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.     

Charge trapping and breakdown in thin SiO2 polysilicon-gate MOS capacitors

Charge trapping during high-field (Fowler-Nordheim) injection in thin SiO₂ films is investigated. Constant and pulsed current injection as well as C-V measurements are used to determine the evolution of trapped charge and interface state densities. The relation between these charges, which can be influenced by temperature and γ radiation, and dielectric breakdown is studied. We establish the dominant role of negative trapped charge.     

Electroluminescence from thin SiO2 layers after Si- and C-coimplantation

In this paper we explore the electroluminescence (EL) properties of thermally grown 350 nm thick SiO₂ layers co-implanted with Si⁺ and C⁺ ions. The implanted fluences were chosen in such a way that peak concentrations of excess Si and C of 5–10 at% were achieved. The devices show a broad photoluminescence (PL) between 2.0 and 3.2 eV with a main peak around 2.7 eV. The broad EL spectra show additional peaks around 3.3 eV and between 2.1 and 2.5 eV which are decreased with increasing Si/C concentration. The shape of the EL spectra does not change with increasing injection currents which implies that various types of defects occur for the different concentrations. The device stability is improved in comparison to Ge or Sn implanted oxide layers.     

Polaritonic and photonic gaps in SiO2/Si and SiO2/air periodic structures

The one-dimensional (1D) photonic crystals (PhC) Si/SiO₂, SiO₂/Si and SiO₂/air are studied to investigate the coexistence and interaction of polaritonic and structural gaps. Optical multilayer calculations as well as infrared reflectance measurements in the 2.7–12 μm range for relevant cases have been carried out. The samples were prepared by standard chemical vapor deposition (CVD) processes. Satisfactory agreement between experimental and calculated results was obtained without fitting. The calculated results verify the presence of a polaritonic gap for thicknesses much lower than the wavelength for the cases SiO₂/Si and SiO₂/air. Including also the case Si/SiO₂, we find the polaritonic peak can be strengthened, unchanged, or extinguished by the interaction between structural and polaritonic effects. All these predictions have been experimentally verified.     

Nitridation of thin SiO2 films in N2 and NH3 plasmas

A low-temperature (700°C) plasma-enhanced nitridation process which improves the dielectric breakdown of thin silicon dioxide (SiO₂) layers is presented. It uses a new, production compatible, parallel plate plasma reactor working at low RF frequencies. Nitrided oxides produce less charge trapping under high field stress, higher breakdown charge and a tighter distribution of breakdown fields than pure SiO₂. More nitrogen is incorporated in films treated in a NH₃ plasma than in a N₂ plasma. However, the latter present better electrical properties.     

The origin of photoluminescence in Ge-implanted SiO2 layers

Ge ions were implanted at 100 keV with 3×10¹⁶ cm⁻² into a 300  nm thick SiO₂ layer on Si. Visible photoluminescence (PL) around 2.1 eV from an as-implanted sample is observed, and faded out by subsequent annealing at 900°C for 2 h. However, PL shows up again after annealing above 900°C at the same peak position. Compared with the as-implanted sample, significant increase of Ge–Ge bonds is measured in X-ray photoelectron spectroscopy, and the formation of Ge nanocrystals with a diameter of 5 nm are observed in transmission electron microscopy from the sample annealed at 1100°C. We conclude that the PL peak from the sample annealed above 900°C is caused by the quantum confinement effects from Ge nanocrystals, while the luminescence from the as-implanted sample is due to some radiative defects formed by Ge implantation.     

单层SiO2物理膜与化学膜激光损伤机理的对比研究

采用离子束溅射沉积技术和溶胶-凝胶技术在K9基片上镀制了厚度相近的SiO₂单层介质膜，用表面热透镜技术对两类膜层分别进行了热吸收及实时动态热畸变实验测试，结合散射光阈值测试及实验前后膜层的显微观测，对相同基底、相同膜层材料而采用不同方法镀制的光学膜层，发现化学膜的强激光损伤阈值远高于相应物理膜；从热力学响应及膜层特性差异的角度揭示了化学膜层的强激光损伤阈值远高于相应物理膜层的微观机理，即物理膜具有高吸收下的致密膜层快传导的基底热冲击效应，而化学膜则有低吸收下的疏松空隙填充慢传导的延缓效应，大量的实验数据及现象都证实了这一结论. 关键词： 强激光辐照损伤 损伤形貌 热冲击 热吸收     

Photoluminescence and electroluminescence investigations at Ge-rich SiO2 layers

Strong blue and violet photo (PL) and electroluminescence (EL) at room temperature was obtained from SiO₂-films grown on crystalline Si, which were either single (SI) or double implanted (DI) with Ge ions and annealed at different temperatures. The PL spectra of Ge-rich layers reach a maximum after annealing at 500–700°C for DI layers or 900–1000°C for SI layers, respectively. Both, PL and EL of 500 nm thick Ge-rich layers are easily visible by the naked eye at ambient light due to their high intensity. Based on excitation spectra we tentatively interpret the blue PL as due to the oxygen vacancy in silicon dioxide.

The EL spectrum of the Ge-implanted oxide correlates very well with the PL one and shows a linear dependence on the injected current over three orders of magnitude. For DI layers much higher injection currents than for SI layers can be achieved. An EL efficiency in the order of 10⁻⁴ for Ge⁺-implanted silicon dioxide was determined.     

SiO2的赝晶化及AlN/SiO2纳米多层膜的超硬效应

采用反应磁控溅射法制备了一系列不同SiO₂层厚度的AlN/SiO₂纳米多层膜，利用X射线衍射仪、高分辨透射电子显微镜和微力学探针表征了多层膜的微结构和力学性能，研究了SiO₂层在多层膜中的晶化现象及其对多层膜生长方式及力学性能的影响. 结果表明，由于受AlN六方晶体结构的模板作用，溅射条件下以非晶态存在的SiO₂层在其厚度小于0.6 nm时被强制晶化为与AlN相同的六方结构赝晶体并与AlN形成共格外延生长. 由于不同模量的两调制层存在晶格错配度，多层膜中产生了拉、压交变的应力场，使得多层膜产生硬度升高的超硬效应. SiO₂随层厚的进一步增加又转变为以非晶态生长，多层膜的外延生长结构受到破坏，其硬度也随之降低. 关键词： 2纳米多层膜')" href="#">AlN/SiO₂纳米多层膜 赝晶化 应力场 超硬效应     

同步辐射光激励的二氧化硅薄膜刻蚀研究

利用热氧化法在硅晶片上生长SiO₂薄膜，结合光刻和磁控溅射技术在SiO₂薄膜表面制备接触型钴掩模，通过掩模方法在硅表面开展了同步辐射光激励的表面刻蚀研究，在室温下制备了SiO₂薄膜的刻蚀图样.实验结果表明：在同步辐射光照射下，通入SF₆气体可以有效地对SiO₂薄膜进行各向异性刻蚀，并在一定的气压范围内，刻蚀率随SF₆气体浓度的增加而增加，随样品温度的下降而升高；如果在同步辐射光照射下，用SF₆和O₂的混合气体作为反应气体，刻蚀过程将停止在SiO₂/Si界面，即不对硅刻蚀，实现了同步辐射对硅和二氧化硅两种材料的选择性刻蚀；另外，钴表现出强的抗刻蚀能力，是一种理想的同步辐射光掩模材料. 关键词： 同步辐射刻蚀 接触型钴掩模 二氧化硅薄膜     

The role of multiple damaged layers at the Si/SiO2 interface on the dielectric breakdown of MOS capacitors

Oxide breakdown in metal-oxide-semiconductor (MOS) devices in the nanometer scale is simulated as a cluster growth depending process in which the local electric field is a function of a randomly varying local dielectric permissivity. Effects of MOS device bias polarity, film thickness and non-uniform defect distributions through the entire oxide film on the breakdown are studied. The slope of the Weibull distribution increases with the oxide thickness in agreement with experimental results.     

Analysis of codeposited Gd2O3/SiO2 composite thin films by phase modulated spectroscopic ellipsometric technique

Tailoring of the refractive index of optical thin films has been a very fascinating as well as challenging topic for developing new generation optical coatings. In the present work a novel Gd₂O₃/SiO₂ composite system has been experimented and probed for its superior optical properties through phase modulated spectroscopic ellipsometry, spectrophotometry and atomic force microscopy. The optical parameters of the composite films have been evaluated using Tauc-Lorentz (TL) formulations. In order to derive the growth dependent refractive index profiles, each sample film has been modeled as an appropriate multilayer structure where each sub-layer was treated with the above TL parameterizations. All codeposited films demonstrated superiority with respect to the band gap and morphological measurements. At lower silica mixing compositions such as in 10-20% level, the composite films depicted superior spectral refractive index profile, band gap as well as the morphology. This aspect highlighted the fact that microstructural densifications in composite films can override the chemical compositions while deciding the refractive index and optical properties in such thin films.     

Novel catalysts: Indium implanted SiO2 thin films

Interactions of Indium (In) and silicon (Si) atoms are known to catalyze certain organic chemical reactions with high efficiency. In an attempt of creating a material that manifests the interactions, In implanted SiO₂ thin films were prepared by ion beam injection and their catalytic abilities for organic chemical reactions were examined. It has been found that, with an injection energy of approximately 0.5 keV, a thin In film is formed on a SiO₂ substrate surface and the In implanted SiO₂ thin film can catalyze an organic chemical reaction. It has been also shown that there is an optimal ion dose for the highest catalytic ability in the film preparation process. Thin-film-type catalyzing materials such as the one proposed here may open a new way to enhance surface chemical reaction rates.     

Study on high-temperature spectra of asymptotic asymmetric-top radical SiO2

Total internal partition sums are calculated in the product approximation at temperatures up to 6000 K for the asymptotic asymmetric-top SiO2 molecule.The rotational partition function and the vibrational partition function are calculated with the rigid-top model and in the harmonic oscillator approximation,respectively.Our values of the total internal partition sums are consistent with the calculated value in the Gaussian program within 0.137% at 296 K.Using the calculated partition functions and the rotationless transition dipole moment squared as a constant,we calculate the line intensities of 001-000 band of SiO2 at normal,medium and high temperatures.Simulated spectra of the 001-000 band of the asymptotic asymmetric-top SiO2 molecule at 2000,5000 and 6000 K are also obtained.     

High and low thermal nitridation of SiO2 thin films

Thin thermal SiO₂ films on crystalline silicon substrate were nitrided at low ammonia pressures (10^-6P_NH310^-1 mbar) for times varying from 1 to 10 h, by means of two techniques. (i) Surface nitridation has been achieved by thermal activation at high temperature (HT), in the range 800–1100°C. (ii) A new process at low temperature (LT), was employed at T ≈ 30°C, under electron-beam irradiation; the nitridation-reaction rate depends on the electron energy (reaching a maximum within the energy range 1 to 2 keV), and on the electron flux. Conduction and electron trapping on the nitrided oxide films depends on the chemical compositions and on the amount of nitrogen incorporated into the bulk of the films and/or at the SiO₂-Si interface.     

Analysis of material modifications induced during laser damage in SiO2 thin films

The damage mechanisms in silica thin films exposed to high fluence 1064 nm nano-second laser pulses are investigated. The thin films under study are made with different techniques (evaporation and sputtering, with and without ion assistance) and the results are compared. The material morphological, optical and structural modifications are locally analyzed with optical microscopy and profilometry, photoluminescence and absorption microscopies. These observations are made for fluences near and above the laser damage threshold, and also in the case of multiple pulse irradiations. An increase in absorption in and around the damages is observed, as well as the generation of different defects that we spatially resolve with absorption and luminescence mappings.     

Esca investigations of some NiO/SiO2 and NiO—Al2 O3 /SiO2 catalysts

The ESCA spectra of a series of NiO/SiO₂ and NiO—Al₂ O₃/SiO₂ catalysts are reported, together with those of some reference compounds. The positions and shapes of the lines, in conjunction with a quantitative surface analysis from relative intensities, allow the identification of different surface phases, e.g. an NiO-like phase in the impregnated catalysts with very low catalytic activity and an Ni talc-like phase in the precipitated catalysts which have higher activity. The addition of Al₂O₃ has a great influence on the surface structure (formation of alumosilicate).     

渐变折射率Ta2O5/SiO2薄膜多脉冲激光损伤特性

采用离子束溅射（IBS）的方式,制备了1064 nm高反射Ta2O5/SiO2渐变折射率光学薄膜。对其光学性能和在基频多脉冲下抗损伤性能进行了分析。 通过渐变折射率的设计方式,很好地抑制了边带波纹,增加了1064 nm反射率。通过对损伤阈值的分析发现,随着脉冲个数的增加,损伤阈值下降明显;但是在20个脉冲数后,损伤阈值（维持在22 J/cm2左右）几乎保持不变直到100个脉冲数。通过Leica显微镜对损伤形貌的观察,发现损伤诱因是薄膜表面的节瘤缺陷。通过扫描电镜（SEM）以及聚集离子束（FIB）对薄膜表面以及断面的观察,证实了薄膜的损伤起源于薄膜表面的节瘤缺陷。进一步研究得出,渐变折射率薄膜在基频光单脉冲下损伤主要是由初始节瘤缺陷引起的,在后续多脉冲激光辐照下初始节瘤缺陷引起烧蚀坑的面积扩大扫过薄膜上的其他节瘤缺陷,引起了其他节瘤缺陷的喷射使损伤加剧,造成损伤的累积效应。     

Spectroscopic and electrical properties of ultrathin SiO2 layers formed with nitric acid

Spectroscopic and electrical properties of ultrathin silicon dioxide (SiO₂) layers formed with nitric acid have been investigated. The leakage current density of the as-grown SiO₂ layers of 1.3 nm thickness is high. The leakage current density is greatly decreased by post-oxidation annealing (POA) treatment at 900 °C in nitrogen, and consequently it becomes lower than those for thermally grown SiO₂ layers with the same thickness. X-ray photoelectron spectroscopy measurements show that high density suboxide species are present before POA and they are markedly decreased by POA. Fourier transformed infrared absorption measurements show that water and silanol group are present in the SiO₂ layers before POA but they are removed almost completely by POA above 800 °C. The atomic density of the as-grown chemical SiO₂ layers is 4% lower than that of bulk SiO₂ layers, while it becomes 12% higher after POA. It is concluded that the high atomic density results from the desorption of water and OH species, and oxidation of the suboxide species, both resulting in the formation of SiO₂. The valence band discontinuity energy at the Si/SiO₂ interface increases from 4.1 to 4.6 eV by POA at 900 °C. The high atomic density enlarges the SiO₂ band-gap energy, resulting in the increase in the band discontinuity energy. The decrease in the leakage current density by POA is attributed to (i) a reduction in the tunneling probability of charge carriers through SiO₂ by the enlargement of the band discontinuity energy, (ii) elimination of trap states in SiO₂, and (iii) elimination of interface states.     

渐变折射率Ta_2O_5/SiO_2薄膜多脉冲激光损伤特性

采用离子束溅射(IBS)的方式,制备了1064nm高反射Ta2O5/SiO2渐变折射率光学薄膜。对其光学性能和在基频多脉冲下抗损伤性能进行了分析。通过渐变折射率的设计方式,很好地抑制了边带波纹,增加了1064nm反射率。通过对损伤阈值的分析发现,随着脉冲个数的增加,损伤阈值下降明显;但是在20个脉冲数后,损伤阈值(维持在22J/cm2左右)几乎保持不变直到100个脉冲数。通过Leica显微镜对损伤形貌的观察,发现损伤诱因是薄膜表面的节瘤缺陷。通过扫描电镜(SEM)以及聚集离子束(FIB)对薄膜表面以及断面的观察,证实了薄膜的损伤起源于薄膜表面的节瘤缺陷。进一步研究得出,渐变折射率薄膜在基频光单脉冲下损伤主要是由初始节瘤缺陷引起的,在后续多脉冲激光辐照下初始节瘤缺陷引起烧蚀坑的面积扩大扫过薄膜上的其他节瘤缺陷,引起了其他节瘤缺陷的喷射使损伤加剧,造成损伤的"累积效应"。