Characterization of ultra-thin SiO2 by capacitance-voltage and charge pumping measurements

In this paper, we present results on electrical measurements of ultra thin SiO₂ layers (from 3.5 nm down to 1.7 nm), used as gate dielectric in metal-oxide-semiconductors (MOS) devices. Capacitance-voltage (C-V) measurements and simulations on MOS capacitors have been used for extracting the electrical oxide thickness. The SiO₂/Si interface and oxide quality have been analyzed by charge pumping (CP) measurements. The mean interface traps density is measured by 2-level CP, and the energy distribution within the semiconductor bandgap of these traps are investigated by 3-level charge pumping measurements. A comparison of the energy distribution of the SiO₂/Si interface traps is made using classical and quantum simulations to extract the surface potential as a function of the gate signal. When the gate oxide thickness <3.5 nm, we prove that it is mandatory to take into account the quantum effects to obtain a more accurate energy distribution of the SiO₂/Si interface traps. We also explain the increase of the apparent interface traps density measured by 2-levels CP with the increase of the oxide thickness, for transistors made from the same technological process.     

Annealing effect on the metal gate effective work function modulation for the Al/TiN/SiO2/p-Si structure

In this work, the thermal annealing effect on the metal gate effective work function (EWF) modulation for the Al/TiN/SiO₂/p-Si(1 0 0) structure was investigated. Compared with the sample of TiN/SiO₂/p-Si(1 0 0) structure, for the sample additionally capped with Al the flat band voltage has a very obvious shift as large as 0.54 V to the negative direction after forming gas annealing. It is also revealed that the thermal budget can effectively influence both the EWF of the gate electrode and the thickness of the gate dielectric layer when a post annealing at 600 °C with different soak times was applied to the samples with Al cap. Material characterization indicates that the diffusion of Al and the formation of Al oxide during annealing should be responsible for all the phenomena. The interface trap density Dit calculated from the high-frequency C-V and the laser-assisted high-frequency C-V curves show that the introduction of Al does not cause reliability problem in the Al/TiN/SiO₂/p-Si structure.     

A comparative study of depth profiling of interface states using charge pumping and low frequency noise measurement in SiO2/HfO2 gate stack nMOSFETs

Charge pumping and low frequency noise measurements for depth profiling have been studied systematically using a set of gate stacks with various combinations of IL and HfO₂ thicknesses. The distribution of generated traps after HCI and PBTI stress was also investigated. The drain-current power spectral density made up all of the traps of IL in 0 < z < T_IL and the traps of HfO₂ in T_IL < z < T_HK. The traps near the Si/SiO₂ interface dominated the 1/f noise at higher frequencies, which is common in SiO₂ dielectrics. For the HfO₂/SiO₂ gate stack, however, the magnitude of the 1/f noise did not significantly change after HCI and PBTI because of more traps in the bulk HfO₂ film than at the bottom of the interface.     

Effect of the spatial distribution of SiO2 thickness on the switching behavior of bistable MOS tunnel structures

Simulations of the reverse current-voltage characteristics of an Al/l-3 nm SiO₂/n-Si tunnel structure are carried out, considering the spatial non-uniformity of oxide thickness. In a certain range of average thickness, these characteristics are S-shaped, exhibiting thereby a bistability. The shift of the turn-on and holding voltages related to the thickness deviation is predicted. The electric overload leads to the displacement of switching voltages as if the deviation of oxide thickness had became larger. Supporting experimental data are also provided.     

Study on electrical characteristics and reliability of fluorinated HfO2 for HKMG

The dielectric properties and reliability of fluorinated HfO₂ have been studied. The fluorinated HfO₂ dielectric treated by NF₃ plasma showed improved dielectric characteristics but resulted in interfacial layer (IL) regrowth during the fluorine plasma treatment process, which led to an oxide capacitance reduction and poor electrical characteristics. Through the analysis of chemical composition and electrical characteristics, it has been revealed that the Hf-O bonds in HfO₂ layer were converted to Hf-F bonds by the plasma treatment and then the dissociated oxygen diffused to the IL. In order to suppress the IL regrowth, newly fluorinated HfO₂ has been developed. Reliability of fluorinated HfO₂ dielectric was sharply improved without a decrease in the oxide capacitance at fluorine plasma treatment conditions of low power and temperature.     

氧化硅RIE刻蚀工艺研究

利用反应等离子刻蚀技术对SiO2进行干法刻蚀,研究了不同刻蚀条件对刻蚀速率、刻蚀选择比、刻蚀面粗糙度、刻蚀均匀性等的影响。分析得出了刻蚀侧壁角度与刻蚀选择比以及抗蚀掩模自身的侧壁角度之间存在的数学关系,这为如何获得垂直的刻蚀侧壁提供了参考。     

氧化硅RIE刻蚀工艺研究

利用反应等离子刻蚀技术对SiO₂进行干法刻蚀, 研究了不同刻蚀条件对刻蚀速率、刻蚀选择比、刻蚀面粗糙度、刻蚀均匀性等的影响。分析得出了刻蚀侧壁角度与刻蚀选择比以及抗蚀掩模自身的侧壁角度之间存在的数学关系, 这为如何获得垂直的刻蚀侧壁提供了参考。     

Fabrication and electrical characteristics of ultrathin (HfO2)x(SiO2)1−x films by surface sol-gel method and reaction-anneal treatment

Hafnium oxide (HfO₂) films were deposited on Si substrates with a pre-grown oxide layer using hafnium chloride (HfCl₄) source by surface sol-gel process, then ultrathin (HfO₂)_x(SiO₂)_1−x films were fabricated due to the reaction of SiO₂ layer with HfO₂ under the appropriate reaction-anneal treatment. The observation of high-resolution transmission electron microscopy indicates that the ultrathin films show amorphous nature. X-ray photoelectron spectroscopy analyses reveal that surface sol-gel derived ultrathin films are Hf-Si-O alloy instead of HfO₂ and pre-grown SiO₂ layer, and the composition was Hf_0.52Si_0.48O₂ under 500 °C reaction-anneal. The lowest equivalent oxide thickness (EOT) value of 0.9 nm of film annealed at 500 °C has been obtained with small flatband voltage of −0.31 V. The experimental results indicate that a simple and feasible solution route to fabricate (HfO₂)_x(SiO₂)_1−x composite films has been developed by means of combination of surface sol-gel and reaction-anneal treatment.     

Profiling of traps in SiO2/Al2O3 gate stack by the charge pumping technique

In this paper, we present our results on the distribution and generation of traps in a SiO₂/Al₂O₃ transistor. The investigation has been carried out by using charge pumping measurements, both variable voltage and frequency techniques, and constant voltage stress.By increasing the amplitude of the gate pulse we observe an increase of the charge recombined per cycle closely related to the contribution of shallow traps near the SiO₂/Al₂O₃ interface. By reducing the pulse frequency we measure an increase in the charge pumping current due to traps located deeper in the Al₂O₃. By combining charge pumping and constant voltage stress measurements, we found that the traps are mostly generated near the Si/SiO₂ interface.     

SOI planar photonic crystal fabrication: Etching through SiO2/Si/SiO2 layer systems using fluorocarbon plasmas

Dry plasma etching of sub-micron structures in a SiO₂/Si/SiO₂ layer system using Cr as a mask was performed in a fluorocarbon plasma. It was determined that the best anisotropy could be achieved in the most electropositive plasma. A gas composition yielding the desired SOI planar photonic crystal structures was optimized from the available process gases, Ar, He, O₂, SF₆, CF₄, c-C₄F₈, CHF₃, using DC bias data sets. Application of the c-C₄F₈/(noble gas) chemistry allowed fabrication of the desired SOI planar photonic crystal. The average etching rates for the pores and ridge waveguide regions were about 71 and 97 nm/min, respectively, while the average SiO₂/Si/SiO₂ to Cr etching selectivity for the ridge waveguide region was about 33:1 in case of the c-C₄F₈/90%Ar plasma with optimized parameters.     

Investigation of Ta2O5/SiO2/4H-SiC MIS capacitors

Tantalum pentoxide (Ta₂O₅) deposited by pulsed DC magnetron sputtering technique as the gate dielectric for 4H-SiC based metal-insulator-semiconductor (MIS) structure has been investigated. A rectifying current-voltage characteristic was observed, with the injection of current occurred when a positive DC bias was applied to the gate electrode with respect to the n type 4H-SiC substrate. This undesirable behavior is attributed to the relatively small band gap of Ta₂O₅ of around 4.3 eV, resulting in a small band offset between the 4H-SiC and Ta₂O₅. To overcome this problem, a thin thermal silicon oxide layer was introduced between Ta₂O₅ and 4H-SiC. This has substantially reduced the leakage current through the MIS structure. Further improvement was obtained by annealing the Ta₂O₅ at 900 °C in oxygen. The annealing has also reduced the effective charge in the dielectric film, as deduced from high frequency C-V measurements of the Ta₂O₅/SiO₂/4H-SiC capacitors.     

Improvement on low-temperature deposited HfO2 film and interfacial layer by high-pressure oxygen treatment

In this study, high-pressure oxygen (O₂ and O₂ + UV light) technologies were employed to effectively improve the properties of low-temperature-deposited metal oxide dielectric films and interfacial layer. In this work, 13 nm HfO₂ thin films were deposited by sputtering method at room temperature. Then, the oxygen treatments with a high-pressure of 1500 psi at 150 °C were performed to replace the conventional high temperature annealing. According to the XPS analyses, integration area of the absorption peaks of O-Hf and O-Hf-Si bonding energies apparently raise and the quantity of oxygen in deposited thin films also increases from XPS measurement. In addition, the leakage current density of standard HfO₂ film after O₂ and O₂ + UV light treatments can be improved from 3.12 × 10⁻⁶ A/cm² to 6.27 × 10⁻⁷ and 1.3 × 10⁻⁸ A/cm² at |Vg| = 3 V. The proposed low-temperature and high pressure O₂ or O₂ + UV light treatment for improving high-k dielectric films is applicable for the future flexible electronics.     

基于SiO2溶胶的稳定性的Cu/SiO2催化体系在化学机械抛光中的应用研究

There is a lot ofhydroxyl on the surface ofnano SiO2 sol used as an abrasive in the chemical mechanical planarization （CMP） process, and the chemical reaction activity of the hydroxyl is very strong due to the nano effect. In addition to providing a mechanical polishing effect, SiO2 sol is also directly involved in the chemical reaction. The stability of SiO2 sol was characterized through particle size distribution, zeta potential, viscosity, surface charge and other parameters in order to ensure that the chemical reaction rate in the CMP process, and the surface state of the copper film after CMP was not affected by the SiO2 sol. Polarization curves and corrosion potential of different concentrations of SiO2 sol showed that trace SiO2 sol can effectively weaken the passivation film thickness. In other words, SiO2 sol accelerated the decomposition rate of passive film. It was confirmed that the SiO2 sol as reactant had been involved in the CMP process of copper film as reactant by the effect of trace SiO2 sol on the removal rate of copper film in the CMP process under different conditions. In the CMP process, a small amount of SiO2 sol can drastically alter the chemical reaction rate of the copper film, therefore, the possibility that Cu/SiO2 as a catalytic system catalytically accelerated the chemical reaction in the CMP process was proposed. According to the van＇t Hoff isotherm formula and the characteristics of a catalyst which only changes the chemical reaction rate without changing the total reaction standard Gibbs free energy, factors affecting the Cu/SiO2 catalytic reaction were derived from the decomposition rate of Cu （OH）2 and the pH value of the system, and then it was concluded that the CuSiO3 as intermediates of Cu/SiO2 catalytic reaction accelerated the chemical reaction rate in the CMP process. It was confirmed that the Cu/SiO2 catalytic system generated the intermediate of the catalytic reaction （CuSiO3） in the CMP process through the removal rate of copper film, infrared spectrum and AFM diagrams in different pH conditions. FinalLy it is concluded that the SiO2 sol used in the experiment possesses stable performance; in the CMP process it is directly involved in the chemical reaction by creating the intermediate of the catalytic reaction （CuSiO3） whose yield is proportional to the pH value, which accelerates the removal of copper film.     

Integration of HfxTayN metal gate with SiO2 and HfOxNy gate dielectrics for MOS device applications

Interaction of Hf_xTa_yN metal gate with SiO₂ and HfO_xN_y gate dielectrics has been extensively studied. Metal-oxide-semiconductor (MOS) device formed with SiO₂ gate dielectric and Hf_xTa_yN metal gate shows satisfactory thermal stability. Time-of-flight secondary ion mass spectroscopy (TOF-SIMS) analysis results show that the diffusion depths of Hf and Ta are less significant in SiO₂ gate dielectric than that in HfO_xN_y. Compared to HfO_xN_y gate dielectric, SiO₂ shows better electrical properties, such as leakage current, hysteresis, interface trap density and stress-induced flat-band voltage shift. With an increase in post metallization annealing (PMA) temperature, the electrical characteristics of the MOS device with SiO₂ gate dielectric remain almost unchanged, indicating its superior thermal and electrical stability.     

二氧化硅纳米花的制备及发光特性研究

采用磁控溅射和化学气相沉积技术制备出二氧化硅纳米花。利用扫描电子显微镜(SEM),X射线光电子能谱(XPS)和傅里叶红外吸收谱(FTIR)对上述纳米结构进行结构表征。用荧光光谱仪(PL)对其光致发光特性进行了研究。结果表明在激发波长为325nm时,在394nm处出现一个发光峰,表现出良好的发光特性。     

MOS devices with tetragonal ZrO2 as gate dielectric formed by annealing ZrO2/Ge/ZrO2 laminate

A Ge-stabilized tetragonal ZrO₂ (t-ZrO₂) film with permittivity (κ) of 36.2 was formed by depositing a ZrO₂/Ge/ZrO₂ laminate and a subsequent annealing at 600 °C, which is a more reliable approach to control the incorporated amount of Ge in ZrO₂. On Si substrates, with thin SiON as an interfacial layer, the SiON/t-ZrO₂ gate stack with equivalent oxide thickness (EOT) of 1.75 nm shows tiny amount of hysteresis and negligible frequency dispersion in capacitance-voltage (C-V) characteristics. By passivating leaky channels derived from grain boundaries with NH₃ plasma, good leakage current of 4.8 × 10⁻⁸ A/cm² at V_g = V_fb − 1 V is achieved and desirable reliability confirmed by positive bias temperature instability (PBTI) test is also obtained.     

On the temperature dependence of series resistance and interface states in Al/SiO2/p-Si (MIS) Schottky diodes

The capacitance-voltage-temperature (C-V-T) and conductance-voltage-temperature (G/w-V-T) characteristics of metal-semiconductor (Al/p-Si) Schottky diodes with thermal growth interfacial layer were investigated by considering series resistance effect in the wide temperature range (80-400 K). It is found that in the presence of series resistance, the forward bias C-V plots exhibit a peak, and experimentally shows that the peak positions shift towards higher positive voltages with increasing temperature, and the peak value of the capacitance has a maximum at 80 K. The C-V and (G/w-V) characteristics confirm that the N_ss and R_s of the diode are important parameters that strongly influence the electric parameters in (Al/SiO₂/p-Si) MIS Schottky diodes. The crossing of the G/w-V curves appears as an abnormality when seen with respect to the conventional behaviour of the ideal MS or MIS Schottky diode. It is thought that the presence of a series resistance keeps this intersection hidden and unobservable in homogeneous Schottky diodes, but it appears in the case of inhomogeneous Schottky diode. In addition, the high frequency (C_m) and conductance (G_m/w) values measured under both reverse and forward bias were corrected for the effect of series resistance to obtain the real diode capacitance.     

Mechanism of selective Si3N4 etching over SiO2 in hydrogen-containing fluorocarbon plasma

This paper describes the mechanism of selective Si₃N₄ etching over SiO₂ in capacitively-coupled plasmas of hydrogen-containing fluorocarbon gas, including CHF₃, CH₂F₂ and CH₃F. The etch rate of Si₃N₄ and SiO₂ is investigated as a function of O₂ percentage in all plasma gases. Addition of O₂ in feed gases causes plasma gas phase change especially H density. The SiO₂ etch rate decreases with increase of O₂ percentage due to the decline of CF_x etchant. The Si₃N₄ etch rate is found to be strong correlated to the H density in plasma gas phase. H can react with CN by forming HCN to reduce polymer thickness on Si₃N₄ surface and promote the removal of N atoms from the substrate. Thus the Si₃N₄ etch rate increases with H intensity. As a result, a relative high selectivity of Si₃N₄ over SiO₂ can be achieved with addition of suitable amount of O₂ which corresponds to the maximum of H density.     

Fabrication of Ge-MOS capacitors with high quality interface by ultra-thin SiO2/GeO2 bi-layer passivation combined with the subsequent SiO2-depositions using magnetron sputtering

Ge-MOS capacitors were fabricated by a novel method of ultra-thin SiO₂/GeO₂ bi-layer passivation (BLP) for Ge surface combined with the subsequent SiO₂-depositions using magnetron sputtering. For the Ge-MOS capacitors fabricated by BLP with O₂, to decrease oxygen content in the subsequent SiO₂ deposition is helpful for improving interface quality. By optimizing process parameters of the Ge surface thermal cleaning, the BLP, and the subsequent SiO₂ deposition, interface states density of 4 × 10¹¹ cm⁻² eV⁻¹ at around mid-gap was achieved, which is approximately three times smaller than that of non-passavited Ge-MOS capacitors. On the contrary, for the Ge-MOS capacitors fabricated by BLP without O₂, interface quality could be improved by an increase in oxygen contents during the subsequent SiO₂ deposition, but the interface quality was worse compared with BLP with O₂.