Thermal cycles, interface chemistry and optical performance of Mg/SiC multilayers

The interplay between optical performance and the thermally activated interface chemistry of periodic Mg/SiC multilayers designed for application at 30.4 nm are investigated by optical (hard X-ray, soft X-ray and ultraviolet ranges, i.e. from 0.154 to 30.4 nm) reflectivity and X-ray emission spectroscopy. The multilayers are prepared by magnetron sputtering and then annealed up to a temperature of 500 °C. Two clear changes take place in the multilayer upon annealing. At first, between 200 and 300 °C a strong decrease of the reflectivity is observed, due to the development of interfacial roughness following the crystallization of the Mg layers. No interfacial compound is detected. Then, between 350 and 400 °C there is formation of the Mg₂Si magnesium silicide at the interfaces following the reaction between the Mg and SiC layers. This also leads to the almost total loss of reflectivity of the multilayer. Thus, this kind of multilayer is thermally stable only for application requiring no heating above 200 °C.     

Introduction of Zr in nanometric periodic Mg/Co multilayers

We study the introduction of a third material, namely Zr, within a nanometric periodic Mg/Co structure designed to work as optical component in the extreme UV (EUV) spectral range. Mg/Co, Mg/Zr/Co, Mg/Co/Zr and Mg/Zr/Co/Zr multilayers are designed, and then characterized in terms of structural quality and optical performances through X-ray and EUV reflectometry measurements, respectively. For the Mg/Co/Zr structure, the reflectance value is equal to 50% at 25.1?nm and 45° of grazing incidence and reaches 51.3% upon annealing at 200°C. Measured EUV reflectivity values of tri-layered systems are discussed in terms of material order within a period and compared to the predictions of the theoretical model of Larruquert. Possible applications are pointed out.     

Development of Al-based multilayer optics for EUV

We report on the development of multilayer optics for the extreme ultra-violet (EUV) range. The optical performance of Al-based multilayer mirrors is discussed with regard to promising reflectivity and selectivity characteristics and the problems of the interfacial roughness for this type of multilayers. We demonstrate a possibility to reduce the average roughness by introducing additional metal layer (W or Mo) rather than depositing a buffer layer at each interface. We have prepared and tested Al/SiC, Al/W/SiC and Al/Mo/SiC multilayers of various periods for the spectral range from 15 to 40 nm, which is the range of increasing interest for high-order harmonic generation, synchrotron radiation and astrophysics. The structure of the three-component systems has been optimized in order to obtain the best reflectivity for each wavelength within the spectral range. We have shown that introduction of refractory metal in Al-based periodic stack can improve the optical performance of multilayer reflecting coatings designed for the EUV applications.     

Co/C and W/Si multilayers deposited by ion-beam sputtering for the soft X-ray range

We deposited Co/C multilayer mirrors for a wavelength of 4.77 nm and W/Si multilayer mirrors for a wavelength of 1.77 nm by use of ion-beam sputtering. The small-angle diffraction spectrum was used to analyze the structure of the multilayers. With a combination of the experimental diffraction spectra and Apeles’ theory for calculation of the interfacial roughnesses of the multilayers, the interfacial roughnesses of Co/C and W/Si are 0.80 nm and 0.60 nm, respectively, which are lower than that of the substrate. The reflectivity of the Co/C multilayer is measured to be about 20% and that of the W/Si multilayer about 1% at the grazing incidence angle of about 12°. Received: 30 May 2000 / Accepted: 1 August 2000 / Published online: 11 February 2002     

The effects of Si3N4 interlayer on the thermal stability and hardness of Ti/TiNx (x = 0.5-1) nanolayered coatings

The polycrystalline Ti/TiN_x multilayer films were deposited by magnetron sputtering, and the as-deposited multilayer coatings were annealed at 500-800 °C for 2-4 h in vacuum. We investigated the effects of annealing temperature and annealing time on the microstructural, interfacial, and mechanical properties of the polycrystalline Ti/TiN_x multilayer films. It was found that the hardness increased with annealing temperature. This hardness enhancement was probably caused by the preferred crystalline orientation TiN(1 1 1). The X-ray reflectivity measurements showed that the layer structure of the coatings could be maintained after annealing at 500 °C and the addition of the Si₃N₄ interlayer to Ti/TiN_x multilayer could improve the thermal stability to 800 °C.     

在19.5 nm处高反在30.4 nm处抑制的双功能薄膜

 研究了极紫外波段的双功能光学元件。采用周期膜叠加的思想,运用遗传方法优化设计了在19.5 nm处高反,在30.4 nm处抑制的双功能多层膜。采用磁控溅射技术制备了多层膜,利用X射线衍射仪测试了多层膜的结构,在国家同步辐射实验室测试了双功能多层膜的反射特性。结果表明：制备出的双功能膜性能与设计相符,在入射角13°,19.5 nm处的反射率达到33.3%,接近传统的19.5 nm周期高反膜的反射率,并且在30.4 nm附近将反射率由1.1%降到9.6×10^-4。     

Structural stability of heat-treated Co/C soft X-ray multilayers fabricated by dual-facing-target sputtering

Thermal stability of Co/C multilayers prepared by a dual-facing-target sputtering system was studied. A picture of the thermally induced changes in the microstructure was obtained using complementary measurement techniques including low-angle and high-angle X-ray diffraction, transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. It was found that the period expansion, reflectivity change and compound formation, that were observed after annealing are caused by structural changes both in the sublayers and at the interfaces. Below 400°C, the period expansion is mainly caused by the graphitization of the amorphous carbon layers, and a significant increase in the reflectivity at grazing incidence was observed. By 500°C, the crystallization and agglomeration of Co layers induce an enormous period expansion and a serious decrease in reflectivity. A small amount of carbide is found to form at this temperature. Our results imply that new multilayer structures, e.g., compound multilayers will have to be developed for use at high temperatures or under high X-ray incident flux.     

Effect of annealing temperature on K-shell X-ray fluorescence parameters of zinc oxide thin films prepared by the sol-gel method

Zinc oxide thin films were grown on a glass substrate by a sol-gel process using a spin-coating technique. The obtained thin films were annealed between 350?°C and 550?°C in 50?°C steps and were then characterized using X-ray diffraction, scanning electron microscopy, and X-ray fluorescence techniques. The samples were stimulated by 59.5?keV gamma rays emitted from an Americium-241 annular radioisotope source. K X-rays emitted by samples were counted using an ultra-low energy germanium detector with a resolution of 150?eV at 5.96?keV. It was found that there was generally a decrease in both the Kβ/Kα X-ray intensity ratios and the K X-ray fluorescence cross sections for zinc oxide between 350?°C and 500?°C, but not at 550?°C. In addition, the X-ray diffraction patterns of the films showed that the transition phase from an amorphous to a polycrystalline hexagonal wurtzite structure was complete at an annealing temperature of 500?°C. The results show that variations in these parameters can be explained by the reorganization of atoms and the charge transfer process due to the effect of the annealing temperature on the elements forming the compounds.     

A redox reaction model for self-heating and aging prediction of Al/CuO multilayers

Sputter-deposited Al/CuO multilayers capable of highly energetic reactions have been the subject of intense studies for tunable initiation and actuation. Designing high performance Al/CuO-based initiator devices definitively requires reliable prediction of their ignition and reaction kinetics including self-heating or ageing as a function of heating rate and environmental conditions. The paper proposes a heterogeneous reaction model integrating an ensemble of basic mechanisms (oxygen diffusion, structural transformations, polymorphic phase changes) that have been collected from recent experimental investigations. The reaction model assumes that the rate of reaction is limited by the transport of oxygen across the growing layer of Al₂O₃ separating Al and CuO. Importantly, we show that the model predicts reasonably all exotherms through a wide range of temperature (ambient – 1000°C), all resulting from a pure diffusion process as experimentally observed for such Al/CuO multilayers. The model shows how the temperature ramp affects the structure of the multilayer and especially the growth of alumina-based interfacial regions. It highlights the importance of the interfacial chemistry evolution such as the native mixture of Al_xCu_yO_z transformation into a thin amorphous alumina, and the polymorphic phase transformation of this latter. The first one occurring at ～350°C results in a loss of continuity of the interface leading to the accelerated redox reaction whereas the second one occurring between 500 and 600°C produces a denser barrier to oxygen diffusion leading to the stop of redox reaction. We finally use the model to simulate thermal annealing as usually performed in accelerated ageing experiments. We theoretically observe and experimentally validate that a two weeks exposure of the multilayers at 200°C starts degrading the multilayers thermal properties whereas when the temperature remains below 200°C, the material keeps its entire integrity.     

Effect of B4C diffusion barriers on the thermal stability of Sc/Si periodic multilayers

The optical properties of Sc/Si periodic multilayers are analyzed at three wavelengths in the X-ray range: 0.154, 0.712 and 12.7 nm. Fitting the reflectivity curves obtained at these three wavelengths enable us to constrain the parameters, thickness, density and roughness of the various layers, of the studied multilayers. Scattering curves were also measured at 12.7 nm on some samples to obtain an estimate of the correlation length of the roughness. Two sets of multilayers are used, with and without B₄C diffusion barrier at the interfaces. To see the efficiency of the B₄C layers the measures are performed after annealing up to 400 °C. A dramatic change of the structure of the Sc/Si multilayer is observed between 100 and 200 °C leading to a strong loss of reflectivity. For the Sc/B₄C/Si/B₄C multilayer the structure is stable up to 200 °C after which a progressive evolution of the stack occurs.     

高反射率Mo/B4C多层膜设计及制备

 运用遗传算法优化设计了Mo/B₄C多层膜结构。入射光入射角度取10°时,设计的理想多层膜膜对数为150,周期为3.59 nm,Gamma值（Mo膜厚与周期的比值）为0.41,峰值反射率为33.29%。采用恒功率模式直流磁控溅射方法制作Mo/B₄C多层膜。通过在Mo/B4C多层膜与基底之间增加15 nm厚的Cr粘附层,提高多层膜与基底的粘附力。另外,还采用调整多层膜Gamma值的方法减小其内应力,调整后多层膜结构周期为3.59 nm, Mo膜厚1.97 nm, B4C膜厚1.62 nm,峰值反射率26.34％。制备了膜对数为150的Mo/B₄C膜并测量了其反射率,在波长7.03 nm处,Mo/B₄C多层膜的近正入射反射率为21.0％。最后对测量结果进行了拟合,拟合得到Mo/B₄C多层膜的周期为3.60 nm,Gamma值0.60,界面粗糙度为0.30 nm。     

月基极紫外相机多层膜反射镜

月基极紫外相机用于月球表面对地球等离子体层辐射出的30.4 nm谱线进行成像观测,多层膜反射镜是月基极紫外相机的重要光学元件。根据月基极紫外相机技术参数,选择了B₄C/Mg,B₄C/Mg₂Si,B₄C/Al,B₄C/Si,Mo/Si等材料,对其周期厚度、材料比例、周期数等参数进行优化。计算了以上材料组合在30.4 nm的反射率曲线。考虑到月球环境的特殊性和材料的物理化学性质,从中选择出Mo/Si和B₄C/Si两种组合,利用磁控溅射进行镀制。Mo/Si和B₄C/Si多层膜在30.4 nm反射率分别达到15.3%和22.8%。     

X-ray properties and interface study of B4C/Mo and B4C/Mo2C periodic multilayers

We present a comparative study of B₄C/Mo and B₄C/Mo₂C periodic multilayer structures deposited by magnetron sputtering. The characterization was performed by grazing incidence X-ray reflectometry at two different energies and high resolution transmission electron microscopy. The experimental results indicate the existence of an interdiffusion layer at the B₄C-on-Mo interface in the B₄C/Mo system. Thus, the B₄C/Mo multilayers were modeled by an asymmetric structure with three layers in each period. The thickness of B₄C-on-Mo interfacial layer was estimated about 1.1 nm. The B₄C/Mo₂C multilayers present less interdiffusion and are well modeled by a symmetric structure without interfacial layers. This study shows that B₄C/Mo₂C structure is an interesting alternative to B₄C/Mo multilayer for X-ray optic applications.     

Structural evolution of ZrO2–mullite nanocomposites from the Si–Al–Zr–O amorphous bulk

ZrO₂–mullite nanocomposites were fabricated by in-situ-controlled crystallization of Si–Al–Zr–O amorphous bulk at 800–1250°C. The structural evolution of the Si–Al–Zr–O amorphous, annealed at different temperatures, was studied by X-ray diffraction, infrared, Laser Raman spectroscopy, field emission scanning electron microscopy, and high-resolution transmission electron microscopy. The materials consisted of an amorphous phase up to 920°C at which phase separation of Si-rich and Al, Zr-rich clusters occurred. The crystalline phases of t-ZrO₂ and mullite were observed at 950°C and 1000°C, respectively. Mullite with a tetragonal structure, formed by the reaction between Al–Si spinel and amorphous silica at low temperature, changed into an orthorhombic structure with the increase of temperature. It was the phase segregation that improved crystallization of the Si–Al–Zr–O amorphous bulk. The anisotropic growth of mullite was observed and the phase transformation from t-ZrO₂ to m-ZrO₂ occurred when the temperature was higher than 1100°C.     

基于遗传算法的30.4 nm多层膜设计

阐述了用遗传算法设计周期和非周期多层膜的原理和实现过程,完成了30.4 nm Mg/SiC周期和非周期多层膜设计,研究了遗传算法中不同种群数和多层膜膜厚取值范围对优化结果的影响.计算发现,种群数的恰当选取是使算法快速达到或逼近最优解的前提,膜厚取值范围的合理选择是提高算法效率的关键.设计得到入射角10°的周期多层膜和15°~22°范围内的宽角多层膜在波长30.4 nm处的反射率依次为56.57%与39.96±0.29%,5°入射的双功能多层膜在波长30.4 nm和58.4 nm处的反射率分别为54.1%和0.1%.结果表明遗传算法也是一种很好的多层膜设计方法.     

Nanostructuring with laser radiation in the nearfield of a tip from a scanning force microscope

Platinum-carbon multilayer mirrors with a bilayer spacing of 50 Å were fabricated in an ultrahigh vacuum electron beam evaporator. The thermal stability of these multilayers was studied under vacuum annealing using X-ray reflectivity and X-ray diffraction. Up to 450°C, the bilayer spacing increases monotonically accompanied by a gradual increase in crystallite size and grain texture. At 500°C multilayer reflection vanishes, platinum crystallites grow abruptly, and there is a strong texture of platinum in the [220] -plane. Possible reasons for thermally induced structural modifications in these multilayers are discussed.     

In-situ and ex-situ study of crystallization behaviour of magnetron sputtered Ni63Zr37 amorphous thin film

ABSTRACT

The stages of crystallization of magnetron sputter-deposited Ni₆₃Zr₃₇ film with mostly amorphous structure have been investigated by differential scanning calorimetry (DSC) and in-situ annealing at 300°C by use of heating stage on a high-resolution transmission electron microscope (HRTEM). These results have been further confirmed by grazing incidence X-ray diffraction analyses of thin film specimens annealed ex-situ at 300°C for various durations. The temperature for crystallization found by DSC has been found to increase from 371°C to 434°C with an increase in heating rate from 3°C/min to 10°C/min, and the apparent activation energy for amorphous to crystalline transformation has been found as ～260.2?kJ/mol from the Kissinger plot. Studies on HRTEM using in-situ heating stage have shown the crystallization to occur on annealing at 300°C for ～10?min. Crystallization at a temperature lower than that found by DSC is attributed to structural relaxation with reduction of free volume due to thermal activation. It has been observed that Ni₃Zr forms first due to its large negative enthalpy of formation, and is followed by the formation of Ni-rich solid solution (Ni_ss) grains. HRTEM studies have shown grain rotation with the formation of partial dislocations at Ni₃Zr-Ni_ss interfaces as well as twinning followed by detwinning with dislocation formation in the Ni_ss matrix possibly to reduce the interfacial energy.     

入射光单色性与界面粗糙度对多层膜反射性能的不同影响

多层膜界面粗糙度、入射光单色性对软X射线多层膜实际反射率均有影响。利用数学卷积积分,理论上推导出一个在入射光不同单色性下精确计算多层膜反射率的公式。利用给出的理论计算公式,简要分析了入射光不同单色性、不同界面粗糙度对Mo/Si多层膜反射率的影响。理论分析发现这两种因素对Mo/Si多层膜反射率影响完全不同:入射光低的单色性不但极大降低Mo/Si多层膜峰值反射率,而且使反射曲线的半峰全宽增加;而界面粗糙度是降低Mo/Si多层膜反射曲线上各点对应值,基本不改变Mo/Si反射曲线的半峰全宽,不改变反射曲线的形状。说明这两个因素在软X射线的长波段对多层膜反射性能的影响不同。     

提高极紫外光谱纯度的多层膜设计及制备

极紫外光刻是实现22nm技术节点的候选技术。极紫外光刻使用的是波长为13.5nm的极紫外光,但在160～240nm波段,极紫外光刻中的激光等离子体光源光谱强度、光刻胶敏感度以及多层膜的反射率均比较高,光刻胶在此波段的曝光会降低光刻系统的光刻质量。从理论和实验两方面验证了在传统Mo/Si多层膜上镀制SiC单层膜可对极紫外光刻中的带外波段进行有效抑制。通过使用X射线衍射仪、椭偏仪以及真空紫外(VUV)分光光度计来确定薄膜厚度、薄膜的光学常数以及多层膜的反射率,设计并制备了[Mo/Si]40SiC多层膜。结果表明,在极紫外波段的反射率减少5%的前提下,带外波段的反射率减少到原来的1/5。     

Iridium/silicon multilayers for extreme ultraviolet applications in the 20-35 nm wavelength range

We have developed an Ir/Si multilayer for extreme ultraviolet (EUV) applications. Normal incidence reflectance measurements of a prototype film tuned to 30 nm wavelength show superior performance relative to a conventional Mo/Si multilayer structure; we also find good stability over time. Transmission electron microscopy and electron dispersive x-ray spectroscopy have been used to examine the microstructure and interface properties of this system: we find amorphous Si layers and polycrystalline Ir layers, with asymmetric interlayer regions of mixed composition. Potential applications of Ir/Si multilayers include instrumentation for solar physics and laboratory EUV beam manipulation.