The effect of Si surface nitridation on the interfacial structure and electrical properties of (La2O3)0.5(SiO2)0.5 high-k gate dielectric films

Thermal stability, interfacial structures and electrical properties of amorphous (La₂O₃)_0.5(SiO₂)_0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH₃ nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH₃ can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.     

Ionizing radiation effects on electrical and reliability characteristics of sputtered Ta2O5/Si interface

This paper describes the effect of ionizing radiation on the interface properties of Al/Ta₂O₅/Si metal oxide semiconductor (MOS) capacitors using capacitance–voltage (C–V) and current–voltage (I–V) characteristics. The devices were irradiated with X-rays at different doses ranging from 100?rad to 1?Mrad. The leakage behavior, which is an important parameter for memory applications of Al/Ta₂O₅/Si MOS capacitors, along with interface properties such as effective oxide charges and interface trap density with and without irradiation has been investigated. Lower accumulation capacitance and shift in flat band voltage toward negative value were observed in annealed devices after exposure to radiation. The increase in interfacial oxide layer thickness after irradiation was confirmed by Rutherford Back Scattering measurement. The effect of post-deposition annealing on the electrical behavior of Ta₂O₅ MOS capacitors was also investigated. Improved electrical and interface properties were obtained for samples deposited in N₂ ambient. The density of interface trap states (D_it) at Ta₂O₅/Si interface sputtered in pure argon ambient was higher compared to samples reactively sputtered in nitrogen-containing plasma. Our results show that reactive sputtering in nitrogen-containing plasma is a promising approach to improve the radiation hardness of Ta₂O₅/Si MOS devices.     

Structural and dielectric properties of Ru-based gate/Hf-doped Ta2O5 stacks

Hf-doped Ta₂O₅ thin films are studied with respect to their composition, dielectric and electrical properties. The incorporation of Hf is performed by sputtering of a 0.7 nm thick Hf layer on top of Ta₂O₅ and subsequent annealing to stimulate diffusion of Hf into Ta₂O₅ and their intermixing. The elemental in-depth distribution of the films is investigated by the time of flight secondary ion mass spectroscopy (ToF-SIMS), which has revealed that Hf and Ta₂O₅ are intermixed throughout the whole thickness. Two sub-layers exist in all the samples - an upper homogeneous Hf-doped Ta₂O₅ sub-layer and a near interfacial region which is a mixture of Ta- and Si-oxides. The X-ray reflectivity (XRR) analysis shows existence of interfacial layer with a thickness of about 1.9-2 nm, irrespectively of the total thickness of the stacks. Metal-oxide-Si structures with Ru and RuO₂ metal electrodes have been prepared and investigated in terms of dielectric constant, effective work function (EWF) and interfacial layer parameters. The influence of post-metallization annealing steps on these parameters was also studied.     

Silicon oxynitride thin films synthesised by the reactive gas pulsing process using rectangular pulses

Silicon oxynitride thin films were synthesised by the reactive gas pulsing process using an argon, oxygen and nitrogen gas mixture from a semiconductor Si target. Argon and nitrogen were introduced at a constant mass flow rate, whereas oxygen gas was periodically supplied using a rectangular pulsed flow rate. The O₂ injection time T_ON (or duty cycle α) was the only varied parameter. The influences of this parameter on the discharge behaviour, on the Si target voltage, and on the resulting chemical composition of the films were investigated. The temporal evolution of the total pressure exhibits exponential shape differing from the rectangular oxygen pulse shape, due to the response time of the gas flowmeter and to the progressive oxidation of the target and the chamber walls. During the T_ON time, the preferential adsorption of the introduced O₂ induces a decay in Si target voltage. Reversion to the nitrided mode is still possible as soon as the O₂ injection is stopped. The elemental analyses assessed by secondary neutral mass spectrometry (SNMS) showed that the O/N ratio within silicon oxynitride films linearly depends on the T_ON time. Increasing the duty cycle α over a certain value results in an oxidised steady state formation during the T_ON time. This formation was observed by real time measurements of the emission lines ratio I(O^*)/I(Ar^*) indicative of the O₂ partial pressure and confirmed by the time derivative of the target voltage. During the T_OFF time, the alternation with the nitrided mode becomes impossible, leading to the specific synthesis of stoichiometric SiO₂ films.     

Thermal stability of atomic-layer-deposited ultra-thin niobium oxide film on Si (1 0 0)

Ultra-thin Nb₂O₅ films with excellent uniformity have been grown on Si (1 0 0) by atomic-layer-deposition using Nb(OC₂H₅)₅ and H₂O precursors, and the corresponding thermal stability has been studied through atomic force microscope, transmission electron microscope and X-ray photoelectron spectroscopy. The results indicate that the ultra-thin (∼3 nm) Nb₂O₅ film is gradually built up into distributed large islands with increasing rapid thermal annealing (RTA) temperature. Meanwhile, both crystalline and amorphous phases are formed in the matrix of Nb₂O₅ annealed at 700 °C. In terms of the as-prepared sample, an interfacial layer (IL) with a thickness of around 1.5 nm is observed, that is composed of niobium silicate (Nb-O-Si). Further, the high temperature RTA leads to a thickened IL, which is attributed to the formation of more Nb-O-Si bonds and new silicon oxide (Si-O-Si) adjacent to the Si (1 0 0).     

Cathode luminescence characteristics of ZnGa2O4 phosphor thin films with the doped activator

The zincgallate (ZnGa₂O₄) phosphor thin film was grown using RF magnetron sputtering system at various process parameters. A ZnGa₂O₄ phosphor thin film was deposited on Si(1 0 0) substrate and annealed by a rapid thermal processor (RTP). The X-ray diffractometer (XRD) patterns indicate that the Mn-doped ZnGa₂O₄ phosphor thin film shows a (3 1 1) main peak and a spinel phase. A ZnGa₂O₄ phosphor thin film has better crystallization due to increased substrate, annealing temperature and deposition time. Also the ZnGa₂O₄:Mn phosphor thin film shows green emission (510 nm, ⁴T₁→⁶A₁), and the ZnGa₂O₄:Cr phosphor thin film shows red emission (705 nm, ⁴A₂→⁴T₂).     

Positive and negative magnetoresistance in Fe3O4-based heterostructures

Fe₃O₄-based heterostructures, including Fe₃O₄/MgO/Fe₃O₄, Fe₃O₄/MgO/Si and Fe₃O₄/SiO₂/Si, were fabricated by magnetron sputtering to investigate the perpendicular-to-plane magneto-transport properties. In the Fe₃O₄/MgO/Fe₃O₄ and Fe₃O₄/MgO/Si heterostructures, the typical magneto-transport properties of single Fe₃O₄ films, such as negative magnetoresistance (MR) and extreme values of MR−T curves at 120 K, were observed, suggesting that the spin polarization of conducting electrons conserves through MgO barrier. MR in the Fe₃O₄/MgO/Fe₃O₄ heterostructure is larger than that in the Fe₃O₄/MgO/Si heterostructure, because the spin of electrons is disturbed in the depletion layer of Si and the SiO₂ layer introduced by Fe₃O₄/MgO growth. The Fe₃O₄/SiO₂/Si heterostructure has a positive MR of 2% at 120 K, which may originate from the scattering of conducting electrons in amorphous SiO₂ and the spin polarization reversal at the Fe₃O₄/SiO₂ interface.     

Structural, electrical and gas-sensing properties of In2O3 : Ag composite nanoparticle layers

The central objective of this study is to investigate (i) size-dependent properties of In₂O₃ nanoparticles and (ii) the role of metal additives in enhancing the gas sensing response. For this purpose, In₂O₃ : Ag composite nanoparticle layers having welldefined individual nanoparticle size and composition have been grown by a two step synthesis method. Thermogravimetric analysis, X-ray diffraction and transmission electron microscopy have been used to study the effect of post-synthesis heat treatment on the size and structure of the nanoparticles. A first-time unambiguous observation of sizedependent lowering of transformation temperature has been explained in terms of lower cohesive energy of surface atoms and increase in surface-to-volume ratio with decrease in nanoparticle size. The gas sensing studies of In₂O₃ as well as the In₂O₃ : Ag composite nanoparticle layers have been studied as a function of size and composition. In₂O₃: Ag composite nanoparticle layers with 15% silver show a sensitivity of 436 and response time of 6 s for 1000 ppm of ethanol in air. Ag additives form a p-type Ag₂O, which interact with n-type In₂O₃ to produce an electron-deficient space-charge layer. In the presence of ethanol, interfacial Ag₂O reduces to Ag, creating an accumulation layer in In₂O₃ resulting in increased sensitivity     

In situ RHEED analysis of epitaxial Gd2O3 thin films grown on Si (001)

Epitaxial Gd₂O₃ thin films were successfully grown on Si (001) substrates using a two-step approach by laser molecular-beam epitaxy. At the first step, a ～0.8 nm thin layer was deposited at the temperature of 200 ^°C as the buffer layer. Then the substrate temperature was increased to 650 ^°C and in situ annealing for 5 min, and a second Gd₂O₃ layer with a desired thickness was deposited. The whole growth process is monitored by in situ reflection high-energy electron diffraction (RHEED). In situ RHEED analysis of the growing film has revealed that the first Gd₂O₃ layer deposition and in situ annealing are the critical processes for the epitaxial growth of Gd₂O₃ film. The Gd₂O₃ film has a monoclinic phase characterized by X-ray diffraction. The high-resolution transmission electron microscopy image showed all the Gd₂O₃ layers have a little bending because of the stress. In addition, a 5–6 nm amorphous interfacial layer between the Gd₂O₃ film and Si substrate is due to the in situ high temperature annealing for a long time. The successful Gd₂O₃/Si epitaxial growth predicted a possibility to develop the new functional microelectronics devices.     

Surface characterization and luminescent properties of SrAl2O4:Eu,Dy nano thin films

SrAl₂O₄:Eu²⁺, Dy³⁺ thin films were grown on Si (1 0 0) substrates in different atmospheres using the pulsed laser deposition (PLD) technique. The effects of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological and photoluminescence (PL) properties of the films were investigated. The films were ablated using a 248 nm KrF excimer laser. Improved PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres compared to those prepared in vacuum. A stable green emission peak at 520 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions was obtained. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The diffusion of adventitious C into the nanostructured layers deposited in the Ar and O₂ atmospheres was most probably responsible for the quenching of the PL intensity after annealing.     

Nanoscale Analysis of Multilayer Interfaces of W/Al2O3/Ti/Cu

W, Al₂O₃ and Ti films were deposited onto a Cu substrate by means of the rf magnetron sputtering method. After deposition, the foils were annealed at various temperatures in vacuum and the interfaces of the films were observed by a field-emission transmission electron microscopy (FE-TEM), after preparing a cross-sectional thin foil using a focused ion beam (FIB) machine. After annealing the foil at 473 and 623 K, no reaction phases were identified at each interface of W/Al₂O₃, Al₂O₃/Ti and Ti/Cu-substrate. However, from the results of compositional analysis at the interface of Al₂O₃/Ti bilayer, after heat-treatment at 623 K, the formation of an oxide layer was suggested even though it was not clearly observed. On the other hand, after heat-treatment at 823 K, the formation of CuTi₂, Cu₃Ti₂ and Cu₄Ti phases were identified at the interface of Ti/Cu bilayers from the compositional analysis of reaction layers after heat-treatment at different temperatures, and the diffusion coefficients and activation energies in the phases were evaluated. In this paper, the influence of heat-treatment on the interfacial behavior of multilayer are discussed on the basis of nanoscale analysis by EDS and HRTEM images.     

Application of spectroscopic ellipsometry to the investigation of the optical properties of cobalt-nanostructured silica thin layers

Spectroscopic ellipsometry is used to investigate optical properties of cobalt-implanted silica thin films. The films under investigation are 250 nm thick thermal SiO₂ layers on Si substrates implanted with Co⁺ ions at energy of 160 keV and at fluences of 10¹⁷ ions/cm² for different temperatures of substrate during implantation (77 and 295 K). Changes due to Co⁺ implantation are clearly observed in the optical response of the films. Optical behaviours are furthermore different for the three implantation temperatures. To understand the optical responses of these layers, the ellipsometric experimental data are compared to different models including interference effects and metal inclusions effects into the dielectric layer. The simulated ellipsometric data are obtained by calculating the interferences of an inhomogeneous layer on a Si substrate. The material within this layer is considered as an effective medium which dielectric function is calculated using the Maxwell-Garnett effective medium approximation. We show that although the structures of these layers are very complicated because of ion-implantation mechanisms, quite simple models can provide relatively good agreement. The possibilities of ellipsometry for the study of the optical properties of such clusters-embedded films are discussed. We especially provide the evidence that ellipsometry can give interesting information about the optical properties of nanostructured layers. This is of special interest in the field of nanostructured layered systems where ellipsometry appears to be a suitable optical characterization technique.     

Active metal brazing of Al2O3 to Kovar® (Fe–29Ni–17Co wt.%) using Copper ABA® (Cu–3.0Si–2.3Ti–2.0Al wt.%)

The application of an active braze alloy (ABA) known as Copper ABA® (Cu–3.0Si–2.3Ti–2.0Al wt.%) to join Al₂O₃ to Kovar® (Fe–29Ni–17Co wt.%) has been investigated. This ABA was selected to increase the operating temperature of the joint beyond the capabilities of typically used ABAs such as Ag–Cu–Ti-based alloys. Silica present as a secondary phase in the Al₂O₃ at a level of ~5 wt.% enabled the ceramic component to bond to the ABA chemically by forming a layer of Si₃Ti₅ at the ABA/Al₂O₃ interface. Appropriate brazing conditions to preserve a near-continuous Si₃Ti₅ layer on the Al₂O₃ and a continuous Fe₃Si layer on the Kovar® were found to be a brazing time of ≤15 min at 1025 °C or ≤2 min at 1050 °C. These conditions produced joints that did not break on handling and could be prepared easily for microscopy. Brazing for longer periods of time, up to 45 min, at these temperatures broke down the Si₃Ti₅ layer on the Al₂O₃, while brazing at ≥1075 °C for 2–45 min broke down the Fe₃Si layer on the Kovar® significantly. Further complications of brazing at ≥1075 °C included leakage of the ABA out of the joint and the formation of a new brittle silicide, Ni₁₆Si₇Ti₆, at the ABA/Al₂O₃ interface. This investigation demonstrates that it is not straightforward to join Al₂O₃ to Kovar® using Copper ABA®, partly because the ranges of suitable values for the brazing temperature and time are quite limited. Other approaches to increase the operating temperature of the joint are discussed.     

An XPS study and electrical properties of Pb1.1Zr0.53Ti0.47O3/PbO/Si (MFIS) structures according to the substrate temperature of the PbO buffer layer

PbO and PZT thin films were deposited on the p-type (1 0 0) Si substrate by the rf magnetron sputtering method with PbO and Pb_1.1Zr_0.53Ti_0.47O₃ targets for the application of the metal-ferroelectric-insulator-semiconductor (MFIS) structure. The MFIS structures with the PbO buffer layer show the good electric properties including a high memory window and a low leakage current density. The maximum value of the memory window is 2.0 V under the applied voltage of 9 V for the Pt/PZT (200 nm, 400 °C)/PbO (80 nm)/Si structures with the PbO buffer layer deposited at the substrate temperature of 300 °C. From the X-ray photoelectron spectroscopy (XPS) results, we could confirm that the substrate temperature of PbO affects the chemical states of the interface between the PbO buffer layer and Si substrate, which results in the inter-diffusion of Pb and the formation of the intermediate phases (PbSiO₃). And the existence of the undesired SiO₂ layer, which is the low dielectric layer, was confirmed at the surface region of the Si substrate by the XPS depth profile analysis.     

Influence of postdeposition annealing on structural properties and electrical characteristics of thin Tm2O3 and Tm2Ti2O7 dielectrics

We describe the structural properties and electrical characteristics of thin thulium oxide (Tm₂O₃) and thulium titanium oxide (Tm₂Ti₂O₇) as gate dielectrics deposited on silicon substrates through reactive sputtering. The structural and morphological features of these films were explored by X-ray diffraction, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and atomic force microscopy, measurements. It is found that the Tm₂Ti₂O₇ film annealed at 800 °C exhibited a thinner capacitance equivalent thickness of 19.8 Å, a lower interface trap density of 8.37 × 10¹¹ eV⁻¹ cm⁻², and a smaller hysteresis voltage of ∼4 mV than the other conditions. We attribute this behavior to the Ti incorporated into the Tm₂O₃ film improving the interfacial layer and the surface roughness. This film also shows negligible degrees of charge trapping at high electric field stress.     

Dy掺杂对Sr2Bi4Ti5O18铁电陶瓷性能的影响

用传统固相烧结法制备了Sr₂Bi_4-xDy_xTi₅ O₁₈(SBDT-x, x=0—0.20)陶瓷样品. x射线衍射分析表明, 微量的Dy掺杂没有影 响Sr₂Bi₄Ti₅O₁₈(SBTi) 原有的层状钙钛 矿结构. 通过研究样品的介电特性, 发现Dy掺杂减小了材料的损耗因子, 降低了样品铁电- 顺电相转变的居里温度. 铁电性能测量结果表明, 随Dy含量的增加, SBDT-x系列样品的剩余 极化先增大, 后减小. 当Dy掺杂量为0.01时, 剩余极化达到最大值, 约为20.1 μC·cm^-2. 掺杂引起剩余极化的变化, 与材料中缺陷浓度、内应力以及晶格畸变程度等因 素有关, 是多种作用机理相互竞争的结果. (Bi₂O₂)²⁺ 层通常被看作是绝缘层和空间电荷库, 对材料的铁电性能起关键作用. 掺杂离子进入(Bi2O₂)²⁺层会导致铁电性能变差. 关键词： 2Bi₄Ti₅O₁₈陶瓷')" href="#">Sr₂Bi₄Ti₅O₁₈陶瓷 Dy掺 杂 铁电性能 居里温度     

Atomic layer deposition of nanolaminate oxide films on Si

Among the methods for depositing thin films, atomic layer deposition is unique for its capability of growing conformal thin films of compounds with a control of composition and thickness at the atomic level. The conformal growth of thin films can be of particular interest for covering nanostructures since it assures the homogeneous growth of the ALD film in all directions, independent of the position of the sample with respect to the incoming precursor flow. Here we describe the technique for growing the HfO₂/Al₂O₃ bilayer on Si substrate and our in situ approach for its investigation by means of synchrotron radiation photoemission. In particular, we study the interface interactions between the two oxides for various thickness compositions ranging from 0.4 to 2.7 nm. We find that the ALD of HfO₂ on Si induces the increase of the interfacial SiO₂ layer, and a change in the band bending of Si. On the contrary, the ALD of Al₂O₃ on HfO₂ shows negligible interaction between layers as the binding energies of Hf4f, Si2p, and O1s core level peaks and the valence band maximum of HfO₂ do not change and the interfacial SiO₂ does not increase.     

Si基铁电Bi3.15Nd0.85Ti3O12多层薄膜的一致取向生长和性能的研究

采用脉冲激光沉积(PLD)技术，利用LSCO/CeO₂/YSZ多异质缓冲层，在Si(100)基 片上成功地制备了c轴一致取向的Bi_3.15Nd_0.85Ti₃O12(BNT)铁电薄膜.利用X射线衍射(XRD)和扫描电镜(SEM)分析测定了薄膜的相结构 、取向和形貌特征，考察了沉积温度和氧分压对BNT薄膜微结构、取向和形貌的影响，确定 了BNT薄膜的最佳沉积条件.对在优化的条件下制备得到的BNT薄膜的C-V曲线测试得到了典型 的蝴蝶形曲线，表明该薄膜具有较好的电极化反转存储特性.最后讨论了BNT薄膜铁电性能与 薄膜取向的相关性. 关键词： 3.15Nd_0.85Ti₃O₁₂')" href="#">Bi_3.15Nd_0.85Ti₃O₁₂ 铁电薄 膜 多层异质结 脉冲激光沉积     

Structural-optical study of high-dielectric-constant oxide films

High-k polycrystalline Pr₂O₃ and amorphous LaAlO₃ oxide thin films deposited on Si(0 0 1) are studied. The microstructure is investigated using X-ray diffraction and scanning electron microscopy. Optical properties are determined in the 0.75-6.5 eV photon energy range using spectroscopic ellipsometry. The polycrystalline Pr₂O₃ films have an optical gap of 3.86 eV and a dielectric constant of 16-26, which increases with film thickness. Similarly, very thin amorphous LaAlO₃ films have the optical gap of 5.8 eV, and a dielectric constant below 14 which also increases with film thickness. The lower dielectric constant compared to crystalline material is an intrinsic characteristic of amorphous films.     

Microstructure and electrical properties of Ba0.5Sr0.5TiO3 thin films prepared on copper foils with La2O3 buffer layers

Ba_0.5Sr_0.5TiO₃ (BST) thin films were deposited on copper foils via sol-gel method with La₂O₃ as a buffer layer. The films were processed in almost inert atmosphere so that the substrate oxidation was avoided while allowing the perovskite film phase to crystallize. The existence of a La₂O₃ buffer layer between the BST thin film and Cu foil improved the dielectric constant and reduced the leakage current density of the BST thin film. Meanwhile, the BST thin film exhibited ferroelectric character at room temperature, which was contrast to the para-electric behavior of the film without the buffer layer. Effects of La₂O₃ buffer layer on the crystallizability and microstructure of BST thin films were also investigated.