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.     

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.     

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.     

Structural, dielectric and pyroelectric studies of Pb1−XCaXTiO3 thin films

Thin films of Pb_1−xCa_xTiO₃ [x=0.20, 0.24 and 0.28] have been prepared on ITO coated Corning glass substrates by sol gel technique. The perovskite phase of PCT films is formed at 650 °C with a polycrystalline tetragonal structure. The tetragonal factor (c/a) decreases with increasing Ca concentration. Dielectric, pyroelectric and ferroelectric studies have been carried out on these films. The effects of introduction of Ca ion in PbTiO₃ have also been discussed.     

Characterization of HfOxNy gate dielectrics using a hafnium oxide as target

Hafnium oxynitride (HfO_xN_y) gate dielectric has been deposited on Si (1 0 0) by means of radio frequency (rf) reactive sputtering using directly a HfO₂ target in N₂/Ar ambient. The thermal stability and microstructural characteristics for the HfO_xN_y films have been investigated. XPS results confirmed that nitrogen was successfully incorporated into the HfO₂ films. XRD analyses showed that the HfO_xN_y films remain amorphous after 800 °C annealing in N₂ ambient. Meanwhile the HfO_xN_y films can also effectively suppress oxygen diffusion during high temperature annealing and prevent interface layer from forming between HfO_xN_y films and Si substrates. AFM measurements demonstrated that surface roughness of the HfO_xN_y films increase slightly as compared to those pure HfO₂ films after post deposition annealing. By virtue of building reasonable model structure, the optical properties of the HfO_xN_y films have been discussed in detail.     

Characteristics of sandwich-structured Al2O3/HfO2/Al2O3 gate dielectric films on ultra-thin silicon-on-insulator substrates

Sandwich-structure Al₂O₃/HfO₂/Al₂O₃ gate dielectric films were grown on ultra-thin silicon-on-insulator (SOI) substrates by vacuum electron beam evaporation (EB-PVD) method. AFM and TEM observations showed that the films remained amorphous even after post-annealing treatment at 950 °C with smooth surface and clean silicon interface. EDX- and XPS-analysis results revealed no silicate or silicide at the silicon interface. The equivalent oxide thickness was 3 nm and the dielectric constant was around 7.2, as determined by electrical measurements. A fixed charge density of 3 × 10¹⁰ cm⁻² and a leakage current of 5 × 10⁻⁷A/cm² at 2 V gate bias were achieved for Au/gate stack /Si/SiO₂/Si/Au MIS capacitors. Post-annealing treatment was found to effectively reduce trap density, but increase in annealing temperature did not made any significant difference in the electrical performance.     

Preparation and electroactive properties of a PVDF/nano-TiO2 composite film

In the present study, poly(vinylidene fluoride) (PVDF)/nano-TiO₂ electroactive film was prepared by coating a substrate with an acetone/DMF solution, which was evaporated at a high temperature (110 °C). The crystallisation behaviour, dynamic mechanical properties and electroactive properties of this PVDF/nano-TiO₂ electroactive film were investigated. The cross-section and surface of the film were observed with a scanning electron microscope (SEM). X-ray diffraction (XRD) results showed that the film containing the PVDF β phase, the desired ferroelectric phase, was obtained by crystallising the mixed solution of nano-TiO₂ and PVDF at 110 °C, while the film containing the α phase was obtained from the crystallisation of the pure PVDF solution at the same temperature. It was found that the storage modulus, the room-temperature dielectric constant and the electric breakdown strength of the composite films were much higher than those of a pure PVDF film. TiO₂ improved the mechanical properties and electroactive properties of the film. The results indicate that PVDF/nano-TiO₂ composite films can be applied to the fabrication of self-sensing actuator devices.     

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.     

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.     

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).     

Large blue shift in the optical band-gap of sol-gel derived Ba0.5Sr0.5TiO3 thin films

In this paper, we report and analyze the large blue shift in the optical band-gap of sol-gel derived Ba_0.5Sr_0.5TiO₃ (BST) thin films. BST films of different thickness (150 nm, 320 nm and 480 nm respectively) were deposited layer by layer onto fused quartz substrates by a spin coating technique. The drying temperature for individual layers (pre-sintering temperature) was varied as 400, 500 and 600 ^°C. A large blue shift in the band-gap was observed (with a value 4.70 eV compared to the bulk value of 3.60 eV) for films pre-sintered at 400 ^°C, which decreased with increase in the pre-sintering temperature. To date such blue shifts have been attributed to grain size reduction, stress and the amorphous nature of the films. Here, the blue shift has been correlated with the presence of charge carriers generated by oxygen vacancies and explained on the basis of the Burstein-Moss effect.     

Surface reaction mechanism of Y2O3 atomic layer deposition on the hydroxylated Si(1 0 0)-2 × 1: A density functional theory study

The surface reaction mechanism of Y₂O₃ atomic layer deposition (ALD) on the hydroxylated silicon surface is investigated by using density functional theory. The ALD process is designed into two half-reactions, i.e., Cp₃Y (Cp = cyclopentadienyl) and H₂O half-reactions. For the Cp₃Y half-reaction, the chemisorbed complex is formed along with the change of metal-Cp bonding from Y-C(π) to Y-C₁(σ). For the H₂O half-reactions, the chemisorbed energies are increased with the relief of steric congestion around yttrium metal center. In addition, Gibbs free energy calculations show that it is thermodynamically favorable for the Cp₃Y half-reactions. By comparing with the reaction of H₂O with {Si}-(O₂)YCp, it is thermodynamically more favorable and kinetically less favorable for the reactions of H₂O with {Si}-OYCp₂ as well as with {Si}-OYCp(OH).     

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.     

Memory Effect of Metal--Insulator--Silicon Capacitors with SiO2/HfO2/Al2O3 Dielectrics

Charge trapping characteristics of the metal-insulator-silicon （MIS） capacitors with Si02/HfO2//A12O3 stacked dielectrics are investigated for memory applications＇. A capacitance-voltage hysteresis memory window as large as 7.3 V is achieved for the gate voltage sweeping of ±12 V, and a fiat-band voltage shift of 1.5 V is observed in terms of programming under 5 V and I ms. Furthermore, the time- and voltage-dependent charge trapping characteristics are also demonstrated, the former is related to charge trapping saturation and the latter is ascribed to variable tunnelling barriers for electron injecting and discharging under different voltages.     

Effects of interface on the dielectric properties of Ba0.6Sr0.4TiO3 thin film capacitors

Ba_0.6Sr_0.4TiO₃ thin films were deposited on Pt/SiO₂/Si substrate by radio frequency magnetron sputtering. High-resolution transmission electron microscopy (HRTEM) observation shows that there is a transition layer at BST/Pt interface, and the layer is about 7-8 nm thickness. It is found that the transition layer was diminished to about 2-3 nm thickness by reducing the initial RF sputtering power. X-ray photoelectron spectroscopy (XPS) depth profiles show that high Ti atomic concentration results in a thick interfacial transition layer. Moreover, the symmetry ν of ?_r-V curve of BST thin film is enhanced from 52.37 to 95.98%. Meanwhile, the tunability, difference of negative and positive remanent polarization (P_r), and that of coercive field (E_C) are remarkably improved.     

Band bending and band alignment at HfO2/HfSixOy/Si interfaces

Band bending and band alignment at HfO₂/SiO₂/Si and HfO₂/Hf/SiO₂/Si interfaces were investigated using X-ray photoelectron spectroscopy. After Hf-metal pre-deposition, a 0.55 eV band bending in Si and a 1.80 eV binding energy decrease for Hf 4f and O 1s of HfO₂ were observed. This was attributed to the introduction of negative space charges at interface by Hf pre-deposition. Band bending decrease and synchronous binding energy increases of O 1s and Hf 4f for HfO₂ were observed during initial Ar⁺ sputtering of the Hf pre-deposited sample. This was interpreted through the neutralization of negative space charges by sputtering-induced oxygen vacancies.     

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.     

Metallo-organic decomposition derived (Ca, Sr)ZrO3 dielectric thin films on Pt coated Si substrate

Metallo-organic decomposition derived dielectric thin films of calcium zirconate doped with various concentrations of strontium ((Ca, Sr)ZrO₃) were prepared on Pt coated silicon substrate. Mainly in this paper, we present the investigations of their structural developments and present their electric and dielectric properties as well. The structural developments show that the CaZrO₃ film has amorphous structure with carbonate existing when annealed at 600 °C, while annealed at 650 °C and above, the carbonate is decomposed and those films crystallize into perovskite phase without preferred orientation. In addition, the prepared (Ca, Sr)ZrO₃ films with their Zr-O bonds affected by strontium doping are homogenous and stable as solid solutions in any concentration of strontium and all Bragg diffraction characteristics for the films shift downward with the increase in the concentration of strontium. Moreover, the electric properties show that the (Ca, Sr)ZrO₃ films have very low leakage current density and high breakdown strength; typically, the CaZrO₃ film annealed at 650 °C has the leakage current density approximately 9.5 × 10⁻⁸ A cm⁻² in the field strength of 2.6 MV cm⁻¹. Furthermore, the dielectric properties show that their dielectric constants are higher than 12.8 with very little dispersion in the frequency range from 100 Hz to 1 MHz and are independent of applied dc bias as well. The dielectric properties, in combination with the electric properties, make the materials promising candidates for high-voltage and high-reliability capacitor applications.     

Structural optimization of HfTiSiO high-k gate dielectrics by utilizing in-situ PVD-based fabrication method

We investigated the optimum structure for Ti-containing Hf-based high-k gate dielectrics to achieve EOT scaling below 1 nm. TiO₂/HfSiO/SiO₂ trilayer and HfTiSiO/SiO₂ bilayer structures were fabricated by a newly developed in-situ PVD-based method. We found that thermal diffusion of Ti atoms to SiO₂ underlayers degrades the EOT-J_g characteristics. Our results clearly demonstrated the impact of the trilayered structure with TiO₂ capping for improving EOT-J_g characteristics of the gate stack. We achieved an EOT scaling of 0.78 nm as well as reduced gate leakage of 7.2 × 10⁻² A/cm² for a TiO₂/HfSiO/SiO₂ trilayered high-k dielectric while maintaining the electrical properties at the bottom interface.     

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.