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.     

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.     

X-ray reflectivity study of hydrogen implanted silicon

The X-ray reflectivity (XRR) technique was used to study monocrystalline silicon samples implanted with H₂ ions at an energy of 31 keV and to the dose of 2 × 10¹⁶ hydrogen atoms/cm². All samples were subsequently isochronally annealed in vacuum at different temperatures in the range from 100 to 900 °C. Although the hydrogen depth distribution was expected to be smooth initially, fringes in the XRR spectra were observed already in the implanted but not annealed sample, revealing the presence of a well-defined film-like structure. Annealing enhances the film top to bottom interface correlation due to structural relaxation, resulting in the appearance of fringes in the larger angular range, already at low annealing temperatures. The thickness of the film decreases slowly up to 350 °C where substantial changes in the roughness are observed, probably due to the onset of larger clusters formation. Further annealing at higher temperatures restores the high correlation of the film interfaces, while the thickness decreases with the temperature more rapidly.     

Surface modification by vacuum annealing for field emission from heavily phosphorus-doped homoepitaxial (1 1 1) diamond

The relationship between field emission properties and C 1s core level shifts of heavily phosphorus-doped homoepitaxial (1 1 1) diamond is investigated as a function of annealing temperature in order to optimize surface carbon bonding configurations for device applications. A low field emission threshold voltage is observed from surfaces annealed at 800 °C for hydrogen-plasma treated surface, while a low field emission threshold voltage of wet-chemical oxidized surface is observed after annealing at 900 °C. The C 1s core level by X-ray photoelectron spectroscopy (XPS) showed a shoulder peak at 1 eV below the main peak over 800 and 900 °C annealing temperature for hydrogen-plasma treated and wet-chemical oxidized surfaces, respectively. When the shoulder peak intensity is less than 10% of the main peak intensity, lower threshold voltages are observed. This is due to the carbon-reconstruction which gives rise to a small positive electron affinity. By increasing annealing temperature, the shoulder peak ratios also increase, which indicates that a surface graphitization takes place. This leads to higher threshold voltages.     

Growth of high-density Ru- and RuO2-composite nanodots on atomic-layer-deposited Al2O3 film

Growth of Ru- and RuO₂-composite (ROC) nanodots on atomic-layer-deposited Al₂O₃ film has been studied for the first time using ion-beam sputtering followed by post-deposition annealing (PDA). X-ray photoelectron spectroscopy analyses reveal that RuO₂ and Ru co-exist before annealing, and around 10% RuO₂ is reduced to metallic Ru after PDA at 900 °C for 15 s. Scanning electron microscopy measurements show that well-defined spherical ROC nanodots are not formed till the PDA temperature is raised to 900 °C. The mean diameter of the nanodots enlarges with increasing PDA temperature whereas the nanodot density decreases, which is attributed to coalescence process between adjacent nanodots. It is further illustrated that the resulting nanodot size and density are weakly dependent on the annealing time, but are markedly influenced by the decomposition of RuO₂. In this article, the ROC nanodots with a high density of 1.6 × 10¹¹ cm⁻², a mean diameter of 20 nm with a standard deviation of 3.0 nm have been achieved for the PDA at 900 °C for 15 s, which is promising for flash memory application.     

Improved dielectric properties of (Pb,Ca)TiO3 thin films prepared by metal-organic decomposition method

(Pb,Ca)TiO₃ (PCT) thin films have been deposited on Pt/Ti/SiO₂/Si substrate by metal-organic decomposition (MOD) technique. The film processing parameters such as drying and annealing temperatures have been optimized to obtain good-quality PCT films. Compositional analysis of the film has been studied by X-ray photoelectron spectroscopy (XPS). The effect of the annealing temperature on the crystalline structure, microstructure and electrical properties have been investigated by X-ray diffraction, atomic force microscopy (AFM) and impedance analyzer, respectively. Amorphous PCT films form at 350 °C and crystallize in the perovskite phase following the isothermal annealing at ?650 °C for 3 h in oxygen ambient. Typical tetragonal structure of the PCT film is evidenced from X-ray diffraction pattern. The grain size in the PCT films increases with an increase in annealing temperature. Significant improvement in the dielectric constant value is observed as compared to other reported work on PCT films. The observed dielectric constant and dissipation factor at 100 kHz for 650 °C annealed PCT films are 308 and 0.015, respectively. The correlation of the film microstructural features and electrical behaviors is described.     

Atomic transport and chemical stability of nitrogen in ultrathin HfSiON gate dielectrics

HfSiO and HfSiON films with thicknesses compatible with the requirements for gate dielectrics alternatives to SiO₂ in ultra-large scale integration silicon-based CMOSFET devices were deposited on an ultrathin HfSiO¹⁵N interfacial layer on Si(001). These structures were submitted to thermal processing routines typical of post-deposition annealing and dopant activation steps in fabrication technology, namely at 450 or 1000 °C, respectively, and in atmospheres of N₂ and/or O₂. N transport and loss were determined by nuclear reaction analysis, including sub-nanometric depth resolution profiling with narrow nuclear reaction resonances. The chemical states of N were accessed by angle-resolved X-ray photoelectron spectroscopy. After annealing at 450 °C, N is seen to be mobile, whereas the chemical environment of N is not changed at this temperature. Annealing at 1000 °C renders N mobile and its most abundant chemical state in near-surface regions is unstable. Annealing in O₂ atmosphere promotes incorporation of O from the gas phase into the films, partly in exchange for N and O atoms and partly by net incorporation of oxygen in the films. The profiles of the newly incorporated O atoms are also determined with sub-nanometric depth resolution by narrow nuclear reaction resonance profiling. PACS 68.60.-p; 68.55.-a; 73.61.Ng; 73.40.Qv     

Effect of substrate temperature on the surface and interface oxidation of NiTi thin films

NiTi shape memory alloy thin films are deposited on pure Cu substrate at substrate ambient temperatures of 300 °C and 450 °C. The surface and interface oxidation of NiTi thin films are characterized by X-ray photoelectron spectroscopy (XPS). After a subsequent annealing treatment the crystallization behavior of the films deposited on substrate at different temperatures is studied by X-ray diffraction (XRD). The effects of substrate temperature on the surface and interface oxidation of NiTi thin films are investigated. In the film surface this is an oxide layer composed of TiO₂. The Ni atom has not been detected on surface. In the film/substrate interface there is an oxide layer with a mixture Ti₂O₃ and NiO in the films deposited at substrate temperatures 300 °C and 450 °C. In the films deposited at ambient temperature, the interface layer contains Ti suboxides (TiO) and metallic Ni.     

Structural, compositional, thermal resistant and hydro-oleophobic properties of fluorine based block-co-polymer films on quartz substrates by wet chemical process

Crack free and smooth surfaces of poly [4,5-difluoro 2,2-bis (trifluoromethyl)-(1,3 dioxole)-co-tetrafluoroethylene] (TFE-co-TFD) thin films have been deposited by wet chemical dip coating technique on polished quartz and glass slide substrates. The deposited films have been subjected to annealing at different temperatures ranging from 100 to 500 °C for 1 h in argon atmosphere. The elemental composition of the as-deposited (xerogel) thin film as well as film annealed at 400 °C was measured by X-ray photoelectron spectroscopy and observed that there was no change in the composition of the film. X-ray diffraction pattern revealed the amorphous behaviour of both as-deposited and film annealed at 400 °C. Surface morphology and elemental composition of the films have been examined by employing scanning electron microscopy attached with energy dispersive X-ray analyser, respectively. It was found that as the annealing temperature increased from 100 to 400 °C, nano-hemisphere-like structures have been grown, which in turn has shown increase in the water contact angle from 122^o to 148^o and oil (peanut) contact angle from 85° to 96°. No change in the water contact angle (122°) has been observed when the films deposited at room temperature were heated in air from 30 to 80 °C as well as exposed to steam for 8 days for 8 h/day indicating thermal stability of the film.     

Highly thermal stable transparent conducting SnO2:Sb epitaxial films prepared on α-Al2O3 (0 0 0 1) by MOCVD

Antimony-doped tin oxide (SnO₂:Sb) single crystalline films have been prepared on α-Al₂O₃ (0 0 0 1) substrates by metal organic chemical vapor deposition (MOCVD). The antimony doping was varied from 2% to 7% (atomic ratio). Post-deposition annealing of the SnO₂:Sb films was carried out at 700-1100 °C for 30 min in atmosphere ambient. The effect of annealing on the structural, electrical and optical properties of the films was investigated in detail. All the SnO₂:Sb films had good thermal stability under 900 °C, and the 5% Sb-doped SnO₂ film exhibited the best opto-electrical properties. Annealed above 900 °C, the 7% Sb-doped SnO₂ film still kept high thermal stability and showed good electrical and optical properties even at 1100 °C.     

Metal contacts to n-GaN

Al, Au, Ti/Al and Ti/Au contacts were prepared on n-GaN and annealed up to 900 °C. The structure, phase and morphology were studied by cross-sectional transmission and scanning electron microscopy as well as by X-ray diffraction (XRD), the electrical behaviour by current-voltage measurements. It was obtained that annealing resulted in interdiffusion, lateral diffusion along the surface, alloying and bowling up of the metal layers. The current-voltage characteristics of as-deposited Al and Ti/Al contacts were linear, while the Au and Ti/Au contacts exhibited rectifying behaviour. Except the Ti/Au contact which became linear, the contacts degraded during heat treatment at 900 °C. The surface of Au and Ti/Au contacts annealed at 900 °C have shown fractal-like structures revealed by scanning electron microscopy. Transmission electron microscopy and XRD investigations of the Ti/Au contact revealed that Au diffused into the n-GaN layer at 900 °C. X-ray diffraction examinations showed, that new Ti₂N, Au₂Ga and Ga₃Ti₂ interface phases formed in Ti/Au contact at 900 °C, new Ti₂N phase formed in Ti/Al contact at 700 and 900 °C, as well as new AlN interface phase developed in Ti/Al contact at 900 °C.     

Enhancement of saturation magnetization in Cr-ion implanted silicon by high temperature annealing

Magnetic properties and microstructure of Cr-implanted Si have been investigated by alternating gradient magnetometer (AGM), superconducting quantum interference device (SQUID) magnetometer, and transmission electron microscopy (TEM). p-Type (1 0 0) Si wafers were implanted at 200 keV at room temperature with a dosage of 1 × 10¹⁶ cm⁻² Cr ions and then annealed at 600-900 °C for 5 min. The effect of annealing on the structure and magnetic properties of Cr-implanted Si is studied. The as-implanted sample shows a square M-H loop at low temperature. Magnetic signal becomes weaker after short time annealing of the as-implanted sample at 600 °C, 700 °C, and 800 °C. However, the 900 °C annealed sample exhibits large saturation magnetization at room temperature. TEM images reveal that the implanting process caused amorphization of Si, while annealing at 900 °C led to partial recovery of the crystal. The enhancement of saturation magnetization can be explained by the redistribution and accumulation of Cr atoms in the vacancy-rich region of Si during annealing.     

Study of electronic structures for Fe thin films deposited on Si- and C-faces of 4H-SiC substrates by soft X-ray emission spectroscopy

Silicon carbide (SiC) is a candidate material for electronic devices to operate upon crucial environment. Electronic states of silicides and/or carbide/graphite formed in metal/SiC contact system are fundamentally important from the viewpoint of device performance.We study interface electronic structure of iron thin film deposited on silicon (Si)- and carbon (C)-face of 4H-SiC(0 0 0 1) by using a soft X-ray emission spectroscopy (SXES). For specimens of Fe (50 nm)/4H-SiC (substrate) contact systems annealed at 700 and 900 °C, the Si L_2,3 emission spectra indicate different shapes and peak energies from the substrate depending on thermal-treated temperature. The product of materials such as silicides is suggested. Further, from comparison of Si L_2,3 emission spectra between Si- and C-face for the same annealing temperature at 700 °C, it is concluded that the similar silicides and/or ternary materials are formed on the two surfaces. However for those of 900 °C, the film on substrate is composed of the different silicide and/or ternary materials.     

Use of TiB2 diffusion barriers for Ni/Au ohmic contacts on p-GaN

The use of a TiB₂ diffusion barrier for Ni/Au contacts on p-GaN is reported. The annealing temperature (25-950 °C) dependence of ohmic contact characteristics using a Ni/Au/TiB₂/Ti/Au metallization scheme deposited by sputtering were investigated by contact resistance measurements and auger electron spectroscopy (AES). The as-deposited contacts are rectifying and transition to ohmic behavior for annealing at ≥500 °C . A minimum specific contact resistivity of ∼3 × 10⁻⁴ Ω cm⁻² was obtained after annealing over a broad range of temperatures (800-950 °C for 60 s). The contact morphology became considerably rougher at the higher end of this temperature range. AES profiling showed significant Ti and Ni outdiffusion through the TiB₂ at 800 °C. By 900 °C the Ti was almost completely removed to the surface, where it became oxidized. Use of the TiB₂ diffusion barrier produces superior thermal stability compared to the more common Ni/Au, whose morphology degrades significantly above 500 °C.     

Characterization and field emission characteristics of carbon nanotubes modified by titanium carbide

Carbon nanotubes (CNTs) were modified by depositing a thin layer of titanium film on the surface using magnetron sputtering method, followed by vacuum annealing at 900 °C for 2 h. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed that the as-deposited thin titanium film reacted with carbon atoms to form titanium carbide after annealing. The experiment results show that the thickness of sputter-deposited titanium film has significant effect on the field emission J-E characteristic of modified CNTs film. The titanium carbide-modified CNTs film obtained by controlling the titanium sputtering time to 2 min showed an improved field emission characteristics with a significant reduction in the turn-on electric field and an obvious increase in the emission current density as well as an improvement in emission stability. The improvement of field emission characteristics achieved is attributed to the low work function and good resistance to ion bombardment of titanium carbide.     

Ultrathin ZrO2 films on Si-rich SiC(0 0 0 1)-(3 × 3): Growth and thermal stability

The growth and thermal stability of ultrathin ZrO₂ films on the Si-rich SiC(0 0 0 1)-(3 × 3) surface have been explored using photoelectron spectroscopy (PES) and X-ray absorption spectroscopy (XAS). The films were grown in situ by chemical vapor deposition using the zirconium tetra tert-butoxide (ZTB) precursor. The O 1s XAS results show that growth at 400 °C yields tetragonal ZrO₂. An interface is formed between the ZrO₂ film and the SiC substrate. The interface contains Si in several chemically different states. This gives evidence for an interface that is much more complex than that formed upon oxidation with O₂. Si in a 4+ oxidation state is detected in the near surface region. This shows that intermixing of SiO₂ and ZrO₂ occurs, possibly under the formation of silicate. The alignment of the ZrO₂ and SiC band edges is discussed based on core level and valence PES spectra. Subsequent annealing of a deposited film was performed in order to study the thermal stability of the system. Annealing to 800 °C does not lead to decomposition of the tetragonal ZrO₂ (t-ZrO₂) but changes are observed within the interface region. After annealing to 1000 °C a laterally heterogeneous layer has formed. The decomposition of the film leads to regions with t-ZrO₂ remnants, metallic Zr silicide and Si aggregates.     

Electrical, structural and surface morphological properties of thermally stable low-resistance W/Ti/Au multilayer ohmic contacts to n-type GaN

A W/Ti/Au multilayer scheme has been fabricated for achieving thermally stable low-resistance ohmic contact to n-type GaN (4.0 × 10¹⁸ cm⁻³). It is shown that the as-deposited W/Ti/Au contact exhibits near linear I-V behaviour. However, annealing at temperature below 800 °C the contacts exhibit non-linear behaviour. After annealing at a temperature in excess of 850 °C, the W/Ti/Au contact showed ohmic behaviour. The W/Ti/Au contact produced specific contact resistance as low as 6.7 × 10⁻⁶ Ω cm² after annealing at 900 °C for 1 min in a N₂ ambient. It is noted that the specific contact resistance decreases with increase in annealing temperature. It is also noted that annealing the contacts at 900 °C for 30 min causes insignificant degradation of the electrical and thermal properties. It is further shown that the overall surface morphology of the W/Ti/Au stayed fairly smooth even after annealing at 900 °C. The W/Ti/Au ohmic contact showed good edge sharpness after annealing at 900 °C for 30 min. Based on the Auger electron spectroscopy and glancing angle X-ray diffraction results, possible explanation for the annealing dependence of the specific contact resistance of the W/Ti/Au contacts are described and discussed.     

Effects of annealing temperature and method on structural and optical properties of TiO2 films prepared by RF magnetron sputtering at room temperature

TiO₂ thin film was deposited on non-heated Si(1 0 0) substrate by RF magnetron sputtering. The as-deposited films were annealed by a conventional thermal annealing (CTA) and rapid thermal annealing (RTA) at 700 and 800 °C, and the effects of annealing temperature and method on optical properties of studied films were investigated by measuring the optical band gaps and FT-IR spectra. And we also compared the XRD patterns of the studied samples. The as-deposited film showed a mixed structure of anatase and brookite. Only rutile structures were found in samples annealed above 800 °C by CTA, while there are no special peaks except the weak brookite B(2 3 2) peak for the sample annealed at (or above) 800 °C by RTA. FT-IR spectra show the broad peaks due to Ti-O vibration mode in the range of 590-620 cm⁻¹ for the as-deposited film as well as samples annealed by both annealing methods at 700 °C. The studied samples all had the peaks from Si-O vibration mode, which seemed to be due to the reaction between TiO₂ and Si substrate, and the intensities of these peaks increased with increasing of annealing temperature. The optical band gap of the as-deposited film was 3.29 eV but it varied from 3.39 to 3.43 eV as the annealing temperature increased from 700 to 800 °C in the samples annealed by CTA. However, it varied from 3.38 to 3.32 eV as the annealing temperature increased from 700 to 800 °C by RTA.     

Origin of ohmic behavior in Ni, Ni2Si and Pd contacts on n-type SiC

Ni, Ni₂Si and Pd contacts were prepared on n-type 4H-SiC and annealed in the temperature range of 750-1150 °C. The annealed contacts were analyzed before and after acid etching, and different features were found in unetched and etched contacts. Carbon left on the SiC surface after the acid etching of Ni₂Si contacts annealed at 960 °C was highly graphitized. In nickel contacts, the graphitization of interface carbon began at 960 °C and increased after annealing at higher temperatures. In palladium contacts, the onset of the interface carbon graphitization was observed after annealing at 1150 °C. For all three types of metallization, the minimal values of contact resistivity were achieved only when the sharp first-order peak at 1585 cm⁻¹ and distinct second-order peak at ∼2700 cm⁻¹ related to the presence of graphitized carbon were detected by Raman spectroscopy after the acid etching of contacts. The properties of unannealed secondary contacts deposited onto etched primary contacts were similar to the properties of the primary contacts unless carbon was selectively etched. The results show that ohmic behavior of Ni-based and Pd contacts on n-type SiC originates from the formation of graphitic carbon at the interface with SiC.