Axel Engel

Optimized glass-ceramic substrate materials for EUVL applications

EUV substrate materials have to meet enhanced requirements with respect to extreme low thermal expansion, high homogeneity and superior surface quality. A SCHOTT R&D program aims at the development of advanced materials covering these various aspects. The glass-ceramic Zerodur (registered trademark) of SCHOTT represents a substrate material currently used for EUV masks and optics of first generation tools due to its extremely low coefficient of thermal expansion (CTE) and its excellent homogeneity. Zerodur(registered trademark) even allows continuous shifting of the position of zero crossing of the CTE-slope to control the thermal expansion behavior according to varying customer requirements: As a result of specifically adjusted process parameters, samples of Zerodur (registered trademark) exhibit a coefficient of thermal expansion CTE < 5 ppb/K corresponding to the lowest expansion class of the SEMI standard P37 (19 to 25°C) for EUV mask blanks. By further variation of process parameters, the position of zero crossing, e.g. at 22.5°C or 30°C, can be varied, revealing an attractive attribute feature of Zerodur (registered trademark). A new dilatometer type reveals an improved reproducibility of ~ 1ppb/K in the temperature range of 0 to 50°C. A series of CTE(0;50°C) measurements with a test-cube of Zerodur (registered trademark) provides information on CTE homogeneity on a cm-scale: no CTE variation was observed within the error of measurements (1ppb/K) for a block exhibiting ± 3.5*10-6 variation in refractive index. CTE variation can cause surface deformations during changing temperature conditions. A Fizeau-Interferometer was used to record surface roughness at two different temperatures. This non- destructive metrology is regarded as a method to distinguish CTE variation < 1ppb/K. The surface deformation of Zerodur (registered trademark) due to elevated temperature was determined to be lower than the resolution. Both methods to analyze the CTE homogeneity of Zerodur (registered trademark) lead to the result of CTE variation below 1 ppb/K. Surface treatment of glass-ceramic material is a major challenge as final finishing of EUV substrates may increase roughness of super-polished surfaces significantly. Improved new glass-ceramic materials demonstrate optimization of glass-ceramic compositions to nearly meeting the specification of surface roughness after a standard finishing process. Recent achievements of material development reveal CTE-performance of this new glass-ceramic to also be adjustable to varying customer needs as already known for Zerodur (registered trademark). These results are regarded as a promising milestone to develop an optimized glass-ceramic material, because the features of the modified New-Glass Ceramic now better match the key requirements of EUVL substrate materials.

Improved materials meeting the demands for EUV substrates

The enhanced demands for substrate materials for next-generation optics and masks have initiated detailed investigations on Zerodur as a proposed EUVL substrate material with focus on thermal expansion behavior and surface roughness. As a result of specifically adjusted process parameters, the coefficient of thermal expansion (CTE) was tailored to be a minimum at 22.5°C. Laboratory samples of Zerodur exhibit a CTE < 5 ppb/K corresponding to the lowest expasnion class of the SEMI standard P37 (19 to 25°C) for EUV mask blanks. By further variation of process parameters, the position of zero crossing, e.g. at 30°C, can be varied, revealing an attractive attribute feature of Zerodur. A new dilatometer type was mounted in 2002 with first operatinoal results revealing an improved reproducibility of ~1ppb/K in the temperature range of 0 to 50°C. A series of CTE measurements with a small block of Zerodur provides information on CTE homogeneity on a cm-scale: No CTE variation was observed within the error of measurements for a block exhibiting ± 3.5*10-6 vairtion in refractinve index. CTE variation can cause surface deformations during changing temperature conditions. A first setup of Fizeau-Interferometer with a current resolution of 0.3 nm rms was used to record surface deformation of Zerodur due to elevated temperature was determined to be lower than the current resolution. Both methods to analyze the CTE homogeneity of Zerodur lead to the result of CTE variation below 1 ppb/K, still identifying todays need to improve metrology further. Final finishing of EUV substrates may increase roughness of super-polished surfaces significantly. Using appropriate processes a to surface roughness < 0.25 nm rms under production conditions can be achieved after final finishing of Zerodur. As an improved Zerodur-type material, recent achievements of material development demonstrate the optimization of glass-ceramic composition to nearly meeting the specification of surface roughness after a standard finishing process. These results are regarded as a promising milestone to develop an optimized glass-ceramic material providnig adjusted thermal expansion behavior and surface processability according to the specific demands of EUV technology.

Reference based optical characterization of glass-ceramic converter for high power white LEDs

Fluorescence techniques are known for their high sensitivity and are widely used as analytical tools and detection methods for product and process control, material sciences, environmental and bio-technical analysis, molecular genetics, cell biology, medical diagnostics and drug screening. According to DIN/ISO 17025 certified standards are used for fluorescence diagnostics having the drawback of giving relative values for fluorescence intensities only. Therefore reference materials for a quantitative characterization have to be related directly to the materials under investigation. In order to evaluate these figures it is necessary to calculate absolute numbers like absorption/excitation cross section and quantum yield. This can be done for different types of dopants in different materials like glass, glass ceramics, crystals or nano crystalline material embedded in polymer matrices. Here we consider a special type of glass ceramic with Ce doped YAG as the main crystalline phase. This material has been developed for the generation of white light realized by a blue 460 nm semiconductor transition using a yellow phosphor or converter material respectively. Our glass ceramic is a pure solid state solution for a yellow phosphor. For the production of such a kind of material a well controlled thermal treatment is employed to transfer the original glass into a glass ceramic with a specific crystalline phase. In our material Ce doped YAG crystallites of a size of several µm are embedded in a matrix of a residual glass. We present chemical, structural and spectroscopic properties of our material. Based on this we will discuss design options for white LEDs with respect to heat management, scattering regime, reflection losses, chemical durability and stability against blue and UV radiation, which evolve from our recently developed material. In this paper we present first results on our approaches to evaluate quantum yield and light output. Used diagnostics are fluorescence (steady state, decay time) and absorption (remission, absorption) spectroscopy working in different temperature regimes (10 - 350 K) of the measured samples in order to get a microscopic view of the relevant physical processes and to prove the correctness of the obtained data.

Glass based fluorescence reference materials used for optical and biophotonic applications

Fluorescence techniques are known for their high sensitivity and are widely used as analytical tools and detection methods for product and process control, material sciences, environmental and biotechnical analysis, molecular genetics, cell biology, medical diagnostics, and drug screening. For routine measurements by fluorescence techniques the existence of an improved quality assurance is one of the basic needs. According to DIN/ISO 17025 certified standards are used for fluorescence diagnostics having the drawback of giving relative values only. Typical requirements onto fluorescence reference materials or standards deal with the verification of the instrument performance as well as the improvement of the data comparability. Especially for biomedical applications fluorescence labels are used for the detection of proteins. In particular these labels consist of nano crystalline materials like CdS and CdSe. The field of Non-Cadmium containing materials is under investigation. In order to evaluate whether glass based materials can be used as standards it is necessary to calculate absolute values like absorption/excitation cross sections or relative quantum yields. This can be done using different quantities of dopands in glass, glass ceramics or crystals. The investigated materials are based on different types of glass, silicate, phosphate and boron glass, which play a dominant role for the absorption and emission mechanism. Additional to the so-called elementary fluorescence properties induced by raw earth elements the formation of defects lead to higher cross sections additionally. The main investigations deal with wavelength accuracy and lifetime of doped glasses, glass ceramics and crystalline samples. Moreover intensity patterns, homogeneity aspects and photo stability will be discussed.

CaF2 for DUV lens fabrication: basic material properties and dynamic light-matter interaction

Lens fabrication for the short wavelengths of the DUV spectral range requires the replacement of glasses, by the crystalline material CaF2. We review mechanism for the interaction of CaF2 with electromagnetic radiation, especially at wavelengths of 193 nm and 157 nm. In the ideal material an absorption process can occur only via a two photon process where charges are separated and an electron--hole pair is created in the material. These excited charges can localize as charge centers or as as localized excitonic state, a bound F--H+-pair. At room temperature all charge centers should recombine within a few pico seconds and no long time change of the optical material properties should be observable. In the real material not only charge center formation but also the stabilization of these charge centers at room temperature due to impurities is identified as a key for the understanding of a radiation induced change of optical material properties.

Fluorescence reference materials used for optical and biophotonic applications

Fluorescence techniques are known for their high sensitivity and are widely used as analytical tools and detection methods for product and process control, material sciences, environmental and bio-technical analysis, molecular genetics, cell biology, medical diagnostics, and drug screening. According to DIN/ISO 17025 certified standards are used for fluorescence diagnostics having the drawback of giving relative values for fluorescence intensities only. Therefore reference materials for a quantitative characterization have to be related directly to the materials under investigation. In order to evaluate these figures it is necessary to calculate absolute numbers like absorption/excitation cross sections and quantum yield. This can be done for different types of dopands in different materials like glass, glass ceramics, crystals or nano crystalline material embedded in polymer matrices. Based on the optical spectroscopy data we will discuss options for characteristic doped glasses and glass ceramics with respect to scattering and absorption regime. It has shown recently for YAG:Ce glass ceramics that for a proper determination of the quantum efficiency in these highly scattering media a reference material with similar scattering and fluorescent properties is required. This may be performed using the emission decay measurement diagnostics, where the decay time is below 100 ns. In this paper we present first results of these aspects using well performing LUMOGEN RED organic pigments for a comparison of mainly transparent glass with glass ceramics doped with various amounts of dopands e.g. ions of raw earth elements and transition metals. The LUMOGEN red is embedded in silica and polyurethane matrices. Characterisations on wavelength accuracy and lifetime for different environmental conditions (temperature, UV irradiation) have been performed. Moreover intensity patterns and results for homogeneity, isotropy, photo and thermal stability will be discussed. In a next step we will show the transfer of the characterisation methods to inorganic fluophores (YAG:Ce) in silicon. Fluorescence (steady state, decay time) and absorption (remission, absorption) spectroscopy working in different temperature regimes (10 ? 350 K) are employed diagnostic methods in order to get a microscopic view of the relevant physical processes and to prove the correctness of the obtained data. The work is funded by BMBF under project number 13N8849.

Flouescence reference materials used for optical and biophotonic applications

Fluorescence techniques are known for their high sensitivity and are widely used as analytical tools and detection methods for product and process control, material sciences, environmental and bio-technical analysis, molecular genetics, cell biology, medical diagnostics, and drug screening. According to DIN/ISO 17025 certified standards are used for fluorescence diagnostics having the drawback of giving relative values for fluorescence intensities only. Therefore reference materials for a quantitative characterization have to be related directly to the materials under investigation. In order to evaluate these figures it is necessary to calculate absolute numbers like absorption/excitation cross sections and quantum yield. This can be done for different types of dopands in different materials like glass, glass ceramics, crystals or nano crystalline material embedded in polymer matrices. Based on the optical spectroscopy data we will discuss options for characteristic doped glasses and glass ceramics with respect to scattering and absorption regime. It has shown recently for YAG:Ce glass ceramics that for a proper determination of the quantum efficiency in these highly scattering media a reference material with similar scattering and fluorescent properties is required. This may be performed using the emission decay measurement diagnostics, where the decay time is below 100 ns. In this paper we present first results of these aspects using well performing LUMOGEN RED organic pigments for a comparison of mainly transparent glass with glass ceramics doped with various amounts of dopands e.g. ions of raw earth elements and transition metals. The LUMOGEN red is embedded in silica and polyurethane matrices. Characterisations on wavelength accuracy and lifetime for different environmental conditions (temperature, UV irradiation) have been performed. Moreover intensity patterns and results for homogeneity, isotropy, photo and thermal stability will be discussed. In a next step we will show the transfer of the characterisation methods to inorganic fluophores (YAG:Ce) in silicon. Fluorescence (steady state, decay time) and absorption (remission, absorption) spectroscopy working in different temperature regimes (10 − 350 K) are employed diagnostic methods in order to get a microscopic view of the relevant physical processes and to prove the correctness of the obtained data. The work is funded by BMBF under project number 13N8849.

Advanced industrial fluorescence metrology used for qualification of high quality optical materials

Schott Glas is developing and producing the optical material for various specialized applications in telecommunication, biomedical, optical, and micro lithography technology. The requirements on quality for optical materials are extremely high and still increasing. For example in micro lithography applications the impurities of the material are specified to be in the low ppb range. Usually the impurities in the lower ppb range are determined using analytical methods like LA ICP-MS and Neutron Activation Analysis. On the other hand absorption and laser resistivity of optical material is qualified with optical methods like precision spectral photometers and in-situ transmission measurements having UV lasers. Analytical methods have the drawback that they are time consuming and rather expensive, whereas the sensitivity for the absorption method will not be sufficient to characterize the future needs (coefficient much below 10-3 cm-1). In order to achieve the current and future quality requirements a Jobin Yvon FLUOROLOG 3.22 fluorescence spectrometer is employed to enable fast and precise qualification and analysis. The main advantage of this setup is the combination of highest sensitivity (more than one order of magnitude higher sensitivity that state of the art UV absorption spectroscopy) and fast measurement and evaluation cycles (several minutes compared to several hours necessary for chemical analytics). An overview is given for spectral characteristics and using specified standards. Moreover correlations to the material qualities are shown. In particular we have investigated the elementary fluorescence and absorption of rare earth element impurities as well as defects induced luminescence originated by impurities.

The Toolbox of Fluorescence Standards: Flexible Calibration Tools for the Standardization of Fluorescence-based Measurements

To improve the reliability of fluorescence data in the life and material sciences and to enable accreditation of fluorescence techniques, standardization concepts are required that guarantee and improve the comparability of fluorescence measurements. At the core of such concepts are simple and evaluated fluorescence standards for the consideration of instrument-specific spectral and intensity distortions of measured signals and for instrument performance validation (IPV). Similarly in need are fluorescence intensity standards for the quantification from measured intensities and for signal referencing, thereby accounting for excitation light-induced intensity fluctuations. These standards should be preferably certified, especially for use in regulated areas like medical diagnostics. This encouraged us to develop liquid and solid standards for different fluorescence parameters and techniques for use under routine measurement conditions in different formates. Special emphasis was dedicated to the determination and control of the spectral responsivity of detection systems, wavelength accuracy, homogeneity of illumination, and intensity referencing for e.g. spectrofluorometers, fluorescence sensors and confocal laser scanning fluorescence microscopes. Here, we will present design concepts and examples for mono- and multifunctional fluorescence standards that provide traceability to radiometric units and present a first step towards a toolbox of standards.

Anorganic fluorescence reference materials for decay time of fluorescence emission

Fluorescence techniques are known for their high sensitivity and are widely used as analytical tools, detection methods and imaging applications for product and process control, material sciences, environmental and bio-technical analysis, molecular genetics, cell biology, medical diagnostics, and drug screening. According to DIN/ISO 17025 certified standards are used for steady state fluorescence diagnostics, a method having the drawback of giving relative values for fluorescence intensities only. Therefore reference materials for a quantitative characterization have to be related directly to the materials under investigation. In order to evaluate these figures it is necessary to calculate absolute numbers such as absorption/excitation cross sections and quantum yield. This has been done for different types of dopands in different materials such as glass, glass ceramics, crystals or nano crystalline material embedded in polymer matrices. Samples doped with several fluophores of different emission wavelengths and decay times are required for fluorescent multiplexing applications. Decay times shorter than 100 ns are of special interest. In addition, a proper knowledge is necessary of quantum efficiency in highly scattering media. Recently, quantum efficiency in YAG:Ce glass ceramics has been successfully investigated. Glass and glass ceramics doped with threefold charged rare earth elements are available. However, these samples have the disadvantage of emission decay times much longer than 1 microsecond, due to the excitation and emission of their optical forbidden electronic transitions. Therefore first attempts have been made to produce decay-time standards based on organic and inorganic fluophores. Stable LUMOGEN RED pigments and YAG:Ce phosphors are diluted simultaneously in silicone matrices using a wide range of concentrations between 0.0001 and 2 wt%. Organic LUMOGEN RED has decay times in the lower nanosecond range with a slight dependency on concentration and temperature. In addition, the well-known decay properties of inorganic YAG:Ce are observed also embedded in silicone matrix. Luminescent silicone layers are obtained with thicknesses between 150 and 300 µm and no change of decay time, which has been determined to be between 60 and 62 ns. Finally, first results are shown for fluorescent CaF2:Pb glass ceramics embedded in a silicate glass matrix. Wavelength accuracy and lifetime are characterized for different environmental conditions such as temperature treatment and UV irradiation. Moreover, intensity patterns, e.g. line profiles and results, are discussed on homogeneity and photo and thermal stability, respectively. Fluorescence (steady state, decay time) and absorption (remission, absorption) spectroscopy are employed as diagnostic methods to get a microscopic view of the relevant physical processes. The work is funded by BMBF under project number 13N8849.