Nitric acid oxidation of Si (NAOS) method for low temperature fabrication of SiO2/Si and SiO2/SiC structures

We have developed low temperature formation methods of SiO₂/Si and SiO₂/SiC structures by use of nitric acid, i.e., nitric acid oxidation of Si (or SiC) (NAOS) methods. By use of the azeotropic NAOS method (i.e., immersion in 68 wt% HNO₃ aqueous solutions at 120 °C), an ultrathin (i.e., 1.3-1.4 nm) SiO₂ layer with a low leakage current density can be formed on Si. The leakage current density can be further decreased by post-metallization anneal (PMA) at 200 °C in hydrogen atmosphere, and consequently the leakage current density at the gate bias voltage of 1 V becomes 1/4-1/20 of that of an ultrathin (i.e., 1.5 nm) thermal oxide layer usually formed at temperatures between 800 and 900 °C. The low leakage current density is attributable to (i) low interface state density, (ii) low SiO₂ gap-state density, and (iii) high band discontinuity energy at the SiO₂/Si interface arising from the high atomic density of the NAOS SiO₂ layer.For the formation of a relatively thick (i.e., ≥10 nm) SiO₂ layer, we have developed the two-step NAOS method in which the initial and subsequent oxidation is performed by immersion in ∼40 wt% HNO₃ and azeotropic HNO₃ aqueous solutions, respectively. In this case, the SiO₂ formation rate does not depend on the Si surface orientation. Using the two-step NAOS method, a uniform thickness SiO₂ layer can be formed even on the rough surface of poly-crystalline Si thin films. The atomic density of the two-step NAOS SiO₂ layer is slightly higher than that for thermal oxide. When PMA at 250 °C in hydrogen is performed on the two-step NAOS SiO₂ layer, the current-voltage and capacitance-voltage characteristics become as good as those for thermal oxide formed at 900 °C.A relatively thick (i.e., ≥10 nm) SiO₂ layer can also be formed on SiC at 120 °C by use of the two-step NAOS method. With no treatment before the NAOS method, the leakage current density is very high, but by heat treatment at 400 °C in pure hydrogen, the leakage current density is decreased by approximately seven orders of magnitude. The hydrogen treatment greatly smoothens the SiC surface, and the subsequent NAOS method results in the formation of an atomically smooth SiO₂/SiC interface and a uniform thickness SiO₂.     

Low temperature fabrication of 5-10 nm SiO2/Si structure using advanced nitric acid oxidation of silicon (NAOS) method

We have developed the advanced nitric acid oxidation of Si (NAOS) method to form relatively thick (5-10 nm) SiO₂/Si structure with good electrical characteristics. This method simply involves immersion of Si in 68 wt% nitric acid aqueous solutions at 120 °C with polysilazane films. Fourier transform infrared absorption (FT-IR) measurements show that the atomic density of the NAOS SiO₂ layer is considerably high even without post-oxidation anneal (POA), i.e., 2.28 × 10²² atoms/cm², and it increases by POA at 400 °C in wet-oxygen (2.32 × 10²² atoms/cm²) or dry-oxygen (2.30 × 10²² atoms/cm²). The leakage current density is considerably low (e.g., 10⁻⁵ A/cm² at 8 MV/cm) and it is greatly decreased (10⁻⁸ A/cm² at 8 MV/cm) by POA at 400 °C in wet-oxygen. POA in wet-oxygen increases the atomic density of the SiO₂ layer, and decreases the density of oxide fixed positive charges.     

Nitric acid method for fabrication of gate oxides in TFT

We have developed low temperature formation methods of SiO₂ layers which are applicable to gate oxide layers in thin film transistors (TFT) by use of nitric acid (HNO₃). Thick (>10 nm) SiO₂ layers with good thickness uniformity (i.e., ±4%) can be formed on 32 cm × 40 cm substrates by the two-step nitric acid oxidation method in which initial and subsequent oxidation is performed using 40 and 68 wt% (azeotropic mixture) HNO₃ aqueous solutions, respectively. The nitric acid oxidation of polycrystalline Si (poly-Si) thin films greatly decreases the height of ridge structure present on the poly-Si surfaces. When poly-Si thin films on 32 cm × 40 cm glass substrates are oxidized at azeotropic point (i.e., 68 wt% HNO₃ aqueous solutions at 121 °C), ultrathin (i.e., 1.1 nm) SiO₂ layers with a good thickness uniformity (±0.05 nm) are formed on the poly-Si surfaces. When SiO₂/Si structure fabricated using plasma-enhanced chemical vapor deposition is immersed in 68 wt% HNO₃, oxide fixed charge density is greatly decreased, and interface states are eliminated. The fixed charge density is further decreased by heat treatments at 200 °C, and consequently, capacitance-voltage characteristics which are as good as those of thermal SiO₂/Si structure are achieved.     

Robust Low Voltage Program-Erasable Cobalt-Nanocrystal Memory Capacitors with Multistacked Al2O3/HfO2/Al2O3 Tunnel Barrier

A n atomic-layer-deposited Al2O3/HfO2/Al2O3 （A/H/A） tunnel barrier is in vestigated for Co nanocrystal memory capacitors. Compared to a single Al2O3 tunnel barrier, the A/H/A barrier can significantly increase the hysteresis window, i.e., an increase by 9 V for ±12 V sweep range. This is attributed to a marked decrease in the energy barriers of charge injections for the A/H/A tunnel barrier. Further, the Co-nanocrystal memory capacitor with the A/H/A tunnel barrier exhibits a memory window as large as 4.1 V for 100 μs program/erase at a low voltage of ±7 V, which is due to fast charge injection rates, i.e., about 2.4× 10^16 cm^-2 s^-1 for electrons and 1.9× 1016 cm^-2 s^-1 for holes.     

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.     

Properties of thick SiO2/Si structure formed at 120 °C by use of two-step nitric acid oxidation method

Thick (i.e., ∼10 nm) SiO₂/Si structure has been formed at 121 °C by immersion of Si in relatively low concentration HNO₃ followed by that in 68 wt.% HNO₃ (i.e., two-step nitric acid (HNO₃) oxidation method of Si, NAOS) and spectroscopic properties and electrical characteristics of the NAOS SiO₂ layers are investigated. The SiO₂ thickness strongly depends on the concentration of HNO₃ aqueous solutions employed in the initial oxidation, and it becomes the largest at the HNO₃ concentration of 40 wt.%. The MOS diodes with the ∼9 nm SiO₂ layer formed by the NAOS method possess a relatively low leakage current density (e.g., 10⁻⁸ A/cm² at the forward bias of 1 V) and it is further decreased by more than one order of magnitude by post-metallization annealing (PMA) in hydrogen at 250 °C. The good leakage characteristic is attributable to atomically flat SiO₂/Si interfaces and high atomic density of 2.30-2.32 × 10²² atoms/cm³ of the NAOS SiO₂ layers. High-density interface states are present in as-prepared SiO₂ layers and they are eliminated by PMA in hydrogen.     

Formation of 10-30 nm SiO2/Si structure with a uniform thickness at ∼120 °C by nitric acid oxidation method

Silicon dioxide (SiO₂) layers with a thickness more than 10 nm can be formed at ∼120 °C by direct Si oxidation with nitric acid (HNO₃). Si is initially immersed in 40 wt.% HNO₃ at the boiling temperature of 108 °C, which forms a ∼1 nm SiO₂ layer, and the immersion is continued after reaching the azeotropic point (i.e., 68 wt.% HNO₃ at 121 °C), resulting in an increase in the SiO₂ thickness. The nitric acid oxidation rates are the same for (1 1 1) and (1 0 0) orientations, and n-type and p-type Si wafers. The oxidation rate is constant at least up to 15 nm SiO₂ thickness (i.e., 1.5 nm/h for single crystalline Si and 3.4 nm/h for polycrystalline Si (poly-Si)), indicating that the interfacial reaction is the rate-determining step. SiO₂ layers with a uniform thickness are formed even on a rough surface of poly-Si thin film.     

Resistive hysteresis and capacitance effect in NiFe2O4/SrTiO3: Nb(1 wt%) junctions

Epitaxial ultrathin NiFe₂O₄ films were deposited on 1 wt% Nb-doped SrTiO₃ (0 0 1) substrates by reactive cosputtering to form junctions with an area of ∼2 mm², and current-voltage curves show rectifying and asymmetrical hysteresis characteristics. The resistance calculated from the current-voltage curves is strongly voltage dependent, and the hysteretic loops with high and low resistive states were observed. The hysteretic loops are considered to stem from the capacitance effect of the highly resistive NiFe₂O₄ layer, which leads to charge accumulation at the interfaces. The results show that the interfaces of the junctions have a large areal capacitance of ∼100 nF/mm² from 300 to 120 K.     

Formation of atomically smooth SiO2/SiC interfaces at ∼120 °C by use of nitric acid oxidation method

Conventional thermal oxidation of SiC requires heating at ∼1100 °C. In the present study, we have developed a method of oxidizing SiC at low temperatures (i.e., ∼120 °C) to form relatively thick silicon dioxide (SiO₂) layers by use of nitric acid. When 4H-SiC(0 0 0 1) wafers are immersed in 40 wt% HNO₃ at the boiling temperature of 108 °C and the boiling is kept for 5 h after reaching the azeotropic point (i.e., 68 wt% HNO₃ at 121 °C), 8.1 nm thick SiO₂ layers are formed on the SiC substrates. High resolution transmission electron microscopy measurements show that the SiO₂/SiC interface is atomically flat and the SiO₂ layer is uniform without bunching. When SiC is immersed in an azeotropic mixture of HNO₃ with water from the first, the SiO₂ thickness is less than 0.3 nm. The metal-oxide-semiconductor (MOS) diodes with the SiO₂ layer formed by the nitric acid oxidation method possess a considerably low leakage current density.     

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.     

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.     

The surface of TiO2 gate of 2DEG-FET in contact with electrolytes for bio sensing use

In order to apply two-dimensional electron-gas-field-effect-transistors (2DEG-FETs) for cell-viability sensors, we investigated the chemical/electrical properties of TiO₂ thin films (13-17 nm) prepared with the sol-gel technique on the gate surface of AlGaAs/GaAs 2DEG-FETs. Photochemical/electrochemical reactions on GaAs surface in electrolytes, which induce the degradation of 2DEG-FET performance, are effectively suppressed by introducing a TiO₂ thin film on the gate area of 2DEG-FETs. Compared to conventional ion-selective FETs (ISFETs), the TiO₂/2DEG-FETs in this study exhibit a high sensitivity (410 mV/mM) for H₂O₂ detection. TiO₂ surfaces show better biocompatibility than GaAs surfaces as demonstrated by direct cell culture on these surfaces.     

Effect of the oxidation process on SiO2/4H-SiC interface electrical characteristics

In this work we have compared the SiO₂/SiC interface electrical characteristics for three different oxidations processes (dry oxygen, water-containing oxygen and water-containing nitrogen atmospheres). MOS structures were fabricated on 8° off-axis 4H-SiC(0 0 0 1) n- and p-type epi-wafers. Electrical characteristics were obtained by I-V measurements, high-frequency capacitance-voltage (C-V) and ac conductance (G-ω) methods. Comparing the results, one observes remarkable differences between samples which underwent different oxidation routes. Among the MOS structures analyzed, the sample which underwent wet oxidation with oxygen as carrier gas presented the higher dielectric strength and lower values of interface states density.     

The effect of interface states, excess capacitance and series resistance in the Al/SiO2/p-Si Schottky diodes

The current-voltage (I-V) characteristics of Al/SiO₂/p-Si metal-insulator-semiconductor (MIS) Schottky diodes were measured at room temperature. In addition the capacitance-voltage (C-V) and conductance-voltage (G-V) measurements are studied at frequency range of 10 kHz-1 MHz. The higher value of ideality factor of 3.25 was attributed to the presence of an interfacial insulator layer between metal and semiconductor and the high density of interface states localized at Si/SiO₂ interface. The density of interface states (N_ss) distribution profile as a function of (E_ss − E_v) was extracted from the forward bias I-V measurements by taking into account the bias dependence of the effective barrier height (Φ_e) at room temperature for the Schottky diode on the order of ≅4 × 10¹³ eV⁻¹ cm⁻²_. These high values of N_ss were responsible for the non-ideal behaviour of I-V and C-V characteristics. Frequency dispersion in C-V and G-V can be interpreted only in terms of interface states. The N_ss can follow the ac signal especially at low frequencies and yield an excess capacitance. Experimental results show that the I-V, C-V and G-V characteristics of SD are affected not only in N_ss but also in series resistance (R_s), and the location of N_ss and R_s has a significant on electrical characteristics of Schottky diodes.     

Band alignment of SiO2/Si structure formed with nitric acid vapor below 500 °C

A relatively thick (i.e., ∼9 nm) SiO₂ layer can be formed by oxidation of Si with nitric acid (HNO₃) vapor below 500 °C. In spite of the low temperature formation, the leakage current density flowing through the SiO₂ layer is considerably low, and it follows the Fowler-Nordheim mechanism. From the Fowler-Nordheim plots, the conduction band offset energy at the SiO₂/Si interface is determined to be 2.57 and 2.21 eV for HNO₃ vapor oxidation at 500 and 350 °C, respectively. From X-ray photoelectron spectroscopy measurements, the valence band offset energy is estimated to be 4.80 and 4.48 eV, respectively, for 500 and 350 °C oxidation. The band-gap energy of the SiO₂ layer formed at 500 °C (8.39 eV) is 0.68 eV larger than that formed at 350 °C. The higher band-gap energy for 500 °C oxidation is mainly attributable to the higher atomic density of the SiO₂ layer of 2.46 × 10²²/cm³. Another reason may be the absence of SiO₂ trap-states.     

Synthesis, structure and magnetic properties in the Nd2O3-Gd2O3 mixed system synthesized at 1200 °C

Phase relation studies in the Gd₂O₃-Nd₂O₃ system have been performed on (Gd_1−xNd_x)₂O₃ samples (0?x?1) with the purpose of performing a systematic study of the composition effects on their structural and magnetic properties. All the samples were synthesized by calcination of the related oxalates at 1200 °C in order to ensure the complete decomposition of the oxalates. Five phase regions, namely an A-type hexagonal, a B-type monoclinic, a C-type cubic solid solution and two biphasic mixtures of the former three phase fields were detected in this system. The magnetic susceptibility measurements showed the presence of antiferromagnetic interactions in all samples. The Curie-Weiss temperature shows a nonlinear dependence on concentration. Deduced effective magnetic moments are close to the free ion values.     

AC conduction mechanisms of Gd1/3Sr2/3FeO3 ceramic

In this study, the AC conductivity of insulating Gd_1/3Sr_2/3FeO₃ was analyzed within the framework of the quantum-mechanical tunneling mechanism (QMT) and the hopping of barrier mechanism (HOB). Experimental data were taken from 20 Hz to 1 MHz and from 80 to 300 K. Observation revealed that the small polaron QMT model is the more suitable mechanism for modeling the AC conductivity of Gd1/3Sr2/3FeO3 at low temperatures.     

XPS analysis of surface chemistry of near surface region of epiready GaAs(1 0 0) surface treated with (NH4)2Sx solution

In this work we analyze the effect of (NH)₂S_x wet treatment on the GaAs(1 0 0) covered with “epiready” oxide layer without any pretreatment in order to check the removal of oxides and carbon-related contamination, and the formation of sulfur species. The sulfidation procedure consisted of epiready sample dipping (at room and 40 °C temperatures) in an ammonium polysulfide solution combined with a UHV flash annealing up to 500 °C.The inspection of the XPS As 2p_3/2 and Ga 2p_3/2 spectra taken at surface sensitive mode revealed: (i) the temperature-dependent reduction of the amount of GaAs oxides and carbon contamination after sulfidation, and almost their complete removal after subsequent annealing, (ii) the creation of sulfur bonds with both Ga and As, with more thermally stable Ga-S bonds, and (iii) the slight reduction in elemental arsenic amount.     

Characterizations of n-type ferromagnetic GaMnN thin film grown on GaN/Al2O3 (0 0 0 1) by metal-organic chemical vapor deposition

A high-quality ferromagnetic GaMnN (Mn=2.8 at%) film was deposited onto a GaN buffer/Al₂O₃(0 0 0 1) at 885 °C using the metal-organic chemical vapor deposition (MOCVD) process. The GaMnN film shows a highly c-axis-oriented hexagonal wurtzite structure, implying that Mn doping into GaN does not influence the crystallinity of the film. No Mn-related secondary phases were found in the GaMnN film by means of a high-flux X-ray diffraction analysis. The composition profiles of Ga, Mn, and N maintain nearly constant levels in depth profiles of the GaMnN film. The binding energy peak of the Mn 2p_3/2 orbital was observed at 642.3 eV corresponding to the Mn (III) oxidation state of MnN. The presence of metallic Mn clusters (binding energy: 640.9 eV) in the GaMnN film was excluded. A broad yellow emission around 2.2 eV as well as a relatively weak near-band-edge emission at 3.39 eV was observed in a Mn-doped GaN film, while the undoped GaN film only shows a near-band-edge emission at 3.37 eV. The Mn-doped GaN film showed n-type semiconducting characteristics; the electron carrier concentration was 1.2×10²¹/cm³ and the resistivity was 3.9×10⁻³ Ω cm. Ferromagnetic hysteresis loops were observed at 300 K with a magnetic field parallel and perpendicular to the ab plane. The zero-field-cooled and field-cooled curves at temperatures ranging from 10 to 350 K strongly indicate that the GaMnN film is ferromagnetic at least up to 350 K. A coercive field of 250 Oe and effective magnetic moment of 0.0003 μ_B/Mn were obtained. The n-type semiconducting behavior plays a role in inducing ferromagnetism in the GaMnN film, and the observed ferromagnetism is appropriately explained by a double exchange mechanism.     

CoPt alloy grown on the WSe2(0 0 0 1) van der Waals surface

The structural and magnetic properties of 3-nm-thick CoPt alloys grown on WSe₂(0 0 0 1) at various temperature are investigated. Deposition at room temperature leads to the formation of a chemically disordered fcc CoPt alloy with [1 1 1] orientation. Growth at elevated temperatures induces L1₀ chemical order starting at 470 K accompanied with an increase in grain size and a change in grain morphology. As a consequence of the [1 1 1] growth direction, the CoPt grains can adopt one of the three possible variants of the L1₀ phase with tetragonal c-axis tilted from the normal to the film plane direction at 54°. The average long-range order parameter is found to be 0.35(±0.05) and does not change with the increase in the deposition temperature from 570 to 730 K. This behavior might be related to Se segregation towards the growing facets and surface disorder effects promoted by a high surface-to-volume ratio. Magnetic studies reveal a superparamagnetic behavior for the films grown at 570 and 730 K in agreement with the film morphology and degree of chemical order. The measurements at 10 K reveal the orientation of the easy axis of the magnetization lying basically in the film plane.