Short- and ultra-short-period multilayer (ML) structures play a crucial role in wavelength dispersive x-ray fluorescence (WD-XRF). In WD-XRF a ML serves as an analyzer crystal to disperse emission lines of light elements in the O-Kα – Al-Kα range (λ=2.36 – 0.834nm). For these reasons, MLs with periods ranging from 1.0 to 2.5nm are very interesting. Due to the short period, the reflectance of such MLs is extremely sensitive to interface imperfections.
Our research focuses on synthesis and characterization of MLs with d-spacing between 2.5 nm and 1.0 nm, combining tungsten (W) absorber with B4C, Si and Al spacers. These combinations show high theoretical reflectance in the full range from C-Kα (4.48nm) all the way down to S-Kα (0.54nm).
By optimizing the ion polishing process: ion species, energy, and polishing frequency, we show that a major improvement in reflectivity can be achieved: with the most optimal ion polishing process, a factor 2x in reflectivity was achieved for 1.0 and 1.1nm MLs, with a record reflectivity of almost 10% at lambda=0.84nm for 1.1nm W/Si.
Nanometer-thin multilayers are crucial in various optical applications, from lithography to x-ray instruments. The interface sharpness between layers determines reflectivity losses. Metrology is vital for understanding the interface forming mechanisms at an atomic level. Single techniques like TEM and XRR provide atomic or electronic density resolution, while XPS data about the compound formation. We extended our metrology portfolio with two in-house customized techniques: XSW and LEIS. The XSW technique is used for the analysis of thin film atomic profiles. The specific analysis of the background in LEIS spectra was used to analyze the interface with sub-nm resolution. A hybrid metrology approach combining these techniques is essential for efficient multilayer characterization. The metrology-driven multilayer growth optimization will be illustrated as an example of W/Si multilayers. By analyzing x-ray reflectivity and XSW data with a single model, we revealed the formation of WSix at W/Si interfaces, leading to poor performance. The introduction of 0.1 nm B4C diffusion barriers improved reflectivity, showing their direct contribution to enhanced performance.
For future photolithography processes, the wavelength of 6 nm may offer improved imaging specs. The perspective of this technology however, will depend critically on the performance of multilayer reflective mirrors, which are likely to be based on La/B. One of the issues is formation of LaxBy compounds at the interfaces, which decreases the optical contrast and reduce the reflectivity. To prevent such chemical interaction, passivation of La by nitrogen has been investigated. We successfully synthesized LaN layers that resulted in a new world record reflectivity of 64% at 6.6 nm at near normal incidence. This reduces the gap to the target of 70%, desired for a next generation lithography.
The thermal stability of La/B and LaN/B multilayers was investigated. The two multilayer systems were found to have comparable subångström period expansion upon annealing in the temperature range of 250°C to 400°C. For La/B multilayers, wide angle x-ray diffraction analysis revealed that the size of LaB 6 crystallites present did not change significantly upon thermal treatment. Using grazing incidence x-ray reflectometry, strong change in the internal structure due to interdiffusion at the interfaces of La/B multilayers was observed after annealing. This, coupled to the unchanged crystallinity, suggested the growth of amorphous lanthanum boride interlayers. At wavelength reflectance, measurements showed that as-deposited LaN/B multilayers had an enhanced optical contrast compared with La/B. During thermal loading, the rate of diffusion-induced reflectance decrease in LaN/B multilayers was slower than in La/B. The enhanced thermal stability of LaN/B was attributed to the slower growth of LaN-B interfaces compared with La-B.
We developed and fabricated a single layer antireflection coating for the molybdenum/silicon multilayer mirrors.The 20 nm thin film of Si0.52C0.16N0.29, deposited by simultaneous electron beam evaporation and nitrogen ion implantation, causes a broadband suppression of the DUV reflectance with a maximum suppression at λ= 285 nm from 58% to 0.3%, corresponding to a factor of 195.
The internal structure of Mo/Si multilayers is investigated during and after thermal annealing. Multilayer period
compaction is shown to result from diffusion induced MoSi2 interlayer growth, reducing optical contrast and changing
the reflected wavelength. We focus on early-stage interface growth observed at relatively low temperatures (100 °C - 300
°C), determining diffusion constants from parabolic interface growth laws. Diffusion constants obey Arrhenius-type
behavior, enabling temperature scaling laws. Using the methods developed, we compare results on Mo/Si based
multilayers designed for enhanced thermal stability and discuss their relevant diffusion behavior. Arrhenius-type
behavior can be observed in all multilayers studied here, and demonstrates reduction of diffusion rates over several
orders of magnitude. The method described here is of general interest for any multilayer application that is subjected to
enhanced thermal loads and demonstrates the enormous technology gain that this type of optics has experienced the last
decade.
We present a computational and experimental study on interface passivation of B4C/La multilayers for
photolithography at wavelengths beyond 13.5 nm. We successfully applied N-plasma treatment to form
interface-localized BN and LaN layers, preventing LaB6 and LaC2 interlayer formation and increasing the optical
contrast. Experiments suggest an improvement of absolute reflection by up to 20% for 200 period multilayers,
with a best-so-far result of 41.5 % at near-normal incidence of 6.7 nm.
We investigated the use of separation, or substrate recovery, layers (SRLs), to enable the reuse of optical substrates after the deposition of multilayer reflective coatings, in particular Mo/Si multilayers as used for EUV lithography. An organic material (polyimide), known from other work to reduce the roughness of the substrate, was applied to the optical substrate. It appeared to be possible to remove the multilayer coating, including the SRL, without any damage or roughening of the substrate surface. The SRL was spin-coated at 1500 to 6000 rpm on different substrate types (Si, quartz, Zerodur) with diameters up to 100 mm. For this range of parameters, the multilayer centroid wavelength value remained unchanged, and its reflectivity loss on applying the SRL was limited typically to 0.7%. The latter was shown to be caused by a minor increase of the SRL surface roughness in the high-spatial-frequency domain. The roughness, characterized with an atomic force microscope, remained constant at 0.2 nm during all stages of the substrate recovery process, independent of the initial substrate roughness.
A new deposition technique that builds on the thermal particle characteristics typical for e-beam deposition is described.
This technique applies magnetron sputtering in a special scheme where these characteristics of the e-beam deposition
method are achieved. The method was used for interface engineering of Mo/Si multilayers, with different barrier layer
materials being tested. Composition of the barrier layers formed was studied using XPS. Results are shown on the
general example of a Mo/B4C/Si/B4C system. The ultra-thin reflectance enhancement B4C barriers can be deposited with
low added stress, resulting in a multilayer stress as low as about -150 MPa. The best interface engineered multilayers
reflect 70.5% at 13.3 nm and 70.15% at 13.5 nm. These results were achieved with 50 period multilayers terminated with
a standard Si layer.
We have investigated the use of separation, or substrate recovery layers (SRL) enabling the re-usage of optics
substrates after deposition of multilayer reflective coatings, in particular Mo/Si multilayers as used for Extreme UV
lithography. An organic material, a polyimide, was applied, from other work known to reduce the roughness of the
substrate 1, 2. It appeared to be possible to remove the multilayer coating, including the SRL, without any damage or
roughening of the substrate surface. The SRL was spin-coated at 1500 - 6000 rpm on different substrate types (Si,
quartz, Zerodur) with diameters up to 100 mm. For this range of parameters, the multilayer centroid wavelength value
remained unchanged, while its reflectivity loss, upon applying the SRL, was limited to typically 0.7%. The latter is
demonstrated to be caused by a minor increase of the SRL surface roughness in the high spatial frequency domain. The
AFM characterized roughness remained constant at 0.2 nm during all stages of the substrate recovery process,
independent of the initial substrate roughness.
Reported are the first calculations and experimental results of the deposition of EUV multilayer coatings that actively suppress the reflectance in the VUV wavelength range. In the undesired 100-200 nm band a factor of five reduction was achieved for one single optical element, while only a minor loss of 4.5% reflectance for λ = 13.5 nm, the operating wavelength of EUVL, was found.
E. Louis, A. Yakshin, E. Zoethout, R. van de Kruijs, I. Nedelcu, S. van der Westen, T. Tsarfati, F. Bijkerk, H. Enkisch, S. Müllender, B. Wolschrijn, B. Mertens
Reported is a summary of the development of EUV Mo/Si multilayer coating technology. Though the results are developed for application in Extreme Ultraviolet Lithography, they are of a broader relevance including optics for astronomy. The coating process used consists of electron beam evaporation in combination with low energy ion beam smoothening. The radiation hardness of these coatings is discussed and methods to reduce the multilayer induced substrate stress. The reflectance of the coatings, which are covered with a special protective capping layer, is typically around 65%, while the non correctable figure error added by the full multilayer stack is controlled to better than 15 picometer.
Reported is a summary of the coating of three elements of the illuminator and three of the projection optics of the EUVL Process Development Tool. The coating process used is e-beam evaporation in combination with low energy ion beam smoothening. The reflectance of the coatings, which are covered with a special protective capping layer, is typically around 65% and the non correctable figure error that is added by the full multilayer stack is controlled to better than 15 picometer.
Reported is the production of multilayer EUV coatings on 25000 mm2 large mirror substrates using e-beam based deposition. The accuracy achieved over the full area and the full multilayer stack amounts to an added figure error of 0.02 nm, i.e. in the sub-atomic distance range, thus meeting the future requirements on EUV coating technology.
Although Mo/Si multilayers are now widely used in EUV lithography development programs, multilayer induced substrate stress continues to be a major issue. Standard stress values of -350 to -450 MPa, reported for Mo/Si systems produced by magnetron sputtering, induce an intolerable deformation of the surface figure of EUV optical components. Stress in e-beam deposited Mo/Si multilayers has not been reported before. At FOM Rijnhuizen, an extensive stress mitigation program has been carried out on multilayers produced by e-beam deposition and medium energy ion polishing. The stress in our standard, high reflectance Mo/Si multilayers is less than -200 MPa. Although e-beam deposition apparently halves the typical stress values obtained by sputter deposition, it is still above the allowable limit for the first lithographic system, the so-called Alpha Tool. To further reduce stress, the influence of the Mo fraction, the number of periods and the multilayer period or d-spacing has been investigated. Varying the Molybdenum fraction in e-beam deposited multilayers results in a similar dependency as reported for magnetron sputtered coatings, though at strongly reduced absolute values. Furthermore, variation of the d-spacing has a small influence on stress. The number of periods however, has no influence on the stress value in the range from 20 to 50 periods. Applying stress mitigation techniques based on adjustment of the Mo fraction, a high reflectance of above 69% at near normal incidence at 13.5 nm has been obtained for multilayers with a stress value of only -33 MPa. This has been achieved by using Mo and Si only. This stress value is sufficiently low to enable the first generations of EUVL optics.
Extreme ultraviolet lithography requires vacuum conditions in the optical train. In order to maintain sufficient energy throughput, reflection reduction of multilayer mirrors due to contamination has to be minimized. We report on oxidation and carbonization experiments on MoSi mirrors under exposure with EUV radiation from a synchrotron. To mimic the effects of EUV radiation we also exposed samples using an electron gun. The oxidation rate was found to be ~0.015 nm/h per mW/mm2 of EUV radiation under vacuum conditions that are typical for a high throughput EUVL system, I.e. 10-6 mbar H2O. This oxidation can to a large extend be suppressed by using smart gas blend strategies during exposure, e.g. using ethanol. A deposition rate of 0.25 nm/h was found when the hydrocarbon pressure of Fomblin was reduced to 10(superscript -9 mbar. We demonstrate that carbonization can be suppressed by admitting oxygen during electron gun exposure.
Frank Scholze, Burkhard Beckhoff, G. Brandt, R. Fliegauf, Roman Klein, Bernd Meyer, D. Rost, Detlef Schmitz, M. Veldkamp, J. Weser, Gerhard Ulm, Eric Louis, Andrey Yakshin, Sebastian Oestreich, Fred Bijkerk
High-accuracy characterization of optical components has been one of the main services of the PTB radiometry laboratory at BESSY I. Now, after the shut down of BESSY I with the end of 1999, PTB is operating two new beamlines suitable for EUV reflectometry at their new laboratory at BESSY II. As at BESSY I, synchrotron radiation from a bending magnet is used for reflectometry but additionally a beamline at an undulator covering the same spectral range from 50 eV to 1800 eV can be used for special applications where, e.g., high radiant power or very high spectral purity is needed. In this paper, the characteristics of the beamlines are presented. We present the results of the beamline characterization on photon flux, spectral resolution, spectral purity and beam stability with special respect to the EUV photon energy range. During the phase of simultaneous operation of BESSY I and II in 1999, a direct comparison was done for reflectance measurements at high equality Mo/Si EUV mirrors. The results showed perfect agreement: (68.98 +/- 0.17)% at BESSY I and (69.10 +/- 0.24)% at BESSY II. The wavelength scale was calibrated using the absorption resonances of Ar, Kr, and Xe whose energies are known with a relative uncertainty of about 10-4. The measured peak positions agreed within this uncertainty.
Mo/S multilayer mirrors have been exposed to intense monochromatic EUV radiation in order to investigate a possible deterioration of the mirror reflectance under different vacuum conditions. Power densities up to 3 mW/mm2 were applied at the PB undulator beamline at BESSY II, applying a hydrocarbon enriched vacuum. The mirror reflectance has been monitored in situ during several hours of exposure. Vacuum pressures of 3 X 10-8 mbar (without hydrocarbons) and 10-7 mbar (with hydrocarbons) at EUV intensities of 3 mW/mm2, respectively 0.2 mW/mm2 have been applied. The reflectance of the mirrors decreased when exposed to EUV radiation in hydrocarbon enriched vacuum, while no loss in reflectance was observed when no hydrocarbons were added to the vacuum. Ozone-cleaning experiments, using UV produced ozone from air at atmospheric pressure, were performed and show that Mo/S mirrors do not suffer from prolonged exposure to ozone.
Eric Louis, Andrey Yakshin, Peter Goerts, Sebastian Oestreich, Edward Maas, M. Kessels, Detlef Schmitz, Frank Scholze, Gerhard Ulm, Stefan Muellender, Markus Haidl, Fred Bijkerk
High performance reflective coatings for EUVL projection systems can be produced by using e-beam evaporation in combination with ion beam smoothening of the interfaces. Using this technique, we recently demonstrated a near normal incidence reflectivity of 69.5%. Another, equally important part of the optimization of the coating process is the lateral control of the thickness of the layers, that is the d-spacing of the coating. In this paper we demonstrate the ability to obtain a uniformity of the d-spacing of the coating of better than +/- 0.05% over a 6' area, both on flat and concave surfaces (uniformity specified in terms of wavelength of maximum reflectance). All reflectance measurements have been carried out at the PTB facilities at the electron storage rings BESSY I and BESSY II in Berlin.
Eric Louis, Andrey Yakshin, Peter Goerts, Sebastian Oestreich, R. Stuik, Edward Maas, M. Kessels, Fred Bijkerk, Markus Haidl, Stefan Muellender, Michael Mertin, Detlef Schmitz, Frank Scholze, Gerhard Ulm
Extensive optimization on the fabrication of Mo/Si multilayer systems is carried out at the FOM Institute Rijnhuizen using e-beam evaporation. The process is being optimized including parameters such as variation of the mirror's center wavelength, the metal fraction, deposition parameters, and the layer composition. Reflectivities of 69.5% are demonstrated at normal incidence, with values of 67 to 69% being routinely achieved, demonstrating the capabilities of the deposition process. Some evidence of smoothening to interface roughness values lower than the roughness of the initial substrate is given. Furthermore, investigation of the temporal behavior of the coatings does not indicate any loss of reflectivity over an eight-month period. An analysis of the multilayer composition and the interface roughness is given. The reflectivity measurements have been carried out at the PTB facilities at the electron storage rings BESSY I and BESSY II in Berlin. The results of measurements at both facilities are found to be identical and accuracy is discussed in detail.
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