Bonding, energies, and band offsets of Si-ZrO2 and HfO2 gate oxide interfaces

New oxides with high dielectric constant are required for gate oxides. ZrO2 is a typical example with ionic bonding. We give the rules for bonding at interfaces between Si and ionic oxides, to satisfy valence requirements and give an insulating interface. Total energies and band offsets are calculated for various (100)Si:ZrO(2) and HfO2 interface structures. The oxygen-terminated interface is found to be favored for devices, because it has no gap states and has a band offset which is rather independent of interfacial bonding.     

Stability and band offsets between Si and LaAlO<Subscript>3</Subscript>

The replacement of traditional SiO₂ with high-k oxides allows the physical thickness of the gate dielectric to be thinner without the tunneling problem in Si-based metal-oxide-semiconductor field-effect transistors. LaAlO₃ appears to be a promising high-k material for use in future ultra large scale integrated devices. In the present paper, the electronic properties of Si/LaAlO₃ (001) heterojunctions are investigated by first-principles calculations. We studied the initial adsorption of Si atoms on the LaAlO₃ (001) surface, and found that Si atoms preferentially adsorb on top of oxygen atoms at higher coverage. The surface phase diagrams indicate that Si atoms may substitute oxygen atoms at the LaO-terminated surface. The band offsets, electronic density of states, and atomic charges are analyzed for the various Si/LaAlO₃ heterojunctions. Our results suggest that the Si/AlO₂ interface is suitable for the design of metal oxide semiconductor devices because the valence and conduction band offsets are both larger than 1 eV.     

Anomalous behavior of the dielectric constant of hafnium silicates: a first principles study

We present an extensive ab initio study of the structural and dielectric properties of hafnium silicates Hf(x)Si(1-x)O(2) that accounts for the observed anomalous dependence on composition of the static dielectric constant in the entire x range. The results reveal that this complex behavior reflects that of the structural development with x, from silica to hafnia, and clarify how different growth processes can also lead to scattered sets of data. Several simple models proposed thus far to explain part of the experimental data are shown to be inadequate. It is argued that silicate layers with low hafnium content form at the HfO(2)/Si interface and play a crucial role in preserving high electron mobility in the channel.     

Ultrathin gate dielectrics for silicon nanodevices

This paper reviews recent progress in structural and electronic characterizations of ultrathin SiO₂thermally grown on Si(100) surfaces and applications of such nanometer-thick gate oxides to advanced MOSFETs and quantum-dot MOS memory devices. Based on an accurate energy band profile determined for the n ⁺ -poly- Si/SiO₂/Si(100) system, the measured tunnel current through ultrathin gate oxides has been quantitatively explained by theory. From the detailed analysis of MOSFET characteristics, the scaling limit of gate oxide thickness is found to be 0.8 nm. Novel MOSFETs with a silicon quantum-dot floating gate embedded in the gate oxide have indicated the multiple-step electron injection to the dot, being interpreted in terms of Coulombic interaction among charged dots.     

A comparative morphological study of electron beam co-deposited binary optical thin films of HfO2:SiO2 and ZrO2:SiO2

A comparative morphology, grain structure and optical properties studies of reactive electron beam co-evaporated mixed thin films of hafnia–silica (HfO₂:SiO₂) and zirconia–silica (ZrO₂:SiO₂) systems have been carried out using atomic force microscopy and phase modulated ellipsometry. The addition of silica, especially with small fractions, has demonstrated altogether different types of evolutions in the microstructure and morphology in these binary thin film systems possibly forming new solid solution phases. Such morphological evolutions are probed through RMS roughness, power spectral density, height–height correlation and autocorrelation analyses of the topographic data acquired through atomic force microscopy. The present investigations indicated that with composition-control morphological quality improvement is more favourable in composite hafnia–silica over the zirconia–silica films. So for ultraviolet optical coating applications which demand low light scattering thin film microstructure, hafnia–silica binary composite system has a definite edge over the zirconia–silica counterpart.     

Growth behavior of high k LaAlO3 films on Si by metalorganic chemical vapor deposition for alternative gate dielectric application

LaAlO₃ (LAO) is explored in this work to replace SiO₂ as the gate dielectric material in metal–oxide–semiconductor field effect transistor. Amorphous LAO gate dielectric films were deposited on Si (0 0 1) substrates by low pressure metalorganic chemical vapor deposition using La(dpm)₃ and Al(acac)₃ sources. The effect of processing parameters such as deposition temperature and precursor vapor flux on growth, structure, morphology, and composition of LAO films has been investigated by various analytical methods deeply. The film growth mechanism on Si is reaction limiting instead of mass transport control. The reaction is thermally activated with activation energy of 37 kJ/mol. In the initial growth stage, Al element is deficient due to higher nucleation barrier on Si. The LAO films show a smooth surface and good thermal stability and remain amorphous up to a high temperature of 850 °C. The electrical properties of amorphous LAO ultrathin films on Si have also been evaluated, indicating LAO is suitable for high k gate dielectric applications.     

Comparative studies of Ge and Si p-channel metal-oxide-semiconductor field-effect-transistors with HfSiON dielectric and TaN metal gate

Ge and Si p-channel metal--oxide--semiconductor field-effect-transistors (p-MOSFETs) with hafnium silicon oxynitride (HfSiON) gate dielectric and tantalum nitride (TaN) metal gate are fabricated. Self-isolated ring-type transistor structures with two masks are employed. W/TaN metal stacks are used as gate electrode and shadow masks of source/drain implantation separately. Capacitance--voltage curve hysteresis of Ge metal--oxide--semiconductor (MOS) capacitors may be caused by charge trapping centres in GeO7340Q, 7325http://cpb.iphy.ac.cn/CN/10.1088/1674-1056/19/5/057302https://cpb.iphy.ac.cn/CN/article/downloadArticleFile.do?attachType=PDF&id=111774Ge substrate, transistor, HfSiON, hole mobilityProject supported by the National Basic Research Program of China (Grant No.~2006CB302704).Ge and Si p-channel metal--oxide--semiconductor field-effect-transistors (p-MOSFETs) with hafnium silicon oxynitride (HfSiON) gate dielectric and tantalum nitride (TaN) metal gate are fabricated. Self-isolated ring-type transistor structures with two masks are employed. W/TaN metal stacks are used as gate electrode and shadow masks of source/drain implantation separately. Capacitance--voltage curve hysteresis of Ge metal--oxide--semiconductor (MOS) capacitors may be caused by charge trapping centres in GeO$_{x}$ ($1Ge;substrate;transistor;HfSiON;hole;mobilityGe and Si p-channel metal-oxide-semiconductor field-effect-transistors(p-MOSFETs) with hafnium silicon oxynitride(HfSiON) gate dielectric and tantalum nitride(TaN) metal gate are fabricated.Self-isolated ring-type transistor structures with two masks are employed.W/TaN metal stacks are used as gate electrode and shadow masks of source/drain implantation separately.Capacitance-voltage curve hysteresis of Ge metal-oxide-semiconductor(MOS) capacitors may be caused by charge trapping centres in GeOx(1 < x < 2).Effective hole mobilities of Ge and Si transistors are extracted by using a channel conductance method.The peak hole mobilities of Si and Ge transistors are 33.4 cm2/(V.s) and 81.0 cm2/(V.s),respectively.Ge transistor has a hole mobility 2.4 times higher than that of Si control sample.     

沉淀过程pH值对铈锆复合氧化物结构与性能的影响

采用加热回流老化技术制备了系列组成为0.6CeO₂-0.4ZrO₂的铈锆复合氧化物,通过N₂物理吸附、Raman光谱、UV-Vis 漫反射光谱等方法对沉淀过程pH值对铈锆复合氧化物结构及储氧性能的影响进行了研究。结果表明,沉淀过程pH值不同,将导致铈锆复合氧化物的组成产生波动,进而影响样品的晶相组成、缺陷性质、结晶程度和孔结构性质。控制沉淀pH值为10.5～11.0,可消除Si的影响,改善铈锆复合氧化物的孔结构,提高相均匀性,提高缺陷浓度,降低结晶度,从而可提高样品的储氧性能。     

Band offsets in heterojunctions formed by oxides with cubic perovskite structure

A number of recent discoveries on heterostructures formed by oxides suggest the emergence of a new direction in microelectronics, the oxide electronics. In the present work, band offsets in nine heterojunctions formed by titanates, zirconates, and niobates with the cubic perovskite structure are calculated from first principles. The effect of strain in contacting oxides on their energy structure; the GW corrections to the band edge positions resulting from many-body effects; and the conduction band edge splitting resulting from spinorbit coupling are consistently taken into account. It is shown that the neglect of the many-body effects can cause errors in the determination of the band offsets, reaching 0.36 eV. The fundamental inapplicability of the transitivity rule often used to determine the band offsets in heterojunctions by comparing the band offsets in a pair of heterojunctions formed by the components of the heterojunction under study with a third common component is demonstrated. The cause of the inapplicability is explained.     

UV assisted low temperature nitridation and post deposition oxidation technique for hafnium oxide gate dielectric

An evaluation of a low temperature method (∼400 °C) for synthesis of nitrogen incorporated hafnia gate dielectric has been reported. This method is based on metal film growth in ammonia ambient and subsequent oxidation under ultraviolet (UV) irradiation. X-ray photoelectronic spectroscopy confirmed the presence of nitrided interface layer with a thickness of ∼12 ?. Equivalent oxide thickness values of around 11.5 ? and leakage current densities lower than 1 × 10⁻⁴ A/cm² at an operation voltage (−1 V) were achieved. The post deposition ultraviolet oxidation process was performed to check the interface oxidation resistance. The interface growth rate showed that as the interface bonding characteristics changed from Si-N to Si-O predominant bonding system of nitrogen incorporated films, the activation energy for oxygen diffusion changed from 18.0 kJ/mol to 9.8 kJ/mol and the activation energy of undoped hafnia films was 2.3 kJ/mol in every growth region.     

Characterisation of sol-gel prepared (HfO2)x(SiO2)1-x (x=0.1, 0.2 and 0.4) by 1H, 13C, 17 O and 29Si MAS NMR, FTIR and TGA

The HfO2-SiO2 system is attracting interest as a possible new dielectric material in semiconductor devices. Knowledge of the location of hafnium within the silica network and the effect hafnium has on the structure will be central to the successful use of this material system in this application. Here, sol-gel techniques have been used to manufacture (HfO2)x(SiO2)1-x samples (x=0.1, 0.2 and 0.4, each heat treated at 250, 500 and 750 degrees C) and these have been characterised by magic angle spinning (MAS) NMR (1H, 13C, 17 O, 29Si), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis. 29Si MAS NMR showed that increasing the hafnia content decreases the connectivity of the silicate network, i.e. increases the range of differently connected SiO4 (Qn) units with more having increased numbers of non-bridging oxygens (i.e. lower n). FTIR and 17 O MAS NMR showed unequivocally that the x=0.4 sample phase-separated at higher temperatures, while in the x=0.1 sample the hafnium was homogeneously mixed into the SiO2 phase without any phase separation.     

Identification of F+ centers in hafnia and zirconia nanopowders

Luminescence properties of undoped hafnia and zirconia nanopowders prepared by solution combustion synthesis were investigated under photo- and electron-beam excitation in 10–400 K temperature range. Along with the main luminescence band revealed in investigated materials at low temperatures at 4.2–4.3 eV and ascribed to the emission of self-trapped excitons, there are luminescence bands due to defects and impurities introduced during sample preparation. At room temperature the latter emissions dominate in the luminescence spectra as the intrinsic self-trapped exciton emission is quenched. Analysis of decay kinetics of defect centers allowed identification of F⁺ centers emission at 2.8 eV with lifetimes ∼3–6 ns in hafnia and zirconia under intra-center excitation.     

Experimental evaluation of interface states during time-dependent dielectric breakdown of GaN-based MIS-HEMTs with LPCVD-SiN_x gate dielectric

We experimentally evaluated the interface state density of Ga N MIS-HEMTs during time-dependent dielectric breakdown(TDDB). Under a high forward gate bias stress, newly increased traps generate both at the Si Nx/Al Ga N interface and the Si Nx bulk, resulting in the voltage shift and the increase of the voltage hysteresis. When prolonging the stress duration, the defects density generated in the Si Nx dielectric becomes dominating, which drastically increases the gate leakage current and causes the catastrophic failure. After recovery by UV light illumination, the negative shift in threshold voltage(compared with the fresh one) confirms the accumulation of positive charge at the Si Nx/Al Ga N interface and/or in Si Nx bulk, which is possibly ascribed to the broken bonds after long-term stress. These results experimentally confirm the role of defects in the TDDB of Ga N-based MIS-HEMTs.     

旋涂法制备氧化锆介质层及其在薄膜晶体管中的应用

采用旋涂法制备了氧化锆介质层薄膜,重点讨论了退火温度以及旋涂转速对薄膜性能的影响及作用机制。研究发现高温后退火一方面使得氧化锆水合物脱水形成氧化锆,另一方面促使氧化锆薄膜结晶。此外,转速较高时,其变化对薄膜厚度及粗糙度无显著影响。当转速为5 000 r/min、退火温度为300℃时,制备的绝缘层厚度具有良好的厚度均匀性,粗糙度为0.7 nm,漏电流为3.13×10^-5 A/cm²（电场强度1 MV/cm）。最终,利用ZrO₂薄膜作为栅极绝缘层,在玻璃基板上制备了铟镓锌氧化物-薄膜晶体管（IGZO-TFT）,其迁移率为6.5 cm²/（V·s）,开关比为2×10⁴。     

单轴应变Si NMOSFET热载流子栅电流模型

热载流子效应产生的栅电流是影响器件功耗及可靠性的重要因素之一,本文基于热载流子形成的物理过程,建立了单轴应变硅NMOSFET热载流子栅电流模型,并对热载流子栅电流与应力强度、沟道掺杂浓度、栅源电压、漏源电压等的关系,以及TDDB(经时击穿)寿命与栅源电压的关系进行了分析研究.结果表明,与体硅器件相比,单轴应变硅MOS器件不仅具有较小的热载流子栅电流,而且可靠性也获得提高.同时模型仿真结果与单轴应变硅NMOSFET的实验结果符合较好,验证了该模型的可行性.     

High‐performance In–Zn–O thin‐film transistors with a soluble processed ZrO2 gate insulator

Spin‐coated zirconium oxide films were used as a gate dielectric for low‐voltage, high performance indium zinc oxide (IZO) thin‐film transistors (TFTs). The ZrO₂ films annealed at 400 °C showed a low gate leakage current density of 2 × 10^–8 A/cm² at an electric field of 2 MV/cm. This was attributed to the low impurity content and high crystalline quality. Therefore, the IZO TFTs with a soluble ZrO₂ gate insulator exhibited a high field effect mobility of 23.4 cm²/V s, excellent subthreshold gate swing of 70 mV/decade and a reasonable I_on/off ratio of ～10⁶. These TFTs operated at low voltages (～3.0 V) and showed high drain current drive capability, enabling oxide TFTs with a soluble processed high‐k dielectric for use in backplane electronics for low‐power mobile display applications. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Complete inheritance of fractal properties during first-order phase transition

We present experimental evidence of complete fractal properties inheritance in the course of first-order phase transition from amorphous to monoclinic or tetragonal zirconia under hydrothermal conditions. This phenomenon takes place either under rapid microwave heating or conventional heating regardless of starting fractal dimension value. Exactly the same effect is observed for hafnia. The similarity of the local structures of amorphous and crystalline zirconia as well as relatively soft crystallization conditions could be the definite reasons for the conservation of the mesostructure in the course of phase transition.     

Atomic transport during growth of ultrathin dielectrics on silicon

Atomic transport in thermal growth of thin and ultrathin silicon oxide, nitride, and oxynitride films on Si is reviewed. These films constitute the gate dielectrics, the “heart” of silicon metal-oxide-semiconductor field-effect transistor (MOSFET) and dynamic random-access memory (DRAM) devices, which are usually thermally grown on the active region of the semiconductor Si substrate. The drive of ultra-large scale integration towards the 0.18 μm channel length and below requires gate dielectrics with thicknesses of 3–4 nm and less, establishing new and very strict material requirements. Knowledge on an atomic scale of dielectric film growth promoted by thermally activated transport mechanisms is essential to the engineering of this fabrication step. In the case of thermal growth of silicon oxide films on Si in dry O₂, the mobile species is O₂ and growth is essentially a diffusion–reaction phenomenon. The thermal growth of silicon nitride and oxynitride films on Si in NH₃, NO and N₂O, on the other hand, involves catalytic dissociation of the original gas molecules at the surfaces and interfaces and diffusion–reaction of different resulting species, like NH₂, NH, H, N, NO, O, and O₂. Hydrogen transport and incorporation is a crucial, ubiquitous issue in thermally grown dielectric films on Si which is also addressed here. A recall is made of the physico-chemical constitution of the involved surfaces and interfaces for each different dielectric material, as well as complementary studies of the gas, gas-surface, and solid phase chemistry. An outline of the unique tools of isotopic substitution and high resolution depth profiling is included.     

Theoretical prediction of ion conductivity in solid state HfO2

A theoretical prediction of ion conductivity for solid state HfO2 is carried out in analogy to ZrO2 based on the density functional calculation. Geometric and electronic structures of pure bulks exhibit similarity for the two materials. Negative formation enthalpy and negative vacancy formation energy are found for YSH (yttria-stabilized hafnia) and YSZ (yttria- stabilized zirconia), suggesting the stability of both materials. Low activation energies (below 0.7 eV) of diffusion are found in both materials, and YSH’s is a little higher than that of YSZ. In addition, for both HfO2 and ZrO2 , the supercells with native oxygen vacancies are also studied. The so-called defect states are observed in the supercells with neutral and +1 charge native vacancy but not in the +2 charge one. It can give an explanation to the relatively lower activation energies of yttria-doped oxides and +2 charge vacancy supercells. A brief discussion is presented to explain the different YSH ion conductivities in the experiment and obtained by us, and we attribute this to the different ion vibrations at different temperatures.     

Surface passivation technology for III-V semiconductor nanoelectronics

The present status and key issues of surface passivation technology for III-V surfaces are discussed in view of applications to emerging novel III-V nanoelectronics. First, necessities of passivation and currently available surface passivation technologies for GaAs, InGaAs and AlGaAs are reviewed. Then, the principle of the Si interface control layer (ICL)-based passivation scheme by the authors’ group is introduced and its basic characterization is presented. Ths Si ICL is a molecular beam epitaxy (MBE)-grown ultrathin Si layer inserted between III-V semiconductor and passivation dielectric. Finally, applications of the Si ICL method to passivation of GaAs nanowires and GaAs nanowire transistors and to realization of pinning-free high-k dielectric/GaAs MOS gate stacks are presented.