postdeposition annealing (PDA). The optimal PDA conditions for low interface trap density were found to be dependent on the PDA duration. The formation of an amorphous interface layer (IL) at the HfO₂/Si interface was observed. The growth was due to oxygen incorporated during thermal annealing that reacts with the Si substrate. The interface traps of the bonding features, defect states, and hysteresis under different PDA conditions were studied using x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), transmission electron microscopy (TEM), and leakage current density–voltage (J–V) and capacitance–voltage (C–V) techniques. The results showed that the HfO₂/Si stack with PDA in oxygen showed better physical and electrical performance than with PDA in nitrogen. Therefore, PDA can improve the interface properties of HfO₂/Si and the densification of HfO₂ thin films.     

Enhancement in thermal stability of atomic layer deposited HfO2 films by using top Hf metal layer

A thin (∼ 0.5 nm) layer of Hf metal was deposited on an atomic layer deposited (ALD) HfO₂ film by the DC sputtering method. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analyses showed that the Hf metal layer transformed into HfO₂ during the post-deposition annealing process. It appears that the HfO₂ layer formed by the oxidation of Hf metal provided the underlying ALD HfO₂ layer with the nucleation sites necessary to decrease the grain-boundary density of the crystallized HfO₂ film. The decrease in the grain-boundary density resulted in a reduction in the Hf-silicate formation and interfacial layer growth during post deposition annealing. This eventually resulted in a smaller increase in the capacitance equivalent thickness (CET) and high-k characteristics in the CET vs. leakage current density curve even after post deposition annealing at 1000 °C.     

Application of non-linear optical second harmonic generation and X-ray absorption and spectroscopies to defect related properties of Hf silicate and Hf Si oxynitride gate dielectrics

Three different Hf oxide based dielectrics have emerged as viable candidates for applications in advanced ULSI devices. This article focuses on two of these: (i) phase separated Hf silicates with (i) 70–85% nano-crystalline HfO₂ with a nano-grain size <2 nm, and 15–30% ～2 nm non-crystalline SiO₂ inclusions, and (ii) Hf Si oxynitride alloys, the most promising of which has a composition, (HfO₂)_0.3(SiO₂)_0.3(Si₃N₄)_0.4 designated as 3/3/4 Hf SiON. X-ray absorption spectroscopy has been applied to identification of defect associated with vacancy structures in phase separated silicates, and network disruption defects in the Hf Si oxynitrides. Optical second harmonic generation is introduced in this article for the first time as a non-invasive approach for detecting macroscopic strain, that is shown to be absent in these low defect density dielectrics, the phase separated Hf silicates, and Hf Si oxynitrides, but present in HfO₂ films, and Hf silicates with lower HfO₂ content, e.g., the 40% HfO₂ film of this article.