Microstructure and dielectric properties of La2O3 doped amorphous SiO2 films as gate dielectric material

As a potential gate dielectric material, the La₂O₃ doped SiO₂ (LSO, the mole ratio is about 1:5) films were fabricated on n-Si (0 0 1) substrates by using pulsed laser deposition technique. By virtue of several measurements, the microstructure and electrical properties of the LSO films were characterized. The LSO films keep the amorphous state up to a high annealing temperature of 800 °C. From HRTEM and XPS results, these La atoms of the LSO films do not react with silicon substrate to form any La-compound at interfacial layer. However, these O atoms of the LSO films diffuse from the film toward the silicon substrate so as to form a SiO₂ interfacial layer. The thickness of SiO₂ layer is only about two atomic layers. A possible explanation for interfacial reaction has been proposed. The scanning electron microscope image shows the surface of the amorphous LSO film very flat. The LSO film shows a dielectric constant of 12.8 at 1 MHz. For the LSO film with thickness of 3 nm, a small equivalent oxide thickness of 1.2 nm is obtained. The leakage current density of the LSO film is 1.54 × 10⁻⁴ A/cm² at a gate bias voltage of 1 V.     

Electrical characteristics of polycrystalline Si layers embedded into high-k Al2O3 gate layers

The electrical characteristics of polycrystalline Si (poly Si) layers embedded into high-k Al₂O₃ (alumina) gate layers are investigated in this work. The capacitance versus voltage (C-V) curves obtained from the metal-alumina-polysilicon-alumina-silicon (MASAS) capacitors exhibit significant threshold voltage shifts, and the width of their hysteresis window is dependent on the range of the voltage sweep. The counterclockwise hysteresis observed in the C-V curves indicates that electrons originating from the p-type Si substrate in the inversion condition are trapped in the floating gate layer consisting of the poly Si layer present between the top and bottom Al₂O₃ layers in the MASAS capacitor. Also, current versus voltage (I-V) measurements are performed to examine the electrical characteristics of the fabricated capacitors. The I-V measurements reveal that our MASAS capacitors show a very low leakage current density, compared to the previously reported results.     

Chemical vapor deposition of ZrxTi1−xO2 and HfxTi1−xO2 thin films using the composite anhydrous nitrate precursors

Zr-Ti and Hf-Ti composite nitrates were successfully developed as single-source precursors for the chemical vapor deposition (CVD) of Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ thin films. The Zr-Ti nitrate can be assumed as a solid solution of the individual Zr and Ti nitrates, and the Zr/Ti molar ratio in the deposited Zr_xTi_1−xO₂ films is consistent with that in the precursor. The Hf-Ti nitrate appears to be a mixture of the Hf and Ti nitrates and the composition of the deposited Hf_xTi_1−xO₂ films depends remarkably on the heating time of precursor. Both Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ films exhibit trade-off properties between band gap and dielectric constant. The obtained results suggest that Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ films are promising candidates for gate dielectric application to improve the scalability and reduce the leakage current of the future complementary metal-oxide-semiconductor (CMOS) devices.     

Band bending measurement of HfO2/SiO2/Si capacitor with ultra-thin La2O3 insertion by XPS

The flat band voltage shifts of HfO₂/SiO₂/nSi capacitors with ultra-thin La₂O₃ insertion at HfO₂/SiO₂ interface have been confirmed using hard X-ray photoelectron spectroscopy (HX-PES). By increasing the amount of La₂O₃ insertion, the binding energy of Si 1s core spectra increases, which means that the surface potential of Si substrate also increases. A voltage drop difference of HfO₂ and La₂O₃ at SiO₂ interface can be estimated to be 0.40 V.     

Study of HfSiO film prepared by electron beam evaporation for high-k gate dielectric applications

The purpose of this paper is to report some experimental results with HfSiO films formed on silicon substrates by electron beam evaporation (EB-PVD) and annealed at different temperatures. The images of atomic force microscope (AFM) indicated that HfSiO film annealed at 900 °C was still amorphous, with a surface roughness of 0.173 nm. X-ray photoelectron spectroscopy (XPS) analysis revealed that the chemical composition of the film was (HfO₂)₃(SiO₂) and Hf-Si-O bonds existed in the annealed film. Electrical measurements showed that the equivalent oxide thickness (EOT) was 4 nm, the dielectric constant was around 6, the breakdown voltage was 10 MV/cm, the fixed charge density was −1.2 × 10¹² cm⁻², and the leakage current was 0.4 μA/cm² at the gate bias of 2 V for 6 nm HfSiO film. The annealing after deposition effectively reduced trapping density and the leakage current, and eliminated hysteresis in the C-V curves. Annealing also induced SiO₂ growth at the interface.     

Microstructure and interfacial properties of HfO2-Al2O3 nanolaminate films

High-k HfO₂-Al₂O₃ composite gate dielectric thin films on Si(1 0 0) have been deposited by means of magnetron sputtering. The microstructure and interfacial characteristics of the HfO₂-Al₂O₃ films have been investigated by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and spectroscopic ellipsometry (SE). Analysis by XRD has confirmed that an amorphous structure of the HfO₂-Al₂O₃ composite films is maintained up to an annealing temperature of 800 °C, which is much higher than that of pure HfO₂ thin films. FTIR characterization indicates that the growth of the interfacial SiO₂ layer is effectively suppressed when the annealing temperature is as low as 800 °C, which is also confirmed by spectroscopy ellipsometry measurement. These results clearly show that the crystallization temperature of the nanolaminate HfO₂-Al₂O₃ composite films has been increased compared to pure HfO₂ films. Al₂O₃ as a passivation barrier for HfO₂ high-k dielectrics prevents oxygen diffusion and the interfacial layer growth effectively.     

Reduced dielectric loss and leakage current in CaCu3Ti4O12/SiO2/CaCu3Ti4O12 multilayered films

The CaCu₃Ti₄O₁₂/SiO₂/CaCu₃Ti₄O₁₂ (CCTO/SiO₂/CCTO) multilayered films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition method. It has been demonstrated that the dielectric loss and the leakage current density were significantly reduced with the increase of the SiO₂ layer thickness, accompanied with a decrease of the dielectric constant. The CCTO film with a 20 nm SiO₂ layer showed a dielectric loss of 0.065 at 100 kHz and the leakage current density of 6×10⁻⁷ A/cm² at 100 kV/cm, which were much lower than those of the single layer CCTO films. The improvement of the electric properties is ascribed to two reasons: one is the improved crystallinity; the other is the reduced free carriers in the multilayered films.     

Effect of Ti doping on Ta2O5 stacks with Ru and Al gates

The Ti-doped Ta₂O₅ thin films (<10 nm) obtained by rf sputtering are studied with respect to their composition, dielectric and electrical properties. The incorporation of Ti is performed by two methods - a surface doping, where a thin Ti layer is deposited on the top of Ta₂O₅ and a bulk doping where the Ti layer is sandwiched between two layers of Ta₂O₅. The effect of the process parameters (the method and level of doping) on the elemental distribution in-depth of the films is investigated by the time of flight secondary ion mass spectroscopy (ToF-SIMS). The Ti and Ta₂O₅ are intermixed throughout the whole thickness but the layers are very inhomogeneous. Two sub-layers exist in all the samples — a near interfacial region which is a mixture of Ta-, Ti-, Si-oxides as well as TaSiO, and an upper Ti-doped Ta₂O₅ sub-layer. For both methods of doping, Ti tends to pile-up at the Si interface. The electrical characterisation is performed on capacitors with Al- and Ru-gate electrodes. The two types of MIS structures exhibit distinctly different electrical behavior: the Ru gate provides higher dielectric permittivity while the stacks with Al electrode are better in terms of leakage currents. The specific metal-dielectric reactions and metal-induced electrically active defects for each metal electrode/high-k dielectric stack define its particular electrical behavior. It is demonstrated that the Ti doping of Ta₂O₅ is a way of remarkable improvement of leakage characteristics (the current reduction with more than four orders of magnitude as compared with undoped Ta₂O₅) of Ru-gated capacitors which originates from Ti induced suppression of the oxygen vacancy related defects.     

Thickness determination of thin and ultra-thin SiO2 films by C-AFM IV-spectroscopy

Conductive atomic force microscopy was used to determine the electrical oxide thickness for five different silicon dioxide layers with thickness in the order of 1.6-5.04 nm. The electrical thickness results were compared with values determined by ellipsometry. A semi-analytical tunnelling current model with one single parameter set was used to superpose current/voltage curves in both the direct tunnelling and the Fowler-Nordheim tunnelling regime regions. The overall electrical oxide thickness was determined by statistical means from results of nearly 3000 IV-curves recorded for different conductive CoCr-coated tips. Good agreement between the shape of model and experimental data was achieved, widely independent of the oxide thickness. Compared with the ellipsometry value, the electrical thickness was larger by a value of 0.36 nm (22%) for the thinnest oxide and smaller by a value of 0.31 nm (6%) for the thickest oxide, while intermediate values yielded differences better than 0.15 nm (<6%). The physical differences between the measurement techniques were shown to contribute to this observation. In addition, statistical deviations between single and multiple measurements using a single tip and using a number of different tips were analysed. The causes, for example, natural oxide thickness variations, tip wear, air humidity induced effects and contaminations, are evaluated and discussed. The method proposed was able to determine the electrical oxide thickness with a standard deviation in the order of ±6-9%. The results suggest that for optimal results it is necessary to perform several repetitions of IV-measurements for one sample and, in addition, to employ more than one tip.     

C-AFM-based thickness determination of thin and ultra-thin SiO2 films by use of different conductive-coated probe tips

The influence of the probe tip type on the electrical oxide thickness result was researched for four differently coated conductive tip types using SiO₂ (oxide) films with optical thickness of 1.7-8.3 nm. For this purpose, conductive atomic force microscopy (C-AFM) was used to measure more than 7200 current-voltage (IV) curves. The electrical oxide thickness was determined on a statistical basis from the IV-curves using a recently published tunnelling model for C-AFM application. The model includes parameters associated with the probe tip types used. The evolution of the tip parameters is described in detail. For the theoretical tip parameters, measured and calculated IV-curves showed excellent agreement and the electrical oxide thickness versus the optical oxide thickness showed congruent behaviour, independent of the tip type. However, differences in the electrical oxide thickness were observed for the different tip types. The theoretical parameters were modified experimentally in order to reduce these differences. Theoretical and experimental tip parameters were compared and their effect on the differences in the electrical oxide thickness is discussed for the different tip types. Overall, it is shown that the proposed model provides a comprehensive framework for determining the electrical oxide thickness using C-AFM, for a wide range of oxide thicknesses and for differently coated conductive tips.     

Trap-controlled behavior in ultrathin Lu2O3 high-k gate dielectrics

Amorphous Lu₂O₃ high-k gate dielectrics were grown directly on n-type (100) Si substrates by the pulsed laser deposition (PLD) technique. High-resolution transmission electron microscope (HRTEM) observation illustrated that the Lu₂O₃ film has amorphous structure and the interface with Si substrate is free from amorphous SiO₂. An equivalent oxide thickness (EOT) of 1.1 nm with a leakage current density of 2.6×10⁻⁵ A/cm² at 1 V accumulation bias was obtained for 4.5 nm thick Lu₂O₃ thin film deposited at room temperature followed by post-deposition anneal (PDA) at 600 °C in oxygen ambient. The effects of PDA process and light illumination were studied by capacitance-voltage (C-V) and current density-voltage (J-V) measurements. It was proposed that the net fixed charge density and leakage current density could be altered significantly depending on the post-annealing conditions and the capability of traps to trap and release charges.     

Influence of initial surface reconstruction on the interface structure of HfO2/GaAs

We show that the bonding structures and electrical properties of the HfO₂/GaAs interface can be controlled by a choice of the reconstruction on the initial GaAs surface. Electron-beam evaporation of HfO₂ onto the c(4 × 4) surface yielded As-O bonds at the interface, while Ga-O bonds were dominant at the interfaces formed on the (2 × 4) and (4 × 6) surfaces. Influences of the initial surface reconstruction on the interface structure persisted even after annealing at 673 K. Electrical characterization of Ir/HfO₂/GaAs capacitors indicated that the interfacial As-O bonds cause weak Fermi level pinning. It was also suggested that the interfaces dominated by the Ga-O bonds have trapping states in the upper half of the GaAs bandgap.     

Gadolinium oxide high-k gate dielectrics prepared by anodic oxidation

The growth and properties of gadolinium oxide (Gd₂O₃) films prepared by anodic oxidation were investigated. Uniform Gd₂O₃ thin film with good oxide quality was obtained. The X-ray diffraction (XRD) pattern of the Gd₂O₃ films showed that they had a poly-crystalline structure. The dielectric constants of Gd₂O₃ films oxidized at 30 and 60 V are 9.4 and 12.2, respectively. The equivalent oxide thickness (EOT) of the Gd₂O₃ stacked oxide is in the range of 5.8-9.4 nm. The MOS capacitor with Gd₂O₃ exhibits interesting electrical properties. Longer oxidation time reduced the leakage current density for 30 V anodic oxidation but increased the leakage current density for 60 V anodic oxidation. This work reveals that Gd₂O₃ could also be an alternative dielectric for Si substrate and therefore, might pave the way to fabricate CMOS devices in the future.     

Properties of K0.5Bi0.5TiO3 thin films deposited on different substrates

K_0.5Bi_0.5TiO₃ thin films were deposited on fused quartz, n-type Si(100) and Pt/TiO₂/SiO₂/Si substrates by repeated coating/dying cycles. X-ray diffraction analysis shows that the films annealed at 700 °C for 10 min present perovskite phase. Atomic force microscopy reveals that the surface morphology is smooth, the grain sizes of the films on Si(100) are quite larger than on fused quartz. The capacitance-voltage hysteresis loops at various sweeping speed are collected as are polarization types. The films in the ON and OFF states are relatively stable. The films also exhibit a hysteresis loop at an applied voltage of 4 V, with a remanent polarization of 9.3 μC/cm² and a coercive voltage of 2 V. The insulating property of negative bias voltage is better than that of positive bias voltage. The transmittance of the films is between 74 and 82% in the wavelength range of 200-2000 nm.     

Phase diagram and dielectric behavior of Ba0.6Sr0.4TiO3 thin films grown on orthorhombic substrates

Using Landau-Devonshire (LD)-type phenomenological model, we investigate the phase diagrams and dielectric behaviors of single-domain single-crystal Ba_0.6Sr_0.4TiO₃ films deposited on orthorhombic substrates. An anisotropic strain factor is introduced to quantitatively calculate the effects of anisotropic in-plane misfit strains. Investigation indicates that anisotropic strains play a crucial role on formation of stable ferroelectric phases and dielectric properties. The anisotropic strains induce tetragonal phases which only contain one in-plane spontaneous polarization component. These phases do not exist in BST films of the same composition under isotropic strains. Moreover, permittivity and tunability of films can reach to maximum when the corresponding spontaneous polarization component disappears at the boundaries of structural phase transition.     

Growth of highly-oriented CaCu3Ti4O12 thin films on SrTiO3 (1 0 0) substrates by a chemical solution route

Highly-oriented CaCu₃Ti₄O₁₂ (CCTO) thin films deposited directly on SrTiO₃ (1 0 0) substrates have been developed successfully using a chemical solution coating method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were employed to characterize the structure and the morphology. It was observed that the CCTO thin films had the 1 μm × 1 μm domain-like microstructure that consists of compact grains of about 0.1 μm in size. The cross sectional SEM image shows that the CCTO grains grow regularly close to the clear interface between the CCTO film and the SrTiO₃ substrate. The result was discussed in terms of lattice mismatch between CCTO and SrTiO₃.     

Composition of Ta2O5 stacked films on N2O- and NH3-nitrided Si

The composition and microstructure of rf sputtered 20 nm Ta₂O₅ on N₂O or NH₃ Rapid Thermal Nitrided (RTN) Si substrates have been investigated by X-ray photoelectron spectroscopy. RTN at 800 and 850 °C is effective to suppress active oxidation of Si. There is no evidence for the presence of SiO₂ at Si interface. A lightly nitrided surface is established in both cases without a formation of detectable oxynitride layer at Si. A layered nature of the films is observed, with stoichiometric tantalum pentoxide at and close to the films’ surface. In the depth, the films are mixed ones whose composition depends on the nitridation ambient. N₂O treatment stimulates oxidation processes during the film deposition while NH₃ nitridation results to a less effective oxidation and produces Ta-silicate like film. The correlation between the composition of the interfacial regions and the nitridation gas is also discussed. The results suggest that hydrogen, as a component of nitridation ambient, plays significant role in the reactions controlling the exact composition of the deposited Ta₂O₅, activating reactions with nitrogen. Nitrogen related reactions likely occur with NH₃ processing but do not with N₂O one. The presence of nitrogen feature is not detected in N₂O-samples spectra at all. In the integration perspective, preliminary RTN of Si in N₂O or NH₃ could be a suitable way to produce layered Ta₂O₅-based films with more or less presence of tantalum silicate with a trace of nitrogen, either only at the interface with Si (N₂O-process) or in the whole film (NH₃-process).     

Electrical behavior of BaZr0.1Ti0.9O3 and BaZr0.2Ti0.8O3 thin films

BaZr_0.1Ti_0.9O₃ and BaZr_0.2Ti_0.8O₃ (BZT) thin films were deposited on Pt/Ti/LaAlO₃ (1 0 0) substrates by radio-frequency magnetron sputtering, respectively. The films were further annealed at 800 °C for 30 min in oxygen. X-ray diffraction θ-2θ and Φ-scans showed that BaZr_0.1Ti_0.9O₃ films displayed a highly (h 0 0) preferred orientation and a good cube-on-cube epitaxial growth on the LaAlO₃ (1 0 0) substrate, while there are no obvious preferential orientation in BaZr_0.2Ti_0.8O₃ thin films. The BaZr_0.1Ti_0.9O₃ films possess larger grain size, higher dielectric constant, larger tunability, larger remanent polarization and coercive electric field than that of BaZr_0.2Ti_0.8O₃ films. Whereas, BaZr_0.1Ti_0.9O₃ films have larger dielectric losses and leakage current density. The results suggest that Zr⁴⁺ ion can decrease dielectric constant and restrain non-linearity. Moreover, the enhancement in dielectric properties of BaZr_0.1Ti_0.9O₃ films may be attributed to (1 0 0) preferred orientation.     

Mechanical stress in ALD-Al2O3 films

Mechanical stress in atomic-layer deposition (ALD)-Al₂O₃ films was investigated at room temperature and during thermal cycling up to 870 °C. The films were generally under tensile stress. Thicker films (25-60 nm) showed a sharp stress increase at about 780-790 °C. X-ray diffraction (XRD)-, X-ray reflectance (XRR)- and X-ray photoelectron spectroscopy (XPS)-measurements indicate an irreversible phase transition from amorphous AlO(OH) to a mixture of different crystalline Al₂O₃-phases. Annealing at higher temperatures leads to a stress reduction as a result of diffusion and recovery processes. The stress behaviour of thinner films (<20 nm) during thermal cycling is quite different. Tensile stress increases with increasing temperature and decreases to nearly the same value during cooling down. The process is continuous and reversible.     

Microstructure and dielectric properties of (Ba0.6Sr0.4)TiO3 thin films grown on super smooth glazed-Al2O3 ceramics substrate

Modified substrates with nanometer scale smooth surface were obtained via coating a layer of CaO-Al₂O₃-SiO₂ (CaAlSi) high temperature glaze with proper additives on the rough-95% Al₂O₃ ceramics substrates. (Ba_0.6Sr_0.4)TiO₃ (BST) thin films were deposited on modified Al₂O₃ substrates by radio-frequency magnetron sputtering. The microstructure, dielectric, and insulating properties of BST thin films grown on glazed-Al₂O₃ substrates were investigated by X-ray diffraction (XRD), atomic force microscope (AFM), and dielectric properties measurement. These results showed that microstructure and dielectric properties of BST thin films grown on glazed-Al₂O₃ substrates were almost consistent with that of BST thin films grown on LaAlO₃ (1 0 0) single-crystal substrates. Thus, the expensive single-crystal substrates may be substituted by extremely cheap glazed-Al₂O₃ substrates.