Low temperature processed hafnium oxide: Structural and electrical properties

In this work hafnium oxide (HfO₂) was deposited by r.f. magnetron sputtering at room temperature and then annealed at 200 °C in forming gas (N₂+H₂) and oxygen atmospheres, respectively for 2, 5 and 10 h. After 2 h annealing in forming gas an improvement in the interface properties occurs with the associated flat band voltage changing from −2.23 to −1.28 V. This means a reduction in the oxide charge density from 1.33×10¹² to 7.62×10¹¹ cm⁻². After 5 h annealing only the dielectric constant improves due to densification of the film. Finally, after 10 h annealing we notice a degradation of the electrical film's properties, with the flat band voltage and fixed charge density being −2.96 V and 1.64×10¹² cm⁻², respectively. Besides that, the leakage current also increases due to crystallization. On the other hand, by depositing the films at 200 °C or annealing it in an oxidizing atmosphere no improvements are observed when comparing these data to the ones obtained by annealing the films in forming gas. Here the flat band voltage is more negative and the hysteresis on the C–V plot is larger than the one recorded on films annealed in forming gas, meaning a degradation of the interfacial properties.     

High temperature characterization of high-κ dielectrics on SiC

We have fabricated thin catalytic metal–insulator–silicon carbide based structure with palladium (Pd) gates using TiO₂ as the dielectric. The temperature stability of the capacitor is of critical importance for use in the fabrication of electronics for deployment in extreme environments. We have evaluated the response to temperatures in excess of 450 °C in air and observed that the characteristics are stable. Results of high temperature characterization are presented here with extraction of interface state density up to 650 °C. The results show that at temperatures below 400 °C the capacitors are stable, with a density of interface traps of approximately 6×10¹¹ cm² eV⁻¹. Above this temperature the C–V and G–V characteristics show the influence of a second set of traps, with a density around 1×10¹³ cm² eV⁻¹, which is close to that observed for slow states near the conduction band edge. The study of breakdown field as a function of temperature shows two distinct regions, below 300 °C where the breakdown voltage has a strong temperature dependence and above 300, where it is weaker. We hypothesize that the oxide layer dominates the breakdown voltage at low temperature and the TiO₂ layer above 300 °C. These results at high temperatures confirms the suitability of the Pd/TiO₂/SiO₂/SiC capacitor structure for stable operation in high temperature environments.     

Influence of rapid thermal annealing on morphological and electrical properties of RF sputtered AlN films

Aluminum nitride films were deposited, at 200 °C, on silicon substrates by RF sputtering. Effects of rapid thermal annealing on these films, at temperatures ranging from 400 to 1000 °C, have been studied. Fourier transform infrared spectroscopy (FTIR) revealed that the characteristic absorption band of Al–N, around 684 cm⁻¹, became prominent with increased annealing temperature. X-ray diffraction (XRD) patterns exhibited a better, c-axis, (0 0 2) oriented AlN films at 800 °C. Significant rise in surface roughness, from 2.1 to 3.68 nm, was observed as annealing temperatures increased. Apart from these observations, micro-cracks were observed at 1000 °C. Insulator charge density increased from 2×10¹¹ to 7.7×10¹¹ cm⁻² at higher temperatures, whereas, the interface charge density was found minimum, 3.2×10¹¹ eV⁻¹cm⁻², at 600 °C.     

Correlation between infrared transmission spectra and the interface trap density of SiO2 films

This work is an attempt to estimate the electrical properties of SiO₂ thin films by recording and analyzing their infrared transmission spectra. In order to study a big variety of films having different infrared and electrical properties, we studied SiO₂ films prepared by low pressure chemical vapor deposition (LPCVD) from SiH₄ + O₂ mixtures at 425 °C and annealed at 750 °C and 950 °C for 30 min. In addition thermally grown gate quality SiO₂ films of similar thickness were studied in order to compare their infrared and electrical properties with the LPCVD oxides. It was found that all studied SiO₂ films have two groups of Si–O–Si bridges. The first group corresponds to bridges located in the bulk of the film and far away from the interfaces, the grain boundaries and defects and the second group corresponds to all other bridges located near the interfaces, the grain boundaries and defects. The relative population of the bulk over the boundary bridges was found equal to 0.60 for the LPCVD film after deposition and increased to 4.0 for the LPCVD films after annealing at 950 °C. Thermally grown SiO₂ films at 950 °C were found to have a relative population of Si–O–Si bridges equal to 3.9. The interface trap density of the LPCVD film after deposition was found equal to 5.47 × 10¹² eV⁻¹ cm⁻² and decreases to 6.50 × 10¹⁰ eV⁻¹ cm⁻² after annealing at 950 °C for 30 min. The interface trap density of the thermally grown film was found equal to 1.27 × 10¹¹ eV⁻¹ cm⁻² showing that films with similar Si–O–Si bridge populations calculated from the FTIR analysis have similar interface trap densities.     

Electrical characterization of HfO2 films obtained by UV assisted injection MOCVD

HfO₂ films were deposited at low temperature (400 °C) by UV assisted injection metal-organic chemical vapor deposition (UVI-MOCVD). A three-step process was used for this study, consisting of (A) Pre-deposition anneal for nitridation; (B) Deposition step; (C) Post-deposition annealing in oxygen. Special attention was paid to the effect of UV exposure during these steps. Films were characterized by physical, optical and electrical techniques. Thickness was determined by different methods (X-ray Reflectrometry (XRR), spectroscopic ellipsometry and transmission electron microscopy) and a good agreement was found for all samples. The HfO₂ permittivity, equivalent oxide thickness (E_OT), flat-band voltage (V_fb) and total charge (Q_t) were extracted from the CV response at high frequency taking into account the HfO₂ and SiO₂ thicknesses obtained by XRR. The calculated permittivity values were in the range 7–13, i.e. lower than theoretical values for the monoclinic phase. Explanations are suggested in the context of the other characterizations. JE_eff characteristics were constructed taking into account the E_OT values (E_eff = V/E_OT). Effective breakdown fields range between 8.7 and 16.9 MV/cm. No dependence of E_eff with UV exposure was found.     

Examination and evaluation of La2O3 as gate dielectric for sub-100 nm CMOS and DRAM technology

High-k gate dielectric La₂O₃ thin films have been deposited on Si(1 0 0) substrates by molecular beam epitaxy (MBE). Al/La₂O₃/Si metal-oxide–semiconductor capacitor structures were fabricated and measured. A leakage current of 3 × 10⁻⁹ A/cm² and dielectric constant between 20 and 25 has been measured for samples having an equivalent oxide thickness (EOT) 2.2 nm. The estimated interface state density D_it is around 1 × 10¹¹ eV⁻¹ cm⁻². EOT and flat-band voltage were calculated using the NCSU CVC program. The chemical composition of the La₂O₃ films was measured using X-ray photoelectron spectrometry and Rutherford backscattering. Current density vs. voltage curves show that the La₂O₃ films have a leakage current several orders of magnitude lower than SiO₂ at the same EOT. Thin La₂O₃ layers survive anneals of up to 900 °C for 30 s with no degradation in electrical properties.     

Breakdown fields and conduction mechanisms in thin Ta2O5 layers on Si for high density DRAMs

The conduction mechanisms and the microstructure of rf sputtered Ta₂O₅ on Si, before and after oxygen annealing at high temperatures (873, 1123 K; 30 min) have been investigated. The as-deposited and annealed at 873 K layers are amorphous whereas crystalline Ta₂O₅ (orthorhombic β-Ta₂O₅ phase) was obtained after O₂ treatment at 1123 K. The results (electrical, X-ray diffraction, transmission electron microscopy) reveal the formation of an interfacial ultrathin SiO₂ layer under all technological regimes used. The higher (493 K) substrate temperature during deposition stimulates the formation of amorphous rather than crystalline SiO₂. It is found that the oxygen heating significantly reduces the oxide charge (Q_f<10¹⁰ cm⁻²) and improves the breakdown characteristics (the effect is more pronounced for the higher annealing temperature). It is accompanied by an increase of the effective dielectric constant (up to 37 after 1123 K treatment). It is established that the influence of the oxygen treatment on the leakage current is different depending on the film thickness, namely: a beneficial effect for the thinner and a deterioration of leakage characteristics for thicker (80 nm) films. A leakage current density as low as 10⁻⁷ A/cm² at 1 MV/cm applied field for 26 nm annealed layers has been obtained. The current reduction is considered to be due to a removal by annealing of certain structural nonperfections present in the initial layers. Generally, the results are discussed in terms of simultaneous action of two opposite and competing processes taking place at high temperatures––a real annealing of defects and an appearance of a crystal phase and/or a neutral traps generation. The contribution of the neutral traps also is involved to explain the observed weaker charge trapping in the as-fabricated films compared to the annealed ones.The conduction mechanism of the as-deposited films is found to be of Poole–Frenkel (PF) type for a wide range of applied fields. A change of the conduction mechanism for the annealed films at medium fields (0.8–1.3 MV/cm) is established. This transition from PF process to the Schottky emission limited current is explained with an annealing of bulk traps (oxygen vacancies and nonperfect bonds). It is concluded that the dominant conduction mechanism in the intermediate fields can be effectively controlled by appropriate technological steps.     

Influence of the annealing temperature on the IR properties of SiO2 films grown from SiH4 + O2

Dispersion analysis was performed on low pressure chemically vapor deposited (LPCVD) SiO₂ films grown from SiH₄ + O₂ at 425 °C. The transmission spectra were analyzed using four Lorentz oscillators within the range 900–1400 cm⁻¹. It was found that the distribution of the SiOSi angles is a superposition of two Gaussians; one corresponding to bridges located in the bulk of the film and one corresponding to bridges located close to the boundaries of the film namely the interfaces of the films and the grain boundaries. The ratio between the bulk like SiOSi bridges over the boundary bridges was found equal to 0.61:1 indicating that films grown from SiH₄ + O₂ contain a higher number of boundary SiOSi bridges relative to those located in the bulk of the film. After annealing for 30 min at temperatures in the range from 550 to 950 °C, films were found to have a lower thickness. The calculated ratio of the two distributions after annealing have shown a clear reduction in the concentration of the boundary bridges as the temperature of annealing increases, in advance of the bridges located in the bulk of the film. For the film annealed at 950 °C for 30 min the ratio was found equal to 4.0:1 which is the same to that of thermally grown films at the same temperature.     

Electrical instability of sintered Ta films on (vacuum evaporated) polysilicon structures

High purity tantalum metal was deposited on finely polished single crystal, polycrystalline silicon substrates and on the thermally grown oxide layers as a combination of Si/SiO₂/poly-Si/Ta, under oil-free ultra-high vacuum conditions, of the order of 6.0 × 10⁻⁹ Torr, at a deposition rate of 2.0 Å s⁻¹, using an e-beam evaporator. The measured resistivity of the as-deposited tantalum films show relatively high resistivity values to that of the bulk. Thermal annealing of these poly-Si/Ta, under argon (with 10% H₂) ambient, shows the increase in the resistivity values at relatively low temperatures, and it was observed that the film's electrical conductivity ceases in the temperature range of 500–600°C. The oxidation properties of tantalum and the possible formation of TaSi₂ and Ta₂O₅ were analysed for from a reliability point of view.     

Vibrational spectroscopy characterization of low-dielectric constant SiOC:H films prepared by PECVD technique

Low-dielectric constant SiOC:H films were prepared by plasma enhanced chemical vapour deposition (PECVD) from trimethyl-silane (H–Si–(CH₃)₃) and ozone (O₃) gas mixture. The samples were preliminarily annealed at 400 °C in N₂ atmosphere and then in N₂+He plasma. Afterwards, they were treated in vacuum at some fixed temperatures in the range between 400 and 900 °C. Structural investigations of the annealed films were carried out by means of vibrational spectroscopy techniques. FT-IR spectrum of a preliminarily treated sample shows absorption bands due to stretching modes of structural groups like Si–CH₃ at 1270 cm⁻¹, Si–O–Si at 1034 cm⁻¹ and C–H_x in the region between 2800 and 3000 cm⁻¹. No significant spectral change was observed in the absorption spectra of samples annealed up to 600 °C, indicating that the preliminarily treated film retains a substantial structural stability up to this temperature. Above 600 °C, absorption spectra show a strong quenching of H-related peaks while the band due to Si–O–Si anti-symmetric stretching mode shifts towards higher energy, approaching the value observed for thermally grown SiO₂. Raman spectra of samples treated at temperatures T500 °C exhibit both D and G bands typical of sp²-hybridised carbon, due to the formation of C–C bonds within the film which is accompanying the release of hydrogen. The intensity of D and G bands becomes more pronounced in samples annealed at higher temperatures, thus suggesting a progressive precipitation of carbon within the oxide matrix.     

Applications of DCIV method to NBTI characterization

The DCIV method was applied to investigate negative bias temperature instability (NBTI) in SiO₂ gate oxides. The DCIV technique, which measures the interface defect density independently from bulk oxide charges, delineates the contribution of the interface defect generation to the overall NBTI measured by the threshold voltage shift, ΔV_TH. The DCIV results obtained during both stress and relaxation phases are generally consistent with the main features of the reaction–diffusion (R–D) model, which suggests positive charge generation/annealing at the Si/SiO₂ interface due to breaking/re-passivation of the Si–H bonds. These results are in agreement with the spin-dependent recombination (SDR) experiments, which reflect the density of the Si dangling bonds at the Si/SiO₂ interface (P_b centers) and its vicinity (E′ centers). Comparison of degradation kinetics as measured by DCIV, charge-pumping, and I_D − V_G (ΔV_TH) techniques, however, suggests that ΔV_TH includes additional contributions, most likely from the oxide bulk charges. For comparison, an NBTI study was also performed on the high-k HfO₂/SiO₂ gate stacks. After adjusting for the high-k related contribution, similar kinetics of the long-term stress interface trap generation was observed in SiO₂ and high-k gate stacks suggesting a common mechanism of the interface degradation.     

Effect of annealing on the properties of low-k nanoporous SiO2 films prepared by sol–gel method with catalyst HF

Using hydrofluoric acid (HF) as catalyst, nanoporous SiO₂ thin film was synthesized by sol–gel method. By scanning electron microscopy, Fourier transform infrared spectra, thermo gravimetric and differential thermal analysis, ellipsometry, capacitance–voltage and current–voltage measurements, the effects of annealing on film properties were discussed in detail. The introduction of HF results in the less polarizability, the preferable microstructures and the improved thermal stability of the nanoporous silica films. After thermal annealing at 450 °C, the crack-free films with strong hydrophobicity, ultra-low dielectric constant of 1.65, porosity of 78%, and leakage current density of 1.3 × 10⁻⁸ A cm⁻² were obtained.     

An investigation of surface state capture cross-sections for metal–oxide–semiconductor field-effect transistors using HfO2 gate dielectrics

MOSFETs and MOSCs incorporating HfO₂ gate dielectrics were fabricated. The I_DS–V_DS, I_DS–V_GS, gated-diode and C–V characteristics were investigated. The subthreshold swing and the interface trap density were obtained. The surface recombination velocity and the minority carrier lifetime in the field-induced depletion region measured from the gated diodes were about 2.73 × 10³ cm/s and 1.63 × 10⁻⁶ s, respectively. The effective capture cross section of surface state was determined to be 1.6 × 10⁻¹⁵ cm² using the gated-diode technique in comparison with the subthreshold swing measurement. A comparison with conventional MOSFETs using SiO₂ gate oxide was also made.     

Ballistic electron emission microscopy studies of the temperature dependence of Schottky barrier height distribution in CoSi2/n-Si(1 0 0) diodes formed by solid phase reaction

Ballistic electron emission microscopy (BEEM) and ballistic electron emission spectroscopy have been performed on polycrystalline and epitaxial CoSi₂/n-Si(1 0 0) contacts at temperatures ranging from −144°C to −20°C. The ultra-thin CoSi₂ films (10 nm) were fabricated by solid state reaction of a single layer of Co (3 nm) or a multilayer of Ti (1 nm)/Co (3 nm)/amorphous-Si(1 nm)/Ti (1 nm) with a Si substrate, respectively. The spatial distribution of barrier height over the contact area obeys a Gaussian function at each temperature. The mean barrier height increases almost linearly with decreasing temperature with a coefficient of −0.23±0.02 meV/K for polycrystalline CoSi₂/Si diodes and −0.13±0.03 meV/K for epitaxial diodes. This is approximately equal to one or one-half of the temperature coefficient of the indirect energy gap in Si, respectively. It suggests that the Fermi level is pinned to different band positions of Si. The width of the Gaussian distribution is about 30–40 meV, without clear dependence on the temperature. The results obtained from conventional current–voltage and capacitance–voltage (I–V/C–V) measurements are compared to BEEM results.     

Electrical properties of MIS capacitor using low temperature electron beam gun—evaporated HfAlO dielectrics

A low effective oxide thickness of 1.45 nm was achieved in HfAlO films deposited by an electron beam gun evaporator on unheated p-Si substrate. A reduction of the leakage current density from 1 × 10⁻⁴ to 4.5 × 10⁻⁷ A/cm², at an electric field 3 MV/cm, with annealing temperature and a breakdown electric field of 10 MV/cm were demonstrated for ultra thin films.     

Optical and electrical characterization of the electron beam gun evaporated TiO2 film

We report measured evolutions of the optical band gap, refractive index and relative dielectric constant of TiO₂ films obtained by electron beam gun evaporation and annealed in an oxygen environment. A negative shift of the flat band voltage with increasing annealing temperatures, for any film thickness, is observed. A dramatic reduction of the leakage current by about four orders of magnitude to 5×10⁻⁶ A cm⁻² (at 1 MV cm⁻¹) after 700°C and 60 min annealing is found for films thinner than 15 nm. The basic carrier transport mechanisms at different ranges of applied voltage such as hopping, space charge limited current and Fowler–Nordheim is established. An equivalent SiO₂ thickness in order of 3.5 nm is demonstrated.     

Optical dispersion analysis within the IR range of thermally grown and TEOS deposited SiO2 films

SiO₂ thin films, with thickness ranging between approximately 13 and 95 nm, have been thermally grown at 950°C in dry oxygen and chemically vapor deposited at low pressures (0.3 Torr) by decomposition of tetraethylorthosilicate (TEOS) at 710°C, on Si (100) substrates. Dispersion analysis was performed on Fourier transform infrared (FTIR) transmission spectra of these films within the range 900–1400 cm⁻¹. It was found that the spectra were best described within this range, by four Lorentz oscillators located near 1060, 1089, 1165 and 1220 cm⁻¹ almost independent of film thickness. The polarization of the oscillators (proportional to their strength) was found to increase slightly, and their widths to decrease, with film thickness. From the study of the FTIR spectra obtained at room temperature, it was suggested that at this temperature, a considerable number of Si–O–Si angles in these SiO₂ films are distributed in a way expected at higher temperatures and that the distribution of the Si–O–Si angles depends on the thermal history of the film and the method of growth.     

Effect of rapid thermal annealing of sputtered aluminium nitride film in an oxygen ambient

Aluminium nitride (AlN) thin films were deposited by radio frequency (RF) magnetron sputtering on p-type silicon (Si) substrate of (1 0 0) orientation using only argon (Ar) gas at substrate temperature of 300 °C. In order to achieve improved electrical properties, we performed post-deposition rapid thermal annealing (RTA). Sputtered AlN films were annealed in an oxygen ambient at temperatures of 600, 700, and 800 °C using RTA for 30 min. The orientation of the AlN crystal in the film was investigated using X-ray diffraction (XRD). The characteristic spectra by functional group were analyzed by Fourier transformation infrared (FTIR) spectroscopy. The electrical properties of the AlN thin films were studied through capacitance–voltage (C–V) characteristics in metal–insulator–semiconductor (MIS) device using the films as insulating layers. The flatband voltages (V_FB) in C–V curves were found to depend on crystal orientations. Negative V_FB was found in the case when AlN (1 0 0) peak was found. Also, when AlN (1 0 3) peak was observed upon increasing the annealing temperature, the value of V_FB was positive and after annealing at 700 °C, AlN (1 0 3) peak intensity was found to be maximum and V_FB was as high as+6.5 V.     

Electrical properties of hafnium silicate films obtained from a single-source MOCVD precursor

In the present work, the potential of hafnium silicate (Hf_xSi_yO₂) films as an alternative gate dielectric to SiO₂ for future technology generations is demonstrated. Thermally stable Hf_xSi_yO₂ films are deposited from a single-source MOCVD precursor. I–V and C–V measurement data are presented and effects of post-deposition annealing on electrical properties are discussed. A 900 °C O₂-anneal shows best results in terms of leakage current characteristics and is, therefore, intensively investigated.     

Study of electrically active defects in n-GaN layer

Deep level defects in both p⁺/n junctions and n-type Schottky GaN diodes are studied using the Fourier transform deep level transient spectroscopy. An electron trap level was detected in the range of energies at E_c−E_t=0.23–0.27 eV with a capture cross-section of the order of 10⁻¹⁹–10⁻¹⁶ cm² for both the p⁺/n and n-type Schottky GaN diodes. For one set of p⁺/n diodes with a structure of Au/Pt/p⁺–GaN/n–GaN/n⁺–GaN/Ti/Al/Pd/Au and the n-type Schottky diodes, two other common electron traps are found at energy positions, E_c−E_t=0.53–0.56 eV and 0.79–0.82 eV. In addition, an electron trap level with energy position at E_c−E_t=1.07 eV and a capture cross-section of σ_n=1.6×10⁻¹³ cm² are detected for the n-type Schottky diodes. This trap level has not been previously reported in the literature. For the other set of p⁺/n diodes with a structure of Au/Ni/p⁺–GaN/n–GaN/n⁺–GaN/Ti/Al/Pd/Au, a prominent minority carrier (hole) trap level was also identified with an energy position at E_t−E_v=0.85 eV and a capture cross-section of σ_n=8.1×10⁻¹⁴ cm². The 0.56 eV electron trap level observed in n-type Schottky diode and the 0.23 eV electron trap level detected in the p⁺/n diode with Ni/Au contact are attributed to the extended defects based on the observation of logarithmic capture kinetics.