Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Formation of W/HfO2/Si gate structures using in situ magnetron sputtering and rapid thermal annealing

The W(150 nm)/HfO₂(5 nm)/Si(100) structures prepared in a single vacuum cycle by rf magnetron sputtering were subjected to rapid thermal annealing in argon. It is found that at an annealing temperature of 950°C, the tungsten oxide WO _x phase and the hafnium silicate HfSi _x O _y phase grow at the W/HfO₂ and HfO₂/Si(100) interfaces, respectively. Herewith, the total thickness of the oxide layeris 30% larger than that of the initial HfO₂ film. In addition, a decrease in the specific capacitance in accumulation C _max and in the dielectric constant k (from 27 to 23) is observed. At an annealing temperature of 980°C, intensive interaction between tungsten and HfO₂ takes place, causing the formation of a compositionally inhomogeneous Hf _x Si _y W _z O oxide layer and further decrease in C _max. It is shown that a considerable reduction in the leakage currents occurs in the W/HfO₂/X/Si(100) structures, where X is a nitride barrier layer.     

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.     

Effect of microstructure on the conductivity of a NASICON-type lithium ion conductor

Sintering temperature is used to control the microstructure of Li_{1 + x + y}Al_xTi_2 − xSi_yP_3 − yO₁₂ (x = 0.3, y = 0.2), a NASICON-type glass-ceramic. Scanning Electron Microscope imaging, X-Ray Diffraction, and Electrochemical Impedance Spectroscopy are employed to show that increase in sintering temperature increases conductivity while generating secondary crystalline phases. Total conductivity is as high as 3.81 × 10⁻⁴ S cm⁻¹ for sintering temperatures above 1000 °C. Crystallization of dielectric phases places the optimal sintering temperature in the 900 °C to 1000 °C range. Thermal analysis of the glass precursor reveals the glass transition, and crystallization temperatures.     

Effect of cation doping on ionic and electronic properties for lanthanum silicate-based solid electrolytes

Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La_9.333 + xSi₆O_26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La₁₀Si₆O₂₇ on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mⁿ⁺) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La₁₀(Si_5.8Al_0.2)O_26.9}-α(FeO_γ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10^− 3 and 2.9 × 10^− 3 under P(O₂) = 1.1 × 10⁴ Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La₁₀(Si_5.8Al_0.2)O_26.9}-0.005(FeO_γ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions.     

Thickness measurement of a thin hetero-oxide film with an interfacial oxide layer by X-ray photoelectron spectroscopy

The general equation T_ove = L cos  θ ln(R_exp/R₀ + 1) for the thickness measurement of thin oxide films by X-ray photoelectron spectroscopy (XPS) was applied to a HfO₂/SiO₂/Si(1 0 0) as a thin hetero-oxide film system with an interfacial oxide layer. The contribution of the thick interfacial SiO₂ layer to the thickness of the HfO₂ overlayer was counterbalanced by multiplying the ratio between the intensity of Si⁴⁺ from a thick SiO₂ film and that of Si⁰ from a Si(1 0 0) substrate to the intensity of Si⁴⁺ from the HfO₂/SiO₂/Si(1 0 0) film. With this approximation, the thickness levels of the HfO₂ overlayers showed a small standard deviation of 0.03 nm in a series of HfO₂ (2 nm)/SiO₂ (2-6 nm)/Si(1 0 0) films. Mutual calibration with XPS and transmission electron microscopy (TEM) was used to verify the thickness of HfO₂ overlayers in a series of HfO₂ (1-4 nm)/SiO₂ (3 nm)/Si(1 0 0) films. From the linear relation between the thickness values derived from XPS and TEM, the effective attenuation length of the photoelectrons and the thickness of the HfO₂ overlayer could be determined.     

Fabrication and characterization of La-doped HfO2 gate dielectrics by metal-organic chemical vapor deposition

La-doped HfO₂ gate dielectric thin films have been deposited on Si substrates using La(acac)₃ and Hf(acac)₄ (acac = 2,4-pentanedionate) mixing sources by low-pressure metal-organic chemical vapor deposition (MOCVD). The structure, thermal stability, and electrical properties of La-doped HfO₂ films have been investigated. Inductive coupled plasma analyses confirm that the La content ranging from 1 to 5 mol% is involved in the films. The films show smaller roughness of ∼0.5 nm and improved thermal stability up to 750 °C. The La-doped HfO₂ films on Pt-coated Si and fused quartz substrates have an intrinsic dielectric constant of ∼28 at 1 MHz and a band gap of 5.6 eV, respectively. X-ray photoelectron spectroscopy analyses reveal that the interfacial layer is Hf-based silicate. The reliable value of equivalent oxide thickness (EOT) around 1.2 nm has been obtained, but with a large leakage current density of 3 A/cm² at V_g = 1V + V_fb. MOCVD-derived La-doped HfO₂ is demonstrated to be a potential high-k gate dielectric film for next generation metal oxide semiconductor field effect transistor applications.     

Optical properties of multilayer structures

The possibility of using the ellipsometry method for investigation of the optical properties of multilayer films and structures is shown. The optical properties of structures HfO₂/SiO₂/Si, HfO₂/Si, ZrO₂/Si, Ta₂O₅/Si, and Al₂O₃/Si are studied. It is found that a layer of hafnium silicate is formed at the interface between the HfO₂ film and Si. Annealing of the structures in oxygen shows that oxides studied are oxygen-permeable and that the thickness of SiO₂ at the film-substrate interface increases. The growth rate of SiO₂ layers depends on the chemical nature of an oxide. Al₂O₃ films are impermeable for oxygen diffusion. The production of layers of alloys (Al₂O₃) _x (HfO₂)_{1 ? x} is optimized, which allows one to obtain layers with a homogeneous distribution of elements over the thickness.     

Effect of annealing temperature on microstructure, hardness and adhesion properties of TiSixNy superhard coatings

A series of TiSi_xN_y superhard coatings with different Si contents were prepared on M42 steel substrates using two Ti and two Si targets by reactive magnetron sputtering at 500 °C. These samples were subsequently vacuum-annealed at 500, 600, 700, 800 and 900 °C, respectively. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), microindenter, Rockwell hardness tester and scratch tester were applied to investigate the microstructure, phase configuration, hardness and adhesion properties of as-deposited and annealed samples. The results indicated that there were two bonds, TiN and Si₃N₄, in all presently deposited TiSi_xN_y thin films, that structure was nanocomposite of nanocrystalline (nc-) TiN embedded into amorphous Si₃N₄ matrices. Annealing treatment below 900 °C played a little role in microstructure and hardness of the coatings although it greatly affected those of steel substrates. The film-substrate adhesion strength was slightly increased, followed by an abrupt decrease with increasing annealing temperature. Its value got to the maximum at 600 °C. Annealing had little effect on the friction coefficient with its value varying in the range of 0.39-0.40.     

Preparation of five-layered Si/SixGe1−x nano-films by RF helicon magnetron sputtering

Five-layered Si/Si_xGe_1−x films on Si(1 0 0) substrate with single-layer thickness of 30 nm, 10 nm and 5 nm, respectively were prepared by RF helicon magnetron sputtering with dual targets of Si and Ge to investigate the feasibility of an industrial fabrication method on multi-stacked superlattice structure for thin-film thermoelectric applications. The fine periodic structure is confirmed in the samples except for the case of 5 nm in single-layer thickness. Fine crystalline Si_xGe_1−x layer is obtained from 700 °C in substrate temperature, while higher than 700 °C is required for Si good layer. The composition ratio (x) in Si_xGe_1−x is varied depending on the applied power to Si and Ge targets. Typical power ratio to obtain x = 0.83 was 7:3, Hall coefficient, p-type carrier concentration, sheet carrier concentration and mobility measured for the sample composed of five layers of Si (10 nm)/Si_0.82Ge_0.18 (10 nm) are 2.55 × 10⁶ /°C, 2.56 × 10¹² cm⁻³, 1.28 × 10⁷ cm⁻², and 15.8 cm⁻²/(V s), respectively.     

Bimodal growth of manganese silicide on Si(1 0 0)

Two different growth modes of manganese silicide are observed on Si(1 0 0) with scanning tunneling microscopy. 1.0 and 1.5 monolayer Mn are deposited at room temperature on the Si(1 0 0)-(2 × 1) substrate. The as-grown Mn film is unstructured. Annealing temperatures between room temperature and 450 °C lead to small unstructured clusters of Mn or Mn_xSi_y. Upon annealing at 450 °C and 480 °C, Mn reacts chemically with the Si substrate and forms silicide islands. The dimer rows of the substrate become visible again. Two distinct island shapes are found and identified as MnSi and Mn₅Si₃.     

Structural and optical properties of nitrogen-incorporated HfO2 gate dielectrics deposited by reactive sputtering

High-k HfO_xN_y thin films with different nitrogen-incorporation content have been fabricated on Si (1 0 0) substrate by means of radio-frequency reactive sputtering method. Analyses from X-ray diffraction (XRD) and atomic force microscopic have indicated that the increase of the crystallization temperature of HfO₂ thin films and the decrease of the roughness root-mean-square value of HfO₂ thin films due to the incorporation of nitrogen. Based on a parameterized Tauc-Lorentz (TL) dispersion model, the optical properties of the HfO_xN_y thin films related to different nitrogen-incorporation content are systematically investigated by spectroscopic ellipsometer. Increase in the refractive index and the extinction coefficient and reduction in band gap with increase of nitrogen-incorporation content are discussed in detail.     

Electrical property of HfOxNy-HfO2-HfOxNy sandwich-stack films

The effects of HfO_xN_y on the electrical property of HfO_xN_y-HfO₂-HfO_xN_y sandwich-stack (signed as SS) films were investigated. Excellent electrical performances were achieved in SS films, with a high dielectric constant of 16 and a low leakage current of ∼2 × 10⁻⁸ A/cm² at 1 MV/cm. Schottky (SK) emission and Frenkel-Poole (PF) emission are found to be the dominant mechanisms for the current conduction behavior. After a long time stress, the flat-band voltage shift in the SS film is much smaller than that in a pure HfO_xN_y film indicating fewer charge traps existed in the SS film. Based on the experiments, the new SS structure is more favorable for the improvement of electrical performances than a pure HfO_xN_y or HfO₂ structure.     

Power-law scaling of proton conductivity in amorphous silicate thin films

Amorphous hafnium silicate, a-Hf_0.1Si_0.9O_x, thin film with thickness of 32, 41, 55, 80, 110, 120, 180 and 320 nm was prepared by multiple spin-cast process and the proton conductivity across the films was measured at intermediate temperatures (100-400 °C) in dry atmosphere. The morphologically- and compositionally-uniform films were prepared on a substrate as confirmed by SEM, RBS and XPS measurements. a-Hf_0.1Si_0.9O_x thin film clearly revealed the H/D isotope effect on ionic conductivity, indicating that protonic conduction is dominant in the measured temperature range. The films did not reveal thickness-dependent proton conductivity in dry air and the σ at given temperatures is almost constant at any thickness. No increment of σ in a-Hf_0.1Si_0.9O_x thin films by reduction of thickness might be related to the absence of the highly-conductive acid network with mesoscopically-sized length because of the relatively low concentration of Brønsted acid sites inside films.     

Study of reactions between HfO2 and Si in thin films with precise identification of chemical states by XPS

Reactions between HfO₂ and Si in HfSiO films during deposition and post-annealing have been studied. Intermixing of HfO₂ and Si is achieved by radio frequency sputtering with HfO₂/Si compound targets, and post-annealing is used to promote the reaction at different temperatures. The structural characteristics of the mixture, HfSiO films, are analyzed by X-ray photoelectron spectroscopy and X-ray diffraction, and a careful assessment of chemical states is performed for precise identification. XPS results show that with ratios of Si:Hf ranging from 0 to 0.3 in HfSiO films, Si fully reacts with HfO₂ to form silicate during deposition. However, SiO₂ appears when the ratio of Si:Hf rises to 1.2. When the annealing temperature reaches 600 °C, decomposition of hafnium silicate is observed and hafnium silicide forms in the bulk of the films. XRD results reveal that HfSiO films remain amorphous with the annealing temperature below 600 °C but crystallize at 800 °C.     

Photoemission studies of pulsed-RF plasma nitrided ultra-thin SiON dielectric layers

Results are presented of a photoemission study of the electronic structure of SiON layers formed by a pulsed-RF decoupled plasma nitration (DPN) of ultra-thin SiO₂ grown base layers approximately 1.0 nm thick. The optical thickness of these device grade nitrided dielectric layers was in the range 1.4-1.6 nm. X-ray photoelectron spectroscopy (XPS) studies indicate that the nitrogen is incorporated in a single chemical environment at concentration levels in the range 15-17%. Angle resolved XPS measurements show that the nitrogen is distributed through the layer, with the binding energy of the N 1s peak at 398.3 eV which is indicative of a Si₃N₄-like chemical species in an oxide environment. High resolution core level photoemission studies of the spin orbit stripped Si 2p⁴⁺ peak revealed full width half maximum values in the range 1.4-1.55 eV, which are significantly larger than the 1.15 eV value reported for SiO₂ layers. Synchrotron radiation photoemission studies of the valence band spectra enable the valence band off-set at the Si/SON interface to be evaluated as 2.3 eV and to infer a conduction band off-set of 2.1 eV.     

Effects of N2 and NH3 remote plasma nitridation on the structural and electrical characteristics of the HfO2 gate dielectrics

The remote plasma nitridation (RPN) of an HfO₂ film using N₂ and NH₃ has been investigated comparatively. X-ray photoelectron spectroscopy and Auger electron spectroscopy analyses after post-deposition annealing (PDA) at 700 °C show that a large amount of nitrogen is present in the bulk film as well as in the interfacial layer for the HfO₂ film nitrided with NH₃-RPN. It is also shown that the interfacial layer formed during RPN and PDA is a nitrogen-rich Hf-silicate. The C-V characteristics of an HfO_xN_y gate dielectric nitrided with NH₃-RPN have a smaller equivalent oxide thickness than that nitrided with N₂-RPN in spite of its thicker interfacial layer.     

X-ray and IR analysis of Cu-Si ferrite

Polycrystalline soft ferrite, Cu_1+xSi_xFe_2−2xO₄ (x=0.0, 0.05, 0.1, 0.15, 0.2 and 0.3) were prepared by standard ceramic technique. The X-ray analysis confirmed the single phase formation of the samples up to x=0.1 beside a second phase for x?0.15. The lattice parameter was found to decrease with composition(x), which is attributed to ionic size difference of cations involved. The bulk density measurements shows two different behavior for x< >0.15. The IR spectra of Cu-Si ferrite system have been analyzed in the frequency range 200-1200 cm⁻¹. It revealed two prominent bands ν₁ and ν₂ which are assigned to tetrahedral and octahedral metal complexes, respectively. The position of the highest frequency band is around 575 cm⁻¹ while the lower frequency band is around 400 cm⁻¹.     

Thermal stability and chemical bonding states of AlOxNy/Si gate stacks revealed by synchrotron radiation photoemission spectroscopy

Annealing-temperature dependence of the thermal stability and chemical bonding states of AlO_xN_y/SiO₂/Si gate stacks grown by metalorganic chemical vapor deposition (MOCVD) using new chemistry was investigated by synchrotron radiation photoemission spectroscopy (SRPES). Results have confirmed the formation of the AlN and AlNO compounds in the as-deposited samples. Annealing the AlO_xN_y samples in N₂ ambient in 600-800 °C promotes the formation of SiO₂ component. Meanwhile, there is no formation of Al-O-Si and Al-Si binding states, suggesting no interdiffusion of Al with the Si substrate. A thermally induced reaction between Si and AlO_xN_y to form volatile SiO and Al₂O is suggested to be responsible for the full disappearance of the Al component that accompanies annealing at annealing temperature of 1000 °C. The released N due to the breakage of the Al-N bonding will react with the SiO₂ interfacial layer and lead to the formation of the Si₃-N-O/Si₂-N-O components at the top of Si substrate. These results indicate high temperature processing induced evolution of the interfacial chemistry and application range of AlO_xN_y/Si gate stacks in future CMOS devices.     

Crystal structure and photoluminescence of (Ba1−x−ySryEux)9Sc2Si6O24

Divalent europium-doped alkaline earth metal silicate phosphors, (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ (x=0.005–0.1, y=0–0.95), have been successfully prepared by solid-state reaction at 1350 °C. The analysis of X-ray diffraction shows that the compounds are in a single phase at the proper concentration of Sr²⁺. At room temperature, the Eu²⁺-activated Ba₉Sc₂Si₆O₂₄ phosphor exhibits a single emission band peaking at about 506 nm. With the increasing content of Sr²⁺, the luminescent intensity of (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ weakens, and the emission peak shifts towards red. Luminescence concentration quenching occurs when Eu²⁺ content x is more than 1 mol% in (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ (y=0/0.2). At low temperatures (Ba_0.9?ySr_yEu_0.1)₉Sc₂Si₆O₂₄ (y=0/0.2) phosphors have two emission bands corresponding to different Eu²⁺ crystallographic sites. The high energy peak (P₁) is quenched at room temperature, while the low energy peak (P₂) weakens much more slowly owing to the energy transfer from P₁ to P₂.